CN1189523C - Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate - Google Patents
Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate Download PDFInfo
- Publication number
- CN1189523C CN1189523C CNB021210349A CN02121034A CN1189523C CN 1189523 C CN1189523 C CN 1189523C CN B021210349 A CNB021210349 A CN B021210349A CN 02121034 A CN02121034 A CN 02121034A CN 1189523 C CN1189523 C CN 1189523C
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- monomer
- nano
- surface treatment
- nano particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a surface treatment method for improving the hydrophobicity of nano calcium carbonate particles. Acrylics copolymer emulsion obtained by emulsion polymerization is used as a surface modifying agent, and nano calcium carbonate slurry is processed by the acrylics copolymer emulsion under the condition of stirring to improve the hydrophobicity of the nano calcium carbonate particles. The surface treatment method has the advantages of simple process and low preparation cost and can be used for evenly and stably coating a thin layer on the surface of the nano particles. In addition, the particle diameter of the processed particles can be well controlled. Under the condition of increasing great quantities of the nano calcium carbonate particles, the toughness of PVC resin can be enhanced, and the aggregation of the calcium carbonate particles can not be caused. Meanwhile, the production cost of PVC can be greatly reduced.
Description
Technical field:
The present invention relates to a kind of surface treatment method that improves hydrophobicity of Nano particles of calcium carbonate.
Background technology:
Lime carbonate is widely used in rubber, coating, papermaking, printing ink, printing, cable, food, medicine, makeup, toothpaste, feed, lubricated wet goods industry-by-industry as a kind of important inorganic chemical product.But because the surface of calcium carbonate powders has many hydroxyls, hydrophilic oleophobic property is obvious, easily forms coacervate in production and storage process, disperses extreme difference, and directly application is had any problem, therefore generally must be through surface treatment.Along with the rise of nano material, also by industrialization, nano level calcium carbonate particles particle diameter is littler in the production of nano-calcium carbonate, and easier the reunion, this just has higher requirement to the surface treatment of nano-calcium carbonate.
Inorganic nano-particle is disperseed to be filled in as in the polymkeric substance such as PVC, can not only reduce the cost of material, and can significantly improve mechanical property such as raw-material toughness.Yet the hydrophilic oleophobic of these particle surfaces, relatively poor with organic bonding properties, and the minimum great surface energy that particle diameter brought of nanoparticle will make it be very easy to take place self reunite, and in case the generation of reuniting, use general mechanical means just to be difficult to it is opened once more, thereby greatly influence the dispersion of inorganic nano-particle in polymeric matrix.Therefore need carry out surface treatment to Nano particles of calcium carbonate, the surface modification to Nano particles of calcium carbonate is broadly divided into two kinds of methods at present: dry method and wet method.
So-called dry method surface treatment is exactly stirring in the powder of the nano-calcium carbonate input high speed kneader, then adds dispersion agent or surface-modifying agent carries out surface treatment; So-called wet method then is directly surface treatment agent or dispersion agent to be joined among the calcium carbonate serosity, and this method can be divided into before the carbonization again and after the carbonization.But owing to cause foam easily in carbonating tower, the method before the carbonization is of little use.
The surface-modifying agent that uses can be divided into following several again:
1. coupling agent surface-modifying agent is as silane coupling agent, titante coupling agent, aluminate coupling agent.Coupling agent is that handling calcium carbonate powders the most frequently used also is a most traditional class surface treatment agent.Its principle be the free proton (deriving from combination water, crystal water, chemical absorbed water and the physical absorption water etc. on calcium carbonate powders surface) that makes various coupling agents and calcium carbonate powders surface in conjunction with and form chemical bond, thereby in the surface coverage of lime carbonate one deck molecular film.
2. inorganics surface-modifying agent is as condensed phosphoric acid, metaphosphoric acid or tetra-sodium.
3. organism surface-modifying agent is as phosphoric acid ester, lipid acid or aliphatic salt, stearic acid etc.
4. polymer surface modification agent is as the reactive fibre element; Graftomer, normally polyacrylic acid (salt) etc.
Above-mentioned some surface-modifying agent (as silane coupling agent) only is applicable to dry process.After in the polymkeric substance such as calcium carbonate particles introducing PVC that above-mentioned method of modifying 1 is handled,, can overflow after the certain hour, environment be polluted, and cause the decline of polymkeric substance qualities such as PVC because coupling agent is generally small molecules.
The calcium carbonate particles that surface-modifying agents such as above-mentioned method of modifying 2,3,4 usefulness inorganicss, organism, polymkeric substance are handled is introduced in the polymkeric substance, though can make some performances of polymkeric substance, increase as erosion-resisting characteristics, but acid of used surface treatment agent and salt can cause polymer thermostable decline simultaneously, and the addition of nanoparticle is also lower, the general 5-6% that only accounts for polymer monomer, little to the reduction contribution of cost.Its reason is that above-mentioned surface modifying method can't make the coating of nanoparticle complete, stablize, therefore the agglomeration traits under the situation that still unresolved inorganic nano-particle addition is bigger.Therefore make the raising of the final performance of product and the reduction of cost all be subjected to great restriction.
As reporting in the 2nd phase of " polyvinyl chloride " calendar year 2001 " it is resin dedicated that situ aggregation method the prepares PVC/ nano-calcium carbonate composite building material " literary composition, with stearic acid, aluminic acid ester etc. nano-calcium carbonate is carried out surface treatment, carry out in-situ polymerization with vinyl chloride monomer.The erosion-resisting characteristics of its product is brought up to the twice of pure polyvinyl chloride resin.The dose relative molecular mass and the dispersion index that make polyvinyl chloride resin of nano-calcium carbonate all increase to some extent.Wherein the equal molecular mass Mn of relative number is 1.09 times of pure PVC, and weight average molecular mass Mw is 1.34 times of pure PVC relatively, and sticking relatively equal molecular mass Mv is 1.33 times of pure PVC, and relative molecular mass distribution Mw/Mn is 1.23 times of pure PVC.This explanation, the adding of nano-calcium carbonate has tangible influence to the molecular weight of PVC, and this also will further have influence on the original various physics-chem characteristics of PVC.But the addition of nano-calcium carbonate at most only accounts for 5.5% of vinyl chloride monomer.And cause thermostability to descend.
And for example mention in " polyvinyl chloride " calendar year 2001 the 4th interim " the ton chloroethylene in-situ-polymerization technology under the existence of nano-calcium carbonate microemulsion " literary composition, develop a kind of polymerization-grade nano-calcium carbonate microemulsified system, can be directly used in the in-situ polymerization of vinylchlorid.When addible amount accounted for vinyl chloride monomer 3%-5%, the shock strength of goods rose to 2-4 times of pure PVC.This method is carried out surface molecular to nano-calcium carbonate earlier and is modified, the microemulsified that forms nano-calcium carbonate disperses, after in the PVC matrix, being filled polymerization behind the chloroethylene polymerization by vinylchlorid, disintegration is the following small-particles of 10 nanometers, nano grain surface and PVC matrix may form three-dimensional net rack node structure, thereby improve the toughness of goods.
Summary of the invention:
The object of the present invention is to provide a kind of surface treatment method that improves hydrophobicity of Nano particles of calcium carbonate.Adopt acrylic acid esters co-polymer emulsion that letex polymerization obtains under stirring condition, the nano-calcium carbonate slurries to be handled and realize improvement hydrophobicity of Nano particles of calcium carbonate as surface-modifying agent.Process is simple, and preparation cost is cheap, can carry out uniform skin layer to nanoparticle and coat, and coats stablely, satisfactory for result, can control the particle diameter of the particle after the processing well.Make under the situation of the nano-calcium carbonate that adds big umber (can add 20% to), not only improve the toughness of polyvinyl chloride resin, and can not cause the reunion of calcium carbonate particles.Can reduce simultaneously the production cost of PVC significantly.
The invention main points: the present invention is a kind of surface treatment method that improves hydrophobicity of Nano particles of calcium carbonate, and the acrylic acid esters co-polymer emulsion that adopts letex polymerization to obtain is handled the improvement that realize hydrophobicity of Nano particles of calcium carbonate to the nano-calcium carbonate slurries as surface-modifying agent under stirring condition.
Surface treatment method of the present invention is finished by following two steps:
A: emulsion polymerization process: the present invention adopts in the prior art commonly used with well known to those skilled in the art, acrylic acid esters co-polymer emulsion and preparation method thereof, that need control is the 1-2% that the consumption of emulsifying agent accounts for the total consumption of monomer, soft monomer and hard monomer ratio of weight and number are 13: 7-10: it is 0.5-3% that 10, the three component acid account for the total consumption of monomer.
B: surface treatment process: the acrylic acid esters co-polymer emulsion that the A step is obtained is added drop-wise in the Nano particles of calcium carbonate slurries under stirring condition, the ratio of control emulsion and Nano particles of calcium carbonate slurry solid content is 1: 9-2: 8, and dropwise and continue to be stirred to Nano particles of calcium carbonate and all coated.
In the above-mentioned A step, the copolymer emulsion of acrylic acid esters co-polymer emulsion for making by acrylic ester monomer polymerization or copolymerization, the solid content of acrylic acid esters co-polymer emulsion is 38-44%.
In the above-mentioned A step, used initiator is used always for the acrylic acid esters co-polymer letex polymerization, and as ammonium persulphate, ammonium persulfate-sodium bisulfite etc., its consumption accounts for the 0.1-0.3% of the total consumption of monomer.
In the above-mentioned A step, used the 3rd component acid is for containing the carboxylic acid of polymerizable double bond.As: methacrylic acid, vinylformic acid or maleic acid.
In the above-mentioned A step, used soft monomer is ethyl propenoate or n-butyl acrylate or 2-EHA, and hard monomer is a methyl methacrylate.Used emulsifying agent also is that prior art is commonly used, as sodium lauryl sulphate, alkylphenol polyoxyethylene etc.
The present invention adopts the surface-modifying agent of acrylic acid esters co-polymer emulsion as Nano particles of calcium carbonate, make the surface of particle superscribe the skim polymkeric substance equably, the covered effect ideal, X-ray photoelectron spectroscopy (XPS) tests out the thickness of polymer covering layer on Nano particles of calcium carbonate surface greatly about about 10nm, and this is consistent with the electromicroscopic photograph result displayed.In addition, also can find out covered effect from the contrast of Fig. 1 and Fig. 2.The acrylic acid esters co-polymer emulsion itself is exactly the softening agent of polyvinyl chloride resin as the surface-modifying agent of Nano particles of calcium carbonate, its introducing not only can not resemble some quality of destroying resin above-mentioned small molecules tensio-active agent and acid, the salt, and the mechanical property to PVC makes moderate progress on the contrary.
Method of the present invention can also be controlled the particle diameter of the particle after the processing well, and improves the hydrophobicity of particle surface effectively, enables with organism affine good.Nano particles of calcium carbonate is not reunited when finding that by transmission electron microscope surface treatment process finishes.
Nano particles of calcium carbonate and vinyl chloride monomer after the employing method surface treatment of the present invention are carried out in-situ suspension polymerization.Dosing umber and can reaching 20% of nano-calcium carbonate can reduce the production cost of PVC greatly.Product process transmission electron microscope after the polymerization and scanning electron microscope are observed and are found that nearly all Nano particles of calcium carbonate all is present in the PVC polymer beads ball equably, and do not reunite, deployment conditions is very good, and the Nano particles of calcium carbonate of aqueous phase is few.The product pellet is processed into the plastics batten, and the transmission electron microscope of section and scanning electron microscopic observation result are constant, and the shock strength test to the plastics batten found that along with the increase of nano-calcium carbonate interpolation umber, the erosion-resisting characteristics of product improves thereupon.When addition was 5%, the erosion-resisting characteristics of PVC matrix material was about 2 times of pure PVC, and when addition was 20%, the erosion-resisting characteristics of PVC matrix material was about 4.5 times of pure PVC.Tensile strength reaches 53.7Kj/m
2
The adding of the nano-calcium carbonate of handling through method of the present invention as can be seen from the following table data is to molecular weight and the almost not influence of molecular weight distribution of PVC, thereby guaranteed that polyvinyl chloride resin can keep original various physics-chem characteristic substantially.
Table 1: molecule measuring test result contrast
| Sample | Add umber | Mn | Mw | Mz | Mv | Mw/Mn |
| Pure PVC | 0 | 56442 | 110483 | 222667 | 102718 | 1.957460 |
| | 20 | 57864 | 119082 | 230090 | 110543 | 2.057961 |
| | 13 | 55213 | 115929 | 228780 | 107398 | 2.099683 |
Mv is sticking relatively equal molecular mass in the table, and Mn is the equal molecular mass of relative number, and Mw is relative weight average molecular mass, and Mz is the equal molecular mass of relative Z, and Mw/Mn is that relative molecular mass distributes.
Description of drawings:
Fig. 1 is undressed Nano particles of calcium carbonate transmission electron microscope photo.
Fig. 2 is the Nano particles of calcium carbonate transmission electron microscope photo of handling through method of the present invention.
Fig. 3 is the transmission electron microscope photo (magnification is 2000) of the composite granule after method surface-treated Nano particles of calcium carbonate of the present invention and vinylchlorid carry out in-situ suspension polymerization.
Fig. 4 is the transmission electron microscope photo (magnification is 80000) of the composite granule after method surface-treated Nano particles of calcium carbonate of the present invention and vinylchlorid carry out in-situ suspension polymerization.
Between 30nm～50nm, the surface is comparatively clean greatly for the diameter of undressed Nano particles of calcium carbonate as can be seen from Figure 1, and particle edges is comparatively clear, and most particles are cube.The diameter of the calcium carbonate particles of process polymer overmold is approximately between 50nm～60nm as can be seen from Figure 2.Diameter is bigger, and seemingly there are a large amount of finely ground particles on the surface, and particle edges is fuzzy, and is rounded mostly.Illustrate that covered effect is good.
A large amount of as can be seen Nano particles of calcium carbonate is filled in the elementary PVC grain ball equably from Fig. 3 and Fig. 4, disperses in order, and aqueous phase does not have Nano particles of calcium carbonate substantially.
Embodiment:
Embodiment 1:
A, letex polymerization:
Soft monomer is selected n-butyl acrylate for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, methacrylic acid (the 3rd component acid) are carried out blend by 11: 9: 0.6 weight ratios, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, is respectively 0.25 gram and 0.55 gram, and two kinds of emulsifier mix in the deionized water of 15 grams, are heated to dissolving fully.The emulsifier solution that dissolving is finished joins in the reactor, adds above-mentioned monomer blend liquid 4.12 grams then, stirs and be warming up to 75 ℃, and disposable adding restrains ammonium persulphate (analytical pure) with 0.06 of 23 gram deionized water dissolvings.When equitemperature gos up to 80 ℃, monomer begins to be initiated, when " turning blue " phenomenon obviously appears in system, keep temperature of reaction at 80 ℃, drip monomer blend liquid 37.08 grams again, drip 0.06 gram ammonium persulphate with 20 gram deionized water dissolvings simultaneously in reactor, the control rate of addition makes all drip thing and dropwises about 1 hour evenly.Continue reaction about 3.5 hours, cooling discharging afterwards.The polymer emulsion solid content that makes at last: 42%.
B, surface treatment:
Take by weighing solid content and be 20% nano-calcium carbonate slurries 405 grams (nano-calcium carbonate dry weight 81 grams) and join in the reactor, stir until system even at normal temperatures.Take by weighing emulsion 21.4 grams (solid content of emulsion is 9 grams) of A step gained, under stirring condition, slowly join among the nano-calcium carbonate slurries equably, continue to stir, wait electron microscopic observation as can be seen Nano particles of calcium carbonate coat when all right, finish surface treatment process.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 20% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 11.2Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2, tensile strength reaches 53.7Kj/m
2
Embodiment 2:
A, letex polymerization:
Soft monomer is selected 2-EHA for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, methacrylic acid (the 3rd component acid) are carried out blend by 10: 10: 0.2 weight ratios, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, is respectively 0.24 gram and 0.48 gram, and two kinds of emulsifier mix in the deionized water of 15 grams, are heated to dissolving fully.The emulsifier solution that dissolving is finished joins in the reactor, adds above-mentioned monomer blend liquid 4.242 grams then, stirs and be warming up to 75 ℃, and disposable adding restrains ammonium persulphate (analytical pure) with 0.021 of 22 gram deionized water dissolvings.When equitemperature gos up to 80 ℃, monomer begins to be initiated, when " turning blue " phenomenon obviously appears in system, keep temperature of reaction at 80 ℃, drip monomer blend liquid 37.178 grams again, drip 0.021 gram ammonium persulphate with 20 gram deionized water dissolvings simultaneously in reactor, the control rate of addition makes all drip thing and dropwises about 1 hour evenly.Continue reaction about 3.5 hours, cooling discharging afterwards.The polymer emulsion solid content that makes at last: 44%.
B, surface treatment:
The nano-calcium carbonate slurry solid content is 22%, takes by weighing 500 grams (nano-calcium carbonate dry weight 110 grams) and joins in the reactor, stirs until system even at normal temperatures.Take by weighing emulsion 27.73 grams (solid content of emulsion is 12.2 grams) of A step gained, under stirring condition, slowly join among the nano-calcium carbonate slurries equably, continue to stir, wait electron microscopic observation as can be seen Nano particles of calcium carbonate coat when all right, finish surface treatment process.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 13% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 7.5Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2, all the other conditions are all identical.
Embodiment 3:
A, letex polymerization:
Soft monomer is selected ethyl propenoate for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, vinylformic acid (the 3rd component acid) are carried out blend by 10: 10: 0.1 weight ratios, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, be respectively 0.34 gram and 0.48 gram, with two kinds of emulsifier mix 15 the gram deionized waters in, be heated to dissolving fully, the emulsifier solution that dissolving is finished joins in the reactor, add above-mentioned monomer blend liquid 4.12 grams then, stir and be warming up to 75 ℃, disposable adding restrains ammonium persulphate (analytical pure) with 0.02 of 23 gram deionized water dissolvings.When equitemperature gos up to 80 ℃, monomer begins to be initiated, when " turning blue " phenomenon obviously appears in system, keep 80 ℃ of temperature of reaction, drip monomer blend liquid 37.08 grams again, drip 0.02 gram ammonium persulphate with 20 gram deionized water dissolvings simultaneously in reactor, the control rate of addition makes all drip thing and dropwises about 1 hour evenly.Continue reaction about 3.5 hours, cooling discharging afterwards.The polymer emulsion solid content that makes at last: 38%.
B, surface treatment:
Take by weighing solid content and be 25% nano-calcium carbonate slurries 400 grams (nano-calcium carbonate dry weight 100 grams), join in the reactor, stir until system even at normal temperatures.Take by weighing emulsion 29.2 grams (solid content of emulsion is 11.1 grams) of A step gained, under stirring condition, slowly join among the nano-calcium carbonate slurries equably, continue to stir, wait electron microscopic observation as can be seen Nano particles of calcium carbonate coat when all right, finish surface treatment process.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 11% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 10.4Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2
Embodiment 4:
A, letex polymerization:
Soft monomer is selected 2-EHA for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, methacrylic acid are carried out blend by 11: 9: 0.4 weight ratio, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, be respectively 0.28 gram and 0.56 gram, with two kinds of emulsifier mix 15 the gram deionized waters in, be heated to dissolving fully, the emulsifier solution that dissolving is finished joins in the reactor, then above-mentioned monomer blend liquid 4.284 grams are added in the reactor, stir, when treating that temperature rises to 75 ℃, disposable adding restrains ammonium persulphate with 0.042 of 20 gram deionized water dissolvings, treat temperature recovery to 80 ℃, monomer begins to be initiated, and when " turning blue " phenomenon obviously occurring etc. system, keeps temperature of reaction at 80 ℃, drip monomer blend liquid 38.556 grams, also in reactor, drip simultaneously with 22 gram deionized water dissolvings, 0.042 gram ammonium persulphate.The control rate of addition makes all drip thing and dropwises about 1 hour evenly.Cooling discharging.The polymer emulsion solid content that makes at last: 40%.
B, surface treatment:
Take by weighing solid content and be 20.5% nano-calcium carbonate slurries 500 grams (nano-calcium carbonate dry weight 102.5 grams) and add in reactor, stir until system even at normal temperatures.Take by weighing emulsion 64.05 grams (solid content of emulsion is 25.62 grams) of A step gained, under stirring condition, slowly join among the nano-calcium carbonate slurries equably, continue to stir, wait electron microscopic observation as can be seen Nano particles of calcium carbonate coat when all right, finish surface treatment process.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 8% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 5.5Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2
Embodiment 5:
A, letex polymerization:
Soft monomer is selected 2-EHA for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, vinylformic acid are carried out blend by 13: 7: 0.1 ratios of weight and number, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, be respectively 0.25 gram and 0.55 gram, then with two kinds of emulsifier mix 15 the gram deionized waters in, be heated to dissolving fully, the emulsifier solution that dissolving is finished joins in the reactor, then above-mentioned monomer blend liquid 4.02 grams are added in the reactor, stir, when treating that temperature rises to 75 ℃, disposable adding restrains ammonium persulphate with 0.04 of 20 gram deionized water dissolvings, when equitemperature gos up to 80 ℃, monomer begins to be initiated, and when " turning blue " phenomenon obviously occurring etc. system, keeps 80 ℃ of temperature of reaction, drip monomer blend liquid 36.18 grams, also in reactor, drip simultaneously with 24 gram deionized water dissolvings, 0.04 gram ammonium persulphate.The control rate of addition makes all drip thing and dropwises about 1 hour evenly.Cooling discharging.The polymer emulsion solid content that makes at last: 42%.
B, surface treatment:
Take by weighing solid content and be 23% nano-calcium carbonate slurries 458 grams (nano-calcium carbonate dry weight 105.34 grams) and add in reactor, stir until system even at normal temperatures.Take by weighing emulsion 41.8 grams (solid content of emulsion is 17.56 grams) of A step gained, under stirring condition, slowly join among the nano-calcium carbonate slurries equably, continue to stir, wait electron microscopic observation as can be seen Nano particles of calcium carbonate coat when all right, finish surface treatment process.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 5% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 5.1Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2, all the other conditions are all identical.
Embodiment 6:
A, letex polymerization:
Soft monomer is selected ethyl propenoate for use, and hard monomer is selected methyl methacrylate for use.Soft monomer, hard monomer, methacrylic acid (the 3rd component acid) are carried out blend by 13: 7: 0.5 weight ratios, be made into monomer blend liquid.Emulsifying agent is selected sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) for use, is respectively 0.3 gram and 0.5 gram, and two kinds of emulsifier mix in the deionized water of 15 grams, are heated to dissolving fully.The emulsifier solution that dissolving is finished joins in the reactor, adds above-mentioned monomer blend liquid 4.12 grams then, stir and be warming up to 75 ℃ of controlled temperature and keep constant, and disposable adding restrains ammonium persulphate (analytical pure) with 0.05 of 23 gram deionized water dissolvings.When equitemperature gos up to 80 ℃, monomer begins to be initiated, when " turning blue " phenomenon obviously appears in system, keep 80 ℃ of temperature of reaction, drip monomer blend liquid 37.08 grams again, drip 0.05 gram ammonium persulphate with 20 gram deionized water dissolvings simultaneously in reactor, the control rate of addition makes all drip thing and dropwises about 1 hour evenly.Continue reaction about 3.5 hours, cooling discharging afterwards.The polymer emulsion solid content that makes at last: 41%.
B, surface treatment:
The nano-calcium carbonate slurry solid content is 20%, takes by weighing 400 grams and joins in the glass beaker of 1000ml, and promptly nano-calcium carbonate dry weight 80 restrains, and stirring at low speed is even until system at normal temperatures with electric mixer.Take by weighing emulsion 24.39 grams of A step gained, the solid content that is emulsion is 10 grams, slowly joins equably among the nano-calcium carbonate slurries that stirring, and stirs, electron microscopic observation coats all right Nano particles of calcium carbonate as can be seen, can think that surface treatment process finishes.
C, polymerization and performance test:
Nano-calcium carbonate after the surface treatment is joined in the conventional polyvinyl chloride suspension polymerization still, and addition is to account for 17% of vinyl chloride monomer consumption.Detailed process is for adding earlier dispersion agent (polyvinyl alcohol, Vltra tears), initiator (peroxy dicarbonate ethylhexyl), water, surface treated nano-calcium carbonate slurries in reactor, back adding monomer (vinylchlorid) stirs under the normal temperature, be warming up to 57 ℃, react.Reacted matrix material after tested, shock strength is 9.97Kj/m
2And the shock strength of not adding the pure PVC of nano-calcium carbonate is 2.49Kj/m
2, tensile strength reaches 51.8Kj/m
2
Claims (3)
1. surface treatment method that improves hydrophobicity of Nano particles of calcium carbonate, the acrylic acid esters co-polymer emulsion that adopts letex polymerization to obtain is handled the nano-calcium carbonate slurries under stirring condition as surface-modifying agent and is realized; Its feature and concrete steps are:
A: emulsion polymerization process: the consumption of emulsifying agent accounts for the 1-2% of the total consumption of monomer, and soft monomer and hard monomer ratio of weight and number are 13: 7-10: 10, the three component acid account for the 0.5-3% of the total consumption of monomer;
Said emulsifying agent is sodium lauryl sulphate, alkylphenol polyoxyethylene or their miscellany in the steps A; Said soft monomer is ethyl propenoate or n-butyl acrylate or 2-EHA; Hard monomer is a methyl methacrylate; Initiator is the miscellany of ammonium persulphate or ammonium persulphate and sodium bisulfite; The acid of the 3rd component is methacrylic acid, vinylformic acid or maleic acid;
B: surface treatment process: the acrylic acid esters co-polymer emulsion that steps A is obtained is added drop-wise in the Nano particles of calcium carbonate slurries under stirring condition, the ratio of control emulsion and Nano particles of calcium carbonate slurry solid content is 1: 9-2: 8, and dropwise and continue to be stirred to Nano particles of calcium carbonate and all coated.
2. according to the surface treatment method of claim 1, it is characterized in that: the copolymer emulsion of acrylic acid esters co-polymer emulsion for being made by acrylic ester monomer polymerization or copolymerization, solid content is 38-44%.
3. according to the surface treatment method of claim 1, it is characterized in that: the consumption of initiator accounts for the 0.1-0.3% of the total consumption of monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021210349A CN1189523C (en) | 2002-05-31 | 2002-05-31 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021210349A CN1189523C (en) | 2002-05-31 | 2002-05-31 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1462773A CN1462773A (en) | 2003-12-24 |
| CN1189523C true CN1189523C (en) | 2005-02-16 |
Family
ID=29742729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021210349A Expired - Fee Related CN1189523C (en) | 2002-05-31 | 2002-05-31 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189523C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347234C (en) * | 2004-08-18 | 2007-11-07 | 上海氯碱化工股份有限公司 | Composite of full filled unplasticizing polyvinyl chloride/calcium carbonate and preparation process thereof |
| KR100930874B1 (en) * | 2005-06-10 | 2009-12-10 | (주)아모레퍼시픽 | Method for preparing the surface-modified powder with water-repellent thin layer on the surface of organic or inorganic particle |
| JP2010514874A (en) * | 2006-12-28 | 2010-05-06 | ヌプレクス レジンズ ビー．ブイ． | Film-forming composition comprising modified nanoparticles and methods of using modified nanoparticles in film-forming compositions |
| CN101469245B (en) * | 2007-12-25 | 2012-03-28 | 比亚迪股份有限公司 | Coating composition and method of preparing the same |
| CN101301598B (en) * | 2008-06-06 | 2012-03-21 | 哈尔滨工业大学 | Surface dewatering process method of inorganic powder material |
| CN102115619B (en) * | 2009-12-31 | 2013-07-24 | 中国科学院化学研究所 | Surface treatment method for aluminum oxide |
| CN102464786B (en) * | 2010-11-10 | 2013-09-18 | 上海华明高技术（集团）有限公司 | Polyacrylate elastomer emulsion and preparation method thereof |
| CN103224648B (en) * | 2013-04-07 | 2014-12-31 | 宜春市科远化工有限公司 | Surface modified nano calcium carbonate and preparation method thereof |
| CN107254211B (en) * | 2017-06-26 | 2020-08-04 | 河北科技大学 | Preparation method of modified nano calcium carbonate powder for high-end water-based paint |
| CN108948794A (en) * | 2018-07-27 | 2018-12-07 | 江西华明纳米碳酸钙有限公司 | The preparation method of pvc plastisol nanometer calcium carbonate |
| JP2023071158A (en) * | 2021-11-10 | 2023-05-22 | 花王株式会社 | Halogenated resin composition |
| CN115232245A (en) * | 2022-07-05 | 2022-10-25 | 鹤山市东海塑料色母有限公司 | Preparation process and modification method of calcium carbonate modifier |
-
2002
- 2002-05-31 CN CNB021210349A patent/CN1189523C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1462773A (en) | 2003-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1040333C (en) | Synthesis of latex capsules | |
| CN1189523C (en) | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate | |
| CN104276877B (en) | Carbon nano-tube modification aqueous-based polymers composite film-coated controlled release fertilizer and preparation method thereof | |
| CN1438253A (en) | Acrylate micro-emulsion with high solid content, its preparation method and use | |
| CN102464839B (en) | Composite toughening modifier for plastics and preparation method thereof | |
| CN1130634A (en) | Encapsulated hydrophilic polymers and their preparation | |
| CN101033360A (en) | Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion | |
| CN101392070B (en) | Industrial preparation method of PVC processing aid | |
| CN1298745C (en) | Method for preparing hollow microspheres self film-formed in latex of low soap system | |
| CN102464786B (en) | Polyacrylate elastomer emulsion and preparation method thereof | |
| CN1305977C (en) | Method for modifying the surface of nano inorganic particles by transfer method | |
| CN1884326A (en) | Porous polypropylene particle suspension solid phase graft-modification method | |
| CN1246351C (en) | Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN107324901A (en) | Polymer-modified composite film-coated controlled release fertilizer of graphene oxide and preparation method thereof | |
| CN101514247B (en) | High-efficiency multifunctional compound enforcing agent and preparation method thereof | |
| CN1757668A (en) | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof | |
| CN101220127B (en) | Nucleocapsid type rubber coordination crosslinking agent | |
| CN1775819A (en) | Method for preparing nano silicon dioxide-acrylate polymeric microball material | |
| CN108531029A (en) | A kind of dopamine coats the preparation method of three-dimensional porous graphene/acrylic ester aquosity anticorrosive paint | |
| CN1279068C (en) | Crosslinked core-shell structure nano-polymer microsphere and its preparation method | |
| CN1285616C (en) | Method for fabricatng compound microsphere of macromolecule/inorganic matter | |
| CN1258544C (en) | Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN1246352C (en) | Nano macromolecule microball of carboxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN113461869B (en) | Metal organic framework-calcium carbonate composite crystal material and preparation method thereof | |
| CN100558808C (en) | Nano calcium carbonate/polystyrene composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |