CN110484022A - A kind of production technology of the nanometer calcium carbonate of transparent membrane - Google Patents

A kind of production technology of the nanometer calcium carbonate of transparent membrane Download PDF

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Publication number
CN110484022A
CN110484022A CN201910845374.6A CN201910845374A CN110484022A CN 110484022 A CN110484022 A CN 110484022A CN 201910845374 A CN201910845374 A CN 201910845374A CN 110484022 A CN110484022 A CN 110484022A
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calcium carbonate
nanometer calcium
transparent membrane
production technology
nanometer
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刘亚雄
姚理修
姚忠修
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Qingzhou Yu Xingai Industry Limited-Liability Co
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Qingzhou Yu Xingai Industry Limited-Liability Co
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
    • C01F11/181Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02Compounds of alkaline earth metals or magnesium
    • C09C1/021Calcium carbonates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02Compounds of alkaline earth metals or magnesium
    • C09C1/021Calcium carbonates
    • C09C1/022Treatment with inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06Treatment with inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/19Oil-absorption capacity, e.g. DBP values
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/21Attrition-index or crushing strength of granulates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/22Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock

Abstract

The invention discloses a kind of production technologies of the nanometer calcium carbonate of transparent membrane, are related to technical field of land improvement, include the following steps: the temperature and concentration that adjust calcium hydroxide, and crystal control agent is added;It is passed through carbon dioxide gas again, when being carbonized to PH=7~8, stop carbonization, it is slowly added by mole 1:1 than the sodium sulphate of preparation and the aqueous solution of barium chloride, continue to stir 30min, until the surface of nanometer calcium carbonate forms coreshell type structure, carbonized carbonaceous slurrying liquid is further continued for PH≤7, it is coated for the first time using fatty acid salt inorganic agent, second using coupling agent and citrate plasticizer cladding, the nanometer calcium carbonate coated is starched and carries out filters pressing, drying and depolymerization, the primary particle size for preparing the nanometer calcium carbonate completed is 30~60nm, after surface treatment, it is between 0.5~1.0 μm that secondary laser particle size analyzer, which detects average grain diameter, with good processing performance, it is good with plastic resin substrate compatibility, for there is the good transparency when plastic film, dispersibility and intensity.

Description

A kind of production technology of the nanometer calcium carbonate of transparent membrane
Technical field
The present invention relates to technical field of land improvement, in particular to the life of a kind of nanometer calcium carbonate applied to transparent membrane Production. art.
Background technique
For packing and the film of coating layer, mainly by polyvinyl chloride, polyethylene, polypropylene, polystyrene and Other resins are made, and have been widely used for the fields such as food, medicine, chemical industry, agricultural, light industry, but due to resin by Oil product is process, and high production cost, effect on environment is big, so it is generally necessary to filler, which is added, reduces cost, it is common Filler are as follows: coarse whiting, light calcium, kaolin, quartz, barium sulfate, white carbon black, talcum powder etc..The addition of common filler can all influence The transparency of film.For only nano barium sulfate, sodium sulphate etc. of transparent membrane, the water solubility of sodium sulphate is very good, in air In be easy absorb moisture, cause the film-strength made poor, the transparency it is poor;Nano barium sulfate since it is than great, same weight Master batch, the membrane area produced by boasting is small, high production cost.
Nanometer calcium carbonate is as a kind of novel filler, with particle size is small, large specific surface area, can increase plastic film Intensity, have specific gravity small, the advantages such as manufacturing cost is low when accomplishing that partial size is very tiny, can be used for filling transparent master batch.But it receives Rice calcium carbonate partial size hour, it is poor with the intermiscibility of plastics to be easy to reunite, and will affect its transparency, the nano-calcium carbonate of scale at present The production of calcium is simultaneously immature, common nanometer calcium carbonate.
Summary of the invention
For disadvantages described above, the present invention provides a kind of production technology of nanometer calcium carbonate applied to transparent membrane, it is intended to Solve the problems, such as that sandy soil soil improvement and difficulty of governance are big.
In order to solve the above technical problems, the technical scheme is that
A kind of production technology of the nanometer calcium carbonate of transparent membrane, includes the following steps:
1) it calcines: taking natural limestone to carry out high-temperature calcination, obtain calcium oxide;
2) it refines: taking calcium oxide screening decontamination obtained in step 1), adding after hot water digests and obtaining concentration is 6~12% Calcium hydroxide suspension;
3) carbonization synthesis: calcium hydroxide suspension addition chemical additives obtained in step 2 are taken, then are transported to stirring In carbonization reactor, while the CO that volumetric concentration is 25~35% is passed through into carbonization reactor2Gas, at 20~30 DEG C into Row carbonization synthetic reaction, when the solution in carbonization reactor is carbonized to PH=7~8, stopping is passed through CO2Gas, be slowly added by The aqueous solution of sodium sulphate and barium chloride that molar ratio 1:1 is prepared, continues 30~60min of stirring, until the surface of nanometer calcium carbonate Coreshell type structure is formed, when being further continued for carbonization slurries to PH≤7, obtains nanometer calcium carbonate slurry;
4) modified: to take nanometer calcium carbonate slurry obtained in step 3), be heated after being warming up to 60~80 DEG C and keep the temperature, rouge is added Fat hydrochlorate carries out the first subsurface cladding, adds coupling agent after stirring 30~60min and citrate carries out the second subsurface Cladding, continues 30~60min of stirring, obtains modified slurry;
5) finished product: taking modified slurry obtained in step 4), is carried out filters pressing, washing, removes water soluble salt;It presses again Filter, drying;Most nanometer calcium carbonate is obtained through crushing depolymerization afterwards.
Wherein, the digestion process of step 2 is to heat calcium oxide made from step 1) after shaft kiln vibration screening decontamination Water carries out digestion reaction, and the temperature of hot water is that 50~70 DEG C, cement-water ratio 1:5~7 are stood old after the slagging-off of multistage spin vibration sieve The change time >=for 24 hours, calcium hydroxide suspension then is made after multistage cyclone hydraulic separators.
Wherein, the chemical additives in step 3) are saccharide compound, and the additional amount of chemical additives is dry for calcium hydroxide The 0.1~1.0% of base total amount.
Wherein, the concentration of the aqueous solution of sodium sulphate and barium chloride is 20~30% in step 3);Additional amount is by generation sulfuric acid The amount of barium accounts for the 3.0~8.0% of calcium carbonate dry weight total amount.
Wherein, the additional amount of fatty acid salt is the 1.5~3.0% of calcium carbonate butt total amount in step 4);Fatty acid salt is The soluble-salt of Long carbon chain fatty acid.
Wherein, coupling agent and citric acid ester plasticizer mass ratio are 2:1 in step 4), and additional amount is that calcium carbonate butt is total The 1.5~3.0% of amount.
Wherein, coupling agent is phosphate coupling agent, and citrate is citric acid tri butyl ester or tributyl 2-acetylcitrate class Environment-friendly plasticizer.
Wherein, during step 5) finished product, modified slurry obtained in step 4) is first subjected to diaphragm filters pressing, is obtained To moisture content be 35~45% filter cake, clear water is then passed through in filter press, after being washed to filters pressing product, then with every The drying of filter press membrane back-pressure water, makes filter cake moisture between 30~35%;It is dried, is most obtained into through broken depolymerization afterwards again Product.
After above-mentioned technical proposal, the beneficial effects of the present invention are:
Since the production technology of the nanometer calcium carbonate of transparent membrane passes through the temperature and concentration of adjusting calcium hydroxide, and crystalline substance is added Shape controlling agent;It is passed through carbon dioxide gas again, when carbonization to PH=7~8, stops carbonization, be slowly added by mole 1:1 a ratio preparation Sodium sulphate and barium chloride aqueous solution, continue stir 30min, until nanometer calcium carbonate surface formed coreshell type structure, then Continue carbonized carbonaceous slurrying liquid to PH≤7, is coated for the first time using fatty acid salt inorganic agent, reduce the oil suction of nanometer calcium carbonate Value, second of compatibility using coupling agent and citrate plasticizer cladding raising nanometer calcium carbonate and plastics will coat Nanometer calcium carbonate slurry carry out filters pressing, drying, depolymerization, prepare the nanometer calcium carbonate of completion primary particle size be 30~60nm, warp After crossing surface treatment, it is to have good processing performance between 0.5~1.0 μm that secondary laser particle size analyzer, which detects average grain diameter, It is good with plastic resin substrate compatibility, for having the good transparency, dispersibility and intensity when plastic film.
Detailed description of the invention
Fig. 1 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention one;
Fig. 2 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention two;
Fig. 3 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention three;
Fig. 4 is the electron microscope picture of the nano-calcium carbonate calcium product in the embodiment of the present invention four.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is further explained.In the following detailed description, only pass through explanation Mode describes certain exemplary embodiments of the invention.Undoubtedly, those skilled in the art will recognize, In In the case where without departing from the spirit and scope of the present invention, described embodiment can be repaired with a variety of different modes Just.Therefore, attached drawing and description are regarded as illustrative in nature, and are not intended to limit the scope of the claims.
Embodiment one:
In the carbonization kettle of 50L, addition concentration be 74g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In Carbonization synthetic reaction is carried out at 20~30 DEG C, opens cooling water, and control temperature is no more than 25 DEG C, when the solution carbonization in reactor When to PH=7~8, it is slowly added into the aqueous solution of sodium sulphate and barium chloride, wherein the ratio of sodium sulphate and barium chloride presses mole 1:1 Than preparation (additional amount accounts for the 5.0% of calcium carbonate dry weight total amount by the amount for generating barium sulfate), after the completion of addition, continue to stir 30~60min was further continued for carbonization until the surface of nanometer calcium carbonate forms coreshell type structure, carbonization slurries to PH≤7, i.e., Obtain nanometer calcium carbonate slurry.Obtained nanometer calcium carbonate slurry is entered into 50L activation pot by pump, is activated, is added the Covering: fatty acid salt inorganic agent (additional amount is the 3.0% of calcium carbonate butt total amount) stirs 30 minutes, coupling is added Agent (additional amount is the 1.5% of calcium carbonate butt total amount), citric acid rouge plasticizer is added simultaneously with coupling agent, and (additional amount is carbonic acid The 1.5% of calcium butt total amount), it stirs 15 minutes, by modified slurry obtained, carries out filters pressing, dry, most being crushed depolymerization afterwards is Nano-calcium carbonate calcium product is obtained, powder is without obvious agglomeration after being crushed.It is carried out using national standard (GB/T19588~2004) Detection, whiteness 96.9%, 22.4 gDOP/100g of oil factor, 32.5 m of specific surface area2/g。
Embodiment two:
In the carbonization kettle of 50L, addition concentration be 85g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, into Row carbonization synthetic reaction, is not turned on cooling water, when the solution in reactor is carbonized to PH=7~8, be slowly added into sodium sulphate and The aqueous solution of barium chloride, wherein (additional amount is by the amount for generating barium sulfate by a mole 1:1 ratio preparation for the ratio of sodium sulphate and barium chloride Account for the 4.0% of calcium carbonate dry weight total amount), after the completion of addition, continue 30~60min of stirring, until the surface of nanometer calcium carbonate Coreshell type structure is formed, is further continued for carbonized carbonaceous slurrying liquid PH≤7 to get nanometer calcium carbonate slurry is arrived.The nano-calcium carbonate that will be obtained Calcium slurry enters 50L activation pot by pump, is activated, addition first time covering: fatty acid salt inorganic agent additional amount is The 2.5% of calcium carbonate butt total amount stirs 30 minutes, coupling agent (additional amount is the 1.0% of calcium carbonate butt total amount) is added, with idol Citric acid rouge plasticizer (additional amount is the 1.5% of calcium carbonate butt total amount) is added in connection agent simultaneously, stirs 15 minutes, will be obtained Modified slurry carries out filters pressing, dry, is most crushed depolymerization afterwards and obtains nanometer calcium carbonate product, and powder is without obvious group after being crushed Poly- phenomenon.It is detected using national standard (GB/T19588~2004), whiteness 96.5%, 23.5 gDOP/ of oil factor 100g, 31.3 m of specific surface area2/g。
Embodiment three:
In the carbonization kettle of 50L, addition concentration be 100g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control The additional amount of preparation be calcium hydroxide butt total amount 0.8%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In Carbonization synthetic reaction is carried out at 20~30 DEG C, is opened cooling water temperature and is no more than 25 DEG C, when the solution in reactor is carbonized to PH When=7~8, it is slowly added into the aqueous solution of sodium sulphate and barium chloride, wherein the ratio of sodium sulphate and barium chloride is matched by a mole 1:1 ratio System (additional amount by generate barium sulfate amount account for the 5.0% of calcium carbonate dry weight total amount), after the completion of addition, continue stirring 30~ 60min is further continued for carbonized carbonaceous slurrying liquid PH≤7 until the surface of nanometer calcium carbonate formation coreshell type structure to get nano-sized carbon is arrived Sour calcium slurry.Obtained nanometer calcium carbonate slurry is entered into 50L activation pot by pump, is activated, first time covering is added: Fatty acid salt inorganic agent additional amount is the 3.0% of calcium carbonate butt total amount, is stirred 30 minutes, and coupling agent is added, and (additional amount is carbon The 1.0% of sour calcium butt total amount), citric acid rouge plasticizer is added simultaneously with coupling agent, and (additional amount is calcium carbonate butt total amount 1.0%) it, stirs 15 minutes, by modified slurry obtained, carries out filters pressing, it is dry, most nano-calcium carbonate is obtained through crushing depolymerization afterwards Calcium product, powder is without obvious agglomeration after being crushed.It is detected using national standard (GB/T19588~2004), whiteness 96.8%, 22.3 gDOP/100g of oil factor, 29.2 m of specific surface area2/g。
Example IV:
In the carbonization kettle of 50L, addition concentration be 110g/L(mass concentration) raw pulp 35L, be added chemical additives, crystal form control The additional amount of preparation be calcium hydroxide butt total amount 1.0%, after be passed through volumetric concentration be 25~35% carbon dioxide gas, In Carry out carbonization synthetic reaction at 20~30 DEG C, open cooling water, when the solution in reactor is carbonized to PH=7~8, slowly plus Enter the aqueous solution of sodium sulphate and barium chloride, wherein (additional amount is by generation by a mole 1:1 ratio preparation for the ratio of sodium sulphate and barium chloride The amount of barium sulfate accounts for the 3.0% of calcium carbonate dry weight total amount), after the completion of addition, continue 30~60min of stirring, until nano-sized carbon The surface of sour calcium forms coreshell type structure, is further continued for carbonized carbonaceous slurrying liquid PH≤7 to get nanometer calcium carbonate slurry is arrived.It will obtain Nanometer calcium carbonate slurry by pump enter 50L activation pot, activated, be added first time covering: fatty acid salt processing Agent additional amount is the 2.5% of calcium carbonate butt total amount, is stirred 30 minutes, and coupling agent is added, and (additional amount is calcium carbonate butt total amount 1.5%), be added simultaneously with coupling agent citric acid rouge plasticizer the 1.5% of calcium carbonate butt total amount (additional amount be), stirring 15 Minute, by modified slurry obtained, filters pressing is carried out, it is dry, it is most crushed depolymerization afterwards and obtains nanometer calcium carbonate product, after being crushed Powder slightly has agglomeration.It is detected using national standard (GB/T19588~2004), whiteness 96.5%, oil factor 23.6 GDOP/100g, 27.8 m of specific surface area2/g。
The common nanometer calcium carbonate of existing market sale being surface-treated using resin acid acid and its ester, is marked using country Quasi- (GB/T19588~2004) are detected, whiteness 96.1,24.5 gDOP/100g of oil factor, 28.3 m of specific surface area2/ g.Now by the performance of the common nano-calcium carbonate calcium product of the nanometer calcium carbonate produced of embodiment one to five and existing market into Row comparison, such as the following table 1:
Table 1
Project Embodiment one Embodiment two Embodiment three Example IV Common product
Whiteness (%) 96.9 96.5 96.8 96.5 96.1
Oil factor (gDOP/100g) 22.4 23.5 22.3 23.6 24.5
Specific surface area (m2/ g) 32.5 31.3 29.2 27.8 28.3
One to four product of above embodiments and common product are applied in the experimental formula of PE product, together with not filled PE Product carries out performance comparison:
(1), it by the mass fraction proportion such as formula of the following table 2, is added in high-speed mixer, is mixed, when stirring reaches 110 It discharges at~125 DEG C.
2 powder application of table is in the test recipe of PE
Project Deal Remarks
PE 78 High pressure polyethylene LDPE blown film grade
PE wax 1 105 DEG C of polyethylene wax softening point
Aluminate coupling agent 1 DL411 type distearyl acyl-oxygen isopropyl Aluminate
Hydroxy silicon oil 0.5 End group is the linear polydimethylsiloxane- of hydroxyl
Toughener 1 Ethylene-propylene diene copolymer EPDM4770
Heat stabilizer 1 Organotin
Paraffin wax lubricants 2.5 50~65 DEG C of fusing point
Powder 0~15 Product, common product and the not filled blank sample of embodiment one to four
(2) kneaded material, is added in double screw extruder, and extrusion temperature is 135~150 DEG C;After being granulated, squeezing Film is cast on casting apparatus out, then drawn obtains oriented film, the mechanical property and light transmission of test gained cast film Performance, light transmission are measured by GB/2410~2008 " transparent plastic light transmittance and haze test method ", as shown in table 3.
The performance test of the powder filled PE of table 3 compares
Project Application examples 1 Application examples 2 Application examples 3 Application examples 4 Application examples 5 Application examples 6
Powder One product of embodiment Two product of embodiment Three product of embodiment Example IV product Common product Powder is not added in blank
Longitudinal tensile strength/MPa 15.6 15.3 14.6 15.3 12.3 10.3
Mould is to tensile strength/MPa 8.8 8.3 7.8 7.5 6.5 4.6
Longitudinal tensile strain rate/% 285 290 300 290 265 345
Cross direction elongation/% 445 460 435 430 405 480
Light transmittance 92.1 91.7 91.6 91.4 87.9 93.5
There is good intensity with respect to application examples 5 by use above example 1, application examples 2, application examples 3,4 gained filler of application examples and is stretched Long rate, and the transparency is high;Filling intensity increase is not added in comparison application examples 6, so this product is for plastic film industry with good Good intensity and elongation, and the transparency is high.
The present invention is not limited to above-mentioned specific embodiment, those skilled in the art from the above idea, Without creative labor, the various transformation made are within the scope of the present invention.

Claims (8)

1. a kind of production technology of the nanometer calcium carbonate of transparent membrane, which comprises the steps of:
1) it calcines: taking natural limestone to carry out high-temperature calcination, obtain calcium oxide;
2) it refines: taking calcium oxide screening decontamination obtained in step 1), adding after hot water digests and obtaining concentration is 6~12% Calcium hydroxide suspension;
3) carbonization synthesis: calcium hydroxide suspension addition chemical additives obtained in step 2 are taken, then are transported to stirring In carbonization reactor, while the CO that volumetric concentration is 25~35% is passed through into carbonization reactor2Gas, at 20~30 DEG C into Row carbonization synthetic reaction, when the solution in carbonization reactor is carbonized to PH=7~8, stopping is passed through CO2Gas, be slowly added by The aqueous solution of sodium sulphate and barium chloride that molar ratio 1:1 is prepared, continues 30~60min of stirring, until the surface of nanometer calcium carbonate Coreshell type structure is formed, when being further continued for carbonization slurries to PH≤7, obtains nanometer calcium carbonate slurry;
4) modified: to take nanometer calcium carbonate slurry obtained in step 3), be heated after being warming up to 60~80 DEG C and keep the temperature, rouge is added Fat hydrochlorate carries out the first subsurface cladding, adds coupling agent after stirring 30~60min and citrate carries out the second subsurface Cladding, continues 30~60min of stirring, obtains modified slurry;
5) finished product: taking modified slurry obtained in step 4), is carried out filters pressing, washing, removes water soluble salt;It presses again Filter, drying;Most nanometer calcium carbonate is obtained through crushing depolymerization afterwards.
2. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 2 Digestion process be calcium oxide made from step 1) is heated after shaft kiln vibration screening decontamination water carry out digestion reaction, hot water Temperature be that 50~70 DEG C, cement-water ratio 1:5~7 still aging time >=for 24 hours, are then passed through after the slagging-off of multistage spin vibration sieve Calcium hydroxide suspension is made after multistage cyclone hydraulic separators.
3. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 3) Described in chemical additives be saccharide compound, the additional amounts of chemical additives be calcium hydroxide butt total amount 0.1~ 1.0%。
4. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, it is characterised in that: step 3) concentration of the aqueous solution of sodium sulphate described in and barium chloride is 20~30%;Additional amount accounts for calcium carbonate by the amount for generating barium sulfate The 3.0~8.0% of dry weight total amount.
5. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 4) Described in fatty acid salt additional amount be calcium carbonate butt total amount 1.5~3.0%;The fatty acid salt is Long carbon chain fat The soluble-salt of acid.
6. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 4) Described in coupling agent and the citric acid ester plasticizer mass ratio be 2:1, additional amount be calcium carbonate butt total amount 1.5~ 3.0%。
7. a kind of production technology of the nanometer calcium carbonate of transparent membrane as claimed in claim 6, which is characterized in that the idol Connection agent is phosphate coupling agent, and the citrate is citric acid tri butyl ester or tributyl 2-acetylcitrate class environment-friendly plasticizer.
8. a kind of production technology of the nanometer calcium carbonate of transparent membrane as described in claim 1, which is characterized in that step 5) During finished product, modified slurry obtained in step 4) is first subjected to diaphragm filters pressing, obtaining moisture content is 35~45% Filter cake, clear water is then passed through in filter press, after being washed to filters pressing product, then with diaphragm filter press back-pressure water dry up, Make filter cake moisture between 30~35%;It is dried again, most obtains finished product through broken depolymerization afterwards.
CN201910845374.6A 2019-09-09 2019-09-09 A kind of production technology of the nanometer calcium carbonate of transparent membrane Pending CN110484022A (en)

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CN111826000A (en) * 2020-07-22 2020-10-27 江西广源化工有限责任公司 High-specific-gravity reinforced composite powder filler and preparation method thereof
CN112480713A (en) * 2020-11-27 2021-03-12 安徽省宣城市华纳新材料科技有限公司 Preparation method of nano calcium carbonate for filling polyethylene transparent film
CN112480714A (en) * 2020-12-01 2021-03-12 连州市凯恩斯纳米材料有限公司 Surface modification method of nano calcium carbonate with particle size less than 20nm
CN112876878A (en) * 2021-01-26 2021-06-01 江西势通钙业有限公司 Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof
CN114212814A (en) * 2021-12-16 2022-03-22 浙江大学 Preparation method of nano calcium carbonate
CN114702814A (en) * 2022-04-29 2022-07-05 浙江驭能新材料科技有限公司 High-transparency flame-retardant TPU (thermoplastic polyurethane) base film and preparation method thereof

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CN102585557A (en) * 2012-01-05 2012-07-18 池州凯尔特纳米科技有限公司 Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film
CN104845410A (en) * 2015-04-02 2015-08-19 扬翔(上海)环保科技有限公司 Preparation and application of plastic modifier
CN105400064A (en) * 2015-11-11 2016-03-16 广东碧盛环球环保材料有限公司 Filling masterbatch and preparation method thereof

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CN102585557A (en) * 2012-01-05 2012-07-18 池州凯尔特纳米科技有限公司 Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film
CN104845410A (en) * 2015-04-02 2015-08-19 扬翔(上海)环保科技有限公司 Preparation and application of plastic modifier
CN105400064A (en) * 2015-11-11 2016-03-16 广东碧盛环球环保材料有限公司 Filling masterbatch and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111826000A (en) * 2020-07-22 2020-10-27 江西广源化工有限责任公司 High-specific-gravity reinforced composite powder filler and preparation method thereof
CN111826000B (en) * 2020-07-22 2021-10-08 江西广源化工有限责任公司 High-specific-gravity reinforced composite powder filler and preparation method thereof
CN112480713A (en) * 2020-11-27 2021-03-12 安徽省宣城市华纳新材料科技有限公司 Preparation method of nano calcium carbonate for filling polyethylene transparent film
CN112480714A (en) * 2020-12-01 2021-03-12 连州市凯恩斯纳米材料有限公司 Surface modification method of nano calcium carbonate with particle size less than 20nm
CN112480714B (en) * 2020-12-01 2021-11-16 连州市凯恩斯纳米材料有限公司 Surface modification method of nano calcium carbonate with particle size less than 20nm
CN112876878A (en) * 2021-01-26 2021-06-01 江西势通钙业有限公司 Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof
CN114212814A (en) * 2021-12-16 2022-03-22 浙江大学 Preparation method of nano calcium carbonate
CN114702814A (en) * 2022-04-29 2022-07-05 浙江驭能新材料科技有限公司 High-transparency flame-retardant TPU (thermoplastic polyurethane) base film and preparation method thereof

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