Fatty acid diglyceride and preparation method and application thereof
阅读说明：本技术 一种脂肪酸二聚甘油酯及其制备方法和应用 (Fatty acid diglyceride and preparation method and application thereof ) 是由 朱新宝 王婉蓉 韩雪 于鹏达 陈露露 李雷声 李瑞铭 于 2021-10-08 设计创作，主要内容包括：本发明属于有机化工技术领域,提供了一种脂肪酸二聚甘油酯及其制备方法和应用。本发明提供了一种脂肪酸二聚甘油酯,具有式I所述结构：式I中,R为烷烃基或烯烃基；所述烷烃基为C-(11)-C-(17)烷烃基；所述烯烃基为C-(11)-C-(17)烯烃基。在本发明中,由于式I中,R为碳链很长的基团,使得脂肪酸二聚甘油酯沸点高且耐热性好。同时,由于脂肪酸二聚甘油酯含有三个羟基,使得脂肪酸二聚甘油酯作为纸张柔软保湿剂时,具有较好的锁水保湿及柔软性能。(The invention belongs to the technical field of organic chemical industry, and provides a fatty acid diglyceride and a preparation method and application thereof. The invention provides a fatty acid diglyceride, which has a structure shown in a formula I: in the formula I, R is alkyl or alkenyl; the alkyl is C 11 ‑C 17 An alkyl group; the alkylene group is C 11 ‑C 17 An alkylene group. In the invention, as R is a group with a long carbon chain in the formula I, the fatty acid diglyceride has high boiling point and good heat resistance. Meanwhile, because the fatty acid diglyceride contains three hydroxyl groups, the fatty acid diglyceride has better water-locking, moisture-keeping and softening performances when being used as a paper softening humectant.)
1. A diglyceride of fatty acids having the structure of formula I:
in the formula I, R is alkyl or alkenyl; the alkyl is C11-C17An alkyl group; the alkylene group is C11-C17An alkylene group.
2. A process for the preparation of diglycerides of fatty acids according to claim 1, which comprises the steps of:
carrying out ring-opening esterification reaction on fatty acid and epichlorohydrin under the action of a phase transfer catalyst to obtain fatty acid epichlorohydrin ester reaction liquid; the carbon chain of the fatty acid is C11-C17Alkyl radicals or C11-C17An alkylene group;
carrying out ring-closing reaction on the fatty acid epichlorohydrin ester reaction liquid and sodium hydroxide, and refining to obtain fatty acid glycidyl ester;
and carrying out ring-opening reaction on the fatty acid glycidyl ester and glycerol under the action of a catalyst to obtain the fatty acid diglyceride.
3. The process according to claim 2, characterized in that the molar ratio between the fatty acid and epichlorohydrin is 1: (2-8).
4. The production method according to claim 2, wherein the phase transfer catalyst is a quaternary ammonium salt; the quaternary ammonium salt comprises one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride; the mass of the phase transfer catalyst is 1-5% of that of the fatty acid.
5. The method according to any one of claims 2 to 4, wherein the temperature of the ring-opening esterification reaction is 60 to 100 ℃; the time of the ring-opening esterification reaction is 0.5-2 h.
6. The production method according to claim 2, wherein the molar ratio of the fatty acid epichlorohydrin ester to the sodium hydroxide in the fatty acid epichlorohydrin ester reaction liquid is 1: (1-2).
7. The preparation method according to claim 2 or 6, wherein the temperature of the ring-closure reaction is 20-80 ℃, and the ring-closure reaction time is 2-8 h.
8. The production method according to claim 2, wherein the molar ratio of the fatty acid glycidyl ester to the glycerin is 1: (3-8).
9. The preparation method according to claim 2 or 8, wherein the temperature of the ring-opening reaction is 60-120 ℃; the ring-opening reaction time is 3-7 h.
10. Use of a diglyceride of fatty acids according to claim 1 or obtained by the method according to any one of claims 2 to 9 as a humectant for softening paper.
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to fatty acid diglyceride and a preparation method and application thereof.
Background
Softeners are a class of chemicals that change the static and dynamic coefficients of friction of the fibers. When the static friction coefficient is changed, the hand feeling is smooth and easy to move on the fiber or fabric; when the coefficient of dynamic friction is changed, the fine structures between the fibers tend to move relative to each other, that is, the fibers or the fabric tend to be deformed. The combined feel of the two is soft. Softness is typically characterized by a softness tester to a specific value.
After the softening agent is added into the papermaking cream, the softening agent can be directionally adsorbed on the surface of the fibers, the hydrophobic groups are arranged outwards, the C-C single bond rotates freely, so that the orderly hydrophobic alkyl chains can slide mutually, the interfacial tension is reduced, the friction coefficient of the fibers is reduced, the friction resistance between the fibers or between the fibers and a human body is reduced, and the fluffy and soft hand feeling is obtained.
Currently, the softener is usually a silicone softener, and the softener is emulsion or microemulsion of polysiloxane and derivatives thereof, so that the fabric or paper has good softness and smooth hand feeling. However, the silicone softener is mostly applied to fabrics, and has a certain softening effect on paper, but the silicone softener is only applied to the surface of the paper, so that the improvement effect on the softness and water retention rate of the paper is limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a fatty acid diglyceride, a preparation method and applications thereof. When the fatty acid diglyceride provided by the invention is used as a paper softening humectant, the softness and the water retention rate of paper are greatly improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fatty acid diglyceride, which has a structure shown in a formula I:
in the formula I, R is alkyl or alkenyl; the alkyl is C11-C17An alkyl group; the alkylene group is C11-C17An alkylene group.
The invention also provides a preparation method of the fatty acid diglyceride, which comprises the following steps:
carrying out ring-opening esterification reaction on fatty acid and epichlorohydrin under the action of a phase transfer catalyst to obtain fatty acid epichlorohydrin ester reaction liquid; the carbon chain of the fatty acid is C11-C17Alkyl radicals or C11-C17An alkylene group;
carrying out ring-closing reaction on the fatty acid epichlorohydrin ester reaction liquid and sodium hydroxide, and refining to obtain fatty acid glycidyl ester;
and carrying out ring-opening reaction on the fatty acid glycidyl ester and glycerol under the action of a catalyst to obtain the fatty acid diglyceride.
Preferably, the molar ratio of the fatty acid to the epichlorohydrin is 1: (2-8).
Preferably, the phase transfer catalyst is a quaternary ammonium salt; the quaternary ammonium salt comprises one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride; the mass of the phase transfer catalyst is 1-5% of that of the fatty acid.
Preferably, the temperature of the ring-opening esterification reaction is 60-100 ℃; the time of the ring-opening esterification reaction is 0.5-2 h.
Preferably, the mole ratio of the fatty acid epichlorohydrin ester to the sodium hydroxide in the fatty acid epichlorohydrin ester reaction liquid is 1: (1-2).
Preferably, the temperature of the ring-closure reaction is 20-80 ℃, and the ring-closure reaction time is 2-8 h.
Preferably, the molar ratio of the fatty acid glycidyl ester to the glycerol is 1: (3-8).
Preferably, the temperature of the ring-opening reaction is 60-120 ℃; the ring-opening reaction time is 3-7 h.
The invention also provides application of the fatty acid diglyceride in the technical scheme or the fatty acid diglyceride prepared by the preparation method in the technical scheme as a paper softening humectant.
The invention provides a fatty acid diglyceride, which has a structure shown in a formula I:
in the formula I, R is alkyl or alkenyl; the alkyl is C11-C17An alkyl group; the alkylene group is C11-C17An alkylene group.
In the invention, as R is a group with a long carbon chain in the formula I, the fatty acid diglyceride has high stability. Each softener molecule contains a hydrophobic alkyl chain, and the hydrophobic alkyl chain is generally composed of 11 to 17 carbon atoms, the more linear the better the softness. Because the fatty acid diglyceride provided by the invention has longer hydrophobic alkyl chains, the defects on the fiber surface can be repaired through the arrangement of the hydrophobic groups and the hydrophilic groups, so that the surface smoothness of the fiber is improved, and the softness of paper is improved. Meanwhile, because the fatty acid diglyceride contains three hydroxyl groups, when the fatty acid diglyceride is used as a paper softening humectant, the water-locking moisturizing and softening performances of paper are remarkably improved.
The invention also provides a preparation method of the fatty acid diglyceride, which comprises the following steps: carrying out ring-opening esterification reaction on fatty acid and epichlorohydrin under the action of a phase transfer catalyst to obtain fatty acid epichlorohydrin ester reaction liquid; the carbon chain of the fatty acid is C11-C17Alkyl radicals or C11-C17An alkylene group; carrying out ring-closing reaction on the fatty acid epichlorohydrin ester reaction liquid and sodium hydroxide, and refining to obtain fatty acid glycidyl ester; and carrying out ring-opening reaction on the fatty acid glycidyl ester and glycerol under the action of a catalyst to obtain the fatty acid diglyceride. The raw materials adopted by the invention are renewable resources, and the cost is low.
Drawings
FIG. 1 is an infrared spectrum of oleic acid, epichlorohydrin oleate, glycidyl oleate and diglycerol oleate in example 1;
FIG. 2 is a scanning electron micrograph of an original facial tissue;
FIG. 3 is a scanning electron micrograph of a tissue paper after using amino silicone oil;
FIG. 4 is a scanning electron micrograph of a tissue paper using diglycerol oleate.
Detailed Description
The invention provides a fatty acid diglyceride, which has a structure shown in a formula I:
in the formula I, R is alkyl or alkenyl; the alkyl is C11-C17An alkyl group; the alkylene group is C11-C17An alkylene group.
In the present invention, the alkyl group preferably includes a straight chain C11-C17Alkyl or branched C11-C17An alkyl group. In the present invention, the alkenyl group preferably includes C containing one double bond or multiple double bonds11-C17An alkylene group, which in particular embodiments of the present invention is preferably C containing one or two double bonds11-C17An alkylene group.
The invention also provides a preparation method of the fatty acid diglyceride, which comprises the following steps:
carrying out ring-opening esterification reaction on fatty acid and epichlorohydrin under the action of a phase transfer catalyst to obtain fatty acid epichlorohydrin ester reaction liquid;
carrying out ring-closing reaction on the fatty acid epichlorohydrin ester reaction liquid and sodium hydroxide, and refining to obtain fatty acid glycidyl ester;
and carrying out ring-opening reaction on the fatty acid glycidyl ester and glycerol under the action of a catalyst to obtain the fatty acid diglyceride.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention carries out ring-opening esterification reaction on fatty acid and epichlorohydrin under the action of a phase transfer catalyst to obtain fatty acid epichlorohydrin ester reaction liquid.
In the present invention, the carbon chain of the fatty acid is C11-C17Alkyl radicals or C11-C17An alkylene group; in a particular embodiment of the invention, the fatty acid particularly preferably comprises stearic acid, oleic acid or linoleic acid.
In the present invention, the phase transfer catalyst is preferably a quaternary ammonium salt; the quaternary ammonium salt preferably includes one or more of benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium chloride (BTMAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, and more preferably benzyltriethylammonium chloride.
In the present invention, the molar ratio of the fatty acid to epichlorohydrin is preferably 1: (2-8), more preferably 1: (3-7), more preferably 1: (3-5). In the present invention, the mass of the phase transfer catalyst is preferably 1 to 5% of the mass of the fatty acid.
In the invention, the temperature of the ring-opening esterification reaction is preferably 60-100 ℃, more preferably 70-90 ℃, and more preferably 90 ℃; the time of the ring-opening esterification reaction is preferably 0.5-2 h.
The fatty acid epichlorohydrin ester reaction liquid is directly subjected to subsequent ring-closing reaction without post-treatment.
After the reaction liquid of the fatty acid epichlorohydrin ester is obtained, the reaction liquid of the fatty acid epichlorohydrin ester and sodium hydroxide are subjected to ring-closing reaction, and the fatty acid glycidyl ester is prepared through refining treatment.
In the present invention, the sodium hydroxide is preferably used in the form of a sodium hydroxide solution; the concentration of the sodium hydroxide solution is preferably 32-48 wt%, and more preferably 32 wt%; the adding mode of the sodium hydroxide solution is preferably dropwise adding, and the sodium hydroxide solution is preferably added within 50-70 min.
In the present invention, the molar ratio of the fatty acid epichlorohydrin ester and the sodium hydroxide in the fatty acid epichlorohydrin ester reaction liquid is preferably 1: (1-2), more preferably 1: 1.4.
in the invention, the temperature of the ring-closure reaction is preferably 20-80 ℃, more preferably 25-70 ℃, and more preferably 30-60 ℃; the time of the ring-closure reaction is preferably 2-8 h.
In the present invention, the refining treatment preferably includes the steps of: filtering the obtained closed-loop reaction material, standing and layering the obtained filtrate, and removing a lower-layer water phase; and washing the crude product with water, and then carrying out reduced pressure distillation to recover excessive epichlorohydrin to obtain the fatty acid glycidyl ester.
In the invention, the washing times are preferably 2-3 times until the washing water is neutral; the volume of water is preferably 20-30% of the volume of the crude product in each water washing.
In the present invention, the degree of vacuum of the reduced pressure distillation is preferably-0.09 MPa; the preferable kettle temperature is 110-140 ℃, and the more preferable kettle temperature is 120-125 ℃. The reduced pressure distillation enables recovery of excess epichlorohydrin.
After the fatty acid glycidyl ester is obtained, the fatty acid glycidyl ester and glycerol are subjected to ring-opening reaction under the action of a catalyst to obtain the fatty acid diglyceride.
In the present invention, the molar ratio of the fatty acid glycidyl ester to the glycerin is preferably 1: (3-8), more preferably 1: (4-7), more preferably 1: (5-6).
In the present invention, the catalyst preferably includes an acidic catalyst or a basic catalyst. In the present invention, the acidic catalyst preferably comprises a protic acid or a lewis acid; the protic acid preferably comprises concentrated hydrochloric acid, concentrated sulfuric acid or perchloric acid; the Lewis acid preferably comprises indium trichloride, antimony trichloride, boron trifluoride diethyl etherate or stannic chloride; the acidic catalyst is preferably used in the form of a solid acid supported on a carrier, which preferably comprises activated carbon or bentonite. In the present invention, the basic catalyst preferably includes sodium hydroxide, potassium hydroxide, strontium hydroxide, or barium hydroxide. In the invention, the mass of the catalyst is preferably 0.5-1% of the total mass of the fatty acid glycidyl ester and the glycerol.
In the present invention, the order of mixing the fatty acid glycidyl ester, glycerin and catalyst preferably includes: firstly, glycerol and a catalyst are mixed, and then fatty acid glycidyl ester is dripped. In the invention, the addition of the fatty acid glycidyl ester is preferably completed within 50-70 min.
In the invention, the temperature of the ring-opening reaction is preferably 60-120 ℃, more preferably 70-110 ℃, and more preferably 70-100 ℃; the time of the ring-opening reaction is preferably 3-7 h.
After the ring-opening reaction, the invention preferably further comprises separating the obtained ring-opening reaction feed liquid, and removing the lower layer glycerol to obtain the fatty acid diglyceride.
The invention also provides application of the fatty acid diglyceride in the technical scheme or the fatty acid diglyceride prepared by the preparation method in the technical scheme as a paper softening humectant.
In the present invention, when the diglyceride of fatty acids is used as a paper softening humectant, it preferably comprises the following steps:
the diglyceride of fatty acid is mixed with the glycerol aqueous solution for use.
In the invention, the mass ratio of glycerin to water in the glycerin water solution is preferably (60-90): (40-10).
In the present invention, the amount of the diglyceride of fatty acids added to the aqueous glycerol solution is preferably 0.1 to 2 wt%.
The method of application is not particularly limited in the present invention, and a method of applying the paper softening humectant well known to those skilled in the art may be adopted, for example, a mixture of fatty acid diglyceride and glycerin aqueous solution is directly applied to the paper to be treated.
The present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 282.5g (1mol) of oleic acid, 323.8g (3.5mol) of epichlorohydrin and 7.1g of benzyltriethylammonium chloride into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and carrying out ring-opening esterification reaction for 1h at 90 ℃ to obtain 613.4g of ring-opening esterification reaction mixture with the acid value of 0.1583 mgKOH/g; after the reaction is finished, cooling to 30 ℃, and dropwise adding 135mL of 32 wt% sodium hydroxide solution into the obtained ring-opening esterification reaction mixture within 60 min; controlling the reaction temperature to be 30 ℃, keeping the temperature and reacting for 4 hours, filtering the obtained closed-loop reaction liquid, standing the filtrate, separating out a lower-layer water phase, and washing the crude product with 80mL of water for 3 times respectively; then the vacuum degree is controlled to be minus 0.09MPa, the kettle temperature is controlled to be 120 ℃, epichlorohydrin is recovered, 319.5g of glycidyl oleate is prepared, and the epoxy value is 0.2483mol/100 g.
460.5g (5mol) of glycerol and 4.7g of hydrochloric acid (the mass concentration is 37%) are added into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, 319.5g (about 1mol) of glycidyl oleate is added dropwise within 60min, the temperature is controlled to be 70 ℃, ring-opening reaction is carried out for 4h, the obtained ring-opening reaction feed liquid is separated to remove the lower layer of excessive glycerol, and 431.2g of the product of diglycerol oleate is obtained, wherein the epoxy value is 0.0111mol/100 g.
FIG. 1 is an infrared spectrum of oleic acid, epichlorohydrin oleate, glycidyl oleate and diglycerol oleate. As can be seen from fig. 1: the infrared characterization spectrum of the oleic acid shows that: at 1710cm-1Has strong C ═ O stretching vibration absorption peak in carboxyl, and is 1415cm-1929cm from-1The existence of carboxyl can be proved by the bending vibration absorption peak of carboxylic acid O-H; in an infrared characterization spectrogram of the epichlorohydrin oleate, a characteristic absorption peak of carboxyl disappears at 1741cm-1The peak appears in strong ester group, wherein C ═ O stretching vibration absorption peak is 1170cm-1The generation of a C-O-C asymmetric stretching vibration absorption peak in an inner ester bond, the disappearance of carboxyl and the appearance of an ester group shows that the chlorohydrin ester intermediate is generated by oleic acid through esterification. In the infrared characterization spectrum of the glycidyl oleate, the glycidyl oleate has a characteristic absorption peak of a chlorohydrin ester intermediate and is 910cm-1An epoxy group asymmetric stretching vibration absorption peak appears, which shows that carboxyl groups disappear, ester groups and epoxy groups are generated, and the generation of the glycidyl oleate is proved. 910cm in infrared characterization spectrogram of diglyceride oleate-1The epoxy group in (1) disappeared at 3386cm-1The formation of diglyceride of oleic acid can be proved by the existence of-OH stretching vibration absorption peak, which indicates that hydroxyl exists in the formed product.
Example 2
Adding 141.3g (0.5mol) of oleic acid, 161.9g (1.75mol) of epichlorohydrin and 3.7g of benzyltriethylammonium chloride into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and carrying out ring-opening esterification reaction for 1h at 70 ℃ to obtain a ring-opening esterification reaction mixture (306.9g) with an acid value of 0.1583 mgKOH/g;
adding 67.5mL of 32 wt% sodium hydroxide solution dropwise into the obtained ring-opening esterification reaction mixture within 60min, controlling the reaction temperature at 50 ℃, reacting for 5h, filtering the obtained ring-closing reaction feed liquid, and standing the obtained filtrate to separate a lower-layer water phase; washing the crude product with 40mL of water for 3 times respectively; and (3) recovering epichlorohydrin and a small part of water from the washed crude product at a vacuum degree of-0.09 MPa and a kettle temperature of 125 ℃ to obtain 151.3g of glycidyl oleate, wherein the epoxy value is 0.2376mol/100 g.
230.3g (2.5mol) of glycerol and 2.3g of sulfuric acid (with the mass concentration of 98%) are added into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, 151.3g (0.5mol) of glycidyl oleate is added dropwise within 60min, the temperature is controlled to be 80 ℃, reaction is carried out for 4h, the obtained ring-opening reaction feed liquid is subjected to liquid separation to remove the lower-layer excess glycerol, and the product, namely the diglycerol oleate is 216.3g, and the epoxy value is 0.0021mol/100 g.
Example 3
284.5g (1mol) of stearic acid, 323.8g (3.5mol) of epichlorohydrin and 7.1g of benzyltriethylammonium chloride are added into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and ring-opening esterification reaction is carried out for 2h at 80 ℃ to obtain 615.4g of ring-opening esterification reaction mixture with the acid value of 0.2467 mgKOH/g.
Adding 135mL of 32 wt% sodium hydroxide solution dropwise into the obtained ring-opening esterification reaction mixture within 60min, controlling the temperature to be 50 ℃, carrying out heat preservation reaction for 5h, filtering the obtained ring-closing reaction feed liquid, standing the obtained filtrate to separate a lower-layer water phase, and washing the crude product with 80mL of water for 3 times respectively; and distilling the washed crude product at the vacuum degree of-0.09 MPa and the kettle temperature of 120 ℃, recovering epoxy chloropropane, and preparing 335.2g of glycidyl stearate with the epoxy value of 0.2258mol/100 g.
Adding 460.5g (5mol) of glycerol and 4.8g of concentrated sulfuric acid (the mass percentage content is 98%) into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, dropwise adding 335.2g (0.99mol) of glycidyl stearate within 60min, keeping the temperature at 80 ℃ for 5 hours, separating the obtained ring-opening reaction feed liquid to remove the lower-layer excessive glycerol, and obtaining 435.1g of the product of diglycerol stearate, wherein the epoxy value is 0.0012eq/100 g.
Example 4
Adding 280.4g (1mol) of linoleic acid, 323.8g (3.5mol) of epichlorohydrin and 7.1g of benzyltriethylammonium chloride into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, controlling the temperature of the ring-opening esterification reaction to be 80 ℃, and carrying out heat preservation reaction for 1.5h to obtain 611.3g of ring-opening esterification reaction mixture, wherein the acid value is 0.3509mg KOH/g.
Adding 135mL of 32 wt% sodium hydroxide solution dropwise into the obtained ring-opening esterification reaction mixture within 60min, controlling the temperature to be 40 ℃, carrying out heat preservation reaction for 3h, filtering the obtained ring-closing reaction feed liquid, standing the obtained filtrate to remove a lower-layer water phase, and washing the crude product with 80mL of water for 3 times respectively; and then recovering epoxy chloropropane from the washed crude product at the vacuum degree of-0.09 MPa and the kettle temperature of 120 ℃ to prepare 309.8g of linoleic acid glycidyl ester with the epoxy value of 0.2322mol/100 g.
460.5g (5mol) of glycerin and 38g of bentonite-supported stannic chloride (wherein the loading amount of stannic chloride is 10 wt%) are added into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, 308.0g (0.92mol) of linoleic acid glycidyl ester is added dropwise within 60min, the temperature is controlled at 70 ℃, after 5 hours of heat preservation, the reaction is filtered and separated to remove the lower layer of excessive glycerin, and 432.5g of linoleic acid diglyceride is obtained, wherein the epoxy value is 0.0015eq/100 g.
Test example
Softness test
The results of the measurement of softness by a softness meter after mixing the fatty acid diglyceride obtained in examples 1 to 4 and commercially available amino silicone oil as softeners with an aqueous glycerol solution (the mass ratio of glycerol to water was 85: 15) and uniformly applying the mixture to a base paper of 100mm by 100mm, and leaving the paper for 24 hours are shown in table 1.
Table 1 softness test results
Mass ratio of softening agent to glycerin aqueous solution
Softness (mN)
Example 1
1:100
37
Example 1
0.5:100
39
Example 2
1:100
36
Example 3
1:100
42
Example 4
1:100
43
Commercially available amino silicone oils
1:100
45
Commercially available amino silicone oils
0.5:100
51
Blank space
0:100
65
As can be seen from table 1: the softness test result of the fatty acid diglyceride coated on paper as the paper softener is superior to that of the amino silicone oil softener, and the invention makes a breakthrough in the aspect of paper softness.
Water retention test
The results of the measurement of the water retention at a certain temperature and a humidity of 60% in the paper obtained in examples 1 to 4 were shown in table 2, in which the diglyceride of fatty acids obtained in examples 1 to 4 and commercially available amino silicone oil as a softening agent were mixed with an aqueous solution of glycerin (the ratio of glycerin to water by mass: 85: 15), and the mixture was uniformly applied to 100mm by 100mm base paper.
Table 2 water retention test results
FIG. 2 is a scanning electron micrograph of an original facial tissue; FIG. 3 is a scanning electron micrograph of a back tissue using amino silicone oil (the mass ratio of amino silicone oil to glycerin aqueous solution is 0.25: 100); FIG. 4 is a scanning electron micrograph of a tissue paper using diglycerol oleate (mass ratio of diglycerol oleate to glycerin aqueous solution is 0.25: 100).
As can be seen from fig. 2 to 4: compared with the fibers of base paper and paper using amino silicone oil, the paper fibers using the diglyceride oleate obtained in the embodiment 1 are more organized, which shows that the fatty acid diglyceride softener provided by the invention can act on the internal structure of paper, is favorable for improving the softness of the paper and is favorable for locking moisture by the fibers; the fatty acid diglyceride provided by the invention is superior to amino silicone oil in the aspects of improving the softness of paper and locking water.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
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