CN109811584A - A kind of preparation method and applications of the aqueous polyurethane fluorescent brightening lotion for paper surface - Google Patents
A kind of preparation method and applications of the aqueous polyurethane fluorescent brightening lotion for paper surface Download PDFInfo
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Abstract
A kind of preparation method and applications of the aqueous polyurethane fluorescent brightening lotion for paper surface, Cyanuric Chloride and acetone are put into three-necked flask, it is stirred under ice bath, it is reacted after p-aminobenzene sulfonic acid is added, 4 are weighed, 4 '-diaminobenzil -2,2 ' disulfonic acid is dissolved in the alkaline solution reaction of NaOH, monoethanolamine reaction is added in heating, obtains Stilbene-based fluorescent brightening small molecule after revolving is dry.Isophorone diisocyanate, polyether Glycols and a small amount of dibutyl tin dilaurate are added in the there-necked flask for being attached to condenser pipe and electric mixer, it places it in water bath with thermostatic control and reacts, by 2,2- dihydromethyl propionic acid and the Stilbene-based fluorescent brightening small molecule of preparation are previously dissolved in organic solvent and are added in three-necked flask, 1 is added after reaction, 4 butanediols the reaction was continued cooling, triethylamine neutralization is added after stirring viscosity reduction with acetone, it adds water and stirs, remove acetone under reduced pressure, the features such as emulsion film forming of this method preparation is good and paper bond strength highly whitened inhibition brightness reversion.
Description
Technical field
The invention belongs to fluorescent whitening agent field, in particular to a kind of aqueous polyurethane fluorescent brightening for paper surface
The preparation method and applications of lotion.
Background technique
Due to the shortage of timber resources, the use of high yield pulp is increasingly taken seriously, but because retains in high yield pulp
A large amount of lignin in timber is also easy to produce quinoid chromophoric group under the action of by external environment, so that paper from yellowing, limit
The application of high yield pulp is made.Fluorescent whitening agent can effectively avoid or inhibit high yield pulp light-induced color reversion, the work of fluorescent whitening agent
It is that sightless ultraviolet light can be absorbed and launch blue light with principle, after the yellow light issued with paper is overlapped, complementary shape
At white light, so that paper brightens.
Jin Qingjun etc. [Acta PhySico-Chimica Sinica, 2015,36 (5): 989-997] researcher has synthesized naphthalimide fluorescence dye
Material and copoly type fluorescence polyaminoester emulsion are applied in coating, and the naphthalimide fluorescent brightening agent of introducing is fluorescent whitening agent
One kind, capable of acting on the naphthalimide whitening effect that paper brightens it and yellowing inhibition, but uses, there is no 4,4 '-diamino
The whitening effect of talan -2,2 '-disulfonic acid is good.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of for the aqueous of paper surface
The preparation method and applications of polyurethane fluorescent brightening lotion have synthesis technology simple, and raw material is easy to get, and are suitable for scale metaplasia
The characteristics of production.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of the aqueous polyurethane fluorescent brightening lotion for paper surface, includes the following steps；
(1) by isophorone diisocyanate (IPDI), polyether Glycols and 1-3 drop catalyst dibutyltin dilaurylate
Mixing, reacts at 80 DEG C；
(2) by 2,2- dihydromethyl propionic acid and the Stilbene-based fluorescent brightening small molecule of synthesis and 5-10ml organic solvent
Mixing is added in (1), reacts at 80 DEG C；
(3) the reaction was continued into (2) for addition 1,4-butanediol, is cooled to 40 DEG C, and 10ml acetone viscosity reduction is added；
(4) it adds triethylamine to neutralize in (3), afterwards plus water emulsification, obtains aqueous polyurethane fluorescent brightening lotion.
In the step (1), isophorone diisocyanate (IPDI) and the molar ratio of polyether Glycols (N210) are
4:(0.5-1.5)；
In the step (2), the molar ratio of 2,2- dihydromethyl propionic acids and isophorone diisocyanate is (0.5-
1): 4.8, the molar ratio of Stilbene-based fluorescent brightening small molecule and 2,2- dihydromethyl propionic acid is (1-3:5)；
In the step (3), the molar ratio of 1,4-butanediol and Stilbene-based fluorescent brightening small molecule is (1:1)；
In the step (4), the molar ratio of 2,2- dihydromethyl propionic acids, triethylamine and water is 1:1:(350-600)；
The Stilbene-based fluorescent brightening small molecule synthesized in the step (2) is commercially available to can also refer to document [fluorescence increasing
White dose, Beijing, chemical engineering industry publishing house, 2004, P50] self-control, the preparation method is as follows:
5.977g Cyanuric Chloride and 40ml acetone are put into three-necked flask, stir 10min under ice bath, keeps its dispersion equal
It is even, after adding 5.62g p-aminobenzene sulfonic acid, first step reaction is carried out, adjusting pH with 10% NaOH aqueous solution is 5 or so,
Control 0~5 DEG C of reaction temperature, react 2.5h, so that it is uniformly dispersed, after weigh 4,4 '-diaminobenzil -2,2 '-two sulphurs
Acid (DSD acid) 6g is dissolved in the alkaline solution of NaOH, while being gradually warming up to 35~40 DEG C, adjusts pH with 10% NaOH aqueous solution
It is 6~7, reacts 3h, being warming up to 80~85 DEG C of addition 2.77g ethanol amines and adjusting pH is 8~8.5, reacts 3h, after reaction
Vacuum filtration, deionized water washing, drying to constant weight at 40 DEG C, and product is saved in drier, and structural formula is as follows:
The molecular weight of polyether Glycols can be 500,700 or 1000 in the step (1).
Organic solvent can be acetone, N-Methyl pyrrolidone, toluene in the step (2).
The reaction time is 2-3h in the step (1).
The reaction time is 3-4h in the step (2).
Emulsification times are 0.5-2.5h in the step (4).
The aqueous polyurethane fluorescent brightening emulsion applications in polyaminoester emulsion there is high yield pulp1 Cultural Paper surface to apply
Glue, good sizability and yellowing inhibition effect.
Beneficial effects of the present invention:
The advantage of the invention is that preventing the photostability of Stilbene-based Fluorescent Brighteners, enhancing paper surface is strong
Degree, and inhibit three kinds of functions of paper from yellowing to be combined together, and from MOLECULE DESIGN angle, Stilbene-based fluorescence is increased
White small molecule in succession in polyurethane chain, and by Phase Inversion Emulsification, substantially increase the stability for brightening lotion itself, and
And preferably due to the water solubility of the talan fluorescent small molecule of preparation, the water solubility of polyaminoester emulsion is increased, due to lotion
Use, greatly reduce the difficulty of film forming, improve paper conjugation.This method synthesis temperature is at 100 DEG C hereinafter, behaviour
Make easy and energy saving.
Specific embodiment
Below with reference to embodiment, invention is further described in detail.
Embodiment 1
February is dripped into the isophorone diisocyanate of 0.024mol, the polyether Glycols (M=500) of 0.003mol and 1
Dilaurylate is added in the 100ml there-necked flask for being attached to condenser pipe and electric mixer, then places it in 80 DEG C of perseverance
After reacting 2h in tepidarium, by the Stilbene-based fluorescent brightening of 2, the 2- dihydromethyl propionic acid of 0.004mol and 0.0016mol
Small molecule is previously dissolved in 10ml acetone and is added in there-necked flask, and after reacting 4h, the 1,4-butanediol that 0.0016mol is added continues instead
It answers, increases its emulsion viscosity, after reacting 1h, be cooled to 40 DEG C, the triethylamine of addition 0.004mol after viscosity reduction is stirred with 4ml acetone
It neutralizes, then plus 76.8g water stirs 30min, removes acetone under reduced pressure, obtains aqueous polyurethane fluorescent brightening lotion.
Embodiment 2
February is dripped into the isophorone diisocyanate of 0.024mol, the polyether Glycols (M=700) of 0.006mol and 3
Dilaurylate is added in the 100ml there-necked flask for being attached to condenser pipe and electric mixer, then places it in 80 DEG C of perseverance
After reacting 3h in tepidarium, the Stilbene-based fluorescence of 2, the 2- dihydromethyl propionic acid of 0.0048mol and 0.00288mol are increased
White small molecule is previously dissolved in 5ml N-Methyl pyrrolidone and is added in there-necked flask, and after reacting 3h, the 1 of 0.00288mol is added,
The reaction was continued for 4- butanediol, increases its emulsion viscosity, after reacting 2h, is cooled to 40 DEG C, is added after stirring viscosity reduction with 10ml acetone
The triethylamine of 0.0048mol neutralizes, and then plus 53.76g water stirs 1.5h, removes acetone under reduced pressure, obtains aqueous polyurethane fluorescence
Brighten lotion.
Embodiment 3
February is dripped into the isophorone diisocyanate of 0.024mol, the polyether Glycols (M=1000) of 0.009mol and 2
Dilaurylate is added in the 100ml there-necked flask for being attached to condenser pipe and electric mixer, then places it in 80 DEG C of perseverance
After reacting 2.5h in tepidarium, the Stilbene-based fluorescence of 2, the 2- dihydromethyl propionic acid of 0.0025mol and 0.0005mol are increased
White small molecule, which is previously dissolved in the toluene of 7.5ml, to be added in there-necked flask, and after reacting 3.5h, Isosorbide-5-Nitrae-fourth two of 0.0005mol is added
The reaction was continued for alcohol, increases its emulsion viscosity, after reacting 2h, is cooled to 40 DEG C, is added after stirring viscosity reduction with 4ml acetone
The triethylamine of 0.0025mol neutralizes, and then plus 40g water stirs 1.5h, removes acetone under reduced pressure, obtains aqueous polyurethane fluorescent brightening
Lotion.
Embodiment 4
February is dripped into the isophorone diisocyanate of 0.024mol, the polyether Glycols (M=1000) of 0.006mol and 3
Dilaurylate is added in the 100ml there-necked flask for being attached to condenser pipe and electric mixer, then places it in 80 DEG C of perseverance
After reacting 2h in tepidarium, by the Stilbene-based fluorescent brightening of 2, the 2- dihydromethyl propionic acid of 0.0048mol and 0.0024mol
Small molecule is previously dissolved in the acetone of 5ml and is added in there-necked flask, and after reacting 4h, the 1,4-butanediol that 0.0024mol is added continues
Reaction increases its emulsion viscosity, after reacting 2h, is cooled to 40 DEG C, is added the three of 0.0048mol after stirring viscosity reduction with 10ml acetone
Ethamine neutralizes, and then plus 60g water stirs 1h, removes acetone under reduced pressure, obtains aqueous polyurethane fluorescent brightening lotion.
Embodiment 5
February is dripped into the isophorone diisocyanate of 0.024mol, the polyether Glycols (M=700) of 0.003mol and 1
Dilaurylate is added in the 100ml there-necked flask for being attached to condenser pipe and electric mixer, then places it in 80 DEG C of perseverance
2h is reacted in tepidarium, the Stilbene-based fluorescent brightening of 2, the 2- dihydromethyl propionic acid of 0.004mol and 0.0024mol is small
Molecule is previously dissolved in the toluene of 5ml and is added in there-necked flask, and after reacting 3h, the 1,4-butanediol that 0.0024mol is added continues instead
It answers, increases its emulsion viscosity, after reacting 2h, be cooled to 40 DEG C, three second of addition 0.004mol after viscosity reduction are stirred with 10ml acetone
Amine neutralizes, and then plus 50g water stirs 2.5h, removes acetone under reduced pressure, obtains aqueous polyurethane fluorescent brightening lotion.
This invention address that using Stilbene-based fluorescent brightening small molecule as chain extender, by it in succession in polyaminoester emulsion
In, prepare it is aqueous it is good, with paper associativity is good, anti-brightness reversion, the polyurethane fluorescent brightening agent emulsion for improving paper anti-tensile, and
And method is easy, it is easy to operate.
Claims (9)
1. a kind of preparation method of the aqueous polyurethane fluorescent brightening lotion for paper surface, which is characterized in that including following
Step；
(1) isophorone diisocyanate (IPDI), polyether Glycols and 1-3 drop catalyst dibutyltin dilaurylate is mixed
It closes, is reacted at 80 DEG C；
(2) 2,2- dihydromethyl propionic acid and the Stilbene-based fluorescent brightening small molecule of synthesis are mixed with 5-10ml organic solvent
It closes, is added in (1), is reacted at 80 DEG C；
(3) the reaction was continued into (2) for addition 1,4-butanediol, is cooled to 40 DEG C, and 10ml acetone viscosity reduction is added；
(4) it adds triethylamine to neutralize in (3), afterwards plus water emulsification, obtains aqueous polyurethane fluorescent brightening lotion.
2. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, in the step (1), the molar ratio of isophorone diisocyanate (IPDI) and polyether Glycols (N210)
For 4:(0.5-1.5)；
In the step (2), the molar ratio of 2,2- dihydromethyl propionic acids and isophorone diisocyanate is (0.5-1):
4.8, the molar ratio of Stilbene-based fluorescent brightening small molecule and 2,2- dihydromethyl propionic acid is (1-3:5)；
In the step (3), the molar ratio of 1,4-butanediol and Stilbene-based fluorescent brightening small molecule is (1:1)；
In the step (4), the molar ratio of 2,2- dihydromethyl propionic acids, triethylamine and water is 1:1:(350-600).
3. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, the Stilbene-based fluorescent brightening small molecule synthesized in the step (2) is commercially available to can also refer to document [fluorescence
Brightening agent, Beijing, chemical engineering industry publishing house, 2004, P50] self-control, the preparation method is as follows:
5.977g Cyanuric Chloride and 40ml acetone are put into three-necked flask, 10min is stirred under ice bath, it is made to be uniformly dispersed,
After adding 5.62g p-aminobenzene sulfonic acid, first step reaction is carried out, adjusting pH with 10% NaOH aqueous solution is 5 or so, control
0~5 DEG C of reaction temperature, react 2.5h, so that it is uniformly dispersed, after weigh 4,4 '-diaminobenzil -2,2 '-disulfonic acid
(DSD acid) 6g is dissolved in the alkaline solution of NaOH, while being gradually warming up to 35~40 DEG C, adjusts pH with 10% NaOH aqueous solution and is
6~7,3h is reacted, being warming up to 80~85 DEG C of addition 2.77g ethanol amines and adjusting pH is 8~8.5, reacts 3h, after reaction very
Empty pump filter, deionized water washing, drying to constant weight at 40 DEG C, and product is saved in drier, and structural formula is as follows:
4. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, the molecular weight of polyether Glycols can be 500,700 or 1000 in the step (1).
5. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, organic solvent can be acetone, N-Methyl pyrrolidone, toluene in the step (2).
6. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, the reaction time is 2-3h in the step (1).
7. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, the reaction time is 3-4h in the step (2).
8. a kind of preparation method of aqueous polyurethane fluorescent brightening lotion for paper surface according to claim 1,
It is characterized in that, emulsification times are 0.5-2.5h in the step (4).
9. a kind of application of the aqueous polyurethane fluorescent brightening lotion for paper surface, which is characterized in that described is aqueous poly-
Urethane fluorescent brightening emulsion applications have a high yield pulp1 Cultural Paper top sizing in polyaminoester emulsion, good sizability and return
Yellow inhibiting effect.
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