CN106564922A - Composite pentaerythritol oleate polyoxyethylene ether active agent modified morphology-controlled nanometer calcium carbonate powder - Google Patents
Composite pentaerythritol oleate polyoxyethylene ether active agent modified morphology-controlled nanometer calcium carbonate powder Download PDFInfo
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- CN106564922A CN106564922A CN201610919711.8A CN201610919711A CN106564922A CN 106564922 A CN106564922 A CN 106564922A CN 201610919711 A CN201610919711 A CN 201610919711A CN 106564922 A CN106564922 A CN 106564922A
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- Prior art keywords
- calcium carbonate
- peto
- carbonate powder
- polyoxyethylene ether
- modified
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses composite pentaerythritol oleate polyoxyethylene ether active agent modified morphology-controlled nanometer calcium carbonate powder, which is prepared by using a carbonization method, wherein the morphology-controlled and excellent-performance calcium carbonate powder is prepared by using ionic liquid/deionized water compounding as the solvent and using the unique adsorption of the ionic liquid on carbon dioxide, and the hyper-branched polysiloxane modified glyceryl oleate polyoxyethylene ether surfactant is prepared by using the hydrosilylation reaction, wherein the active agent has effects of excellent dispersing, excellent emulsification and excellent film forming, significantly improves the hydrophobicity of the calcium carbonate powder surface, and does not contain harmful groups so as not to adversely affect the resin group during the hot processing process and provide the excellent filling reinforcement effect.
Description
Technical field
The present invention relates to modified calcium carbonate technical field, more particularly to a kind of compound PETO polyoxyethylene ether
The modified morphology controllable nano-calcium carbonate powder body of activating agent.
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 for 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 filling-modified effect is had a strong impact on, need to carry out it surface modification treatment, to improve its performance.
Dry method coating modification process is carried out using stearic acid or soap more than presently commercially available nano-calcium carbonate powder body, this
Although the powder body that the processing method of a little classifications is obtained is improved at aspects such as dispersibility, oil factor, activation grades,
It is, because its temperature tolerance is poor, not to be suitable for high temperature process environment, the matrix material to filling can produce harmful effect, using model
It is with effect.《Composite modifier is modified to the surface of nano-calcium carbonate》One text is using 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 group
Poly-, surface active degree is improved, hydrophobicity is improved, and temperature tolerance is more preferably, it is to avoid the defect of stearic acid modifying agent, but and it draws
The lauric acid for entering has certain corrosivity to metal, and modified calcium carbonate powder use range is still restricted, and is not order
The modification result of people's satisfaction.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of compound PETO polyoxy second
The modified morphology controllable nano-calcium carbonate powder body of alkene ether activating agent.
The present invention is achieved by the following technical solutions：
A kind of modified morphology controllable nano-calcium carbonate powder body of compound PETO polyoxyethylene ether activating agent, the nanometer
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, it is combined Ji Wusi
Alcohol Oleic acid ester APEO activating agent 0.2-0.5, deionized water 200-500, ionic liquid 1-20, dodecyl sodium sulfate
0.01-0.02。
Described compound PETO polyoxyethylene ether activating agent is obtained by the raw material of following weight portion：Oleic acid 2-
5th, tetramethylolmethane 1-2, Feldalat NM 0.01-0.02, oxirane 0.5-3, pi-allyl Ethoxysilane 5-20, four（Dimethyl second
Thiazolinyl 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, appropriate dehydrated alcohol；Preparation method is：
（1）First by Oleic acid and pi-allyl Ethoxysilane input reaction vessel, 95% ethanol is subsequently added, and is added appropriate
Dilute hydrochloric acid solution, regulation system pH value is 4-5, and stirring reaction 5-6h under the conditions of 60-80 DEG C is reacted Jing sucking filtration after terminating, washed
Wash, vacuum drying treatment, obtain allyl silicane grafting Oleic acid it is standby；
（2）By allyl silicane grafting Oleic acid and four（Dimethyl ethenyl siloxy）Silane mixture, and Pt/C catalyst is added,
Under nitrogen atmosphere reaction system is heated to into 50-60 DEG C, reacts 5-10h, reacted Jing sucking filtration, alcohol after terminating and wash, obtain hyperbranched
Polysiloxane-modified Oleic acid is standby；
（3）The modified Oleic acid of the hyperbranched polyorganosiloxane for preparing, Feldalat NM, tetramethylolmethane are put in reaction vessel, and to system
In be passed through nitrogen, 12-16h is reacted under the conditions of 180-200 DEG C after being uniformly mixed, reaction terminates rear system cooling discharging,
Obtain the modified PETO of hyperbranched polyorganosiloxane standby；
（4）The modified PETO of hyperbranched polyorganosiloxane, KOH catalyst are sequentially added in autoclave, it is close
Heating and stirring system are opened after closing, and is passed through nitrogen, processed is thoroughly mixed under the conditions of 158-165 DEG C, processed
It is 0.01-0.05MPa that pressure in kettle is controlled after finishing, and then puts into oxirane, stirring reaction 6-8h, and reaction is added after terminating
Appropriate dilute hydrochloric acid regulation system pH obtains final product described compound PETO polyoxy second in neutrality, subsequent cooling discharge
Alkene ether activating agent.
Described ionic liquid is：The double fluoroform sulphurs of 1- butyl -3- Methylimidazole. hexafluorophosphates, 1,3- methylimidazoles
One or two in imide salts.
The modified morphology controllable nano-calcium carbonate of described a kind of compound PETO polyoxyethylene ether activating agent
Raw powder's production technology is comprised the following steps：
（1）First ionic liquid, deionized water are put into respectively in reaction vessel, under nitrogen atmosphere strong agitation mixing 20-
30min, is subsequently heated to 80-85 DEG C by system, and then adds calcium oxide, grinding stirring digestion 2-3h to form calcium hydroxide
Slurry, it is standby after ageing 10-15h；
（2）The deionized water of 30-50 weight portions is taken, compound PETO polyoxyethylene ether activating agent, dodecane is added
Base sodium sulfonate, stirring makes it be completely dissolved rear emulsion implantation step（1）In the serosity of preparation, in being uniformly mixed backward system
Carbon dioxide is passed through, continues to stop ventilation when stirring reaction to system pH stabilizes to neutrality, and continue stirring mixing 50-
80min, reaction terminates rear system and filters, and filtrate is scrubbed, be vacuum dried, dispersion obtains final product the nano-calcium carbonate powder body.
Advantages of the present invention is as follows
（1）During preparation of nanometer calcium carbonate by carbonization powder body, mixed as solvent body using ionic liquid/deionized water
System, using adsorptivity of the ionic liquid to carbon dioxide, improves the concentration of carbon dioxide in solvent, and yield is higher, while logical
The morphology controllable of the achievable calcium carbonate powder of the concentration of ionic liquid and carbon dioxide is overregulated, surface property is obtained more excellent
Different product.
（2）Using hydrosilylation, it is prepared for a kind of modified olein of new hyperbranched polyorganosiloxane and gathers
Oxygen ethylene ether surface active agent, this activating agent has good dispersion, emulsifying, film-formation result, significantly improves powder surface
Hydrophobicity, while without harmful group, having no adverse effects to resin group in hot procedure, filler reinforcement effect is more
It is good.
Specific embodiment
A kind of modified morphology controllable nano-calcium carbonate powder body of compound PETO polyoxyethylene ether activating agent, should
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, it is combined Ji Wusi
Alcohol Oleic acid ester APEO activating agent 0.2, deionized water 200,1- butyl -3- Methylimidazole .s hexafluorophosphates 1, dodecyl
Sodium sulfonate 0.01.
Wherein it is combined PETO polyoxyethylene ether activating agent to be obtained by the raw material of following weight portion：Oleic acid 2, season
Penta tetrol 1, Feldalat NM 0.01, 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 side
Method is：
（1）First by Oleic acid and pi-allyl Ethoxysilane input reaction vessel, 95% ethanol is subsequently added, and is added appropriate
Dilute hydrochloric acid solution, regulation system pH value is 4, and stirring reaction 5h under the conditions of 60 DEG C reacts Jing sucking filtration, washing, vacuum after terminating
Dried, obtains allyl silicane grafting Oleic acid standby；
（2）By allyl silicane grafting Oleic acid and four（Dimethyl ethenyl siloxy）Silane mixture, and Pt/C catalyst is added,
Under nitrogen atmosphere reaction system is heated to into 50 DEG C, reacts 5h, reacted Jing sucking filtration, alcohol after terminating and wash, obtain hyperbranched poly silica
The modified Oleic acid of alkane is standby；
（3）The modified Oleic acid of the hyperbranched polyorganosiloxane for preparing, Feldalat NM, tetramethylolmethane are put in reaction vessel, and to system
In be passed through nitrogen, 12h is reacted under the conditions of 180 DEG C after being uniformly mixed, reaction terminates rear system cooling discharging, obtains hyperbranched
Polysiloxane-modified PETO is standby；
（4）The modified PETO of hyperbranched polyorganosiloxane, KOH catalyst are sequentially added in autoclave, it is close
Heating and stirring system are opened after closing, and is passed through nitrogen, under the conditions of 158 DEG C processed is thoroughly mixed, be disposed
It is 0.01MPa to control pressure in kettle afterwards, then puts into oxirane, and stirring reaction 6h, reaction adds appropriate dilute salt after terminating
Sour regulation system pH obtains final product described compound PETO polyoxyethylene ether activating agent in neutrality, subsequent cooling discharge.
The modified nano calcium carbonate raw powder's production technology is comprised the following steps：
（1）First ionic liquid, deionized water are put into respectively in reaction vessel, under nitrogen atmosphere strong agitation mixing 20min,
Subsequently system is heated to into 80 DEG C, and then adds calcium oxide, grinding stirring digestion 2h to form calcium hydroxide slurry, be aged 10h
It is standby afterwards；
（2）The deionized water of 30 weight portions is taken, compound PETO polyoxyethylene ether activating agent, dodecyl sulphur is added
Sour sodium, stirring makes it be completely dissolved rear emulsion implantation step（1）In the serosity of preparation, it is uniformly mixed in backward system and is passed through
Carbon dioxide, continues to stop ventilation when stirring reaction to system pH stabilizes to neutrality, and continues stirring mixing 50min,
Reaction terminates rear system and filters, and filtrate is scrubbed, be vacuum dried, dispersion obtains final product the nano-calcium carbonate powder body.
Obtained nano-calcium carbonate powder characteristic test result is：
Granularity D50：82.5nm；Viscosity：26.5mPa.s；Activation grade：98%；Oil factor：23.1；Settling volume：0.72ml/g.
Claims (4)
1. the morphology controllable nano-calcium carbonate powder body that a kind of compound PETO polyoxyethylene ether activating agent is modified, it is special
Levy and be, the nano-calcium carbonate powder body is made up of the raw material of following weight portion：Calcium oxide 30-50, carbon dioxide（Technical pure）It is suitable
Amount, compound PETO polyoxyethylene ether activating agent 0.2-0.5, deionized water 200-500, ionic liquid 1-20, ten
Dialkyl sulfonates 0.01-0.02.
2. a kind of modified morphology controllable of compound PETO polyoxyethylene ether activating agent as claimed in claim 1 is received
Rice calcium carbonate powder, it is characterised in that described compound PETO polyoxyethylene ether activating agent is by following weight portion
Raw material be obtained：Oleic acid 2-5, tetramethylolmethane 1-2, Feldalat NM 0.01-0.02, oxirane 0.5-3, pi-allyl Ethoxysilane
5-20, four（Dimethyl ethenyl siloxy）Silane 5-20,95% ethanol 150-300, KOH catalyst 0.005-0.01, Pt/C are urged
Agent 0.001-0.005, appropriate dilute hydrochloric acid solution, appropriate dehydrated alcohol；Preparation method is：
（1）First by Oleic acid and pi-allyl Ethoxysilane input reaction vessel, 95% ethanol is subsequently added, and is added appropriate
Dilute hydrochloric acid solution, regulation system pH value is 4-5, and stirring reaction 5-6h under the conditions of 60-80 DEG C is reacted Jing sucking filtration after terminating, washed
Wash, vacuum drying treatment, obtain allyl silicane grafting Oleic acid it is standby；
（2）By allyl silicane grafting Oleic acid and four（Dimethyl ethenyl siloxy）Silane mixture, and Pt/C catalyst is added,
Under nitrogen atmosphere reaction system is heated to into 50-60 DEG C, reacts 5-10h, reacted Jing sucking filtration, alcohol after terminating and wash, obtain hyperbranched
Polysiloxane-modified Oleic acid is standby；
（3）The modified Oleic acid of the hyperbranched polyorganosiloxane for preparing, Feldalat NM, tetramethylolmethane are put in reaction vessel, and to system
In be passed through nitrogen, 12-16h is reacted under the conditions of 180-200 DEG C after being uniformly mixed, reaction terminates rear system cooling discharging,
Obtain the modified PETO of hyperbranched polyorganosiloxane standby；
（4）The modified PETO of hyperbranched polyorganosiloxane, KOH catalyst are sequentially added in autoclave, it is close
Heating and stirring system are opened after closing, and is passed through nitrogen, processed is thoroughly mixed under the conditions of 158-165 DEG C, processed
It is 0.01-0.05MPa that pressure in kettle is controlled after finishing, and then puts into oxirane, stirring reaction 6-8h, and reaction is added after terminating
Appropriate dilute hydrochloric acid regulation system pH obtains final product described compound PETO polyoxy second in neutrality, subsequent cooling discharge
Alkene ether activating agent.
3. a kind of modified morphology controllable of compound PETO polyoxyethylene ether activating agent as claimed in claim 1 is received
Rice calcium carbonate powder, it is characterised in that described ionic liquid is：1- butyl -3- Methylimidazole. hexafluorophosphates, 1,3- diformazans
One or two in base imidazoles bis-trifluoromethylsulfoandimide salt.
4. a kind of modified morphology controllable of compound PETO polyoxyethylene ether activating agent as claimed in claim 1 is received
The preparation method of rice calcium carbonate powder, it is characterised in that its preparation method is comprised the following steps：
（1）First ionic liquid, deionized water are put into respectively in reaction vessel, under nitrogen atmosphere strong agitation mixing 20-
30min, is subsequently heated to 80-85 DEG C by system, and then adds calcium oxide, grinding stirring digestion 2-3h to form calcium hydroxide
Slurry, it is standby after ageing 10-15h；
（2）The deionized water of 30-50 weight portions is taken, compound PETO polyoxyethylene ether activating agent, dodecane is added
Base sodium sulfonate, stirring makes it be completely dissolved rear emulsion implantation step（1）In the serosity of preparation, in being uniformly mixed backward system
Carbon dioxide is passed through, continues to stop ventilation when stirring reaction to system pH stabilizes to neutrality, and continue stirring mixing 50-
80min, reaction terminates rear system and filters, and filtrate is scrubbed, be vacuum dried, dispersion obtains final product the nano-calcium carbonate powder body.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500332A (en) * | 2017-09-29 | 2017-12-22 | 广西华洋矿源材料有限公司 | A kind of preparation method of high-quality superfine light calcium carbonate |
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- 2016-10-21 CN CN201610919711.8A patent/CN106564922A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500332A (en) * | 2017-09-29 | 2017-12-22 | 广西华洋矿源材料有限公司 | A kind of preparation method of high-quality superfine light calcium carbonate |
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