CN106398315A - Shape-controllable nano calcium carbonate powder modified by grafted AOS (Alpha Olefin Sulfonate) polyoxyethylene ether treating agent and preparation method thereof - Google Patents
Shape-controllable nano calcium carbonate powder modified by grafted AOS (Alpha Olefin Sulfonate) polyoxyethylene ether treating agent and preparation method thereof Download PDFInfo
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- CN106398315A CN106398315A CN201610919712.2A CN201610919712A CN106398315A CN 106398315 A CN106398315 A CN 106398315A CN 201610919712 A CN201610919712 A CN 201610919712A CN 106398315 A CN106398315 A CN 106398315A
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- aos
- calcium carbonate
- polyoxyethylene ether
- carbonate powder
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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
- 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
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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
- 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
- C09C3/10—Treatment with macromolecular organic compounds
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- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses shape-controllable nano calcium carbonate powder modified by a grafted AOS (Alpha Olefin Sulfonate) polyoxyethylene ether treating agent and a preparation method thereof. An ionic liquid/deionized water composite is taken as a solvent, the shape-controllable calcium carbonate powder with higher performance is prepared through a carbonization method by means of the unique adsorbability of the ionic liquid for carbon dioxide, and a novel hyper-branched polysiloxane-grafted AOS polyoxyethylene ether surfactant is prepared via a hydrosilylation reaction to perform surface treatment on the nano calcium carbonate powder. The modified nano calcium carbonate powder has favourable dispersity and hydrophobicity, and does not have any adverse effect on resin under a high heat condition at the same time.
Description
Technical field
The present invention relates to modified calcium carbonate technical field, more particularly, to a kind of grafting AOS polyoxyethylene ether inorganic agent modification
Morphology controllable nano-calcium carbonate powder body and preparation method thereof.
Background technology
Calcium carbonate powder is a kind of very common inorganic material, and it is mainly used in papermaking, rubber, plastics, coating, oil
As reinforced filling in the products such as ink.It is even nano level that the pearl filler adopting in actual use mostly is micron order
Product, the pearl filler of these minute yardsticks has very high surface energy, in the base bad dispersibility, caking of easily reuniting, from
And have a strong impact on filling-modified effect, need it is carried out surface modification treatment, to improve its serviceability.
Presently commercially available nano-calcium carbonate powder body is many to carry out dry method coating modification process using stearic acid or soap, this
Although the powder body that the processing method of a little classifications obtains all is improved at aspects such as dispersibility, oil factor, activation grades,
It is because its temperature tolerance is poor, is not suitable for high temperature process environment, harmful effect can be produced to the matrix material of filling, using model
It is with effect.《The surface modification to nano-calcium carbonate for the composite modifier》One literary composition utilizes lauric acid and two pungent/certain herbaceous plants with big flowers acid glyceride polyoxies
Vinyl Ether composite product carries out wet-process modified process to nano-calcium carbonate, and modified nano-calcium carbonate powder body is difficult to roll into a ball
Poly-, surface active degree improves, hydrophobicity improves, and temperature tolerance is more preferably, it is to avoid the defect of stearic acid modifying agent, but and it draws
The lauric acid entering has certain corrosivity to metal, and modified calcium carbonate powder range is still restricted, and is not order
The satisfied modification result of people.
Content of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of grafting AOS polyoxyethylene ether inorganic agent
Modified morphology controllable nano-calcium carbonate powder body and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of modified morphology controllable nano-calcium carbonate powder body of grafting AOS polyoxyethylene ether inorganic agent, this nano-calcium carbonate powder body
It is made up of the raw material of following weight portion：Calcium oxide 30-50, carbon dioxide（Technical pure）In right amount, grafting AOS polyoxyethylene ether is processed
Agent 0.4-0.8, deionized water 300-500, ionic liquid 1-25, dehydrated alcohol 30-50.
Described grafting AOS polyoxyethylene ether inorganic agent is obtained by the raw material of following weight portion：Alpha-olefin sodium sulfonate（AOS）
1-5, oxirane 0.5-2, pi-allyl Ethoxysilane 5-20, four（Dimethyl ethenyl siloxy）Silane 5-20,95% ethanol
150-300, KOH catalyst 0.005-0.01, Pt/C catalyst 0.001-0.005, appropriate dilute hydrochloric acid solution, dehydrated alcohol are fitted
Amount；Preparation method is：
（1）First alpha-olefin sodium sulfonate is put in reaction vessel with pi-allyl Ethoxysilane, be subsequently added 95% ethanol, and plus
Enter appropriate dilute hydrochloric acid solution, regulation system pH value is 4-5, stirring reaction 3-5h under the conditions of 40-50 DEG C reacts warp after terminating
Sucking filtration, washing, vacuum drying treatment, obtain allyl silicane grafting alpha-olefin sodium sulfonate standby；
（2）Allyl silicane is grafted alpha-olefin sodium sulfonate and four（Dimethyl ethenyl siloxy）Silane mixture, and add Pt/
Reaction system is heated to 50-60 DEG C by C catalyst under nitrogen atmosphere, reacts 5-10h, and reaction is washed through sucking filtration, alcohol after terminating,
Obtain hyperbranched polyorganosiloxane modified alpha-alkene sulfonic acid sodium standby；
（3）Hyperbranched polyorganosiloxane modified alpha-the alkene sulfonic acid sodium of preparation, KOH catalyst are sequentially added in autoclave,
Open heating and stirring system after airtight, and be passed through nitrogen, be thoroughly mixed processed under the conditions of 150-160 DEG C, place
Manage and after finishing, control pressure in kettle to be 0.01-0.05MPa, then put into oxirane, stirring reaction 4-5h, reaction adds after terminating
Entering appropriate dilute hydrochloric acid regulation system pH is in neutrality, and subsequent cooling discharge obtains final product described grafting AOS polyoxyethylene ether and processes
Agent.
Described ionic liquid is：The double fluoroform sulphur of 1- butyl -3- Methylimidazole. hexafluorophosphate, 1,3- methylimidazole
One of imide salts or two kinds.
A kind of preparation side of the modified morphology controllable nano-calcium carbonate powder body of described grafting AOS polyoxyethylene ether inorganic agent
Method comprises the following steps：
（1）First ionic liquid, deionized water are put in reaction vessel respectively, under nitrogen atmosphere strong agitation mixing 20-
System is subsequently heated to 80-85 DEG C by 30min, and then adds calcium oxide, grinds stirring digestion 2-3h, forms calcium hydroxide
Slurry, standby after ageing 10-15h；
（2）AOS polyoxyethylene ether inorganic agent will be grafted and put in dehydrated alcohol, stirring will make it be completely dissolved, and resulting solution is injected
Step（1）In the serosity of preparation, it is uniformly mixed, is kept stirring for state, be passed through carbon dioxide in system, to system
Stop ventilation when pH stable is neutral, and continue stirring mixing 1-2h, reaction terminates rear system and filters, filtrate is scrubbed,
Vacuum drying, dispersion obtain final product described nano-calcium carbonate powder body.
Advantages of the present invention is as follows：
（1）In the preparation process of calcium carbonate powder, it is combined as solvent using ionic liquid/deionized water, using ionic liquid
The body adsorptivity unique to carbon dioxide, effectively raises the concentration of carbon dioxide in solution so that the production of Calcium Carbonate is imitated
Rate is higher, and raw material availability is higher, and can realize the pattern of powder body by adjusting ionic liquid concentration and carbon dioxide usage amount
Controlled, obtain the more excellent calcium carbonate powder of performance.
（2）Using hydrosilylation, it is prepared for a kind of AOS polyoxyethylene ether of new hyperbranched polyorganosiloxane grafting
Surfactant, this activating agent has excellent heat stability and the compatibility with resin system, its modified nano-sized carbon
Sour calcium powder body not only has good dispersibility and hydrophobicity, in the case of hyperpyrexia, resin is had no adverse effects simultaneously.
Specific embodiment
A kind of modified morphology controllable nano-calcium carbonate powder body of grafting AOS polyoxyethylene ether inorganic agent, this nano-calcium carbonate
Powder body is made up of the raw material of following weight portion：Calcium oxide 30, carbon dioxide（Technical pure）In right amount, at grafting AOS polyoxyethylene ether
Reason agent 0.4, deionized water 300,1- butyl -3- Methylimidazole. hexafluorophosphate 1, dehydrated alcohol 30.
A kind of modified morphology controllable nano-calcium carbonate powder body of described grafting AOS polyoxyethylene ether inorganic agent, described
Grafting AOS polyoxyethylene ether inorganic agent is obtained by the raw material of following weight portion：Alpha-olefin sodium sulfonate（AOS）1st, oxirane 0.5,
Pi-allyl Ethoxysilane 5, four（Dimethyl ethenyl siloxy）Silane 5,95% ethanol 150, KOH catalyst 0.005, Pt/C
Catalyst 0.001, appropriate dilute hydrochloric acid solution, appropriate dehydrated alcohol；Preparation method is：
（1）First alpha-olefin sodium sulfonate is put in reaction vessel with pi-allyl Ethoxysilane, be subsequently added 95% ethanol, and plus
Enter appropriate dilute hydrochloric acid solution, regulation system pH value be 4, stirring reaction 3h under the conditions of 40 DEG C, reaction terminate after through sucking filtration, wash
Wash, vacuum drying treatment, obtain allyl silicane grafting alhpa olefin sodium sulfonate standby；
（2）Allyl silicane is grafted alpha-olefin sodium sulfonate and four（Dimethyl ethenyl siloxy）Silane mixture, and add Pt/
Reaction system is heated to 50 DEG C by C catalyst under nitrogen atmosphere, reacts 5h, and reaction is washed through sucking filtration, alcohol after terminating, and obtains over-expense
Change polysiloxane-modified alpha-olefin sodium sulfonate standby；
（3）Hyperbranched polyorganosiloxane modified alpha-the alkene sulfonic acid sodium of preparation, KOH catalyst are sequentially added in autoclave,
Open heating and stirring system after airtight, and be passed through nitrogen, be thoroughly mixed processed under the conditions of 150 DEG C, processed
Control pressure in kettle to be 0.01MPa after finishing, then put into oxirane, stirring reaction 4h, reaction adds appropriate dilute after terminating
Hydrochloric acid regulation system pH is in neutrality, and subsequent cooling discharge obtains final product described grafting AOS polyoxyethylene ether inorganic agent.
This modified nano calcium carbonate raw powder's production technology comprises the following steps：
（1）First ionic liquid, deionized water are put in reaction vessel respectively, under nitrogen atmosphere strong agitation mixing 20min,
Subsequently system is heated to 80 DEG C, and then adds calcium oxide, grind stirring digestion 2h, form calcium hydroxide slurry, be aged 10h
Standby afterwards；
（2）AOS polyoxyethylene ether inorganic agent will be grafted and put in dehydrated alcohol, stirring will make it be completely dissolved, and resulting solution is injected
Step（1）In the serosity of preparation, it is uniformly mixed, is kept stirring for state, be passed through carbon dioxide in system, to system
Stop ventilation when pH stable is neutral, and continue stirring mixing 1h, reaction terminates rear system and filters, and filtrate is scrubbed, true
Sky is dried, dispersion obtains final product described nano-calcium carbonate powder body.
Prepared nano-calcium carbonate powder characteristic test result is：
Granularity D50：85nm；Viscosity：22.4mPa.s；Activation grade：95%；Oil factor：25.8；Settling volume：0.82ml/g.
Claims (4)
1. a kind of modified morphology controllable nano-calcium carbonate powder body of grafting AOS polyoxyethylene ether inorganic agent is it is characterised in that this is received
Rice calcium carbonate powder is made up of the raw material of following weight portion：Calcium oxide 30-50, carbon dioxide（Technical pure）In right amount, grafting AOS gathers
Oxygen vinyl Ether inorganic agent 0.4-0.8, deionized water 300-500, ionic liquid 1-25, dehydrated alcohol 30-50.
2. the modified morphology controllable nano-calcium carbonate calcium powder of a kind of grafting AOS polyoxyethylene ether inorganic agent as claimed in claim 1
Body is it is characterised in that described grafting AOS polyoxyethylene ether inorganic agent is obtained by the raw material of following weight portion：Alpha-olefin sulfonic acid
Sodium（AOS）1-5, oxirane 0.5-2, pi-allyl Ethoxysilane 5-20, four（Dimethyl ethenyl siloxy）Silane 5-20,
95% ethanol 150-300, KOH catalyst 0.005-0.01, Pt/C catalyst 0.001-0.005, appropriate dilute hydrochloric acid solution, anhydrous
Appropriate amount of ethanol；Preparation method is：
（1）First alpha-olefin sodium sulfonate is put in reaction vessel with pi-allyl Ethoxysilane, be subsequently added 95% ethanol, and plus
Enter appropriate dilute hydrochloric acid solution, regulation system pH value is 4-5, stirring reaction 3-5h under the conditions of 40-50 DEG C reacts warp after terminating
Sucking filtration, washing, vacuum drying treatment, obtain allyl silicane grafting alpha-olefin sodium sulfonate standby；
（2）Allyl silicane is grafted alpha-olefin sodium sulfonate and four（Dimethyl ethenyl siloxy）Silane mixture, and add Pt/
Reaction system is heated to 50-60 DEG C by C catalyst under nitrogen atmosphere, reacts 5-10h, and reaction is washed through sucking filtration, alcohol after terminating,
Obtain hyperbranched polyorganosiloxane modified alpha-alkene sulfonic acid sodium standby；
（3）Hyperbranched polyorganosiloxane modified alpha-the alkene sulfonic acid sodium of preparation, KOH catalyst are sequentially added in autoclave,
Open heating and stirring system after airtight, and be passed through nitrogen, be thoroughly mixed processed under the conditions of 150-160 DEG C, place
Manage and after finishing, control pressure in kettle to be 0.01-0.05MPa, then put into oxirane, stirring reaction 4-5h, reaction adds after terminating
Entering appropriate dilute hydrochloric acid regulation system pH is in neutrality, and subsequent cooling discharge obtains final product described grafting AOS polyoxyethylene ether and processes
Agent.
3. the modified morphology controllable nano-calcium carbonate calcium powder of a kind of grafting AOS polyoxyethylene ether inorganic agent as claimed in claim 1
Body is it is characterised in that described ionic liquid is：1- butyl -3- Methylimidazole. hexafluorophosphate, 1,3- methylimidazole double three
One of fluorine sulfonamide or two kinds.
4. the modified morphology controllable nano-calcium carbonate calcium powder of a kind of grafting AOS polyoxyethylene ether inorganic agent as claimed in claim 1
The preparation method of body is it is characterised in that its preparation method comprises the following steps：
（1）First ionic liquid, deionized water are put in reaction vessel respectively, under nitrogen atmosphere strong agitation mixing 20-
System is subsequently heated to 80-85 DEG C by 30min, and then adds calcium oxide, grinds stirring digestion 2-3h, forms calcium hydroxide
Slurry, standby after ageing 10-15h；
（2）AOS polyoxyethylene ether inorganic agent will be grafted and put in dehydrated alcohol, stirring will make it be completely dissolved, and resulting solution is injected
Step（1）In the serosity of preparation, it is uniformly mixed, is kept stirring for state, be passed through carbon dioxide in system, to system
Stop ventilation when pH stable is neutral, and continue stirring mixing 1-2h, reaction terminates rear system and filters, filtrate is scrubbed,
Vacuum drying, dispersion obtain final product described nano-calcium carbonate powder body.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610919712.2A CN106398315A (en) | 2016-10-21 | 2016-10-21 | Shape-controllable nano calcium carbonate powder modified by grafted AOS (Alpha Olefin Sulfonate) polyoxyethylene ether treating agent and preparation method thereof |
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| CN201610919712.2A CN106398315A (en) | 2016-10-21 | 2016-10-21 | Shape-controllable nano calcium carbonate powder modified by grafted AOS (Alpha Olefin Sulfonate) polyoxyethylene ether treating agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835119A (en) * | 2019-12-12 | 2020-02-25 | 上海大学(浙江·嘉兴)新兴产业研究院 | Modified nano titanium dioxide and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835119A (en) * | 2019-12-12 | 2020-02-25 | 上海大学(浙江·嘉兴)新兴产业研究院 | Modified nano titanium dioxide and preparation method thereof |
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Application publication date: 20170215 |