CN112794827A - High-weather-resistance and aging-resistance grafted dibenzoxazole stilbene type fluorescent whitening agent and preparation method thereof - Google Patents
High-weather-resistance and aging-resistance grafted dibenzoxazole stilbene type fluorescent whitening agent and preparation method thereof Download PDFInfo
- Publication number
- CN112794827A CN112794827A CN202011628668.2A CN202011628668A CN112794827A CN 112794827 A CN112794827 A CN 112794827A CN 202011628668 A CN202011628668 A CN 202011628668A CN 112794827 A CN112794827 A CN 112794827A
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- CN
- China
- Prior art keywords
- resistant
- fluorescent whitening
- whitening agent
- aging
- dibenzoxazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000006081 fluorescent whitening agent Substances 0.000 title claims abstract description 45
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 title claims abstract description 27
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 235000021286 stilbenes Nutrition 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 32
- 230000002087 whitening effect Effects 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 7
- 229920003023 plastic Polymers 0.000 claims abstract description 7
- 238000009987 spinning Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- -1 cyclane Chemical class 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- WZSOEUAQKKEHFE-UHFFFAOYSA-N 2-chloro-2-phenylacetonitrile Chemical compound N#CC(Cl)C1=CC=CC=C1 WZSOEUAQKKEHFE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- FRQPHGSNRQEKOX-UHFFFAOYSA-N 6h-benzo[c][1,2]benzoxazine Chemical compound C1=CC=C2NOC3=CC=CC=C3C2=C1 FRQPHGSNRQEKOX-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000215 hyperchromic effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
- C07D263/64—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings linked in positions 2 and 2' by chains containing six-membered aromatic rings or ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Artificial Filaments (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The invention relates to a fluorescent whitening agent, in particular to a high-weather-resistance and ageing-resistant grafted dibenzoxazole stilbene type fluorescent whitening agent, a preparation method thereof and the technical field of fluorescent whitening materials. The chemical structural formula is as follows:
Description
Technical Field
The invention relates to a fluorescent whitening agent, in particular to a high-weather-resistance and ageing-resistant grafted dibenzoxazole stilbene type fluorescent whitening agent, a preparation method thereof and the technical field of fluorescent whitening materials.
Background
The fluorescent whitening agent is a compound which can emit blue-violet visible light after absorbing ultraviolet light (with the wavelength of 350-400nm), and the wavelength of the compound is 400-470 nm. According to the optical complementary principle, the blue-violet visible light can make the complementary color of yellow light white, so that the white or light-colored product can obtain the effects of whitening and brightening.
The fluorescence phenomenon is discovered from G.G Stoves in 1852, and the fluorescence theory is established, which has a history of 162 years; in 1934, ICI company synthesized the fluorescent whitening agent with practical prospect in item 1, the fluorescent whitening agent was DSD acid, and in 1941, Bayer first realized the industrialization of fluorescent whitening agent varieties, from this point on, driven the development of scientific research and production in this field.
The fluorescent whitening agent can be divided into two categories of water-soluble and water-insoluble according to the application, wherein the water-soluble whitening agent is mainly used in the industries of textile, paper, coating and detergent, and the water-insoluble whitening agent is mainly used in the industries of plastics, rubber and the like.
Conventional optical brighteners suffer from the following disadvantages: the fluorescent whitening agent has poor compatibility with the main material and is easy to precipitate on the surface of the product, so that the appearance quality of the product is influenced; the fluorescent whitening agent has poor weather resistance and aging resistance, and products using the fluorescent whitening agent are easy to yellow in the using process and have poor whitening and hyperchromic properties.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a synthesis method of the high-weather-resistance and aging-resistance grafted dibenzoxazine stilbene fluorescent whitening agent, and finds that the compatibility of the high-weather-resistance and aging-resistance grafted dibenzoxazine stilbene fluorescent whitening agent and a main material is greatly improved and the weather-resistance and aging-resistance performance is obviously improved by testing the application performance of the high-weather-resistance and aging-resistance grafted dibenzoxazine stilbene fluorescent whitening agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent has a chemical structural formula as follows:
preferably, the fluorescent whitening agent has a semi-hindered amine or hindered amine group in its molecular structure that is resistant to ozone aging.
Preferably, the fluorescent whitening agent has a molecular structure with the semi-hindered amine or the R in the hindered amine group which is resistant to ozone aging, wherein R comprises straight-chain alkane, cyclane, benzene and benzene derivatives.
Preferably, the fluorescent whitening agent has a molecular structure with semi-hindered amine or R in hindered amine group which is resistant to ozone aging, and the grafting position is any position in 2, 3, 4 and 5 positions of benzoxazole.
A preparation method of a high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent comprises and is not limited to the following two processes: sulfur oxidation and cyanobenzyl chloride.
Preferably, the sulfur oxidation process synthesis line comprises the following steps:
step 1:
step 2:
wherein R is any one or two of alkane, cyclane, aromatic hydrocarbon or benzene derivatives as the optimization, and the nitrile group benzyl chloride method process synthesis line is as follows: the method comprises the following three steps:
step 1:
step 2:
and step 3:
an application of high weather-resistant and ageing-resistant grafted dibenzoxazole stilbene fluorescent whitening agent in whitening and hyperchromic of plastics, spinning fiber, rubber and paint.
Compared with the traditional dibenzoxazole stilbene fluorescent whitening agent, the invention has the following advantages:
1. the compatibility with organic main materials is better, and the product is less prone to be separated out from the surface of the product.
2. The weather resistance and aging resistance are better.
The high weather-resistant aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent can obviously whiten and color-increase plastics and plastic spinning products, and is a novel fluorescent whitening agent with functional performance.
Detailed Description
The invention is further described below by means of specific embodiments.
Example 1: a sulfur oxidation method, wherein the chemical reaction comprises the following steps of 1:
chemical reaction step 2:
example 2: a nitrile benzyl chloride process, wherein the chemical reaction step 1:
chemical reaction step 2:
chemical reaction step 3:
whitening and hyperchromic testing:
the high weather-resistant and ageing-resistant grafted dibenzoxazine stilbene fluorescent whitening agent is added into PP in a proportion of 0.03 percent, and compared with the traditional dibenzoxazine stilbene fluorescent whitening agent, the whitening effect is superior to that of the traditional dibenzoxazine stilbene fluorescent whitening agent.
Weather resistance and aging resistance test:
the high weather-resistant and aging-resistant grafted dibenzoxazine stilbene fluorescent whitening agent is added into PP in a proportion of 0.05 percent, and compared with the traditional dibenzoxazine stilbene fluorescent whitening agent, the weather-resistant and aging-resistant grafted dibenzoxazine stilbene fluorescent whitening agent has better weather-resistant and aging-resistant effects than the traditional dibenzoxazine stilbene fluorescent whitening agent.
| Fluorescent whitening agents of the invention | Conventional optical brighteners | |
| Aging for 7 days | The appearance color is not changed | The appearance color is not changed |
| Aging for 14 days | The appearance color is not changed | The appearance color is not changed |
| Aging for 28 days | The appearance color is not changed | The appearance color has no obvious change |
| Aging for 56 days | The appearance color is not changed | The appearance color has no obvious change |
| Aging for 112 days | The appearance color is not changed | The appearance color turns yellow slightly |
Claims (8)
1. A high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent is characterized by having a chemical structural formula as follows:
2. the high weather-resistant aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent of claim 1 which is characterized in that: the molecular structure of the fluorescent whitening agent has semi-hindered amine or hindered amine group which resists ozone aging.
3. The high weather-resistant aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent of claim 2, which is characterized in that: the molecular structure of the fluorescent whitening agent has semi-hindered amine resisting ozone aging or R in hindered amine group, wherein R comprises straight-chain alkane, cyclane, benzene and benzene derivatives.
4. The high weather-resistant aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent of claim 2, which is characterized in that: the molecular structure of the fluorescent whitening agent has semi-hindered amine or R in hindered amine group which resists ozone aging, and the grafting position is any position in 2, 3, 4 and 5 positions of benzoxazole.
5. The preparation method of the high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent according to claim 3 or 4, which is characterized in that: including and not limited to the following two processes: sulfur oxidation and cyanobenzyl chloride.
6. The preparation method of the high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent according to claim 5, which is characterized in that a sulfur oxidation process synthesis line comprises the following steps:
step 1:
step 2:
wherein R is any one or two of alkane, cyclane, aromatic hydrocarbon or benzene derivatives.
7. The preparation method of the high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent according to claim 5, which is characterized in that the synthesis line of the nitrile benzyl chloride method is as follows: the method comprises the following three steps:
step 1:
step 2:
and step 3:
8. the application of the high weather-resistant and aging-resistant grafted dibenzoxazole stilbene fluorescent whitening agent according to claim 1, which is characterized in that: it can be used for whitening and coloring plastics, spinning fiber, rubber and paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011628668.2A CN112794827A (en) | 2020-12-31 | 2020-12-31 | High-weather-resistance and aging-resistance grafted dibenzoxazole stilbene type fluorescent whitening agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011628668.2A CN112794827A (en) | 2020-12-31 | 2020-12-31 | High-weather-resistance and aging-resistance grafted dibenzoxazole stilbene type fluorescent whitening agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112794827A true CN112794827A (en) | 2021-05-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011628668.2A Pending CN112794827A (en) | 2020-12-31 | 2020-12-31 | High-weather-resistance and aging-resistance grafted dibenzoxazole stilbene type fluorescent whitening agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112794827A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1072917A (en) * | 1962-12-17 | 1967-06-21 | Kodak Ltd | The use of bisbenzoxazole stilbenes as fluorescent brightening agents for solid polymeric material |
| CN1337954A (en) * | 1999-01-27 | 2002-02-27 | 西巴特殊化学品控股有限公司 | Process for the preparation of 4,4'-bis (2-benoxazolyl) stilbenes |
| CN1606574A (en) * | 2001-12-21 | 2005-04-13 | 西巴特殊化学品控股有限公司 | Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties |
| CN101166511A (en) * | 2005-04-28 | 2008-04-23 | 西巴特殊化学制品控股公司 | Use of benzotriazole derivatives for photostabilisation |
| CN101516861A (en) * | 2006-10-09 | 2009-08-26 | 科莱恩金融(Bvi)有限公司 | Method for producing bisbenzoxazoles |
-
2020
- 2020-12-31 CN CN202011628668.2A patent/CN112794827A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1072917A (en) * | 1962-12-17 | 1967-06-21 | Kodak Ltd | The use of bisbenzoxazole stilbenes as fluorescent brightening agents for solid polymeric material |
| CN1337954A (en) * | 1999-01-27 | 2002-02-27 | 西巴特殊化学品控股有限公司 | Process for the preparation of 4,4'-bis (2-benoxazolyl) stilbenes |
| CN1606574A (en) * | 2001-12-21 | 2005-04-13 | 西巴特殊化学品控股有限公司 | Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties |
| CN101166511A (en) * | 2005-04-28 | 2008-04-23 | 西巴特殊化学制品控股公司 | Use of benzotriazole derivatives for photostabilisation |
| CN101516861A (en) * | 2006-10-09 | 2009-08-26 | 科莱恩金融(Bvi)有限公司 | Method for producing bisbenzoxazoles |
Non-Patent Citations (2)
| Title |
|---|
| 张金延 等: ""荧光增白剂OB-1的合成及表征"", 《辽宁化工》 * |
| 王晓英 等: ""荧光增白剂中苯并噁唑环的合成"", 《染料与染色》 * |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20210514 |