CN114990927A - Imidazoline quaternary ammonium salt cationic paper softening agent and preparation method thereof - Google Patents
Imidazoline quaternary ammonium salt cationic paper softening agent and preparation method thereof Download PDFInfo
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- CN114990927A CN114990927A CN202210602831.0A CN202210602831A CN114990927A CN 114990927 A CN114990927 A CN 114990927A CN 202210602831 A CN202210602831 A CN 202210602831A CN 114990927 A CN114990927 A CN 114990927A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- 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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- C07D233/04—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 plant oleic acid cyclic imidazoline; and 2, step: carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain plant oleic acid cyclic imidazoline quaternary ammonium salt; and step 3: mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 smoothing effect of paper are obviously 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
Softening agents are compounds whose molecular structure contains a long-chain hydrocarbon group at one end and a polar or reactive group at the other end that can be bonded to the fiber. Molecules of the softening agent can form hydrophobic groups on the surface of the fiber to be adsorbed outwards, so that the dynamic and static friction factors of the fiber substance are reduced, and smooth and soft hand feeling is obtained. The softening agent is divided into an anionic softening agent, a cationic softening agent and a non-ionic softening agent, wherein the cationic softening agent has better antistatic property and better soft smoothness, and can reduce the static friction factor between fibers.
Reference may be made to cn201811122209.x and CN202010038062.7 for studies in this respect.
CN200810025673.7 discloses a preparation method of a dialkyl amide imidazoline quaternary ammonium salt type paper softener, which comprises the steps of preparing a dialkyl amide imidazoline intermediate by taking stearic acid and diethylenetriamine as raw materials, and adding isopropanol and dimethyl sulfate into the dialkyl amide imidazoline intermediate to obtain the dialkyl amide imidazoline quaternary ammonium salt type paper softener.
CN202010038062.7 discloses a preparation method of amide imidazoline dimethyl sulfate fabric softener, in the method, stearic acid is heated and melted, diethylenetriamine is added and nitrogen is introduced to obtain imidazoline, then the prepared imidazoline is mixed with isopropanol solvent and heated to 85 ℃, and dimethyl sulfate is added to obtain active cation imidazoline.
The problems of the scheme are as follows: the softness and smoothness of the paper are improved to some extent, but the effect is slightly poor.
The scheme needs to solve the problems that: 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, which can effectively improve the softness and smoothness of paper without destroying the performances of other parameters of the paper such as bulk, pulp whiteness, electrolyte resistance, alkali resistance and the like.
The present invention is not specifically described: nM for nanomole/liter,. mu.M for micromole/liter,. mM for millimole/liter, M for mol/liter.
A preparation method of imidazoline quaternary ammonium salt cationic paper softener comprises the following steps:
step 1: preparing plant oleic acid cyclic imidazoline;
step 2: carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain plant oleic acid cyclic imidazoline quaternary ammonium salt;
and step 3: mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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: cottonseed oleic acid, lauric acid, palmitoleic acid, soybean oleic acid, linoleic acid and eleostearic acid.
Preferably, the vegetable oil acid consists of at least two of palmitoleic acid, soybean oil acid and linoleic acid;
the weight ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1: 0.8-1.2: 0 to 1.2.
Preferably, the step 1 specifically comprises: adding vegetable oleic acid and diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing reactants; gradually heating the reactants to 200-240 ℃ under the low pressure of 0.09kPa, and keeping the temperature for reacting for about 2.5-3 h; 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 the product until the product is condensed into a faint yellow solid imidazoline intermediate product;
the weight ratio of the vegetable oleic acid to the diethylenetriamine is 10: 1 to 2.1.
Preferably, the step 2 specifically comprises: putting the imidazoline intermediate product into a flask, and adding a first organic solvent; heating and stirring, dropwise adding dimethyl sulfate into a flask in several times, reacting for 5-6 h, and distilling the product under reduced pressure to remove excess water and unreacted dimethyl sulfate to obtain cyclic imidazoline quaternary ammonium salt of vegetable oleic acid;
the weight ratio of the imidazoline intermediate product, the first organic solvent and the dimethyl sulfate is 10: 4-5: 5.
preferably, the step 3 specifically comprises: transferring the plant 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 a product to a finished product;
the weight ratio of the plant oleic acid cyclic imidazoline quaternary ammonium salt to the emulsifier to the deionized water to the second organic solvent is 16-20: 5-6: 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 glycerol.
Preferably, the emulsifier is any one or more of peroxydodecyl ammonium chloride, hexadecyltrimethyl ammonium chloride and hexadecyl pyridine bromide.
Preferably, the first organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyl aldehyde, diethylene glycol, isopropanol and glycerol.
The imidazoline quaternary ammonium salt cationic paper softener is prepared by the method.
The invention has the beneficial effects that:
according to the invention, vegetable oleic acid is used as a hydrophobic group in the softening agent, after the softening agent is added into paper pulp, the hydrophilic group is adsorbed on the fiber, the hydrophobic group is arranged outwards, the fiber is coated by the vegetable oleic acid group, and the full and smooth hand feeling is obtained; the softening agent is used as a cationic softening agent, has positive charges and extremely high affinity to fibers, and is easier to adsorb; the vegetable oil acid contains saturated acid and unsaturated acid, so that the softener provides smooth hand feeling for paper, and also provides the paper with elastic and warm hand feeling.
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FIG. 1 is a process chart of performance test 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 a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Description of the reagents
The vegetable oil involved in the invention is domestic industrial vegetable oleic acid.
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 170 parts of cottonseed oleic acid and 36 parts of diethylenetriamine in parts by mass, adding into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants; starting a vacuum pump to keep the pressure at 0.09kPa, simultaneously gradually heating the reactants to 220 ℃, keeping the temperature for reacting 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 the product until the imidazoline intermediate product is condensed into a light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: putting 100 parts of imidazoline intermediate product obtained in the step (1) into a flask, and adding 40 parts of diethylene glycol and glycerol mixture; heating and stirring the mixture according to the following steps of: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into imidazoline by times according to the mass ratio of 1, reacting for 5.5 hours, and removing redundant water and unreacted dimethyl sulfate through reduced pressure distillation to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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, emulsifying at 50 ℃, and cooling the product to obtain a finished product.
Example 2
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 120 parts of palmitoleic acid and 25 parts of diethylenetriamine by weight parts, adding into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 200 ℃ and the temperature was maintained 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 until the product is condensed into a pale yellow solid imidazoline intermediate product.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are taken and placed into a flask, and 25 parts of diethylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 5 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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, emulsifying at 60 ℃, and cooling the product to obtain a finished product.
Example 3
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 150 parts of lauric acid and 15 parts of diethylenetriamine in parts by mass, adding into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 235 ℃ and the temperature was maintained for about 2.5 h. 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 until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: and (2) taking 100 parts of imidazoline intermediate product obtained in the step (1), putting the imidazoline intermediate product into a flask, and adding 50 parts of isopropanol. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 5.5 h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 60 parts of isopropanol, emulsifying at 60 ℃, and cooling the product to obtain a finished product.
Example 4
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 180 parts of linoleic acid and 37 parts of diethylenetriamine by weight parts, adding the weighed materials into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 240 ℃ and the temperature was maintained for about 3 hours. Stopping heating to naturally cool the intermediate product to about 110 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: and (2) putting 50 parts of imidazoline intermediate product obtained in the step (1) into a flask, and adding a proper amount of 25 parts of triethylene glycol monobutyl aldehyde. Heating and stirring the imidazole intermediate product: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 5 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 60 parts of triethylene glycol monobutyl aldehyde, emulsifying at 45 ℃, and cooling the product to obtain a finished product.
Example 5
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 200 parts of eleostearic acid and 40 parts of diethylenetriamine, adding the materials into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 230 ℃ and the temperature was maintained for about 3 h. 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 until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: and (2) putting 100 parts of imidazoline intermediate product obtained in the step (1) into a flask, and adding 50 parts of glycerol. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 monobutyl aldehyde, emulsifying at 50 ℃, and cooling the product to obtain a finished product.
Example 6
(1) Preparing the plant oleic acid cyclic imidazoline: weighing 100 parts of soybean oleic acid and 20 parts of diethylenetriamine, adding the soybean oleic acid and the 20 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 213 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 110 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: and (2) putting 100 parts of imidazoline intermediate product obtained in the step (1) into a flask, and adding 50 parts of dipropylene glycol. Heating and stirring the imidazole intermediate product: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 monobutyl aldehyde, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 7
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid and linoleic acid according to the mass ratio of 1: adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The pressure was maintained at 0.09kPa by starting the vacuum pump while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: and (2) putting 100 parts of imidazoline intermediate product obtained in the step (1) into a flask, and adding 50 parts of dipropylene glycol. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 50 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 8
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid and soybean oleic acid in a mass ratio of 1: adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 9
(1) Preparing the plant oleic acid cyclic imidazoline: according to the mass parts, the soybean oleic acid and the linoleic acid are weighed to have the mass ratio of 1: adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyltrimethylammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 10
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass ratio of 1: 1: and (2) adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The pressure was maintained at 0.09kPa by starting the vacuum pump while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the product is condensed into a pale yellow solid imidazoline intermediate product.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 11
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass ratio of 1: 0.8: 1.2 adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying plant 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: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 12
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass ratio of 1: 1.2: 1.2 adding 120 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Example 13
(1) Preparing the plant oleic acid cyclic imidazoline: weighing palmitoleic acid and soybean oleic acid in a mass ratio of 1: and adding 120 parts of 0.8 parts of mixed vegetable oleic acid and 25 parts of diethylenetriamine 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 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are placed into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dripping dimethyl sulfate into the imidazoline intermediate product in a fractional manner, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, 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 hexadecyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Comparative example 1
(1) Preparation of oleic acid cyclic imidazoline: weighing 120 parts of stearic acid and 25 parts of diethylenetriamine by weight, adding the stearic acid and the diethylenetriamine into a reaction bottle, continuously stirring, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 ℃ and the temperature was maintained for about 2.5 h. Stopping heating to naturally cool the intermediate product to about 100 ℃, pouring the product into a container while the product is hot, and continuously cooling until the imidazoline intermediate product is condensed into light yellow solid.
(2) Carrying out quaternization reaction on the oleic acid cyclic imidazoline to obtain the plant oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol are added. Heating and stirring the imidazole intermediate: dimethyl sulfate 2: 1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in a mass ratio of 1, and reacting for 6 hours. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid.
(3) Mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of oleic acid, 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 hexadecyltrimethylammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol, emulsifying at 55 ℃, and cooling the product to obtain a finished product.
Performance testing
The test process is shown in figure 1, the pulp concentration is 30%, the pulp proportioning is northern pine: goldfish short fiber 28%: 72 percent. The mode of adding the paper softening agent in examples 1-13 and comparative example is set as pulp addition, the dosage is 0.25 kg/ton pulp, and the pH value of white water is 8.23.
And (3) softness testing: in the standard, the softness of paper is measured according to a PY-H613 softness tester, in the test, when a test head presses a sample into a gap for a certain depth (referring to the 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 the softness, and the softness is expressed by millinewtons, the smaller the softness value is, the softer the sample is.
Smoothness testing: smoothness testing is determined according to paper and board smoothness determination (the Cocker method) GB/T456-2002idt ISO 5627: 1995.
Filling power: effect of softening agent finishing of pulp the bulkiness of the pulp after sheeting was evaluated by a method of measuring the thickness of paper, with a standard of 1.05-1.15mm per double layer.
The softener stability was tested as follows:
electrolyte resistance: 3g of the sample was weighed into a 150mL beaker and 2% MgCl was added 2 ·6H 2 97mL of O solution is stirred uniformly and then is kept stand for 24h, and the stability of the emulsion in the beaker is observed.
Alkali resistance: weighing 3g of the sample, placing the sample in a 100mL beaker, adding 97mL of soda solution with pH value of 11, stirring uniformly, standing for 4h, and observing the stability of the emulsion in the beaker.
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 oil acid hydrophobic group softener has higher softening effect, smoothing effect, bulk and pulp whiteness compared with the stearic acid hydrophobic group softener. When the vegetable oil acid hydrophobic group is a mixed vegetable oil acid hydrophobic group, the softening effect and the smoothing effect are further improved.
The following conclusions can be drawn from the above tests:
1. it can be demonstrated by examples 1 to 13 that: when the vegetable oil acid is the mixed oleic acid of the soybean oil acid, the palmitoleic acid and the linoleic acid, the softening agent has more excellent performance.
2. It can be demonstrated by examples 1 to 13 and comparative example 1 that: when the vegetable oleic acid hydrophobic group softening agent has better modification effect on paper than stearic acid hydrophobic group softening agent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of imidazoline quaternary ammonium salt cationic paper softener is characterized by comprising the following steps:
step 1: preparing plant oleic acid cyclic imidazoline;
step 2: carrying out quaternization reaction on the plant oleic acid cyclic imidazoline to obtain plant oleic acid cyclic imidazoline quaternary ammonium salt;
and step 3: mixing and emulsifying the cyclic imidazoline quaternary ammonium salt of vegetable oleic acid, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener.
2. The method of making the imidazoline quaternary cationic paper softener of claim 1, wherein the vegetable oleic acid is selected from at least one of the following: cottonseed oleic acid, lauric acid, palmitoleic acid, soybean oleic acid, linoleic acid and eleostearic acid.
3. The method of making the imidazoline quaternary cationic paper softener of claim 1 wherein the vegetable oleic acid is comprised of at least two of palmitoleic acid, soy oleic acid, linoleic acid;
the weight ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1: 0.8-1.2: 0 to 1.2.
4. 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, raising the temperature to 100 ℃ under the protection of nitrogen, and mixing reactants; gradually heating the reactants to 200-240 ℃ under the low pressure of 0.09kPa, and keeping the temperature to react for about 2.5-3 h; 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 the product until the product is condensed into a faint yellow solid imidazoline intermediate product;
the weight ratio of the vegetable oleic acid to the diethylenetriamine is 10: 1 to 2.1.
5. The method of claim 4, wherein step 2 is specifically: putting the imidazoline intermediate product into a flask, and adding a first organic solvent; heating and stirring, dropwise adding dimethyl sulfate into a flask in several times, reacting for 5-6 h, and distilling the product under reduced pressure to remove excess water and unreacted dimethyl sulfate to obtain cyclic imidazoline quaternary ammonium salt of vegetable oleic acid;
the weight ratio of the imidazoline intermediate product, the first organic solvent and the dimethyl sulfate is 10: 4-5: 5.
6. the method of claim 5, wherein step 3 is specifically: transferring the plant 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 a product to a finished product;
the weight ratio of the plant oleic acid cyclic imidazoline quaternary ammonium salt to the emulsifier to the deionized water to the second organic solvent is 16-20: 5-6: 3-4: 9 to 12.
7. The method of claim 6, wherein the second organic solvent is one or more of dipropylene glycol, triethylene glycol monobutyl aldehyde, diethylene glycol, isopropanol, and glycerin.
8. The method of claim 6, wherein the emulsifier is any one or more of a peroxydodecylammonium chloride, a cetyltrimethylammonium bromide, and a cetylpyridinium bromide.
9. The method of claim 5, wherein the first organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyraldehyde, diethylene glycol, isopropanol, and glycerol.
10. An imidazoline quaternary ammonium salt cationic paper softener prepared by the method of any one of claims 1 to 9.
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