CN105949349B - A kind of chitosan-based hyper-dispersant and preparation method thereof - Google Patents
A kind of chitosan-based hyper-dispersant and preparation method thereof Download PDFInfo
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- CN105949349B CN105949349B CN201610308701.0A CN201610308701A CN105949349B CN 105949349 B CN105949349 B CN 105949349B CN 201610308701 A CN201610308701 A CN 201610308701A CN 105949349 B CN105949349 B CN 105949349B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- 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
- C09D7/65—Additives macromolecular
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
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- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of chitosan-based hyper-dispersants and preparation method thereof, belong to chemical field and field of pharmaceutical preparations, specific method is the condensation reaction first with Cyanuric Chloride and arylamine, one monochloro-sym-triazine derivative of hydrophobicity is prepared, then one monochloro-sym-triazine derivative of hydrophobicity is grafted to after chitosan and prepares chitosan-based hyper-dispersant with sodium hydroxymethane sulfonate progress sulfomethylation again.Preparation method provided by the present invention and simple for process, has high dispersibility and excellent dispersion stabilization to low polarity organic pigment.
Description
Technical field
The invention belongs to chemical field and field of pharmaceutical preparations, and in particular to a kind of chitosan-based hyper-dispersant and
Preparation method.
Background technology
Organic pigment is widely used in the fields such as coating, printing and dyeing due to high photostability and light fastness.But
The surface of these materials is made of condensed-nuclei aromatics, and cohesive force is strong, therefore is easily reunited, and is not easy to disperse, especially in water-based system
It is even more so.Though can obtain stable dispersion by chemic modified method, chemic modified method can destroy the knot of these materials
Structure influences its final performance.In comparison, the physical method for making organic pigment be dispersed using dispersant is simple and effective,
It is also current most widely used method.Small molecular surfactant easily aligns on material surface, reduce interfacial tension and
It is primarily used in dispersion.But its hydrophilic radical is not firm in low polar particle surface combination, lipophilic group carbon chain length
Spend short, space steric effect deficiency, to which small molecule dispersant easily desorbs from particle surface and leads to scattered particle
It reassembles.
Macromolecule dispersing agent, also known as hyper-dispersant contain multiple anchoring groups in this macromolecular, particle surface can shape
At multi-point-anchoring, absorption fastness is improved, is not easy to desorb, and polyester, polyethers, polyolefin or the polymerization of polyacrylate equal solventization
Chain can generate enough steric hindrances and play effective stabilization than traditional dispersant lipophilic group regimental commander.Hyper-dispersant soaks
Quickly fully, in base-material solid content is high for particle, it is good with stability to be uniformly dispersed.Although the dispersion performance of hyper-dispersant is compared with small molecule
Dispersant is improved, but undesirable for the dispersion effect of low polar material, this is primarily due to dispersion effect by particle
The polarity effect on surface is larger, and because these material surfaces are mostly condensed-nuclei aromatics, nonpolarity or polarity are very low, do not have for oversubscription
The group of powder anchoring, therefore dispersion effect unobvious.Aromatic ring is introduced the synthesis of anionic macromolecular as anchoring group to contain
Dispersant of the water-soluble macromolecule of aromatic ring as organic pigment can not only assign hyper-dispersant high dispersion performance, but also
Can also be the good dispersion stabilization of pigment holding after dispersion, therefore, the water soluble polymer containing aromatic ring is as super in recent years
The developmental research of dispersant has obtained the attention of people.Currently, such dispersant mainly has polystyrene-acrylic compounds, polyphenyl
Ethylene maleic acid (ester) class, kayexalate and its copolymer etc..But such dispersant is mostly used styrene monomer,
After monomer determines, prepared by dispersant in aromatic ring structure it is immutable, and the interaction force between phenyl ring and condensed ring
It is limited, also necessarily determine that these dispersants need further to improve to the dispersibility and stability of material.
Invention content
The object of the present invention is to provide a kind of chitosan-based hyper-dispersants and preparation method thereof, that is, utilize Cyanuric Chloride
Carry out condensation reaction with arylamine and prepare one monochloro-sym-triazine derivative of hydrophobicity, by after on the derivatives graft to chitosan again with hydroxyl
Metilsulfate carries out sulfomethylation and prepares chitosan-based hyper-dispersant, to solve the low polarity organic pigment of condensed-nuclei aromatics class
Scattering problem in water.Such hyper-dispersant not only has good dissolubility energy, but also anchoring group contains multiple aromatic rings,
There is excellent dispersion performance to organic pigment, have broad application prospects.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of chitosan-based hyper-dispersant in the present invention, structure are：
In formula (I), R1、R2It is independently selected from Formulas I a, Formulas I b and Formulas I c；
R4, R5, R6It is independently selected from H, Cl, Br, NO2、OH、CH3、OCH3；
M is H or alkali metal；
X is 10%-90%；
Y is 0-50%；
Z is 5%-50%.
Preferably, the R1、R2It is respectively selected from Ia, Ib.
Preferably, the R4, R5, R6For H.
Preferably, the M is sodium or potassium.
Preferably, the x is 50%-70%.
Preferably, the y is 0%-10%.
Preferably, the z is 20%-30%.
A kind of preparation method of chitosan-based hyper-dispersant in the present invention, specifically comprises the following steps：
A. the preparation of one monochloro-sym-triazine derivative of hydrophobicity containing arylamine：Cyanuric Chloride is dissolved in tetrahydrofuran, is cooled to
0-5 DEG C, arylamine is added, keeps reaction material liquid pH=4-7, reacts 2-12 hours, continuously adds arylamine, be warming up to 30-50 DEG C, instead
It answers 2-20 hours, is cooled to room temperature, reaction solution is poured into water precipitation product, filter, dry a monochloro-sym-triazine derivative；
B. the sulfonating reaction of chitosan：It is added to sodium hydroxymethane sulfonate wiring solution-forming in the aqueous solution of chitosan, keeps
Reaction material liquid pH=7-10,30-50 DEG C is reacted 2-4 hours, after reaction, obtains sulfated chitosan solution；
C. the graft reaction of sulfated chitosan and one monochloro-sym-triazine derivative of hydrophobicity containing arylamine：Arylamine hydrophobicity one will be contained
Monochloro-sym-triazine derivative is dissolved in tetrahydrofuran, is added in sulfated chitosan aqueous solution, continues under 70-80 DEG C, pH=10-11 anti-
It answers 2-10 hours, is cooled to room temperature, product is precipitated to 1-2 in the pH value for adjusting reaction system, and filtering is chitosan-based superly dry
Dispersant solid product.
The beneficial effects of the present invention are the chitosan-based hyper-dispersant that the present invention obtains contains dredging for multiple arylamine combinations
Aqueous group, to the anchorage effect that low polarity condensed-nuclei aromatics organic pigment has had, the good water solubility of sulfonic group assigns it to having
Machine pigment good dispersibility in water.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, but do not limit the invention in any way.
Embodiment 1：
In 500mL beakers, it is added 9.26g Cyanuric Chlorides (0.0503mol), 100mL tetrahydrofurans, after stirring and dissolving,
It is cooled to 0-5 DEG C, 4.65g aniline (0.05mol) is added, pH value control is reacted 2 hours in 5-6.Continuously add 4.65g aniline
(0.05mol) is warming up to 40 DEG C, and pH value control is reacted 4 hours in 6-7.It is cooled to room temperature, reaction solution is poured into 500mL water
Product is precipitated, filters, it is dry, obtain the monochloro-sym-triazine derivative containing phenyl ring.
By in 33g chitosan solution 400mL water, pH 9-10 are adjusted with NaOH solution, are warming up to 30-50 DEG C, 21g is added
Sodium hydroxymethane sulfonate reacts 4 hours；Tetrahydrofuran 400mL is added, is warming up to 70 DEG C, an above-mentioned monochloro-sym-triazine derivative is added,
The reaction was continued 6 hours；It is cooled to room temperature, with the pH=1-2 of the HCl regulation systems of 6moL/L, product is precipitated, filters, washs, does
Dry product.
Embodiment 2：
The difference is that, aniline is replaced to synthesize a corresponding monochloro-sym-triazine derivative with naphthylamines with above-described embodiment 1, then
It is reacted with chitosan and sodium hydroxymethane sulfonate reaction product, obtains naphthalene-ring containing chitosan-based hyper-dispersant, other conditions and reality
It is consistent to apply example 1.
Embodiment 3：
The difference is that, aniline synthesis is replaced to contain with naphthylamines in two contracting reactions of Cyanuric Chloride with above-described embodiment 1
There is a monochloro-sym-triazine derivative of phenyl ring and naphthalene nucleus, then reacted with chitosan and sodium hydroxymethane sulfonate reaction product, obtains containing benzene
The chitosan-based hyper-dispersant of ring and naphthalene nucleus, other conditions are consistent with embodiment 1.
Based on above-mentioned, the chitosan-based hyper-dispersant that the present invention obtains contains the hydrophobic group of multiple arylamine combinations, right
The anchorage effect that low polarity condensed-nuclei aromatics organic pigment has had, sulfonic group is good water-soluble to assign it to organic pigment in water
Good dispersibility.
Claims (8)
1. a kind of chitosan-based hyper-dispersant, which is characterized in that its structure is：
In formula (I), R1、R2It is independently selected from Formulas I a, Formulas I b and Formulas I c；
R4, R5, R6It is independently selected from H, Cl, Br, NO2、OH、CH3、OCH3；
M is H or alkali metal；
X is 10%-90%；
Y is 0-50%；
Z is 5%-50%.
2. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the R1、R2Be respectively selected from Ia,
Ib。
3. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the R4, R5, R6For H.
4. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the M is sodium or potassium.
5. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the x is 50%-70%.
6. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the y is 0%-10%.
7. a kind of chitosan-based hyper-dispersant according to claim 1, which is characterized in that the z is 20%-30%.
8. a kind of preparation method of such as chitosan-based hyper-dispersant of claim 1-7 any one of them, which is characterized in that including
Following steps：
A. the preparation of one monochloro-sym-triazine derivative of hydrophobicity containing arylamine：Cyanuric Chloride is dissolved in tetrahydrofuran, 0-5 is cooled to
DEG C, arylamine is added, keeps reaction material liquid pH=4-7, reacts 2-12 hours, continuously adds arylamine, is warming up to 30-50 DEG C, reaction
It 2-20 hours, is cooled to room temperature, reaction solution is poured into water precipitation product, filter, dry a monochloro-sym-triazine derivative；
B. the sulfonating reaction of chitosan：It is added to sodium hydroxymethane sulfonate wiring solution-forming in the aqueous solution of chitosan, keeps reaction
Material liquid pH=7-10,30-50 DEG C is reacted 2-4 hours, after reaction, obtains sulfated chitosan solution；
C. the graft reaction of sulfated chitosan and one monochloro-sym-triazine derivative of hydrophobicity containing arylamine：It is equal that one chlorine of arylamine hydrophobicity will be contained
Pyrrolotriazine derivatives are dissolved in tetrahydrofuran, are added in sulfated chitosan aqueous solution, the reaction was continued under 70-80 DEG C, pH=10-11 2-
10 hours, it is cooled to room temperature, product is precipitated to 1-2 in the pH value for adjusting reaction system, and filtering is chitosan-based ultra-dispersedly dry
Agent solid product.
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| CN109679398B (en) * | 2018-12-17 | 2023-03-14 | 江苏丽王科技股份有限公司 | Hyper-dispersant for polyurethane-based water-based paint and preparation method thereof |
| CN115893625B (en) * | 2022-10-26 | 2023-09-15 | 中国石油化工股份有限公司 | Biological desulfurizing agent for removing organic sulfur in press-back liquid and preparation method thereof |
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Inventor after: Xu Dan Inventor after: Yang Jingjing Inventor after: Liu Guangxiang Inventor after: Li Jian Inventor after: Zhou Hong Inventor after: Xue Mengwei Inventor before: Yang Jingjing Inventor before: Liu Guangxiang Inventor before: Li Jian Inventor before: Xu Dan Inventor before: Zhou Hong Inventor before: Xue Mengwei |
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