CN106588801B - Dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application - Google Patents
Dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application Download PDFInfo
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- CN106588801B CN106588801B CN201611185026.3A CN201611185026A CN106588801B CN 106588801 B CN106588801 B CN 106588801B CN 201611185026 A CN201611185026 A CN 201611185026A CN 106588801 B CN106588801 B CN 106588801B
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- calcium carbonate
- whitening agent
- carbonate powder
- heavy calcium
- fluorescent whitening
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 239000000843 powder Substances 0.000 title claims abstract description 52
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 45
- 239000006081 fluorescent whitening agent Substances 0.000 title claims abstract description 41
- 150000001991 dicarboxylic acids Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000005282 brightening Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- TYWAOIBYSDORAH-UHFFFAOYSA-N 1,2-bis(4-aminophenyl)ethane-1,2-dione Chemical compound C1=CC(N)=CC=C1C(=O)C(=O)C1=CC=C(N)C=C1 TYWAOIBYSDORAH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229960004050 aminobenzoic acid Drugs 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 3
- 241000276489 Merlangius merlangus Species 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- -1 weaving Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HDWLUGYOLUHEMN-UHFFFAOYSA-N Dinobuton Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)OC(C)C HDWLUGYOLUHEMN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000425573 Talanes Species 0.000 description 1
- NCSHGROOCJHAFK-UHFFFAOYSA-N [Cl].N#CC#N Chemical compound [Cl].N#CC#N NCSHGROOCJHAFK-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Abstract
The present invention provides a kind of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, which is characterized in that the dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent is following structural formula 1:The purpose of the present invention is to provide a kind of preparation method and application of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, and this method is simple, and the prices of raw materials are cheap, and technique is environmentally protective.It using fluorescent whitening agent of the invention treated heavy calcium carbonate powder whiteness with higher, brightness, also has preferable mobility and dispersibility, is a kind of excellent multipurpose fluorescence brightening agent.
Description
Technical field
The present invention relates to fluorescent whitening agent technical fields, and in particular to a kind of dicarboxylic acids heavy calcium carbonate powder fluorescent brightening
Agent and its preparation method and application.
Background technique
China in the planning of " 12th Five-Year Plan " new material development using exploitation and resource, environmental harmony new material as mainly examining
Core index solves the problems, such as shortage of resources by developing new material.China has formd fairly perfect material S&T condition,
There is apparent resources advantage and technical advantage, but the overall capability of independent innovation is also weaker in certain field of new materials, tool
There are new material product and the technology of independent intellectual property right also fewer, especially in heavy calcium carbonate powder fluorescent brightening material side
Face is innovative insufficient.
Fluorescent whitening agent have very high quantum yield, processed matrix can be brightened effectively, increase it is gorgeous.Fluorescence increases
White agent molecule has biggish conjugated system, can absorbing wavelength range in the ultraviolet light of 300~400nm or so, and launch
Wave-length coverage 420~450nm or so blue-fluorescence, thus compensate in matrix as blue light missing and caused by visually
Yellowing.It makes one to feel that processed matrix is brighter clean, more bright-coloured by making up blue light.Fluorescent whitening agent is widely used in making
The numerous areas such as paper, weaving, detergent, plastics, ink, leather, ultraviolet absorber, developer, the market demand are huge.
Powdered whiting is widely used as maximum inorganic filler due to the advantages that raw material is wide, price is low, nontoxic
In CABLE MATERIALS, synthetic leather, polyethylene film, the filler material or raw material of the products such as foamed plastics, plastic pipe, paper.Heavy carbon
Sour calcium powder body has higher requirements to its whiteness and glossiness, has numerous plastics in the market, makes as maximum packing material, people
The dedicated fluorescent whitening agent such as paper and detergent, but the powders fluorescent whitening agent such as powdered whiting is rare, the market demand is urgent,
It is huge.
Carbonic acid powder surface have free calcium ions and hydroxyl, in the market existing fluorescent whitening agent product be difficult effectively with
Effectively bonding or adsorption occur for powder surface ion or group, therefore shortage can be brightened effectively, blast heavy calcium carbonate
The fluorescent brightening material of body.
Summary of the invention
In view of the above deficiencies, the purpose of the present invention is to provide a kind of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent and
Preparation method and application, the dicarboxylic acids calcium powder body fluorescent whitening agent synthetic method is simple, and the prices of raw materials are cheap, technique green
Environmental protection.It, can be with by testing the optical property of dicarboxylic acids fluorescent whitening agent and to heavy calcium carbonate powder fluorescent brightening effect
Will become apparent from the dicarboxylic acids fluorescent whitening agent has stronger binding ability with stronger uv absorption property, to dicalcium powder body
With significantly brighten, blast effect, treated calcium carbonate powder mobility with higher and dispersibility have both auxiliary surface
Modifying function is a kind of high-performance coarse whiting powder fluorescent brightening, surface modifying material, has great promotion and application space.
Specifically, the solution of the present invention are as follows: a kind of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, the dicarboxyl
Sour heavy calcium carbonate powder fluorescent whitening agent is following structural formula 1:
The invention also discloses the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, features simultaneously
It is, comprising the following steps:
Step 1: 4,4'- diaminobenzil -2,2'- disulfonic acid aqueous solution is added in Cyanuric Chloride aqueous solution,
A period of time is stirred to react under the conditions of 0~5 DEG C；
Step 2: the mixture ph of regulating step 1 is 3~4, is then added to dodecyldimethylamine base ertiary amine solution
In the mixture of step 1, a period of time is reacted under conditions of 30~40 DEG C；
Step 3: it is 8~9 that p-aminobenzoic acid is added into the mixture of step 2 and maintains reaction system pH, 80~
A period of time is reacted under conditions of 90 DEG C；
Step 4: inorganic salts are added after cooling, dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent is made to be precipitated and collect；
Wherein, Cyanuric Chloride, 4,4'- diaminobenzil -2,2'- disulfonic acid, dodecyldimethylamine base tertiary amine, to ammonia
The ratio of the amount of the substance of yl benzoic acid are as follows: 1.9~2.1:0.9~1.1:1.8~2.1:1.9~2.2.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, in the step 1, trimerization
In chlorine cyanogen aqueous solution, the corresponding 200~250mL water of every 19~21mmol Cyanuric Chloride；
In 4,4'- diaminobenzil -2,2'- disulfonic acid aqueous solutions, every 9~11mmol 4,4'- diamino hexichol second
Alkene -2,2'- disulfonic acid corresponds to 198~205mL water.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, 4, the 4'- diamino
The pH value of talan -2,2'- disulfonic acid aqueous solution is 7~8.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, pH value passes through Na2CO3Regulation.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, the dodecyldimethylamine
Corresponding 9~11mL organic solvent the dimethylformamide of every 18~21mmol dodecyldimethylamine base tertiary amine in base ertiary amine solution
(DMF)。
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, the reaction of the step 1
Time is 1.5~2 hours, and the reaction time of the step 2 is 9~10 hours, and the reaction time of the step 3 is 7~8
Hour.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, the inorganic salts in step 4 are
Sodium chloride.
In the preparation method of above-mentioned dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, in the step 1,4,
4'- diaminobenzil -2,2'- disulfonic acid aqueous solution is added in Cyanuric Chloride aqueous solution in the form being added dropwise；
Dodecyldimethylamine base ertiary amine solution is added in the mixture of step 1 in the step 2 in the form being added dropwise.
The invention also discloses a kind of purposes of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent as described above, use
In the modified application of heavy calcium carbonate powder fluorescent brightening and surface.
The present invention is compared with the traditional method, and is had the advantage that
1. effectively chemical bonding can occur with calcium carbonate powder surface ion for fluorescent whitening agent product of the present invention, it is firmly combined
Degree is high；
2. product of the present invention has stronger uv absorption property, can significantly brighten, blast heavy calcium carbonate powder；
3. fluorescent whitening agent product of the present invention has surface modifying function to heavy calcium carbonate powder, treated, and powder has
Preferable mobility.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum of the dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent of embodiment 1；
Fig. 2 is purple in the optical performance test of the dicarboxylic acids heavy calcium carbonate powder aqueous solutions of optical brighteners of embodiment 1
Outer absorption spectrogram.
Specific embodiment
Claim of the invention is described in further detail With reference to embodiment, but is not constituted to this
Any restrictions of invention, the modification of any limited times made within the scope of the invention as claimed, still in right of the invention
In claimed range.
Embodiment 1
20mmol Cyanuric Chloride is added in 200mL ice water, ice bath.10mmol 4,4'- diamino hexichol second is then added dropwise
The mixed liquor of alkene -2,2'- disulfonic acid (DSD acid) and 200mL distilled water (adds appropriate 20mmol Na2CO3), stirring, 0~5 DEG C, instead
Answer 2h.30~40 DEG C are warming up to, 20mmol Na is added2CO3.20mmol dodecyldimethylamine base tertiary amine and 10mLDMF is then added dropwise
Mixed liquor, temperature control react 10h.80~90 DEG C are warming up to, 20mmol p-aminobenzoic acid is added, 10%Na is added dropwise2CO3Solution dimension
System pH 8~9 is held, temperature control reacts 8h.It is cooled to room temperature, 60g sodium chloride is added, stirring filters, and is dried in vacuo to obtain dicarboxylic acids
Heavy calcium carbonate powder fluorescent whitening agent, yield 92%.
Embodiment 2
19mmol Cyanuric Chloride is added in 250mL ice water, ice bath.11mmol 4,4'- diamino hexichol second is then added dropwise
The mixed liquor of alkene -2,2'- disulfonic acid (DSD acid) and 198mL distilled water (adds appropriate 20mmol Na2CO3), stirring, 0~5 DEG C, instead
Answer 2h.30~40 DEG C are warming up to, 20mmol Na is added2CO3.21mmol dodecyldimethylamine base tertiary amine is then added dropwise and 9mLDMF is mixed
Liquid is closed, temperature control reacts 10h.80~90 DEG C are warming up to, 22mmol p-aminobenzoic acid is added, 10%Na is added dropwise2CO3Solution maintains
System pH 8~9, temperature control react 8h.It is cooled to room temperature, 60g sodium chloride is added, stirring filters, and is dried in vacuo to obtain dicarboxylic acids weight
Matter calcium carbonate powder fluorescent whitening agent, yield 91%.
Embodiment 3
21mmol Cyanuric Chloride is added in 225mL ice water, ice bath.9mmol 4,4'- diaminobenzil-is then added dropwise
The mixed liquor of 2,2'- disulfonic acid (DSD acid) and 205mL distilled water (adds appropriate 20mmol Na2CO3), stirring, 0~5 DEG C, reaction
2h.30~40 DEG C are warming up to, 20mmol Na is added2CO3.18mmol dodecyldimethylamine base tertiary amine is then added dropwise and 11mLDMF is mixed
Liquid is closed, temperature control reacts 10h.80~90 DEG C are warming up to, 19mmol p-aminobenzoic acid is added, 10%Na is added dropwise2CO3Solution maintains
System pH 8~9, temperature control react 8h.It is cooled to room temperature, 60g sodium chloride is added, stirring filters, and is dried in vacuo to obtain dicarboxylic acids weight
Matter calcium carbonate powder fluorescent whitening agent, yield 90%.
Structure of matter test
The present invention carries out structure of matter test, nucleus magnetic hydrogen spectrum figure using product of the nucleus magnetic hydrogen spectrum method to the embodiment of the present invention 1
As shown in Figure 1:
Hydrogen modal data (400MHz；DMSO-d6,δ):0.84(6H,CH3),1.21-1.60(48H,(CH2)12),2.99
(12H,(CH3)2N),3.08(4H,2CH2), 7.58-8.45 (14H, ArH), 7.87 (2H, CH=CH), 9.23 (2H, NH),
10.74(2H,NH)。
Optical performance test
The present invention carries out optical performance test, ultraviolet suction using product of the ultraviolet absorption spectroscopy to the embodiment of the present invention 1
It is as shown in Figure 2 to receive spectrogram:
It is 10 that dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, which is configured to concentration,-6The aqueous solution of mol/L carries out optical
It can test.
Test result shows that dicarboxylic acids fluorescent whitening agent has stronger UV absorption, and maximum trans- absorption peak is located at
344nm。
It brightens and the modified performance test in surface
The aqueous solution 100mL that dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent mass concentration is 0.02% is prepared, processing
The heavy calcium carbonate powder of 100g different grain size and whiteness.
Specific practice is as follows: the heavy calcium carbonate powder of different qualities being put into the solution of appropriate above-mentioned concentration, room temperature
30min is stirred, is drained, it is dry, Gao Bai can be obtained, highlight and with the heavy calcium carbonate powder compared with polymolecularity.
Experimental result confirmation, heavy calcium carbonate powder of the dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent to different qualities
Have significant whitening effect: when concentration is 0.02%, 400~3000 mesh, the heavy calcium carbonate powder that whiteness is 89~95 increases
Add between whiteness value 1~2.5；Brightening treated, powder has preferable dispersibility and mobility.
Above-described is only presently preferred embodiments of the present invention, all made within the scope of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should be included within the scope of the present invention.
Claims (2)
1. a kind of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent, which is characterized in that the dicarboxylic acids heavy calcium carbonate
Body fluorescent whitening agent is following structural formula 1:
2. a kind of purposes of dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent as described in claim 1, which is characterized in that its
The application modified for heavy calcium carbonate powder fluorescent brightening and surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611185026.3A CN106588801B (en) | 2016-12-20 | 2016-12-20 | Dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611185026.3A CN106588801B (en) | 2016-12-20 | 2016-12-20 | Dicarboxylic acids heavy calcium carbonate powder fluorescent whitening agent and its preparation method and application |
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| Publication Number | Publication Date |
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| CN106588801A CN106588801A (en) | 2017-04-26 |
| CN106588801B true CN106588801B (en) | 2019-08-13 |
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| CN107311952A (en) * | 2017-07-06 | 2017-11-03 | 广西碳酸钙产业化工程院有限公司 | A kind of preparation method and applications of calcium carbonate powder brightening agent and surfactant |
| CN107446375A (en) * | 2017-07-08 | 2017-12-08 | 广西壮族自治区工程技术研究院 | The synthesis and application of tetrasulfonic acid sodium EMA quaternary ammonium salt fluorescent whitening agent |
| CN107602486B (en) * | 2017-09-14 | 2021-05-25 | 贺州学院 | Dipyrimidyl diphenylethylene fluorescent whitening agent and preparation method and application thereof |
| CN107641336B (en) * | 2017-10-11 | 2019-05-21 | 贺州学院 | A kind of alanine pyrimidine radicals fluorescent whitening agent and its preparation method and application |
| CN107754721A (en) * | 2017-10-12 | 2018-03-06 | 贺州学院 | Stilbene disulfonic acid natrium surfactant and its synthetic method and application |
| CN107915690A (en) * | 2017-11-28 | 2018-04-17 | 贺州学院 | A kind of synthesis and application of heavy calcium carbonate powder brightening agent |
| CN107641337B (en) * | 2017-11-28 | 2019-05-21 | 贺州学院 | A kind of amion acetic acid pyrimidine radicals fluorescent whitening agent and its preparation method and application |
| CN107857738A (en) * | 2017-11-28 | 2018-03-30 | 贺州学院 | The synthesis and application of hexadecylamino pyrrolotriazine derivatives |
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| SI2302132T1 (en) * | 2009-09-17 | 2012-12-31 | Blankophor Gmbh Co. Kg | Disulfo-type fluorescent whitening agents |
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Application publication date: 20170426 Assignee: Guangxi Yongyuan Construction Engineering Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980054213 Denomination of invention: Fluorescent whitening agent for dicarboxylic acid heavy calcium carbonate powder and its preparation method and application Granted publication date: 20190813 License type: Common License Record date: 20231227 |