CN101898104B - Method for cationization of surface of microcapsule with urea resin as capsule wall - Google Patents
Method for cationization of surface of microcapsule with urea resin as capsule wall Download PDFInfo
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- CN101898104B CN101898104B CN2010102306437A CN201010230643A CN101898104B CN 101898104 B CN101898104 B CN 101898104B CN 2010102306437 A CN2010102306437 A CN 2010102306437A CN 201010230643 A CN201010230643 A CN 201010230643A CN 101898104 B CN101898104 B CN 101898104B
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Abstract
The invention relates to a method for cationization of a surface of a microcapsule with a urea resin as a capsule wall by utilizing epoxypropyltrimethyl ammonium chloride, comprising the following steps: at room temperature, adding the microcapsule with the urea resin as the capsule wall and NaOH in a dispersed solvent and evenly stirring; adding the epoxypropyltrimethyl ammonium chloride in the mixed solution and heating the reaction system up to 60-70 DEG C and reacting for 60-120min to obtain a coarse microcapsule product having the cationic surface; placing the coarse microcapsule product having the cationic surface in an ethanol solution to be washed, filtering, changing a fresh ethanol solution to wash and filter the coarse microcapsule product, and repeating the operations for many times; and after washing, drying for 8-15h in a vacuum dryer to obtain the finished microcapsule product having the cationic surface. The invention improves the retention of the reversible thermochromatic microcapsule in paper pulp, reduces production cost and improves the quality of paper products. And the method of the invention is simple and practical.
Description
Technical field
The present invention relates to a kind of method of surface of microcapsule cationization, particularly a kind of is the method for the surface of microcapsule cationization of cyst wall to Lauxite through the epoxypropyl trimethylammonium chloride ammonium.
Background technology
Through attaching the reversible temperature induced color changing microcapsules reversible temperature induced color changing cheque paper of can manufacturing paper with pulp in starching, the cyst material of the reversible temperature induced color changing microcapsules of function admirable is a Lauxite at present, and the Lauxite surface is a nonionic.The keep mechanism of the reversible temperature induced color changing microcapsules of this type of nonionic in paper pulp is that fiber is to its physical absorption and mechanical retention effect; This has just caused reversible temperature induced color changing microcapsules retention low; It is serious to run off at wet end, has increased production cost greatly, has also strengthened water treatment difficulty off the net; In addition, the two sides aberration difference of the cheque paper of being manufactured paper with pulp is obvious, has influenced product quality.The surface of fiber has negative electrical charge; Surface at reversible temperature induced color changing microcapsules makes up cation; The suction-operated of increased fiber and reversible temperature induced color changing microcapsules, corresponding reversible temperature induced color changing microcapsules keeping in paper pulp, the production cost of reduction cheque paper of improving; In addition the microcapsules of surperficial cationization can in and anionic trash, improve the operation of wet end of machine system, reduce the consumption of cationic auxiliary.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the prior art, provide a kind of improve reversible temperature induced color changing microcapsules in paper pulp what keep, reduce production costs, improve quality of paper products is the method for the surface of microcapsule cationization of cyst wall to Lauxite.
According to technical scheme provided by the invention, said to being that the method for the surface of microcapsule cationization of cyst wall comprises the steps: with the Lauxite
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in dispersion solvent; Obtain mixed system, the dispersion solvent of adding is 88～98 weight portions, adding be that the microcapsules of cyst wall are 2～4.5 weight portions with the Lauxite; The NaOH that adds is 0.01～0.9 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 0.3～6 weight portion;
B, the reaction system of step a is warming up to 60～70 ℃ and react 60～120min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeated several times, the washing back obtained surperficial cationization microcapsules finished product in dry 8～15 hours in vacuum desiccator.
Said dispersion solvent is water, absolute ethyl alcohol, benzene, acetone or oxolane.
The reaction temperature of reaction system is controlled at 65 ℃ among the step b.
The present invention has improved reversible temperature induced color changing microcapsules keeping in paper pulp, has reduced production cost, improved quality of paper products, and method of the present invention is simple.
The specific embodiment
Inquire into catalyst, dispersion solvent, epoxypropyl trimethylammonium chloride ammonium and reaction temperature, time below to the surface of microcapsule ionization and to reversible temperature induced color changing cheque paper Effect on Performance.
1, the influence of the kind of catalyst and consumption
Epoxy radicals is by two carbon atoms and the three-membered ring that oxygen atom is formed, and two carbon atoms and an oxygen atom make epoxy radicals have resonance qualitly on same plane.The electronegativity of oxygen atom is bigger than carbon atom, causes the static polarization, makes oxygen atom cloud density increase on every side.Simultaneously the normal bond angle that squints far away of the bond angle in the three-membered ring makes epoxide ring have very big tension force, unstable chemcial property.But so just on epoxy radicals, form two reactive activity centers: the carbon atom that oxygen atom that cloud density is high and cloud density are low.When electrophilic reagent near the time with regard to the attack oxygen atom, when nucleopilic reagent near the time attack carbon atom then, and react rapidly, cause the fracture of carbon-oxygen bond, make epoxy ring-opening.Difference according to the active hydrogen kind; The reaction of epoxy radicals and active hydrogen can be divided into nucleophilic addition and electrophilic addition reaction; Corresponding catalyst is acidity and base catalyst, inquires into the influence to the surface of microcapsule cationization of HCl and two kinds of catalyst of NaOH below.
Table 1HCl consumption is to the influence of surface of microcapsule cationization and paper properties thereof
Annotate: microcapsules 5g, water 200ml, epoxypropyl trimethylammonium chloride ammonium 0.02mol, 70 ℃ of temperature, time 30min.
Different hydrochloric acid consumptions are as shown in table 1 to the influence of microcapsules cationization and paper properties.Can find out that the surperficial cationization efficient of microcapsules is lower under the acidic catalyst system, increasing the hydrochloric acid consumption can not significantly improve, and its reason possibly be that the addition reaction of hydroxyl and epoxy radicals is nucleophilic addition, is easy under the alkali condition carry out;-NH2 and epoxy radicals can be carried out electrophilic addition reaction, help the carrying out of this reaction under the acid condition, but in microcapsules, mainly exist with the amide groups form, and its reactivity reduces greatly, so the microcapsules cationization efficient under the acid condition is very low.Acidic catalyst can not effectively be realized reversible temperature induced color changing surface of microcapsule cationization.Acid ionization is also less to the influence of cheque paper aberration, compares with the microcapsules that do not carry out surface ionization, and the retention of microcapsules in paper pulp changes very little, explains that acidic catalyst can not effectively realize the surperficial cationization of microcapsules.
With NaOH is that catalyst is as shown in table 2 to the influence of surface of microcapsule cationization; Compare and to find out with table 1; NaOH is the surperficial cationization that catalyst can effectively be realized microcapsules, and the raising of cation ionization degree helps microcapsules keeping in paper, and value of chromatism is along with the raising of cation ionization degree also increases; The microcapsules that are cationization help its keeping in paper pulp; Because fiber surface is an anion, the microcapsules of surperficial cationization add and also help keeping of fiber, and the retention of fiber also increases gradually.Increase along with the NaOH consumption; The cation ionization degree of microcapsules begins to increase gradually; After the ratio of NaOH and GTMA was greater than 0.09: 1, the surperficial cation ionization degree of microcapsules decreased, and this is because alkalescence strengthens; The hydrolysis of corresponding epoxy radicals and Ionized group strengthens, and reacts as follows.Can find out that from the course of reaction of microcapsules and epoxypropyl trimethylammonium chloride ammonium the existence of base catalyst makes the hydroxyl of microcapsules be transformed into negative oxygen ion in the reaction system, has strengthened the nucleophilie nucleus ability of hydroxyl greatly, thereby has significantly improved reaction efficiency and reaction rate; The reactivity of the hydrogen atom on the amide groups is just littler, is difficult to react with epoxy radicals under the room temperature, and other has the research report, amide groups under alkali condition also can with epoxy radicals generation addition reaction.Therefore, more excellent catalyst was NaOH, and the mass ratio of NaOH and microcapsules is 0.5%～2.0%, and the mol ratio of NaOH: GTA can realize the surperficial cationization of microcapsules preferably at 0.06: 1～0.12: 1, and optimum consumption is 0.09: 1.
Table 2NaOH consumption is to the influence of surface of microcapsule cationization and paper properties thereof
Annotate: microcapsules 5g, water 200ml, epoxypropyl trimethylammonium chloride ammonium 0.02mol, reaction temperature is 70 ℃, the reaction time is 30min.
2, the influence of dispersion solvent
Can know from aforementioned research; With water is in the cationization reaction of dispersion solvent; The existence of water can cause two side reactions: the one, and the hydrolysis of cationic reagent; The accessory substance that generates after the hydrolysis does not have the cationization ability, thereby the valid density of cationic reagent in the reaction system is reduced, and reaction efficiency descends; The 2nd, aqueous solvent decomposes the cation group of generation, makes cation group break away from microcapsules, causes the decline of reaction efficiency equally.Can solvent have also determined cationic reagent better contact with microcapsules with catalyst to react.The present invention selects several kinds of different solvents such as ethanol, benzene, acetone and oxolane, compares the cationization effect of microcapsules, and the result is as shown in table 3.
Table 3 solvent species is to the influence of surface of microcapsule cation ionization degree
Can find out that from table 3 with respect to water, other nonaqueous solvents all improve the surperficial cation ionization degree of microcapsules to a certain extent, the cation ionization degree difference of various nonaqueous solvents is less, and is the highest with the cation ionization degree of absolute ethyl alcohol.Microcapsules behind the cationization are easy to from reaction system, separate through means such as filtrations, and solvent and cationic reagent are easy to reuse, and the solvent utilization rate is high, and therefore, optimum solvent is an absolute ethyl alcohol.
3, the influence of microcapsules and GTMA concentration
Fixedly GTMA, NaOH and absolute ethyl alcohol consumption in the course of reaction, changing microcapsules concentration influences ionized performance to investigate concentration parameter, and the result is as shown in table 4.Along with the increase of microcapsules concentration, cation ionization degree also has increase slightly, because the cationization of microcapsules and GTMA is the surface reaction of microcapsules; Therefore, guarantee to improve its concentration on the basis that microcapsules fully disperse as far as possible, make full use of cationic reagent; Microcapsules concentration can be 2.0～4.5% (with respect to the mass ratio of reaction system in the research; Down together), consider too high microcapsules concentration dispersing and mixing difficulty, optimal concentration is 4.0%.
Table 4 microcapsules concentration is to the influence of surperficial cation ionization degree
The cationization reaction of microcapsules occurs in surface of microcapsule; The surface area of microcapsules is a key factor under certain volume; The concentration of cationic reagent also influences very big; Inquire into of the influence of GTMA concentration below to cation ionization degree, fixing other parameter constants such as solvent volume, microcapsules concentration, temperature and time in the research, GTMA concentration is as shown in table 5 to the influence of microcapsules cation ionization degree.
Table 5GTMA concentration is to the influence of surperficial cation ionization degree
Can find out from table 5; Raising GTMA concentration has also increased the effective collision with the surface of microcapsule active group, has improved surperficial cation group quantity, after GTMA concentration is greater than 0.4mol/L; Surface of microcapsule cation ionization degree increase rate is very little; Therefore, GTMA concentration can realize the cationization of surface of microcapsule preferably between 0.3～0.5mol/L, and optimal concentration is 0.4mol/L.
4, the influence of reaction temperature and time
The reaction temperatures affect reaction rate, rising temperature fast reaction speed, but side reaction speed also accelerates, and therefore, needs to select preference temperature, and Influence of Temperature is as shown in table 6.Can find out, can realize the cationization of surface of microcapsule between 60～70 ℃ preferably, carry out the most effective of surperficial cationization at 65 ℃, the surface of microcapsule cation ionization degree is maximum under this temperature, and Optimal Temperature is chosen 65 ℃.
Table 6 reaction temperature is to the influence of surperficial cation ionization degree
Fixing other conditions are constant; Inquire into the influence of reaction time to cation ionization degree, the influence in reaction time is as shown in table 7, along with the increase in reaction time; Cation ionization degree is the trend of increase; The amplitude that cation ionization degree increases after the reaction time surpasses 60min is very little, considers that from energy resource consumption and production efficiency the suitable reaction time is advisable with 60～120min.
Table 7 reaction time is to the influence of surperficial cation ionization degree
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
What adopt cationization not is the reversible temperature induced color changing cheque paper of manufacturing paper with pulp of the microcapsules of cyst wall with the Lauxite, and the wet end addition method is manufactured paper with pulp, and is the consumption 0.6% (with respect to the pulp quality metering) of the microcapsules of cyst wall with the Lauxite, and paper basis weight is 70g/m
2, the value of chromatism of paper is 12.5, is that the retention in paper of microcapsules of cyst wall is high with the Lauxite, and then corresponding value of chromatism is high, and the mutation analysis through the Aberration of Paper value is the variation of retention of the microcapsules of cyst wall with the Lauxite.
Adopt the present invention to being that the microcapsules of cyst wall carry out surperficial cationization with the Lauxite, the cationization method be with:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium (being cationic reagent) of cyst wall with the Lauxite and stirs in water; Obtain mixed system, the dispersion solvent of adding is 88 weight portions, adding be that the microcapsules of cyst wall are 2 weight portions with the Lauxite; The NaOH that adds is 0.01 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 0.3 weight portion;
B, the reaction system of step a is warming up to 60 ℃ and react 120min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeats 6 times, washing back drying in vacuum desiccator obtained surperficial cationization microcapsules finished product in 15 hours.
The surperficial cationization microcapsules that employing the is produced reversible temperature induced color changing cheque paper of manufacturing paper with pulp, the wet end addition method is manufactured paper with pulp, microcapsules consumption 0.6% (with respect to the pulp quality metering), paper basis weight is 70g/m
2, the value of chromatism of paper is 15.2, the retention of microcapsules obviously increases.
Embodiment 2
What adopt cationization not is the reversible temperature induced color changing cheque paper of manufacturing paper with pulp of the microcapsules of cyst wall with the Lauxite, and the wet end addition method is manufactured paper with pulp, and is the consumption 0.7% (with respect to the pulp quality metering) of the microcapsules of cyst wall with the Lauxite, and paper basis weight is 72g/m
2, the value of chromatism of paper is 14.1.
Adopt the present invention to the Lauxite be cyst wall microcapsules carry out surperficial cationization, the cationization method be with:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in absolute ethyl alcohol; Obtain mixed system, the dispersion solvent of adding is 98 weight portions, adding be that the microcapsules of cyst wall are 4.5 weight portions with the Lauxite; The NaOH that adds is 0.9 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 6 weight portions;
B, the reaction system of step a is warming up to 70 ℃ and react 120min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeats 4 times, washing back drying in vacuum desiccator obtained surperficial cationization microcapsules finished product in 8 hours.
The surperficial cationization microcapsules that employing the is produced reversible temperature induced color changing cheque paper of manufacturing paper with pulp, the wet end addition method is manufactured paper with pulp, microcapsules consumption 0.7% (with respect to the pulp quality metering), paper basis weight is 72g/m
2, the value of chromatism of paper is 16.5.
Embodiment 3
What adopt cationization not is the reversible temperature induced color changing cheque paper of manufacturing paper with pulp of the microcapsules of cyst wall with the Lauxite, and the wet end addition method is manufactured paper with pulp, and is the consumption 0.5% (with respect to the pulp quality metering) of the microcapsules of cyst wall with the Lauxite, and paper basis weight is 65g/m
2, the value of chromatism of paper is 12.1.
Adopt the present invention to the Lauxite be cyst wall microcapsules carry out surperficial cationization, the cationization method be with:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in benzene; Obtain mixed system, the dispersion solvent of adding is 90 weight portions, adding be that the microcapsules of cyst wall are 3 weight portions with the Lauxite; The NaOH that adds is 0.4 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 3.5 weight portions;
B, the reaction system of step a is warming up to 65 ℃ and react 100min, obtains the thick product of surperficial cationization microcapsules;
C, place anhydrous solution washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeats 8 times, washing back drying in vacuum desiccator obtained surperficial cationization microcapsules finished product in 12 hours.
The surperficial cationization microcapsules that employing the is produced reversible temperature induced color changing cheque paper of manufacturing paper with pulp, the wet end addition method is manufactured paper with pulp, microcapsules consumption 0.5% (with respect to the pulp quality metering), paper basis weight is 65g/m
2, the value of chromatism of paper is 14.8.
Embodiment 4
What adopt cationization not is the reversible temperature induced color changing cheque paper of manufacturing paper with pulp of the microcapsules of cyst wall with the Lauxite, and the wet end addition method is manufactured paper with pulp, and is the consumption 0.7% (with respect to the pulp quality metering) of the microcapsules of cyst wall with the Lauxite, and paper basis weight is 70g/m
2, the value of chromatism of paper is 15.1.
Adopt the present invention to the Lauxite be cyst wall microcapsules carry out surperficial cationization, the cationization method be with:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in acetone; Obtain mixed system, the dispersion solvent of adding is 96 weight portions, adding be that the microcapsules of cyst wall are 4 weight portions with the Lauxite; The NaOH that adds is 0.8 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 5 weight portions;
B, the reaction system of step a is warming up to 68 ℃ and react 80min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeats 6 times, washing back drying in vacuum desiccator obtained surperficial cationization microcapsules finished product in 9 hours.
The surperficial cationization microcapsules that employing the is produced reversible temperature induced color changing cheque paper of manufacturing paper with pulp, the wet end addition method is manufactured paper with pulp, microcapsules consumption 0.7% (with respect to the pulp quality metering), paper basis weight is 70g/m
2, the value of chromatism of paper is 17.3.
Embodiment 5
What adopt cationization not is the reversible temperature induced color changing cheque paper of manufacturing paper with pulp of the microcapsules of cyst wall with the Lauxite, and the wet end addition method is manufactured paper with pulp, and is the microcapsules consumption 0.65% (with respect to the pulp quality metering) of cyst wall with the Lauxite, and paper basis weight is 70g/m
2, the value of chromatism of paper is 14.0.
Adopt the present invention to the Lauxite be cyst wall microcapsules carry out surperficial cationization, the cationization method be with:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in oxolane; Obtain mixed system, the dispersion solvent of adding is 96 weight portions, adding be that the microcapsules of cyst wall are 2.5 weight portions with the Lauxite; The NaOH that adds is 0.05 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 0.5 weight portion;
B, the reaction system of step a is warming up to 62 ℃ and react 112min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeats 7 times, washing back drying in vacuum desiccator obtained surperficial cationization microcapsules finished product in 10 hours.
The cationization microcapsules that employing the is produced reversible temperature induced color changing cheque paper of manufacturing paper with pulp, the wet end addition method is manufactured paper with pulp, microcapsules consumption 0.65% (with respect to the pulp quality metering), paper basis weight is 70g/m
2, the value of chromatism of paper is 16.7.
Claims (2)
1. one kind to being the method for the surface of microcapsule cationization of cyst wall with the Lauxite, it is characterized in that this method comprises the steps:
A, at ambient temperature; Adding is microcapsules, NaOH and the epoxypropyl trimethylammonium chloride ammonium of cyst wall with the Lauxite and stirs in dispersion solvent; Obtain mixed system, the dispersion solvent of adding is 88～98 weight portions, adding be that the microcapsules of cyst wall are 2～4.5 weight portions with the Lauxite; The NaOH that adds is 0.01～0.9 weight portion, and the epoxypropyl trimethylammonium chloride ammonium of adding is 0.3～6 weight portion;
Said dispersion solvent is water, absolute ethyl alcohol, benzene, acetone or oxolane;
B, the reaction system of step a is warming up to 60～70 ℃ and react 60～120min, obtains the thick product of surperficial cationization microcapsules;
C, place absolute ethyl alcohol washing back to filter the thick product of surperficial cationization microcapsules, replace new ethanolic solution washing and filtering again, repeated several times, the washing back obtained surperficial cationization microcapsules finished product in dry 8～15 hours in vacuum desiccator.
2. as claimed in claim 1 to being the method for the surface of microcapsule cationization of cyst wall with the Lauxite, it is characterized in that: the reaction temperature of reaction system is controlled at 65 ℃ among the step b.
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| US6368361B1 (en) * | 1999-05-18 | 2002-04-09 | Ito En, Ltd. | Manufacturing process of antibacterial fiber |
| CN101171933A (en) * | 2007-10-22 | 2008-05-07 | 江苏正本净化节水科技实业有限公司 | Method for synthesizing natural substance modified fungistat |
| CN101274248A (en) * | 2007-12-28 | 2008-10-01 | 哈尔滨工业大学 | Surface treating method of microcapsule for polymer based composite self-repair |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368361B1 (en) * | 1999-05-18 | 2002-04-09 | Ito En, Ltd. | Manufacturing process of antibacterial fiber |
| CN101171933A (en) * | 2007-10-22 | 2008-05-07 | 江苏正本净化节水科技实业有限公司 | Method for synthesizing natural substance modified fungistat |
| CN101274248A (en) * | 2007-12-28 | 2008-10-01 | 哈尔滨工业大学 | Surface treating method of microcapsule for polymer based composite self-repair |
Non-Patent Citations (1)
| Title |
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| 周家达等.苯乙烯马来酸酐共聚物的阳离子化改性及其应用.《中华纸业》.2007,第28卷(第2期),47-50. * |
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