CN104863010A - Modification method for improving anti-shear ability of modified filler surface compound - Google Patents
Modification method for improving anti-shear ability of modified filler surface compound Download PDFInfo
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- CN104863010A CN104863010A CN201510271953.6A CN201510271953A CN104863010A CN 104863010 A CN104863010 A CN 104863010A CN 201510271953 A CN201510271953 A CN 201510271953A CN 104863010 A CN104863010 A CN 104863010A
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Abstract
The invention discloses a modification method for improving the anti-shear ability of a modified filler surface compound. The method comprises the following steps: adding industrial starch into water, then carrying out gelatinization treatment to obtain a mixture solution; adding a fatty acid type hydrophobic modifying agent into the mixture solution to carry out hydrophobic treatment to the mixture solution; adding a suspended filler to be mixed with the solution; cooling the mixture solution; adding a phosphate crosslinking agent solution, so as to conduct crosslinking treatment on the mixture. Compared with the existing technology, the modification technology related to the modification method disclosed by the invention greatly improves the anti-shear ability of the modified filler surface compound, and greatly provides the practicability for the modified filler in the paper-making industry.
Description
Technical field
The present invention relates to field of papermaking, be specifically related to a kind of method of modifying improving the anti-shear ability of modified filler surface complex.
Background technology
In modern paper industry, filler has become the second largest paper making raw material that consumption is only second to fiber.Filler can improve brightness and the opacity of paper, improves smoothness and the evenness of paper, increases the flexibility of paper simultaneously, reduces hygroscopicity and the deformation extent of paper, the most important thing is the production cost effectively reducing paper.But excessively add when filling out, because filler hinders interfibrous combination, paper strength character is declined, this is because customary filler, self property there is larger difference with the main component fiber of paper, when filler joins in paper, filler is not only difficult to the combination stronger with processbearing astrocyte, also can because being filled in the combination between fiber between cut staple.In order to reduce the negative effect adding and fill out and cause paper strength, usually filler is necessarily processed.Wherein, carrying out organically-modified to filler is a most popular at present research field, and such as, the preparation of cladded type GCC, refers at the coated one deck organic high molecular compound of inorganic filler surface.Macromolecule crosslink agent is sprayed in powder in liquid form, can be coated on powder surface, define the charged macromolecule layer of one deck in kneader through stirring, grinding, dry process by electrostatic and adhesive attraction.Wherein polymer completes the coating function at powder surface in two ways: one first monomer is adsorbed on powder surface, causes its polymerization, thus form very thin polymer film on surface.Another kind adds in powder after polymer dissolution is in appropriate solvent, excludes solvent formed coated when Polymer adsorption is on the surface of powder.And the organic high molecular compound adopted at present mainly contains starch and derivative, cellulose and its derivates, polyacrylamide and shitosan etc.
At present, research about filler starch conversion has many documents, but its research just provides the effect of final modified filler mostly, and seldom have and specialize in for the performance of modified filler own, this technical study anti-shear ability of modified filler, in the process of papermaking, shearing force is the important parameter affecting filler gathering situation, and the size of modified filler anti-shear ability directly affects the technical process of follow-up papermaking.This research have studied the process conditions obtaining the good anti-shear ability of modified filler surface complex, thus solves very well or relax paper strength and the contradictory relation adding the amount of filling out, and can bring very large practical value.
Summary of the invention
The object of the present invention is to provide a kind of method of modifying improving the anti-shear ability of modified filler surface complex, modified filler is prepared by this modified technique, greatly can improve anti-shear ability, the particle diameter of the modified filler assembled is in the process being subject to shear action, and surface complex is without obviously coming off.
Technical solution of the present invention is as follows.
Improve a method of modifying for the anti-shear ability of modified filler surface complex, comprise the steps:
1) industrial starch is added to the water, carries out gelatinization process afterwards, obtain mixture solution;
2) add fatty acid hydrophobically modified agent solution and hydrophobic treatments is carried out to mixture solution;
3) filler adding suspended state mixes;
4) cooling process is carried out to mixture solution;
5) add phosphoric acid salt cross-linking agent solution and crosslinking Treatment is carried out to mixture.
In said method, described industrial starch is industrial starch, to comprise in cornstarch, technical grade farina, technical grade tapioca or technical grade sweet potato starch more than one.
In said method, the quality of industrial starch is 5%-30% with packing quality ratio.
In said method, step 1) in, the concrete steps of described gelatinization process are: first to industrial starch cold compress 5-30min in cold water, carry out hyperthermic treatment again, rise to 70-95 DEG C, and gelatinization time is 10-150min at 70-95 DEG C, reaction mixing speed is 100-700rpm.
In said method, the addition of described fatty acid hydrophobically modified agent solution meets: the solute fatty acid hydrophobic modifier of fatty acid hydrophobically modified agent solution is 0.5%-8.5% with packing quality ratio.
In said method, the solute fatty acid hydrophobic modifier in described fatty acid hydrophobically modified agent solution is higher fatty acid salt, comprises odium stearate, sodium palmitate, enuatrol or linoleic acid sodium.
In said method, step 2) in, the reaction time of described hydrophobic treatments is 10-40min, and mixing speed is 200-500rpm.
In said method, step 3) in, described filler is papermaking filler, comprises kaolin, and calcium carbonate or talcum powder, add deionized water in filler.
In said method, step 4) in, describedly to mixture solution carry out the lowering the temperature concrete steps of process be: be cooled to 30-90 DEG C, reaction mixing speed is 100-700rpm, and the mode of described cooling is Temperature fall.
10, the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, it is characterized in that: step 4) in, the described phosphoric acid salt cross-linking agent solution that adds to the concrete steps that mixture carries out crosslinking Treatment is: after being cooled to design temperature, add mass fraction be 0.5%-3% phosphoric acid salt cross-linking agent solution proceed crosslinking Treatment, reaction 20-40min terminate; Described phosphoric acid salt crosslinking agent is sodium trimetaphosphate or calgon.
The present invention adopts higher fatty acid salt to be hydrophobically modified modifier, its dominant mechanism is and gelatinization state industrial starch generation recombination reaction, make industrial starch obtain certain hydrophobicity, reduce the dissolution rate of starch in water, use higher fatty acid salt odium stearate.
The present invention adopts industrial starch first to carry out the mode of gelatinization process.
The cooling method that the present invention adopts is Temperature fall, is conducive to the industrial starch that is dissolved in the water and odium stearate is separated out from water, reduces the solubility of starch in water, thus is well attached to calcium carbonate surface.
The present invention adopts crosslinking agent calgon, and its mechanism is that the water-soluble low molecular weight industrial starch generation cross-linking reaction cut off because of shearing force is separated out from water; Meanwhile, the cross-linking reaction between industrial starch is also conducive to the industrial starch be not attached on calcium carbonate and is attached on calcium carbonate.The cross-linking reaction of sodium trimetaphosphate is divided into two kinds: physical crosslinking and chemical crosslinking.Physical crosslinking: on sodium trimetaphosphate, the hydrogen bond of electronegative group and starch molecular chain is had an effect, makes the effect of hydrogen bond reduce.Chemical crosslinking: because the electronegativity of oxygen is greater than phosphorus, so phosphorus is with certain electropositive, the oxygen effect on the hydroxyl of such phosphorus and glucose unit, connects glucose unit.The present invention substantially increases the anti-shear ability of modified filler surface complex in industrial starch modification GCC process.
Compared with prior art, advantage of the present invention is:
Modification GCC, respectively in the first two hour that shear rate is 1000rpm and 2000rpm, its modified filler particle diameter along with shear action continue do not change, now coated fine of modification GCC, anti-shear ability is strong.And when shear rate is 3000rpm, the particle diameter of modification GCC occurs obviously increasing after slightly reducing.After gained modification GCC is manufactured paper with pulp into paper, under identical ash content condition, the GCC through starch conversion is more much smaller than the negative effect of unmodified GCC to the intensity of paper.And all anti-raw certain change of itself character such as whiteness, opacity, granularity and distribution thereof, and affect the result of use of paper.This technique significantly improve add fill out time faced by paper strength decline problem, improve the anti-shear ability of modified filler composite surface, starch coated GCC effect is fine.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Detailed description of the invention
Do specifically to describe in detail further to the present invention below in conjunction with specific embodiment, but embodiments of the present invention are not limited thereto, for the technological parameter do not indicated especially, can refer to routine techniques and carry out.
Embodiment 1
According to the flow process shown in Fig. 1.First, technical grade cornstarch 2g is mixed with the suspension of 3% (mass percent), cold compress 10min, then heat up gradually under 200rpm mixing speed and be heated to 95 DEG C, at 95 DEG C of insulation gelatinization 50min, then 4.0% sodium stearate solution (quality relative to GCC) is added, after reaction 30min, add the GCC (powdered whiting) of suspended state, GCC mass concentration is that 20% (mass ratio of starch consumption and filler is 1:5, the amount of odium stearate and the mass ratio of GCC are 1:25), Temperature fall to 60 DEG C, do not add calgon, continue reaction 30min, namely modified calcium carbonate is obtained.
Embodiment 2
First, technical grade cornstarch 2g is mixed with the suspension of 3%, cold compress 10min, then heat up gradually under 200rpm mixing speed and be heated to 95 DEG C, at 95 DEG C of insulation gelatinization 50min, then 4.0% sodium stearate solution (quality relative to GCC) is added, after reaction 30min, add the GCC (powdered whiting) of suspended state, GCC mass concentration is that 20% (mass ratio of starch consumption and filler is 1:5, the amount of odium stearate and the mass ratio of GCC are 1:25), Temperature fall to 60 DEG C, add the calgon that mass concentration is 3% (quality relative to GCC), continue reaction 30min, namely modified calcium carbonate is obtained.
Embodiment 3
First, technical grade cornstarch 2g is mixed with the suspension of 3%, cold compress 10min, then heat up gradually under 200rpm mixing speed and be heated to 95 DEG C, at 95 DEG C of insulation gelatinization 50min, then 4.0% sodium stearate solution (quality relative to GCC) is added, after reaction 30min, add the GCC (powdered whiting) of suspended state, GCC mass concentration is that 20% (mass ratio of starch consumption and filler is 1:5, the amount of odium stearate and the mass ratio of GCC are 1:25), Temperature fall to 50 DEG C, add the calgon that mass concentration is 3% (quality relative to GCC), continue reaction 30min, namely modified calcium carbonate is obtained.
The modified calcium carbonate that above embodiment obtains is spent deionized water, not coated starch in removing suspension, then to be put in baking oven 105 DEG C and to be dried to over dry, then carry out the measurement of modification GCC particle diameter, the degree of change of size reflects the power of anti-shear ability.
Result is as follows:
In the consumption situation of constant precipitation temperature and calgon, in the first two hour that shear rate is 1000rpm and 2000rpm, the particle diameter of modification GCC along with shear action continue do not change, coated fine of now modification GCC is described, anti-shear ability is strong.And when shearing speed/when spending for 3000rpm, when shearing 130min, obviously increasing appears after just slightly reducing in modification GCC particle diameter, what this technique was described improves anti-shear ability.The comparison content of table 1 modification GCC and unmodified GCC is as follows:
The granularity of table 1 modification GCC and distribution thereof
Note: unmodified GCC and the ratio of modification GCC in table are: higher value/smaller value
As can be known from Table 1, the specific area of modification GCC is about 1/6 of the specific area of unmodified GCC, this is because coating modification makes modification GCC have larger particle diameter, thus reduce its specific area, this to be conducive to reducing in paper-making process other chemical reagent as the use of sizing agent.In addition, the span of modification GCC and uniformity are about 1/17 and 1/11 of unmodified GCC respectively, and this illustrates that this modifying process effectively improves the domain size distribution of modification GCC, thus serve conclusive effect to raising anti-shear ability.
By the modification GCC of case study on implementation 1 and 2 gained, under shear action, record the particle size under the different shear action time, result is as shown in table 2:
Table 2
As seen from the above table, along with the increase of shear action time, the particle diameter that with the addition of the modification GCC of calgon first reduces rear increase, and do not use the particle diameter of the modification GCC of calgon to reduce always.The anti-shear ability of modified filler surface complex is strong.
By the modification GCC of case study on implementation 2 and 3 gained, under shear action, record the particle size under the different shear action time, result is as shown in table 3:
Table 3
Be 50 DEG C of obtained modification GCC at precipitation temperature, in shear time 60min, change of size 6.3 μm, and be 60 DEG C of obtained modification GCC at precipitation temperature, within the same time, change of size 4.6 μm.Visible precipitate temperature is that the anti-shear ability of 50 DEG C of obtained modification GCC surface complexs is compared with being 60 DEG C of obtained modification GCC higher than precipitation temperature.
After the modification GCC that this technique is obtained is manufactured paper with pulp into, it measures the physical property of paper, find content of ashes be between 20%-35% in, modification GCC adds the tensile index filling out paper and adds than unmodified GCC the tensile index filling out paper and at least improve 25 percentage points, can find that modification GCC adds the burst index filling out paper and adds than unmodified GCC the burst index filling out paper and at least improve 30 percentage points.Modification GCC adds the tear index filling out paper, and to add than unmodified GCC the tear index filling out paper at least high 45 percentage points.Illustrate that the anti-shear ability of modified filler surface complex is good, decrease the negative effect adding and fill out and paper strength is caused.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (10)
1. improve a method of modifying for the anti-shear ability of modified filler surface complex, it is characterized in that, comprise the steps:
1) industrial starch is added to the water, carries out gelatinization process afterwards, obtain mixture solution;
2) add fatty acid hydrophobically modified agent solution and hydrophobic treatments is carried out to mixture solution;
3) filler adding suspended state mixes;
4) cooling process is carried out to mixture solution;
5) add phosphoric acid salt cross-linking agent solution and crosslinking Treatment is carried out to mixture.
2. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, is characterized in that:
Described industrial starch is industrial starch, to comprise in cornstarch, technical grade farina, technical grade tapioca or technical grade sweet potato starch more than one.
3. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, is characterized in that: the quality of industrial starch is 5%-30% with packing quality ratio.
4. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, it is characterized in that: in step 1), the concrete steps of described gelatinization process are: first to industrial starch cold compress 5-30min in cold water, carry out hyperthermic treatment again, rise to 70-95 DEG C, and gelatinization time is 10-150min at 70-95 DEG C, reaction mixing speed is 100-700rpm.
5. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, is characterized in that: the addition of described fatty acid hydrophobically modified agent solution meets: the solute fatty acid hydrophobic modifier of fatty acid hydrophobically modified agent solution is 0.5%-8.5% with packing quality ratio.
6. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 5, it is characterized in that: the solute fatty acid hydrophobic modifier in described fatty acid hydrophobically modified agent solution is higher fatty acid salt, comprises odium stearate, sodium palmitate, enuatrol or linoleic acid sodium.
7. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, is characterized in that: step 2) in, the reaction time of described hydrophobic treatments is 10-40min, and mixing speed is 200-500rpm.
8. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, is characterized in that:
In step 3), described filler is papermaking filler, comprises kaolin, and calcium carbonate or talcum powder, add deionized water in filler.
9. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, it is characterized in that: in step 4), described to mixture solution carry out lower the temperature process concrete steps be: be cooled to 30-90 DEG C, reaction mixing speed is 100-700rpm, and the mode of described cooling is Temperature fall.
10. the method for modifying of the anti-shear ability of raising modified filler surface complex according to claim 1, it is characterized in that: in step 4), the described phosphoric acid salt cross-linking agent solution that adds to the concrete steps that mixture carries out crosslinking Treatment is: after being cooled to design temperature, add mass fraction be 0.5%-3% phosphoric acid salt cross-linking agent solution proceed crosslinking Treatment, reaction 20-40min terminate; Described phosphoric acid salt crosslinking agent is sodium trimetaphosphate or calgon.
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Cited By (6)
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| CN106368056A (en) * | 2016-08-26 | 2017-02-01 | 吴肖颜 | Calcium carbonate used for papermaking filler and preparation method thereof |
| CN106590058A (en) * | 2016-11-30 | 2017-04-26 | 华南理工大学 | Calcium carbonate-starch-based papermaking filler and semi-drying preparation process thereof |
| CN106638124A (en) * | 2016-12-19 | 2017-05-10 | 华南理工大学 | Modification method for improving ash content of paper and paper strength during high concentration filling process in starch modification |
| CN106968130A (en) * | 2017-03-30 | 2017-07-21 | 天长市天达纸箱纸品厂 | A kind of preparation method of corrugated paper Cypres |
| CN109266044A (en) * | 2018-11-14 | 2019-01-25 | 陶伟珍 | A kind of preparation method of rubber modification infusorial earth filler |
| CN109679378A (en) * | 2018-12-29 | 2019-04-26 | 东升新材料（山东）有限公司 | A kind of starch coating modification calcium carbonate and preparation method thereof |
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2015
- 2015-05-23 CN CN201510271953.6A patent/CN104863010A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106368056A (en) * | 2016-08-26 | 2017-02-01 | 吴肖颜 | Calcium carbonate used for papermaking filler and preparation method thereof |
| CN106590058A (en) * | 2016-11-30 | 2017-04-26 | 华南理工大学 | Calcium carbonate-starch-based papermaking filler and semi-drying preparation process thereof |
| CN106638124A (en) * | 2016-12-19 | 2017-05-10 | 华南理工大学 | Modification method for improving ash content of paper and paper strength during high concentration filling process in starch modification |
| CN106638124B (en) * | 2016-12-19 | 2019-04-09 | 华南理工大学 | A kind of method of modifying improving ash content of paper and paper strength during starch conversion high concentration filler |
| CN106968130A (en) * | 2017-03-30 | 2017-07-21 | 天长市天达纸箱纸品厂 | A kind of preparation method of corrugated paper Cypres |
| CN106968130B (en) * | 2017-03-30 | 2019-03-19 | 天长市天达纸箱纸品厂 | A kind of preparation method of corrugated paper Cypres |
| CN109266044A (en) * | 2018-11-14 | 2019-01-25 | 陶伟珍 | A kind of preparation method of rubber modification infusorial earth filler |
| CN109679378A (en) * | 2018-12-29 | 2019-04-26 | 东升新材料（山东）有限公司 | A kind of starch coating modification calcium carbonate and preparation method thereof |
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