CN103755937B - Toluylene ester is birdsed of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent - Google Patents
Toluylene ester is birdsed of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent Download PDFInfo
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Abstract
The invention discloses a kind of toluylene ester to birds of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent, comprise the steps: 4,4-toluylene dioctyl phthalate, anhydrous methanol, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst and vitriol oil mixing, temperature rising reflux reacts, and leaves standstill after reaction; Get supernatant liquid, add phenylmalonate, BDO, polyoxyethylene glycol and molybdic chloride, then temperature rising reflux reaction; Get the supernatant liquid after step reaction, obtain described toluylene ester through aftertreatment and to birds of the same feather flock together mould assembly fluorescence blast brightening agent.Present invention process is simple, removes from and uses the corrosion of strong acid to equipment and the use of great lot of water resources, easy to operate.Fluorescence blast brightening agent prepared by the present invention and the pigment of other colors with the use of, be applied in coating, papermaking, stone paper produce, to orchid green red trichromatism light, there is significant blast and increase gorgeous effect, have excellent provide protection to pigment dyestuff simultaneously.
Description
Technical field
The present invention relates to toluylene ester to birds of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent.
Background technology
White dyes can absorb sightless UV-light, (wavelength region is about 360-380nm), be converted to the visible ray of the longer blue light of wavelength or purple, reflect than the more visible ray of original incident wavelength in 400-600nm scope simultaneously, thus goods are seemed more in vain, brighter, more bright-coloured, white dyes is also a kind of color conditioners, it coordinates with other three looks pigment and has blast and increase gorgeous effect, be widely used in multiple fields such as papermaking, weaving, coating, make green brighter gorgeous, redness is more beautiful.But owing to being subject to the restriction of utilisation technology, the function that white dyes increases gorgeous amendment as other color blasts is not also fully excavated, real can needing with the whitening agent that other pigment mates completely is developed, although main existing problems are some white dyess also really to be had and increases gorgeous effect to other three looks blasts, but actual effect is color representation has outmoded sensation, have impact on color blast and increase gorgeous aesthetic feeling.A kind of toluylene ester of the present invention is birdsed of the same feather flock together mould assembly fluorescence blast brightening agent, overcomes the defect that prior art exists.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of toluylene ester and birdss of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent, to overcome the above-mentioned defect that prior art exists.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
Toluylene ester of the present invention is birdsed of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent, comprises the steps:
(1) by 4,4-toluylene dioctyl phthalate, anhydrous methanol, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst and vitriol oil mixing, be warming up to 80 ~ 90 DEG C, back flow reaction 4 ~ 6 hours, leave standstill, isolate lower floor's solution after reaction;
(2) get reacted supernatant liquid, add phenylmalonate, BDO, polyoxyethylene glycol and molybdic chloride, then be warming up to 160 ~ 180 DEG C of back flow reaction 3 ~ 5 hours, standing, separating catalyst, except sub-cloud solution;
(3) step (2) reacted supernatant liquid is got, add sodium hydroxide, stir 1 ~ 2 hour at 90 ~ 110 DEG C, distill out residual solvent by decompression method, and then add the deionized water 200 parts of less than 10 DEG C, filtration obtains filter cake, filter cake washes five times with the deionized water of less than 10 DEG C again, then uses dehydrated alcohol recrystallization, obtains faint yellow solid thing, toluylene ester is birdsed of the same feather flock together mould assembly fluorescence blast brightening agent, and its chemical structural formula is as follows:
N=5 ~ 9 in formula, m=6 ~ 8, p=4 ~ 8.
Each composition weight number is as follows:
Wherein the vitriol oil refers to that mass concentration is the vitriol oil of 98%.
Described doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst, prepared by following steps:
(1) by ZrOCl
2, nano chromium carbide, nano-zirconium carbide, be added in deionized water, open high speed dispersor 1500 revs/min, temperature rises to 70 DEG C, immediately silver ammino solution is joined mixed solution relaying continuation of insurance temperature 2 hours, then stops high speed dispersor stirring, be down to normal temperature, after static 5 hours, filtering precipitate, cleans 3 times with 50 parts of deionized waters at every turn, chlorion and nitrate ion in scavenger precipitation thing, and be dried to moisture at 120 DEG C and all evaporate;
(2) by the product of (1) step, flood 3 hours in the sulphuric acid soln of 10%, roasting 3.5 hours at putting into 630 DEG C, obtain doping doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst.
In above-mentioned steps, each composition weight number is as follows: deionized water 100 parts, ZrOCl
210 parts, nano chromium carbide 0.6 part, nano-zirconium carbide 0.5 part, 25% silver ammino solution 50 parts.
The present invention utilizes novel solid acid as catalyzer, prepares toluylene ester to birds of the same feather flock together mould assembly fluorescence blast brightening agent by synthesis, and technique is simple, removes from and uses the corrosion of strong acid to equipment and the use of great lot of water resources, easy to operate.The pigment preparing fluorescence blast brightening agent and other colors of the present invention with the use of, be applied in coating, papermaking, stone paper produce, to orchid green red trichromatism light, there is significant blast and increase gorgeous effect, have excellent provide protection to pigment dyestuff simultaneously.
Embodiment
Provide present pre-ferred embodiments below, to describe technical scheme of the present invention in detail.
Embodiment 1
One, toluylene ester is birdsed of the same feather flock together the synthesis step of mould assembly fluorescence blast brightening agent:
(a) chemical composition: 4,4 '-toluylene dioctyl phthalate 120 parts, anhydrous methanol 50 parts, phenylmalonate 100 parts, BDO 40 parts, polyoxyethylene glycol 50 parts, 98% vitriol oil 0.2 part, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 6 parts, molybdic chloride 0.03 part, 10 parts, sodium hydroxide;
(b) preparation method: add 4 in the four-hole boiling flask with stirring, 4 '-toluylene dioctyl phthalate 120 parts, anhydrous methanol 50 parts, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 6 parts, 98% vitriol oil 0.2 part, be warming up to 80 DEG C, back flow reaction 6 hours, and return line with the frozen water cooling of 7 DEG C, need leave standstill after reaction, isolate lower floor's solution;
C () gets the supernatant liquid that (b) reacts, add phenylmalonate 100 parts, BDO 40 parts, polyoxyethylene glycol 50 parts, molybdic chloride 0.03 part, then be warming up to 160 DEG C of back flow reaction 5 hours, and standing, separating catalyst, except sub-cloud solution;
D () gets the supernatant liquid that (c) reacts, add 10 parts, sodium hydroxide, stir 1 hour at 110 DEG C, distill out residual solvent by decompression method, and then add the deionized water 200 parts of less than 10 DEG C, filter and obtain filter cake, filter cake washes five times with the deionized water of less than 10 DEG C again, then use dehydrated alcohol recrystallization, obtain faint yellow solid thing, toluylene ester is birdsed of the same feather flock together mould assembly fluorescence blast brightening agent
Two, adulterate SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst, prepared by following steps:
(a) chemical composition, deionized water 100 parts, ZrOCl
210 parts, nano chromium carbide 0.6 part, nano-zirconium carbide 0.5 part
25% silver ammino solution 50 parts;
B () is by ZrOCl
2, nano chromium carbide, nano-zirconium carbide, be added in deionized water, open high speed dispersor 1500 turns
/ point, temperature rises to 70 DEG C, immediately silver ammino solution is joined mixed solution relaying continuation of insurance temperature 2 hours, stop high speed dispersor stirring again, be down to normal temperature, after static 5 hours, filtering precipitate, each use 50 parts of deionized waters clean 3 times, chlorion and nitrate ion in scavenger precipitation thing, and are dried to moisture at 120 DEG C and all evaporate;
C (), by the product of (b) process, floods 3 hours, roasting 3.5 hours at putting into 630 DEG C in the sulphuric acid soln of 10%, obtain doping doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst.
Embodiment 2
One, toluylene ester is birdsed of the same feather flock together the synthesis step of mould assembly fluorescence blast brightening agent:
(a) chemical composition: 4,4 '-toluylene dioctyl phthalate 150 parts, anhydrous methanol 30 parts, phenylmalonate 150 parts, BDO 20 parts, polyoxyethylene glycol 100 parts, 98% vitriol oil 0.1 part, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 10 parts, molybdic chloride 0.01 part, 20 parts, sodium hydroxide;
(b) preparation method: add 4 in the four-hole boiling flask with stirring, 4 '-toluylene dioctyl phthalate 150 parts, anhydrous methanol 30 parts, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 10 parts, 98% vitriol oil 0.1 part, be warming up to 90 DEG C, back flow reaction 4 hours, and return line with the frozen water cooling of 5 DEG C, need leave standstill after reaction, isolate lower floor's solution;
C () gets the supernatant liquid that (b) reacts, add phenylmalonate 150 parts, BDO 20 parts, polyoxyethylene glycol 100 parts, molybdic chloride 0.01 part, then be warming up to 180 DEG C of back flow reaction 3 hours, and standing, separating catalyst, except sub-cloud solution;
D () gets the supernatant liquid that (c) reacts, add 20 parts, sodium hydroxide, stir 2 hours at 90 DEG C, distill out residual solvent by decompression method, and then add the deionized water 200 parts of less than 10 DEG C, filter and obtain filter cake, filter cake washes five times with the deionized water of less than 10 DEG C again, then use dehydrated alcohol recrystallization, obtain faint yellow solid thing, toluylene ester is birdsed of the same feather flock together mould assembly fluorescence blast brightening agent.
Two, adulterate SO
4 2-/ ZrO
2the preparation method of-AgCl type mixed crystal solid acid catalyst is with embodiment 1.
Embodiment 3
One, toluylene ester is birdsed of the same feather flock together the synthesis step of mould assembly fluorescence blast brightening agent:
(a) chemical composition: 4,4 '-toluylene dioctyl phthalate 135 parts, anhydrous methanol 40 parts, phenylmalonate 125 parts, BDO 30 parts, polyoxyethylene glycol 75 parts, 98% vitriol oil 0.15 part, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 8 parts, molybdic chloride 0.02 part, 15 parts, sodium hydroxide;
(b) preparation method: add 4 in the four-hole boiling flask with stirring, 4 '-toluylene dioctyl phthalate 135 parts, anhydrous methanol 40 parts, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst 8 parts, 98% vitriol oil 0.15 part, be warming up to 85 DEG C, back flow reaction 5 hours, and return line with the frozen water cooling of 6 DEG C, need leave standstill after reaction, isolate lower floor's solution;
C () gets the supernatant liquid that (b) reacts, add phenylmalonate 125 parts, BDO 30 parts, polyoxyethylene glycol 75 parts, molybdic chloride 0.02 part, then be warming up to 170 DEG C of back flow reaction 4 hours, and standing, separating catalyst, except sub-cloud solution;
D () gets the supernatant liquid that (c) reacts, add 15 parts, sodium hydroxide, stir 1.5 hours at 100 DEG C, distill out residual solvent by decompression method, and then add the deionized water 200 parts of less than 10 DEG C, filter and obtain filter cake, filter cake washes five times with the deionized water of less than 10 DEG C again, then use dehydrated alcohol recrystallization, obtain faint yellow solid thing, toluylene ester is birdsed of the same feather flock together mould assembly fluorescence blast brightening agent.
Two, adulterate SO
4 2-/ ZrO
2the preparation method of-AgCl type mixed crystal solid acid catalyst is with embodiment 1.
Application Example
Application Example: get toluylene ester of the present invention and to birds of the same feather flock together mould assembly fluorescence blast brightening agent 30 grams of (being equivalent to 0.01 mol wt), naphthols AS reds 5 grams, dehydrated alcohol 500 parts, dehydrated alcohol is heated to about 50 DEG C, add toluylene ester again to birds of the same feather flock together mould assembly fluorescence blast brightening agent, finally add pigment, abundant stirring stir well even after, leave standstill 24 hours, overanxious throw out.
Comparative example: get VBL white dyes 8.7 grams (being equivalent to 0.01 mol wt), naphthols AS red 5 grams, dehydrated alcohol 500 parts, dehydrated alcohol is heated to about 50 DEG C, add VBL white dyes again, finally add pigment, abundant stirring stir well even after, leave standstill 24 hours, overanxious throw out.Naphthols AS red chemical structural formula is as follows:
Respectively get Application Example and comparative example solution 50 milliliters, join respectively in the paper surface-sizing coating of 1000 milliliters, form two groups of applying glue coating, prepare red facial tissue respectively, with body paper 105 grams/meter
2.
Measuring method color reflection mode Density Measuring Instrument PRB03-36921, use UVA-340 fluorescent ultra-violet lamp determination data are as follows:
Table 1
Just can reach a conclusion from the detection of Application Example and comparative example: toluylene ester of the present invention mould assembly fluorescence blast brightening agent of birdsing of the same feather flock together has good blast to increase gorgeous effect, and by ageing-resistant degree mensuration, have excellent provide protection to pigment dyestuff.
Claims (4)
1. toluylene ester is birdsed of the same feather flock together a preparation method for mould assembly fluorescence blast brightening agent, it is characterized in that, comprises the steps:
(1) by 4,4 '-toluylene dioctyl phthalate, anhydrous methanol, doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst and vitriol oil mixing, be warming up to 80 ~ 90 DEG C, back flow reaction 4 ~ 6 hours, leave standstill, isolate lower floor's solution after reaction;
(2) get reacted supernatant liquid, add phenylmalonate, BDO, polyoxyethylene glycol and molybdic chloride, then be warming up to 160 ~ 180 DEG C of back flow reaction 3 ~ 5 hours, standing, separating catalyst, except sub-cloud solution;
(3) step (2) reacted supernatant liquid is got, add sodium hydroxide, stir 1 ~ 2 hour at 90 ~ 110 DEG C, residual solvent is distilled out by decompression method, and then add the water of less than 10 DEG C, filter and obtain filter cake, filter cake washes five times with the deionized water of less than 10 DEG C again, then use dehydrated alcohol recrystallization, obtain described toluylene ester and to birds of the same feather flock together mould assembly fluorescence blast brightening agent.
2. method according to claim 1, is characterized in that, the parts by weight of each component are as follows:
3. method according to claim 1, is characterized in that, described doping SO
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst, prepared by following steps:
(1) by ZrOCl
2, nano chromium carbide, nano-zirconium carbide be added in deionized water, open high speed dispersor 1500 revs/min, temperature rises to 70 DEG C, immediately silver ammino solution is joined mixed solution relaying continuation of insurance temperature 2 hours, then stops high speed dispersor stirring, be down to normal temperature, leave standstill after 5 hours, filtering precipitate, cleans 3 times with 50 parts of deionized waters at every turn, chlorion and nitrate ion in scavenger precipitation thing, and be dried to moisture at 120 DEG C and all evaporate;
(2) by the product of (1) step, flood 3 hours in the sulphuric acid soln of 10%, roasting 3.5 hours at putting into 630 DEG C, obtain the SO that adulterates
4 2-/ ZrO
2-AgCl type mixed crystal solid acid catalyst.
4. method according to claim 3, is characterized in that, each composition weight number is as follows: deionized water 100 parts, ZrOCl
210 parts, nano chromium carbide 0.6 part, nano-zirconium carbide 0.5 part, 25% silver ammino solution 50 parts.
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| CN201310750365.1A CN103755937B (en) | 2013-12-31 | 2013-12-31 | Toluylene ester is birdsed of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent |
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|---|---|---|---|
| CN201310750365.1A CN103755937B (en) | 2013-12-31 | 2013-12-31 | Toluylene ester is birdsed of the same feather flock together the preparation method of mould assembly fluorescence blast brightening agent |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039782A (en) * | 1990-12-11 | 1991-08-13 | Lever Brothers Company, Division Of Conopco, Inc. | Polymeric whitening agent |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN103447053A (en) * | 2013-07-09 | 2013-12-18 | 上海东升新材料有限公司 | Preparation method of SO4<2->/ZrO2-WO-AgBr mixed crystal solid acid carrier catalyst |
-
2013
- 2013-12-31 CN CN201310750365.1A patent/CN103755937B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039782A (en) * | 1990-12-11 | 1991-08-13 | Lever Brothers Company, Division Of Conopco, Inc. | Polymeric whitening agent |
| CN101654894A (en) * | 2009-09-11 | 2010-02-24 | 山西青山化工有限公司 | Preparation method of toluylene triazine liquid fluorescent brightener composite |
| CN103447053A (en) * | 2013-07-09 | 2013-12-18 | 上海东升新材料有限公司 | Preparation method of SO4<2->/ZrO2-WO-AgBr mixed crystal solid acid carrier catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "聚合型荧光增白剂";曹成波等;《化工学报》;20050331;第56卷(第3期);第375-381页 * |
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Denomination of invention: Method for preparing toluylene ester polymeric type fluorescence brightening and coloring agent Effective date of registration: 20191225 Granted publication date: 20160406 Pledgee: Bank of Hangzhou, Limited by Share Ltd, Shanghai branch Pledgor: Shanghai Dongsheng New Materials Co., Ltd. Registration number: Y2019310000035 |
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Date of cancellation: 20210813 Granted publication date: 20160406 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANDONG DONGSHENG NEW MATERIAL Co.,Ltd. Registration number: Y2019310000035 |
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