CN108299247A - A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof - Google Patents
A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof Download PDFInfo
- Publication number
- CN108299247A CN108299247A CN201810093832.0A CN201810093832A CN108299247A CN 108299247 A CN108299247 A CN 108299247A CN 201810093832 A CN201810093832 A CN 201810093832A CN 108299247 A CN108299247 A CN 108299247A
- Authority
- CN
- China
- Prior art keywords
- pyrene trisulfonic
- preparation
- water
- hydroxyls
- trisulfonic acid
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/43—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Abstract
The invention discloses a kind of 8 (allyloxys) 1 of fluorescent monomer, 3,6 pyrene trisulfonic acids and preparation method thereof, 8 hydroxyl 1 of raw material, 8 (allyloxys) 1 are made after being reacted with the heating of 3 chloropropeneizations of liquid in the system of sodium hydrate aqueous solution in 3,6 pyrene trisulfonic acid trisodiums, 3,6 pyrene trisulfonic acid solution.This law preparation method is simple, and each reaction condition is easy to realize；The present invention compared with the existing technology, using water as reaction dissolvent, reduces the cost of production product, not can cause environmental pollution.
Description
Technical field
The invention belongs to water treatment agent preparation field more particularly to a kind of water-soluble fluorescent monomer 8- (allyloxy) -1,
3,6- pyrene trisulfonic acids and preparation method thereof.
Background technology
The concentration of recirculated water sewerage disposing agent is detected, conventional method is first to clear up organophosphor at Phos, so
After measure total phosphorus concentration, this method needs that other reagents are added, and process is more complicated, and can not track disappearing for water treatment agent
Rate is consumed, dosage is controlled.To solve this problem, people using fluorescent tracer technique measure recirculated water in polymer it is dense
Degree, to realize to the accurate detection of system and Adding medicine control.
Fluorescent monomer copolymerization is by the water treatment agent monomer containing unsaturated double-bond and not only to contain unsaturated double-bond but also contain
The monomer of fluorescent characteristic is copolymerized, the method to prepare fluorescent tracing water treatment agent.Fluorescent monomer must have good glimmering
Optical property, to reduce the influence to water treatment agent treatment effect, it is also necessary to there is good water solubility.United States Patent (USP)
US6321644B1 discloses a series of fluorescent monomers and preparation method thereof containing unsaturated double-bond, but the monomer preparation process makes
Use dimethyl sulfoxide (DMSO)（DMSO）As reaction dissolvent, there is certain toxicity, can cause environmental pollution in distillation process.
Invention content
The object of the present invention is to provide a kind of fluorescent monomer 8- (allyloxy) -1 containing unsaturated double-bond, 3,6- pyrenes three
Sulfonic acid, the monomer fluorescence is functional, can participate in preparing fluorescent tracing water treatment agent.
The preparation method green of above-mentioned fluorescent monomer, environmental-friendly, building-up process is using cheap, safety water as reaction
Solvent, reaction process carry out in same reaction unit, are not required to detach, and easy to operate, production cost is relatively low.
For achieving the above object, the present invention uses technical solution below：
A kind of fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids, the fluorescent monomer is using water as reaction dissolvent, by 8- hydroxyls
- 1,3,6 pyrene trisulfonic acid trisodium salt monomer of base is carried out reacting with chlorallylene and is made under alkaline condition；The wherein described fluorescent monomer
Structural formula be：
A kind of preparation method of above-mentioned fluorescent monomer, using following steps system
It is standby：8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodiums and water are added in the container equipped with reflux condensate device, sodium hydroxide is added, stirs
It mixes 15-20min and chloropropene is added dropwise after adjusting temperature is 60-80 DEG C, continue to react at 60-80 DEG C after being added dropwise to complete, it is cooling
To room temperature, the fluorescent monomer is made, the reaction time is more than or equal to 6 hours；Preferably, the reaction time is that 6-10 is small
When.
Further, the amount ratio of the chloropropene and 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium substances is 1.2-6.0:1；Institute
The rate of addition for stating chloropropene is 0.8-1.2g/min.
Further, the mass ratio of the 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodiums and water is 1:20-25.
Further, the sodium hydroxide is sodium hydrate solid or sodium hydroxide solution；The sodium hydroxide of the addition
The amount of substance is 1.2-2.0 with the amount ratio of -1,3,6 pyrene trisulfonic acid trisodium substance of 8- hydroxyls:1.
Water is a kind of cheap, safe and pollution-free green solvent, can be solved using water as reaction dissolvent most of organic
Solvent bank come it is inflammable, explosive, volatile, be easy the shortcomings that pollution environment, in recent years, organic synthesis in water phase increasingly at
For the hot spot of organic chemistry research.
The present invention is using water as reaction dissolvent, and by 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodiums carry out substitution reaction with chlorallylene
It is prepared for a kind of fluorescent monomer 8- (allyloxy) -1 containing unsaturated double-bond, 3,6- pyrene trisulfonic acid fluorescent monomers.
Advantageous effect
（1）The eutrophy elements such as the not phosphorous, nitrogen of fluorescent monomer prepared by the present invention are a kind of novel Green Water Treatment Reagents.Its
Preparation method green environment is friendly, and building-up process is using cheap, safety water as reaction dissolvent, and reaction process is in same reaction
It is carried out in device, is not required to detach, easy to operate, production cost is relatively low.
（2）Containing there are three the strong sulfonic group of hydrophily in water-soluble fluorescent monomer molecule prepared by the present invention, it is water-soluble compared with
It is good, containing unsaturated double-bond, copolyreaction can be participated in and prepare polymer, also can be used alone.
（3）Water-soluble fluorescent monomer fluorescence property prepared by the present invention is good, can accurately detect concentration in water, can
It is used to prepare fluorescent tracing water treatment agent, water treatment agent can be quickly and easily measured by the measurement to fluorescent tracing substance and exist
Drug concentration in system, to realize on-line checking and automatic chemical feeding to water treatment agent.
Description of the drawings
Fig. 1 is 99% standard 8- (allyloxy) -1, the nucleus magnetic hydrogen spectrum of 3,6- pyrene trisulfonic acid fluorescent monomers.
Fig. 2 is that 8- (allyloxy) -1, the nucleus magnetic hydrogen spectrum of 3,6- pyrene trisulfonic acid fluorescent monomers is made in embodiment 1.
Specific implementation mode
Embodiment 1：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.80ml (wherein sodium hydroxide is 0.010mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 15 minutes at normal temperatures.After temperature is adjusted to 80 DEG C, chloropropene 2.31g is added dropwise（0.030mol）, the dropwise addition of chloropropene
Speed is 0.8-1.2g/min, continues to react while stirring at 80 DEG C 6 hours after the completion, is cooled to room temperature, and 8- (allyl oxygen is made
Base) -1,3,6- pyrene trisulfonic acid fluorescent monomers, products collection efficiency 91wt%.
According to Fig. 1 and Fig. 2 comparisons it is found that 8- (allyloxy) -1, the production of 3,6- pyrene trisulfonic acid fluorescent monomers in embodiment 1
Rate is 91%.
Embodiment 2：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.80ml (wherein sodium hydroxide is 0.010mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 15 minutes at normal temperatures.After temperature is adjusted to 80 DEG C, chloropropene 1.54g is added dropwise（0.020mol）, the dropwise addition of chloropropene
Speed is 0.8-1.2g/min, continues to react while stirring at 80 DEG C 6 hours after the completion, is cooled to room temperature, and 8- (allyl oxygen is made
Base) -1,3,6- pyrene trisulfonic acid fluorescent monomers, products collection efficiency 87wt%.
Embodiment 3：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.72ml (wherein sodium hydroxide is 0.009mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 15 minutes at normal temperatures.After temperature is adjusted to 60 DEG C, chloropropene 0.693g is added dropwise（0.009mol）, the dropwise addition of chloropropene
Speed is 0.8-1.2g/min, continues to react while stirring at 60 DEG C 6 hours after the completion, is cooled to room temperature, and 8- (allyl oxygen is made
Base) -1,3,6- pyrene trisulfonic acid fluorescent monomers, products collection efficiency 49wt%.
Embodiment 4：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.56ml (wherein sodium hydroxide is 0.007mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 20 minutes at normal temperatures.After temperature is adjusted to 70 DEG C, chloropropene 0.539g is added dropwise（0.007mol）, the dropwise addition of chloropropene
Speed is 0.8-1.2g/min, continues to react while stirring at 70 DEG C 7 hours after the completion, is cooled to room temperature, and 8- (allyl oxygen is made
Base) -1,3,6- pyrene trisulfonic acid fluorescent monomers, products collection efficiency 58wt%.
Embodiment 5：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.80ml (wherein sodium hydroxide is 0.010mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 15 minutes at normal temperatures.After temperature is adjusted to 80 DEG C, chloropropene 0.77g is added dropwise（0.010mol）, the dropwise addition of chloropropene
Speed is 0.8-1.2g/min, continues to react while stirring at 60 DEG C 6 hours after the completion, is cooled to room temperature, and 8- (allyl oxygen is made
Base) -1,3,6- pyrene trisulfonic acid fluorescent monomers, products collection efficiency 60wt%.
Embodiment 6：In the three-necked flask of 100ml plus 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium 2.62g (0.005mol),
50% sodium hydroxide solution 0.80ml (wherein sodium hydroxide is 0.010mol), is added 50ml water, with heatable magnetic stirring apparatus
It stirs 15 minutes at normal temperatures.After temperature is adjusted to 80 DEG C, chloropropene 0.77g is added dropwise（0.010mol）, continue after the completion
It is reacted while stirring at 80 DEG C 10 hours, is cooled to room temperature, 8- (allyloxy) -1,3,6- pyrene trisulfonic acid fluorescent monomers, production is made
Produce rate is 48wt%.
Claims (6)
1. a kind of fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids, which is characterized in that the fluorescent monomer is anti-with water
Solvent is answered, by 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodium salt monomers are carried out reacting with chlorallylene and are made under alkaline condition.
2. the preparation method of fluorescent monomer described in a kind of claim 1, which is characterized in that prepared using following steps：
8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodiums and water are added in container equipped with reflux condensate device, sodium hydroxide is added, stirs 15-
Chloropropene is added dropwise after adjusting temperature is 60-80 DEG C in 20min, continues to react at 60-80 DEG C after being added dropwise to complete, is cooled to room
The fluorescent monomer is made in temperature；Wherein the reaction time is more than or equal to 6 hours.
3. preparation method according to claim 2, which is characterized in that the chloropropene and 8- hydroxyls -1,3,6 pyrene trisulfonic acids
The amount ratio of trisodium substance is 1.2-6.0:1；The rate of addition of the chloropropene is 0.8-1.2g/min.
4. preparation method according to claim 2, which is characterized in that the 8- hydroxyls -1,3,6 pyrene trisulfonic acid trisodiums and water
Mass ratio be 1:20-25.
5. preparation method according to claim 2, which is characterized in that the sodium hydroxide is sodium hydrate solid or hydrogen-oxygen
Change sodium solution；The sodium hydroxide of the addition is 1.2-2.0 with the amount ratio of -1,3,6 pyrene trisulfonic acid trisodium substance of 8- hydroxyls:1.
6. preparation method according to claim 2, which is characterized in that the reaction time is 6-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810093832.0A CN108299247A (en) | 2018-01-31 | 2018-01-31 | A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810093832.0A CN108299247A (en) | 2018-01-31 | 2018-01-31 | A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108299247A true CN108299247A (en) | 2018-07-20 |
Family
ID=62867158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810093832.0A Pending CN108299247A (en) | 2018-01-31 | 2018-01-31 | A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879783A (en) * | 2019-01-11 | 2019-06-14 | 河南清水源科技股份有限公司 | A kind of water-soluble fluorescent monomer, water soluble fluorescence tracer type water treatment agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312644B1 (en) * | 1999-12-16 | 2001-11-06 | Nalco Chemical Company | Fluorescent monomers and polymers containing same for use in industrial water systems |
| CN1642626A (en) * | 2002-03-28 | 2005-07-20 | 纳尔科公司 | Method of monitoring membrane separation processes |
-
2018
- 2018-01-31 CN CN201810093832.0A patent/CN108299247A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312644B1 (en) * | 1999-12-16 | 2001-11-06 | Nalco Chemical Company | Fluorescent monomers and polymers containing same for use in industrial water systems |
| CN1642626A (en) * | 2002-03-28 | 2005-07-20 | 纳尔科公司 | Method of monitoring membrane separation processes |
Non-Patent Citations (1)
| Title |
|---|
| KEYING WU ET AL.: "Preparation and properties of β-cyclodextrins polymer used as calcium carbonate scale inhibitor containing fluorescent groups", 《RES CHEM INTERMED》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879783A (en) * | 2019-01-11 | 2019-06-14 | 河南清水源科技股份有限公司 | A kind of water-soluble fluorescent monomer, water soluble fluorescence tracer type water treatment agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106442686B (en) | A kind of chiral metal organic framework polymer sensor and its preparation method and application | |
| CN109796971B (en) | Nitrogen-doped red fluorescent carbon quantum dot and preparation method and application thereof | |
| CN100528933C (en) | Calcium polyaspartate and preparation method thereof | |
| CN108299247A (en) | A kind of water-soluble fluorescent monomer 8- (allyloxy) -1,3,6- pyrene trisulfonic acids and preparation method thereof | |
| Xu et al. | Room temperature multicomponent polymerizations of alkynes, sulfonyl azides, and N-protected isatins toward oxindole-containing poly (N-acylsulfonamide) s | |
| Chen et al. | Construction of unconventional fluorescent poly (amino ester) polyols as sensing platform for label-free detection of Fe3+ ions and l-cysteine | |
| Weng et al. | Novel multi-component photofunctional nanohybrids for ratio-dependent oxygen sensing | |
| CN102004094B (en) | Method for detecting content of benzoyl peroxide in flour | |
| CN108587607A (en) | The luminescent metal organic framework material and its preparation method and application detected for Thiocyanate ion in water | |
| CN109970990B (en) | Terbium coordination polymer and preparation method and application thereof | |
| CN108530556B (en) | A kind of preparation method for the Modified kelp polysaccharide that acts synergistically | |
| CN103242476B (en) | A kind of preparation method with the acrylic polymers of fluorescent characteristic | |
| CN102442984A (en) | Synthesis method of water-soluble fluorescent monomer | |
| CN114486835B (en) | Rapid detection method for tryptophan in food by using cholesteric chiral molecular clamp | |
| KR101183956B1 (en) | Water soluble conjugated polymer for chemical sensors and biosensors, method for producing the same and fluorescent cyanide sensor containing the same | |
| CN102680309A (en) | Method for measuring carbonic acid content in Sevelamer carbonate | |
| CN102617779B (en) | 2,3,4,5-tetraphenylsilole-based water-soluble polymer and its preparation method and use | |
| CN108328753A (en) | A kind of fluorescent tracing type antisludging agent and its preparation method and application | |
| CN1048993C (en) | Prepn. method of water soluble sulfonated phenylethylene copolymer | |
| CN109053955B (en) | Water-soluble and temperature-responsive fluorescent polymer based on sulfone and preparation method thereof | |
| CN116217921B (en) | Phosphorus-containing in-situ flame-retardant polyamide | |
| CN110818658A (en) | Preparation method of tricyano dihydrofuran-quinolone complex | |
| CN112239515A (en) | Imidazole magnetic ionic liquid containing alkyl chain as well as preparation method and application thereof | |
| CN111426683B (en) | Method for detecting sulfonylureas drug components in hypoglycemic health products | |
| CN112142179B (en) | Inorganic polymer dephosphorizing agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |
Application publication date: 20180720 |
|
| RJ01 | Rejection of invention patent application after publication |