CN101967298A - Novel nano calcium carbonate used for plastic film and preparation method thereof - Google Patents
Novel nano calcium carbonate used for plastic film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses novel nano calcium carbonate used for a plastic film and a preparation method thereof. A Ca(OH)2 suspension and CO2 are carbonized in a reactor to generate the nano calcium carbonate, and then the obtained nano calcium carbonate is subjected to liquid phase coating treatment or is directly subjected to mixed coating by using dried nano calcium carbonate and a surfactant to obtain nano calcium carbonate powder which is highly dispersed and surface-activated. The invention has the advantages that: the process is simple, the nano calcium carbonate is effectively dispersed in a polymer and a remarkable enhancement effect can be achieved on the premise of ensuring the transparency. The nano calcium carbonate prepared by adopting the invention can remarkably improve the mechanical property of a polyolefin material; after the nano calcium carbonate is used for polyethylene plastic, the tension strength of the material is greatly improved; and after the nano calcium carbonate is used for a polyolefin film, a fish eye is free, and the high transparency of the film is maintained.
Description
Technical field
The present invention relates to a kind of preparation method of nano-calcium carbonate, relate in particular to a kind of novel nano lime carbonate that is used for plastics film and preparation method thereof.
Background technology
Nano-calcium carbonate is a kind of crucial functional inorganic filling, and is cheap with it, color and luster is pure white, over-all properties is good and be widely used in the macromolecule product.But, because the lime carbonate of long time without surface modification affinity general and polymkeric substance is relatively poor, thereby cause easily and in the superpolymer base-material, disperse the inhomogeneous boundary defect that causes two kinds of materials, increase along with loading level, these shortcomings are more obvious, add that particle surface electrostatic interaction and surface energy are higher, easily form coacervate.In order to improve the improvement of nano-calcium carbonate to the macromolecular material performance, to carry out surface modification treatment to it, properties-correcting agent can effectively reduce the surface energy of lime carbonate, lime carbonate can be dispersed in the polymkeric substance better, and have good interface to combine with polymkeric substance, so the selection of properties-correcting agent has been played vital role for the widespread use of lime carbonate.
The current inorganic materials CaCO that is used for filled polyolefin
3Consumption accounts for more than 80%, and talcum powder accounts for 10%, kaolin, silicon dirt etc. about 5%～15%.CaCO
3With the most use is the 400-1250 order, and the consumption of nano-calcium carbonate in polyolefine also seldom, one of them important reasons is exactly that dispersion and the interface of nano-calcium carbonate in polyolefine with high-specific surface area causes quality product to improve in conjunction with difference, especially in film product, higher to the requirement of lime carbonate.As used lime carbonate in the Biaxially oriented multilayer polypropylene film of Japanese Tung Sai Lu Co., Ltd invention is with higher fatty acid modification [CN1575974,2004], Imerys Minerals Ltd. prepares air-permeating film less than the lime carbonate of 1 μ m by two-way stretch with the d50 that grinds preparation, the properties-correcting agent of lime carbonate mainly is stearic acid [CN1541243A, 2002], Prince Oil Synthesis Paper Co., Ltd is the calcium carbonate-filled in resin film of 70-200ml/100g with oil-absorption(number), obtained good impressionability energy, the transitivity and the rate of drying [CN1215649A, 1998] of printing ink have been accelerated.
Used lime carbonate all needs to carry out earlier activation treatment in the above patent, could bring into play the filling effect of lime carbonate to greatest extent.Different products requires also different to the modification of lime carbonate, for example: film is one of topmost Application Areas of polyolefin resin, and market has a wide range of applications in fields such as agricultural, packings.Because nano-calcium carbonate difficulties in dispersion in polyolefine is easy to form aggregate and influences mechanical properties in films and the transparency.
Summary of the invention
The objective of the invention is: provide a kind of good stability, transparency high be used for novel nano lime carbonate of plastics film and preparation method thereof.
Technical scheme of the present invention is: a kind of novel nano lime carbonate that is used for plastics film consists of by mass percentage:
CaCO
3 70％-99.9％
Surface treatment agent 0.1%-30%
Surface treatment agent is dispersion agent and coupling agent, and the mass percentage content of dispersion agent is at 0-15%, and the mass percentage content of coupling agent is at 0-15%.Dispersion agent is the organism with long carbochain, and the carbonatoms in the organic molecule is between 8-30, as longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, lauric acid salt extremely.Coupling agent is one or more in silane coupling agent, titanate coupling agent, boric acid ester coupler, aluminate coupling agent, aluminum-zirconium coupling agent, aluminium titanium composite coupler, the aluminium zirconium composite coupler, preferably contains the coupling agent of long carbochain.
A kind of preparation method who is used for the novel nano lime carbonate of plastics film may further comprise the steps:
(1) Wingdale being cleaned the back calcines at high temperature kiln, through getting calcium hydroxide slurry after purifying, digestion, the ageing, calcium hydroxide slurry is put into carbonization reactor, feed carbonic acid gas and carry out carbonization, add the crystal formation control agent at carbonization process, obtain the nano-calcium carbonate slurry, the crystal formation control agent is one or more the mixture in sulfuric acid, phosphoric acid, citric acid, sucrose, beet sugar, the maltose, the limestone calcination temperature is 800-1500 ℃, is preferably 900-1200 ℃; The digestion temperature is 20-95 ℃, is preferably 70-90 ℃; Digestion time is 1-48h, preferred 4-16h; The slurry concentration of calcium hydroxide is 1-40%, is preferably 5-20%; Concentration of carbon dioxide is that 1-100% (v), is preferably 20-50% (v); Carbonization temperature is 1-80 ℃, is preferably 5-25 ℃; The pH value of carbonization terminal point slurry is between 6.5-7.
(2) nano-calcium carbonate is wet-process modified: the nano-calcium carbonate slurry adding properties-correcting agent under 1-80 ℃ according to step (1) preparation carries out surface activation process and surface coating; After adding dispersion agent earlier and making the nano-calcium carbonate stable dispersion, the dispersion churning time is 30-120min, adds coupling agent then, stir 10-120min after, the slurry that modification is good filters, dry, pulverize, can obtain to have the nano-calcium carbonate of excellent heat resistance.The mass concentration of nano-calcium carbonate slurry is at 2-20%.
(3) dry method modification of nano-calcium carbonate: join in the high speed mixer behind the nano-calcium carbonate slurries filtration, drying, pulverizing according to (1) preparation, add surface treatment agent at a certain temperature and carry out surface treatment, directly obtain the nano-calcium carbonate of modification.Heating temperature is 80-150 ℃, preferred 100-140 ℃; Rotating speed 500-10000 commentaries on classics/min, preferred 500-3000 commentaries on classics/min; Mixing time is 2-120min, preferred 10-60min.Coupling agent can also can directly add in first wiring solution-forming adding, is injected into high speed mixer behind the preferred wiring solution-forming.Dispersion agent 1-60min after coupling agent adds discharging behind the restir 1-60min.
The invention has the beneficial effects as follows: have better hydrophobic nature by the nano-calcium carbonate surface after the surface treatment modification, can effectively prevent the reunion between the calcium carbonate granule, it can be scattered in polymkeric substance, the especially polyolefine better.Can extrude injection moulding or blown film with screw extrusion press again with after polymkeric substance and some auxiliary agents mix by the high speed mixer heating.Its advantage is that technology is simple, and nano-calcium carbonate is scattered in the polymkeric substance efficiently, has tangible reinforced effects under the prerequisite that guarantees transparency.Adopt the nano-calcium carbonate of the present invention's preparation can significantly improve the mechanical property of polyolefine material, when add 20% modified nano calcium carbonate in the vinyon after, the tensile strength of material has significantly improved 42.5%.In addition, in all right required polyolefin film, no flake, and keep the good transparency of film.
Embodiment
The novel nano lime carbonate that is used for plastics film, composition is specifically as follows CaCO by mass percentage
3: surface treatment agent 80%: 20%, dispersion agent in the surface treatment agent: 10%, coupling agent 10%.
The novel nano lime carbonate that is used for plastics film, composition is specifically as follows CaCO by mass percentage
3: surface treatment agent 70%: 30%, dispersion agent in the surface treatment agent: 15%, coupling agent 15%.
The novel nano lime carbonate that is used for plastics film, composition is specifically as follows CaCO by mass percentage
3: surface treatment agent 99.9%: 0.1%, dispersion agent in the surface treatment agent: 0.05%, coupling agent 0.05%
The novel nano lime carbonate that is used for plastics film, composition is specifically as follows CaCO by mass percentage
3: surface treatment agent 90%: 10%, dispersion agent in the surface treatment agent: 2%, coupling agent 8%.
Below specific embodiments of the invention are further described, and in conjunction with the Comparative Examples explanation beneficial effect that the present invention produced.
Embodiment 1:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 0.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma.Heating magma is warming up to 80 ℃ and stirred 5 minutes, adds 1.0% and (is equivalent to CaCO
3) stearic acid, stirred 40 minutes, add the NaOH of 6% (being equivalent to stearic acid).Filter, dry, pulverize.Take by weighing certain titanic acid ester properties-correcting agent of 3% (being equivalent to lime carbonate), in ethanol, the lime carbonate of stearic acid modified mistake is joined in the solvent, continue to stir 30 minutes, filter the back oven dry and pulverize, make product 60 ℃ of following heating for dissolving.
Embodiment 2:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water 80 ℃ digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 0.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma is filtered, dries, is pulverized.Take by weighing certain titanic acid ester properties-correcting agent of 3% (being equivalent to lime carbonate), in ethanol, unmodified lime carbonate joins in the solvent 60 ℃ of following heating for dissolving, continues to stir 30 minutes, filters the back oven dry and pulverizes, and makes product.
Embodiment 3:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water 80 ℃ digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 0.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma is filtered, dries, is pulverized.Get 2000g lime carbonate and join in the high speed mixer, Heating temperature is 110 ℃, and rotating speed 1500 commentaries on classics/min stir 15min, add the silane coupling agent 40g that configures, discharging behind the restir 20min.
Embodiment 4:
With the modified nano calcium carbonate 600g of embodiment 1 preparation, high density polyethylene(HDPE) 2400g under the condition of heating, uniform mixing in high-speed mixer, discharging is carried out granulation with twin screw extruder, the twin screw extruder temperature is at 120-180 ℃.Dry after the granulation, be injection molded into the dumbbell shaped batten, normal temperature was placed 24 hours, Performance Detection.
Comparative example 1:
Get high density polyethylene(HDPE) 3Kg, adopt injection moulding machine to be injection molded into the standard batten, prune batten, thermostat container was placed 24 hours.
Embodiment 5:
Adopt electronic universal tester that the sample of embodiment 2 and comparative example 1 is carried out Experiments of Machanics, performance is as shown in table 1, as can be seen from Table 1, the tensile strength of adding the purer PE of PE of 20% modified calcium carbonate improves 42.5%, thereby explanation modified calcium carbonate and PE resin have consistency preferably.
Table 1 mechanical property
Embodiment 6:
Embodiment 4 and comparative example 1 product are carried out TG (thermal weight loss test) relatively, as table 2.The TG testing method is: temperature range: 30-900 ℃, and heat-up rate: 20 ℃/min, atmosphere: nitrogen.
The initial heat decomposition temperature of table 2 batten
| Sequence number | Initial heat decomposition temperature/℃ |
| Embodiment 4 | 492.78 |
| Comparative example 1 | 486.76 |
By the TG test result as seen, the adding of modified nano calcium carbonate has improved the initial heat decomposition temperature of PE in the embodiment of the invention.
Comparative example 2:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water 80 ℃ digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 0.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma, heating magma is warming up to 80 ℃ and stirred 5 minutes, adds 1.5% and (is equivalent to CaCO
3) stearic acid, stirred 1 hour.Filter the back oven dry and pulverize, make product.
Embodiment 7:
Viscosity test: the sample of embodiment 1, embodiment 2, comparative example 2 is joined in the dioctyl phthalate (DOP) (DOP), blending ratio is 1: 3, adopts the agitator high-speed stirring 5 minutes, places after 1 hour, adopt rotational viscosimeter to carry out viscosity measurement, measure temperature and be controlled at 25 ℃.Test result such as table 4:
Table 4 viscosity test result
| Example | Viscosity, mPaS |
| Embodiment 1 | 200 |
| Embodiment 2 | 360 |
| Comparative example 2 | 880 |
As seen from Table 4, embodiment of the invention institute viscosimetric is significantly less than comparative example.
Embodiment 8:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water 80 ℃ digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 0.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma is filtered, dries, is pulverized.Take by weighing 3% and (be equivalent to CaCO
3) certain titanic acid ester properties-correcting agent,, in ethanol, the lime carbonate of modification is joined in the mixed solvent of ethanol and water 60 ℃ of following heating for dissolving, continue to stir 30 minutes, filter the back oven dry and pulverize, make product.
Embodiment 9:
Wingdale is cleaned the back 1000 ℃ of calcinings, add water 80 ℃ digest Ca (OH)
2Slurries are transferred to film and disperse in the carbonization reactor, add 1.5% (with respect to Ca (OH)
2) sucrose.Feed 30% (CO v)
2Carry out carbonization at 17 ℃,, continue ventilation 10 minutes, obtain 8% nanometer CaCO when pH reduces to 6.8
3Magma, heating magma is warming up to 80 ℃ and stirred 5 minutes, adds 2.0% and (is equivalent to CaCO
3) oleic acid, stirred 40 minutes, filter, oven dry, pulverize.Take by weighing the boric acid ester properties-correcting agent of 1.5% (being equivalent to lime carbonate), 80 ℃ of following heating for dissolving in water continue to stir 50 minutes, filter the back oven dry and pulverize, and make product.
Embodiment 10:
Get the modified nano calcium carbonate 150g of embodiment 8 and embodiment 9 preparations respectively, high density polyethylene(HDPE) 1425g, new LDPE (film grade) 1425g, join low speed uniform mixing in the high-speed mixer, be heated to 90 ℃, high-speed stirring 15 minutes, discharging, carry out granulation with twin screw extruder, the twin screw extruder temperature is dried after the granulation at 120-180 ℃, is blow molded into the thick film of 10 ± 0.2 μ m, sample preparation, thermostat container was placed 24 hours.
Comparative example 3:
Get high density polyethylene(HDPE) 1500g, new LDPE (film grade) 1500g joins low speed uniform mixing in the high-speed mixer, is heated to 90 ℃, high-speed stirring 15 minutes, discharging is carried out granulation with twin screw extruder, and the twin screw extruder temperature is at 120-180 ℃, dry after the granulation, be blow molded into the thick film of 10 ± 0.2 μ m, sample preparation, thermostat container was placed 24 hours.
With the film of preparation among the embodiment 10 and the film in the comparative example 3, carry out TG (thermal weight loss test) relatively, test result is respectively as table 3.
The temperature of initial decomposition of table 3 film
| Sequence number | Initial heat decomposition temperature/℃ |
| Embodiment 10 (embodiment 8) | 486.10 |
| Embodiment 10 (embodiment 9) | 486.27 |
| Comparative example 3 | 485.78 |
The adding of modified nano calcium carbonate has improved the initial heat decomposition temperature of film in the embodiment of the invention.
Embodiment 11:
Adopt electronic universal tester that the sample of embodiment 8, embodiment 9, comparative example 3 is carried out Experiments of Machanics, performance is as shown in table 5.
Table 5 mechanical property
Show that the adding of modified nano calcium carbonate in the embodiment of the invention has improved the tensile strength of film.
Comparative example 4:
Get the modified calcium carbonate 150g of preparation among the embodiment 3, high density polyethylene(HDPE) 1425g, new LDPE (film grade) 1425g, join low speed uniform mixing in the high-speed mixer, be heated to 90 ℃, high-speed stirring 15 minutes, discharging, carry out granulation with twin screw extruder, the twin screw extruder temperature is dried after the granulation at 120-170 ℃, is blow molded into the thick film of 10 ± 0.2 μ m, sample preparation, thermostat container was placed 24 hours.
Embodiment 12:
Appearance transparent property testing: get among the embodiment 10 and to adopt 5% lime carbonate embodiment 10 (embodiment 8) to add to adopt in film that PE blew out, the comparative example 3 the employing 5% lime carbonate interpolation film that PE blew out in the film that PE blew out that do not add lime carbonate and the comparative example 4, carry out the appearance transparence evaluation and test, see through film and observe the object of same color, the result shows: adopt and adopt the film appearance that PE blew out that does not add lime carbonate transparent, even in the comparative example 3, defectives such as flake, crazing are not arranged; It is transparent equally, evenly and do not have defectives such as flake, crazing to adopt 5% lime carbonate (embodiment 8) to add the film appearance that PE blew out, has represented the good dispersiveness of nano-calcium carbonate in the polyvinyl resin system of the present invention's production; And the PE film that adopts common single stearic acid modified nano-calcium carbonate (comparative example 4) to fill, color jaundice, transparency be low, open defect such as flake is arranged, and shows that this modified nano calcium carbonate is dispersed relatively poor in the PE film.This shows that the nano-calcium carbonate of method preparation proposed by the invention has solved the technical problem that existing film is sneaked into filler, has improved dispersiveness, and then has improved the appearance of films performance.
Claims (8)
1. novel nano lime carbonate that is used for plastics film is characterized in that: form by mass percentage:
CaCO
3 70％-99.9％
Surface treatment agent 0.1%-30%
Described surface treatment agent is dispersion agent and coupling agent, the mass percentage content of dispersion agent is at 0-15%, the mass percentage content of coupling agent is at 0-15%, described dispersion agent is the organism with long carbochain, carbonatoms in the organic molecule is between 8-30, and coupling agent is one or more in silane coupling agent, titanate coupling agent, boric acid ester coupler, aluminate coupling agent, aluminum-zirconium coupling agent, aluminium titanium composite coupler, the aluminium zirconium composite coupler.
2. preparation method who is used for the novel nano lime carbonate of plastics film is characterized in that: may further comprise the steps:
(1) Wingdale being cleaned the back calcines at high temperature kiln, through purifying, digestion, get calcium hydroxide slurry after the ageing, calcium hydroxide slurry is put into carbonization reactor, feed carbonic acid gas and carry out carbonization, add the crystal formation control agent at carbonization process, obtain the nano-calcium carbonate slurry, described crystal formation control agent is a sulfuric acid, phosphoric acid, citric acid, sucrose, beet sugar, the mixture of one or more in the maltose, the limestone calcination temperature is 800-1500 ℃, the digestion temperature is 20-95 ℃, digestion time is 1-48h, the slurry concentration of calcium hydroxide is 1-40%, concentration of carbon dioxide is that (v), carbonization temperature is 1-80 ℃ to 1-100%, and the pH value of carbonization terminal point slurry is between 6.5-7;
(2) the nano-calcium carbonate slurry for preparing according to step (1), in the time of 1-80 ℃, add surface treatment agent and carry out surface activation process and surface coating, add dispersion agent earlier and make the nano-calcium carbonate stable dispersion, the dispersion churning time is 30-120min, add coupling agent again, after stirring 10-120min, the slurry that modification is good filters, dry, pulverize and get final product;
(3) join in the high speed mixer after the nano-calcium carbonate slurries filtration for preparing according to step (1), drying, the pulverizing, add surface treatment agent at a certain temperature and carry out surface treatment, dispersion agent adds after coupling agent, Heating temperature is 80-150 ℃, rotating speed 500-10000 commentaries on classics/min, mixing time is 2-120min.
3. a kind of preparation method who is used for the novel nano lime carbonate of plastics film according to claim 2, its feature is being: described carbonization reactor can be that intermittently bubbling style reactor, supergravity reactor, film disperse little mixing reactor.
4. a kind of preparation method who is used for the novel nano lime carbonate of plastics film according to claim 2, it is characterized in that: the mass concentration of described nano-calcium carbonate slurry is at 2-20%.
5. a kind of preparation method who is used for the novel nano lime carbonate of plastics film according to claim 2, it is characterized in that: the limestone calcination temperature in the step (1) is preferably 900-1200 ℃, the digestion temperature is preferably 70-90 ℃, the preferred 4-16h of digestion time, the slurry concentration of calcium hydroxide is preferably 5-20%, concentration of carbon dioxide is preferably 20-50%, and (v), carbonization temperature is preferably 5-25 ℃; The preferred 100-140 of Heating temperature in the step (1) ℃, the preferred 500-3000 commentaries on classics/min of rotating speed, the preferred 10-60min of mixing time.
6. a kind of novel nano lime carbonate that is used for plastics film according to claim 1 is characterized in that: described dispersion agent is one or more mixing in Palmiticacid, stearic acid, oleic acid, the isometric chain fatty acid of lauric acid and the salt thereof.
7. a kind of novel nano lime carbonate that is used for plastics film according to claim 1 is characterized in that: the shape of lime carbonate can be spindle-type, cube type, ball-type, pelletron type, and its average particle size range is 20nm-3 μ m.
8. a kind of novel nano lime carbonate that is used for plastics film according to claim 1, it is characterized in that: the addition of novel nano lime carbonate in polymkeric substance can be 1%-80% by mass percent.
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