A kind of surface treatment method of nano-calcium carbonate of filled PVC plastipaste
Technical field
The present invention relates to inorganic material-modified method, specifically a kind of surface treatment method of nano-calcium carbonate of filled PVC plastipaste.
Background technology
PVC plastipaste is by the paste-form dispersion system of the Homogeneous phase mixing such as PVC paste resin, softening agent, solid filling material and other auxiliary agents, paid close attention to widely because its process for processing has the advantages such as technique is simple, cost is low, economic benefit is high, and be applied to the fields such as automobile, leather, ink, coating, seal gum, tackiness agent, building materials.For automobile industry, PVC plastipaste is mainly used in being processed to form priming paint, requires that it has good thixotropy in the application of reality, in use (spraying) process, show low-viscosity because of high speed shear, be easy to spraying, levelling, do not produce sagging after spray coating.
Nano-calcium carbonate is as the main function stopping composition of PVC plastipaste, and its particle form, particle diameter and surface treatment are very large on the impact of plastipaste rheological property, wherein have the greatest impact with calcium carbonate surface process.The fatty acid molecule one end being usually used in calcium carbonate surface process is hydrophilic carboxyl, can form Chemical bond, thus prevent calcium carbonate particles from reuniting with calcium carbonate surface; The other end is oil loving Long carbon chain, can reduce the surface energy of calcium carbonate particles, improves the consistency between calcium carbonate and softening agent.But the calcium carbonate of stearic acid surface process easily produces solvation effect in plastipaste, cause system viscosity to increase, stability is bad.And Long carbon chain and PVC paste interlaminar resin are without chemical reaction, reactive force is weak, causes plastipaste yield value lower.
In recent years, constantly someone attempts using various treatment agent to carry out surface modification to nano-calcium carbonate, and the pertinent literature found is as follows: the preparation method disclosing a kind of heat-resisting calcium carbonate of coupling agent surface modification in Chinese patent Chinese invention patent CN103555006A.The method is dissolved in organic solvent after tung oil, tung oil acid anhydride and part silane coupling agent KH55O Homogeneous phase mixing, uses it for calcium carbonate first time surface treatment, then adds dioctyl sebacate and Tritolyl Phosphate continuation process.Gained calcium carbonate surface defines one deck tung oil protective membrane, and resistance toheat is good, and it is tightr that coupling agent can make calcium carbonate contact with protective membrane.But the method technique is comparatively complicated, and gained calcium carbonate-filled PVC plastipaste viscosity is higher, and dioctyl sebacate and Tritolyl Phosphate etc. will aggravate plastipaste system solvation, cause plastipaste stability in storage to decline.
A kind of preparation method of anti-corrosive paints nanometer grade calcium carbonate is disclosed in Chinese invention patent CN103555032A.Its one-time surface process adopts the compound of silane coupling agent KH580 and antioxidant, and secondary surface preparation adopts the compound of ammonium molybdate, Propenoic acid, 2-methyl, isobutyl ester and Gum Rosin.Gained nano-calcium carbonate has good lipophilic-hydrophobic property, and simultaneously because Gum Rosin has the effect forming coating, the coating that it is filled has etch-proof effect, but poor for thixotropy during filled PVC plastipaste.
The surface modifying method of current nano-calcium carbonate is difficult to give the good thixotropy of its PVC plastipaste of filling, higher yield value and rheological stability.
Summary of the invention
The present invention is directed to existing nono calcium carbonate modified method Problems existing, a kind of surface treatment method of the nano-calcium carbonate for filling vehicle paint base PVC plastipaste is provided.Present method uses the composite mixture of saturated fatty acid and ricinoleate ester sodium sulfate to carry out surface treatment to nano-calcium carbonate, and the nano-calcium carbonate after process effectively can improve the thixotropy of filled PVC plastipaste, yield value and rheological stability etc.
The present invention mainly realizes based on following principle:
Wet process surface treatment technique is carried out for the nano-calcium carbonate of particle diameter between 40 ~ 80nm, uses the composite mixture of saturated fatty acid and ricinoleate ester sodium sulfate to carry out surface treatment to nano-calcium carbonate.
Saturated fatty acid can give nano-calcium carbonate good oleophilic drainage performance, has good consistency to most polymers system, and the mutual entanglement between the Long carbon chain in its molecule can improve the thixotropy of PVC plastipaste to a certain extent.Ricinoleate ester sodium sulfate is introduced in surface-modifying agent, the carboxylic acid ion that ester group in its molecule generates in the basic conditions can with the calcium binding of calcium carbonate molecular surface, and the polarity sulfonic group in its molecule and the electrostatic interaction between calcium ion further enhance the covered effect of surface treatment agent, increase the distance between calcium carbonate granule, effectively improve the dispersiveness of powder thus improve yield value and the rheological stability of the plastipaste system of filling.Simultaneously due to the existence of the strong polar group of sulfonic group, easily physical crosslinking point is produced because of the interaction between polarity in filled polymer, increase physical crosslinking density, enhance the network structure formed between calcium carbonate and superpolymer, because its strong network structure can improve its rheological stability at lay up period while improving plastipaste yield value.Therefore, the PVC plastipaste through the nanon calcium carbonatefilled of saturated fatty acid and ricinoleate ester sodium sulfate complex treatment can obtain good thixotropy, yield value, and rheological stability.
The concrete technical scheme of the present invention is as follows:
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) be delivered in surface processing trough by the nano-calcium carbonate slurries after carbonating, control temperature, at 50 ~ 80 DEG C, stirs, and obtains nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 2 ~ 4% of calcium carbonate dry matrix amount, Keep agitation 60 ~ 90min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent by mass ratio be 1: 0.5 ~ 3 saturated fatty acid and ricinoleate ester sodium sulfate form;
(3) by modified calcium carbonate slurries obtained above more after filtration, dry, pulverize and sieve, can product be obtained.
Above-described ricinoleate ester sodium sulfate to be esterification carbon atom number be 1 ~ 5 ricinoleate ester sodium sulfate salt, be preferably in methyl ricinolcic acid sodium sulfate, ricinolic acid ethyl ester sodium sulfate, ricinolic acid butyl ester sodium sulfate one or more.
Above-described saturated fatty acid to be carbon atom number be 18 ~ 22 saturated fatty acid, be preferably in stearic acid, eicosanoic acid, behenic acid one or more.
Preferably, the specific surface area of above-described nano-calcium carbonate is 20-25m
2/ g.
The preparation method of above-described surface treatment agent, comprise the steps: to add sodium hydroxide or potassium hydroxide in the hot water of 95 ~ 100 DEG C, add-on is 10 ~ 17% of saturated fatty acid consumption, add saturated fatty acid after abundant dissolving again and carry out saponification reaction, finally add ricinoleate ester sodium sulfate, after abundant stirring, obtain surface treatment agent.
Compared with prior art, beneficial effect of the present invention:
1, present method adopts saturated fatty acid and ricinoleate ester sodium sulfate is composite carries out wet process surface treatment to nano-calcium carbonate, and the nano-calcium carbonate of gained effectively can improve the thixotropy of filled PVC plastipaste, yield value and rheological stability etc.
2, be applied to PVC plastipaste through present method surface-treated nano-calcium carbonate to fill, the thixotropic loop area of the plastipaste of gained is 2.01 × 10
4~ 3.30 × 10
4pa/S, yield value is 189 ~ 316Pa, and viscosity is 4894 ~ 6548mPaS, and its performance is all better than single saturated fatty acid modification.
3, present method technique is simple, and cost is low, processing ease, is suitable for industrial production, has good economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is product viscosity change curve;
Identify in figure: 1,2,3 be respectively embodiment 1, embodiment 2 and comparative example 1 be applied to preparation PVC plastipaste time product viscosity over time with change curve storage period.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but be not limited to protection scope of the present invention.
The preparation of the nano-calcium carbonate slurries described in following examples after carbonating:
(1) diluted by the milk of lime after refining, ageing 36-72h, proportion is adjusted to 1.055-1.070, and control temperature is 20-26 DEG C, is then transported to the bubbling carbonizing tower with stirring;
(2) pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 6-10m3/h, and carbonic acid gas volume content is 25-35%, when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area controls as 20-25m
2/ g.
embodiment 1
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) will specific surface area be 21.3m after carbonating
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 50 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 2.5% of calcium carbonate dry matrix amount, Keep agitation 90min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent is that the stearic acid of 1:1 and methyl ricinolcic acid sodium sulfate form by mass ratio;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 110 DEG C, pulverizes, and finally crosses 100 mesh sieves, namely obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 95 DEG C, add sodium hydroxide, add-on is 12% of stearic acid dosage, add stearic acid after abundant dissolving again and carry out saponification reaction, finally add methyl ricinolcic acid sodium sulfate, after abundant stirring, obtain surface treatment agent.
embodiment 2
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) will specific surface area be 22.8m after carbonating
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 60 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 2% of calcium carbonate dry matrix amount, Keep agitation 80min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent is that the eicosanoic acid of 1:2 and ricinolic acid ethyl ester sodium sulfate form by mass ratio;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 100 DEG C, pulverizes, and finally crosses 100 mesh sieves, namely obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 95 DEG C, add sodium hydroxide, add-on is 10% of eicosanoic acid consumption, add eicosanoic acid after abundant dissolving again and carry out saponification reaction, finally add ricinolic acid ethyl ester sodium sulfate, after abundant stirring, obtain surface treatment agent.
embodiment 3
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) will specific surface area be 21.5m after carbonating
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 70 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 3.5% of calcium carbonate dry matrix amount, Keep agitation 70min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent is that the behenic acid of 1:3 and ricinolic acid ethyl ester sodium sulfate form by mass ratio;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 90 DEG C, pulverizes, and finally crosses 100 mesh sieves, namely obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 100 DEG C, add sodium hydroxide, add-on is 15% of behenic acid consumption, add behenic acid after abundant dissolving again and carry out saponification reaction, finally add ricinolic acid ethyl ester sodium sulfate, after abundant stirring, obtain surface treatment agent.
embodiment 4
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) will specific surface area be 24.8m after carbonating
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 80 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 4% of calcium carbonate dry matrix amount, Keep agitation 60min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent by mass ratio be the stearic acid of 1:0.5, behenic acid and ricinolic acid butyl ester sodium sulfate forms, wherein the mass ratio of stearic acid and behenic acid is 1:3;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 100 DEG C, pulverizes, and finally crosses 100 mesh sieves, namely obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 100 DEG C, add sodium hydroxide, add-on is 17% of saturated fatty acid consumption, add saturated fatty acid after abundant dissolving again and carry out saponification reaction, finally add ricinolic acid butyl ester sodium sulfate, after abundant stirring, obtain surface treatment agent.
embodiment 5
A surface treatment method for the nano-calcium carbonate of filled PVC plastipaste, comprises the following steps:
(1) will specific surface area be 22.3m after carbonating
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 75 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add surface treatment agent, wherein the add-on of surface treatment agent is 3% of calcium carbonate dry matrix amount, Keep agitation 70min, completes the surface modification of nano-calcium carbonate; Described surface treatment agent is that the stearic acid of 1:1 and ricinolic acid diethylene glycol dilaurate sodium sulfate form by mass ratio;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 90 DEG C, pulverizes, and finally crosses 100 mesh sieves, namely obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 100 DEG C, add sodium hydroxide, add-on is 12% of stearic acid dosage, add stearic acid after abundant dissolving again and carry out saponification reaction, finally add ricinolic acid diethylene glycol dilaurate sodium sulfate, after abundant stirring, obtain surface treatment agent.
comparative example 1
(1) just after carbonating, specific surface area is 21.3m
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 50 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add stearic acid surface treatment agent, wherein stearic add-on is 2.5% of calcium carbonate dry matrix amount, Keep agitation 90min, completes the surface modification of nano-calcium carbonate;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 110 DEG C, pulverize, finally 100 mesh sieves, namely obtain nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 95 DEG C, add sodium hydroxide, and add-on is 12% of stearic acid dosage, adds stearic acid again and carry out saponification reaction after fully dissolving, and after fully stirring, obtains surface treatment agent.
comparative example 2
(1) just after carbonating, specific surface area is 21.3m
2the nano-calcium carbonate slurries of/g are delivered in surface processing trough, and control temperature, at 50 DEG C, stirs, and obtain nano-calcium carbonate suspension slurry;
(2) under whipped state, add methyl ricinolcic acid sodium sulfate surface treatment agent, wherein the add-on of methyl ricinolcic acid sodium sulfate is 2.5% of calcium carbonate dry matrix amount, Keep agitation 90min, completes the surface modification of nano-calcium carbonate;
(3) the nano-calcium carbonate slurries after surface modification are carried out filter-press dehydration process, usage chain band drying machine is dried, and drying temperature is 110 DEG C, pulverize, finally 100 mesh sieves, namely obtain nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface treatment agent, step is as follows: in the hot water of 95 DEG C, add sodium hydroxide, and add-on is 12% of methyl ricinolcic acid sodium sulfate consumption, adds methyl ricinolcic acid sodium sulfate again and carry out saponification reaction after fully dissolving, after abundant stirring, obtain surface treatment agent.
the application test of embodiment and comparative example product
The nano-calcium carbonate calcium product each embodiment and comparative example obtained is applied to PVC plastipaste according to a conventional method and fills, and the concrete formula of preparation PVC plastipaste is as shown in table 1.Each embodiment and comparative example gained PVC plastipaste performance as shown in table 2.
Table 1:PVC formulation of plastisol
Component |
Mass percent (%) |
PVC paste resin |
27 |
Blending resin |
15 |
Nano-calcium carbonate |
20 |
Dioctyl phthalate (DOP) |
38 |
Table 2:PVC plastipaste performance products performance
Sample |
Thixotropic loop area/(Pa/S) |
Yield value/Pa |
Viscosity/(mPaS) |
Embodiment 1 |
27340.3 |
295 |
4546 |
Embodiment 2 |
20135.0 |
289 |
4646 |
Embodiment 3 |
28432.9 |
198 |
4894 |
Embodiment 4 |
33059.1 |
316 |
5352 |
Embodiment 5 |
28974.1 |
301 |
6317 |
Comparative example 1 |
9673.1 |
87 |
5844 |
Comparative example 2 |
10692.0 |
128 |
4450 |
In upper table, thixotropic loop area is measured for using rotational rheometer, and yield value obtain for carrying out Ben-Hur linear fit to thixotropic loop test first paragraph curve, and viscosity uses the measurement of Brookfield viscosmeter.All samples is tested after all placing 1d.As can be seen from the table, adopt saturated fatty acid and ricinoleate ester sodium sulfate composite to nano-calcium carbonate carry out surface-treatment applications in prepare PVC plastipaste time, the performance of product is all better than single saturated fatty acid or the surface treatment of ricinoleate ester sodium sulfate.
The PVC plastipaste of embodiment 1,2 and comparative example 1 gained is placed 0d, 2d, 5d, 10d, 15d, 20d, 30d, 45d respectively, through measuring the change curve of viscosity as shown in Figure 1.Obtain from detected result, through adopting saturated fatty acid and ricinoleate ester sodium sulfate is composite carries out surface to nano-calcium carbonate, the stability of the PVC plastipaste product of preparation is better, and adopts single saturated fatty acid Treatment Stability poor, and the viscosity of product increases along with the time and increases.