CN103952760A - Preparation method of modified calcium carbonate whisker for papermaking coating - Google Patents
Preparation method of modified calcium carbonate whisker for papermaking coating Download PDFInfo
- Publication number
- CN103952760A CN103952760A CN201410195681.1A CN201410195681A CN103952760A CN 103952760 A CN103952760 A CN 103952760A CN 201410195681 A CN201410195681 A CN 201410195681A CN 103952760 A CN103952760 A CN 103952760A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- whisker
- carbonate whisker
- coating
- preparation
- 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.)
- Pending
Links
Abstract
The invention discloses a preparation method of a modified calcium carbonate whisker for papermaking coating. The method comprises the operation steps of 1) preparing a calcium carbonate whisker suspension by measuring according to the mass of a calcium carbonate whisker; 2) controlling the temperature of the calcium carbonate whisker suspension under a water bath condition, adding a modifier, stirring, and reacting; 3) performing vacuum suction filtration on a product subjected to the treatment, washing with acetone, performing vacuum drying, and grinding and sieving to obtain a modified fine calcium carbonate whisker. The preparation method disclosed by the invention adopts an aluminum-titanium compound coupling agent as the modifier, and performs surface modification on the calcium carbonate whisker; the obtained calcium carbonate whisker is higher in activation grade, lower in oil absorption value and viscosity and greatly-improved in dispersing property. The modified calcium carbonate whisker is used for processing of papermaking coating, and can be used for significantly improving the mechanical property, printing property and optical property of coating paper.
Description
Technical field
The present invention relates to a kind of calcium carbonate crystal whisker that is applied to paper making and cloth coating, specifically a kind of preparation method of the modified calcium carbonate whisker for paper making and cloth coating.
Background technology
Calcium carbonate crystal whisker is as a kind of green material of super quality and competitive price, wide material sources, and production technique is simple, to HUMAN HEALTH, is the advanced composite material strengthening and toughening agent that a kind of mechanical property is superior, and application is had a bright future, and has the very strong market development and is worth.China's limestone resource is abundant, is the main source of preparing calcium carbonate crystal whisker, and along with the intensification day by day of globalization of world economy, resources advantage is changed into economic advantages in an urgent demand China.But calcium carbonate crystal whisker consistency is poor, in medium, be difficult to dispersedly, easily cause boundary defect, greatly restricted the using value of calcium carbonate crystal whisker.
Therefore, be necessary calcium carbonate modifying surface, to improve its surperficial physics-chem characteristic, strengthen the consistency of the matrixes such as itself and organic polymer or resin and the dispersiveness in organic matrix, improve the overall characteristic of matrix material.
Had not yet to see and adopted aluminium titanium composite coupler to calcium carbonate crystal whisker surface modification, with the relevant report that improves whisker surface modification effect and reduce costs.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aluminium titanium composite coupler that adopts and as properties-correcting agent, prepares the preparation method of modified calcium carbonate whisker, make the calcium carbonate crystal whisker degree of activation that obtains higher, oil-absorption(number) and viscosity are lower, dispersing property is very significantly improved, calcium carbonate crystal whisker after modification, for paper making and cloth coating processing, can have been improved to mechanical property, printing performance and the optical property of Coated Paper significantly.
The present invention solves the problems of the technologies described above with following technical scheme:
The preparation method of a kind of modified calcium carbonate whisker for paper making and cloth coating of the present invention, comprises following operation steps:
1. calcium carbonate crystal whisker is mixed with to mass concentration and is 8% suspension, and be placed in 70～85 ℃ of water-baths;
2. by consumption, be to add in above-mentioned suspension after the aluminium titanium composite coupler of calcium carbonate crystal whisker over dry quality 7～9% dissolves with acetone soln, stir and react 60～80min;
3. by the product vacuum filtration after above-mentioned processing, with washing with acetone, vacuum-drying is also ground and is sieved, and obtains tiny calcium carbonate crystal whisker after modification.
Described step 3. in, the vacuum-drying time is 12h, drying temperature is 100 ℃.
Described step 3. in, product is crossed 200 mesh sieves.
Aluminium titanium composite coupler of the present invention is the OL-AT series composite coupler that Shanxi Province chemical research institute develops on aluminate coupling agent and titanate coupling agent basis, and it has had both the feature of titanate ester and aluminate coupling agent.Aluminium titanium composite coupler has two inorganic groups and an organo-functional group, in molecule, a part of group can carry out combination with inorganic materials, another part group can form chemical reaction or electrostatic adhesion with organism, therefore can increase the point of application mutually combining between differing materials, and processing temperature is low, coupling speed is fast, cheap.By to adding the surface modification of the whisker of Paper Coating system, improve the over-all properties of paper, adapt to the needs of the paper-making industry of high speed development, create larger economic worth.
The present invention adopts aluminium titanium composite coupler as properties-correcting agent, and calcium carbonate crystal whisker is carried out to surface modification, and the calcium carbonate crystal whisker degree of activation obtaining is higher, and oil-absorption(number) and viscosity are lower, and dispersing property is very significantly improved.Calcium carbonate crystal whisker after modification, for paper making and cloth coating processing, can improve mechanical property, printing performance and the optical property of Coated Paper significantly.
Degree of activation is one of important indicator of evaluating surface modification effect, and degree of activation is higher, and hydrophobicity is higher, and finishing effect is better.Oil-absorption(number) can reflect the degree of calcium carbonate surface modifying, and oil-absorption(number) is larger, and calcium carbonate is just many at the lubricant that adds absorption in man-hour, and tooling cost is high, and affects organic processing characteristics.Viscosity has reflected the consistency of calcium carbonate and nonpolar organic matter, and viscosity is less, and whisker consistency in organic medium is stronger, and degree of scatter is higher, and modified effect is better.
The measuring method of degree of activation is referring to the chemical industry standard HG/T2567-94 of the People's Republic of China (PRC): in 250mL beaker, add 200mL water, then the modified calcium carbonate whisker that adds 5g, through magnetic stirring apparatus, with 120 turn/min constant speed, stir 5min, static 30min, collect suspension part, at 105 ± 5 ℃, dry to constant weight, weigh, measure degree of activation.
The measuring method reference standard GB-T5211.15-1988 of oil-absorption(number): the calcium carbonate crystal whisker that accurately takes 5g modification, be placed on sheet glass, with drop-burette, drip dioctyl phthalate (DOP), each add-on is no more than 10, drip dioctyl phthalate (DOP) to forming the uniform paste of denseness, just not brokenly do not split, again sticky sticking on flat board, be titration end point, oil-absorption(number) is with volume or the quality representation of the required oil of every 100g product
The measuring method of viscosity: at 25 ℃ by calcium carbonate crystal whisker before and after modification and whiteruss in mass ratio 1:10 mechanical stirring mix, its viscosity of the use U.S. LVDV-2+ of Brookfield company rotary viscosity instrumentation.
Modified crystal whiskers is applied to Paper Coating system, measures the performance of Coated Paper as tensile strength, bursting strength and tearability variation, and printing performance is as surface strength and ink absorption, and optical property is as durability of coating.
Embodiment
Embodiment 1
30g calcium carbonate crystal whisker is placed in to there-necked flask, adds the water of 345ml, take and be made into the suspension that mass concentration is 8%, suspension is placed in to 85 ℃ of heating in water bath and stirs.Respectively 2.1g, 2.4g, 2.7g aluminium titanium composite coupler are dissolved in 10ml acetone soln, are marked as formula 1, formula 2 and formula 3.Coupling agent after dissolving is slowly added in suspension, stir, at 85 ℃ of water bath with thermostatic control reaction 60min, after question response finishes, product vacuum filtration, with washing with acetone, to wash away the coupling agent of residual not complete reaction in the whisker after modification.Vacuum-drying 12h at 100 ℃.Grind 200 mesh sieves, obtained tiny calcium carbonate crystal whisker product after modification.Measure degree of activation, oil-absorption(number) and the viscosity of different ingredients calcium carbonate crystal whisker.As shown in table 1, at properties-correcting agent consumption, be 7～9%, modified crystal whiskers degree of activation is higher, and oil-absorption(number) and viscosity are lower, and surface property changes, and dispersiveness is improved.
Before table 1 modification and with properties-correcting agent consumption, change calcium carbonate crystal whisker degree of activation, oil-absorption(number), viscosity variation
Embodiment 2
30g calcium carbonate crystal whisker is placed in to there-necked flask, adds the water of 345ml, take and be made into the suspension that mass concentration is 8%, suspension is placed in heating in water bath and stirs.2.4g aluminium titanium composite coupler is dissolved in 10ml acetone soln.Coupling agent after dissolving slowly adds in suspension, stirs, respectively at 70 ℃, 80 ℃, 85 ℃ water bath with thermostatic control reaction 60min, obtain filling a prescription 4, the modified product of formula 5 and formula 2, product vacuum filtration, with washing with acetone, to wash away the coupling agent of residual not complete reaction in the whisker after modification.Vacuum-drying 12h at 100 ℃.Grind 200 mesh sieves, obtained tiny calcium carbonate crystal whisker after modification.Measure degree of activation, oil-absorption(number) and the viscosity of different ingredients calcium carbonate crystal whisker.As shown in table 2, at modification temperature, be 70～85 ℃, two kinds of modified crystal whiskers degree of activation improve significantly, and oil-absorption(number) and viscosity significantly reduce.
Before table 2 modification and vary with temperature calcium carbonate crystal whisker degree of activation, oil-absorption(number), viscosity and change
Embodiment 3
30g calcium carbonate crystal whisker is placed in to there-necked flask, adds the water of 345ml, take and be made into the suspension that mass concentration is 8%, suspension is placed in 85 ℃ of heating in water bath and stirs.2.4g aluminium titanium composite coupler is dissolved in 10ml acetone soln.Coupling agent after dissolving slowly adds in suspension, stir, respectively at 85 ℃ of water bath with thermostatic control reaction 60min, 70min and 80min, obtain filling a prescription 2, the modified product of formula 7 and formula 8, product vacuum filtration, with washing with acetone, to wash away the coupling agent of residual not complete reaction in the whisker after modification.Vacuum-drying 12h at 100 ℃.Grind 200 mesh sieves, obtained tiny calcium carbonate crystal whisker.Measure degree of activation, oil-absorption(number) and the viscosity of different ingredients calcium carbonate crystal whisker.As shown in table 3, in modification time, be 60～80min, modified crystal whiskers degree of activation is very high, and oil-absorption(number) and viscosity are lower, and modified effect is remarkable, and the surface property of whisker changes, and dispersiveness is improved.
Before table 3 modification, change with temporal evolution calcium carbonate crystal whisker degree of activation, oil-absorption(number), viscosity
Table 4 body paper and add the ratio of filling out 20% before and after modified calcium carbonate whisker Coated Paper mechanical property detect
Embodiment 4
Calcium carbonate crystal whisker before and after modification adds in paper coating system, makes different ingredients paper coating, application of paints after the coating of paper, test paper tensiometry performance variation.
From table 4, the coating of different ingredients is little on the impact of whiteness and thickness, but tensile index, tear index, burst index and folding endurance are had to considerable influence.Paper after coating is all greatly improved compared with the every mechanical property of body paper.Contrast 2 kinds of different formulation for coating material simultaneously, adding paper tensile index, tear index, burst index and the folding endurance of aluminium titanium modified calcium carbonate whisker is all the paper of modified crystal whiskers higher than containing, because aluminium titanium composite coupler is a kind of material with bifunctional, hydrogen bonded is passed through on the calcium carbonate crystal whisker surface of its inorganic functional group and needle-like, and another part group can form with the negative charge of paper fibre electrostatic interaction, increase the point of application of fiber and whisker, bonding strength between paper fibre is strengthened.In addition, after modification, calcium carbonate crystal whisker agglomeration improves, and coating is evenly distributed, and also makes Coated Paper obtain higher intensity.
Table 5 adds the ratio of filling out 20% modification front and back Coated Paper printing performance and detects
Embodiment 5
Surface strength and the ink absorption of measuring respectively the whisker Coated Paper containing whisker Coated Paper before modification with after containing modification, evaluation detects paper printing characteristic and changes.
From table 5, different ingredients coating is very large on the surface strength impact of paper, adds coupling agent modified whisker surface strength of paper to improve 22.5% compared with modification front surface intensity, modified crystal whiskers add effective printing performance that improves Coated Paper.A little less than the surface strength size of paper has reflected the strong adhesion of coating and paper, this sticking power is mainly by adsorption.Calcium carbonate crystal whisker after modification disperses well in coating and coating, the a large amount of unsaturated bond energy of calcium carbonate crystal whisker particle surface and other components in coating form very strong van der Waals interaction, thereby form coating structure more closely, the surface strength of coating improves.
Ink absorption is determined by the pore texture of paper, and containing the Coated Paper of whisker after modification compared with modification before ink absorption slight reduction, because the median size of calcium carbonate crystal whisker declines after modification, be filled into the average pore that coatingsurface has further reduced coatingsurface, printing ink absorption is declined to some extent.Therefore, after modification, Coated Paper obtains better printability.
Embodiment 6
Probe into the weathering resistance of the whisker Coated Paper containing whisker Coated Paper before modification with after containing modification, evaluate detection paper optical property and change.
The coating whiteness changing value of paper before and after table 6 body paper and modification
From table 6, after the ultra violet lamp after 12h, the whiteness of Coated Paper is all on a declining curve, but body paper is different with the coating whiteness decline before and after modification, and the paper coating whiteness that contains calcium carbonate crystal whisker declines still less, and the decline of body paper whiteness is very fast.Hence one can see that, and the whisker component in coating can effectively absorb ultraviolet ray, slows down the brightness reversion speed of coating.Containing the paper coating whiteness of whisker after modification, decline before compared with modification slower, after modification, Coated Paper obtains better optics adaptive.
Claims (3)
1. for a preparation method for the modified calcium carbonate whisker of paper making and cloth coating, it is characterized in that, comprise following operation steps:
1. calcium carbonate crystal whisker is mixed with to mass concentration and is 8% suspension, and be placed in 70～85 ℃ of water-baths;
2. by consumption, be to add in above-mentioned suspension after the aluminium titanium composite coupler of calcium carbonate crystal whisker over dry quality 7～9% dissolves with acetone soln, stirring reaction 60～80min;
3. by the product vacuum filtration after above-mentioned processing, with washing with acetone, vacuum-drying is also ground and is sieved, and obtains tiny calcium carbonate crystal whisker after modification.
2. according to claim 1 for the preparation method of the modified calcium carbonate whisker of paper making and cloth coating, it is characterized in that, described step 3. in, the vacuum-drying time is 12h, drying temperature is 100 ℃.
3. according to claim 1 for the preparation method of the modified calcium carbonate whisker of paper making and cloth coating, it is characterized in that, described step 3. in, product is crossed 200 mesh sieves.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195681.1A CN103952760A (en) | 2014-05-09 | 2014-05-09 | Preparation method of modified calcium carbonate whisker for papermaking coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195681.1A CN103952760A (en) | 2014-05-09 | 2014-05-09 | Preparation method of modified calcium carbonate whisker for papermaking coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103952760A true CN103952760A (en) | 2014-07-30 |
Family
ID=51330101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410195681.1A Pending CN103952760A (en) | 2014-05-09 | 2014-05-09 | Preparation method of modified calcium carbonate whisker for papermaking coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103952760A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592839A (en) * | 2014-12-30 | 2015-05-06 | 成都新柯力化工科技有限公司 | Special coating liquid for stone paper coating and preparation method thereof |
| CN110075555A (en) * | 2019-04-19 | 2019-08-02 | 贺州学院 | A kind of method of modified heavy calcium carbonate microwave intermittently drying |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2139606A (en) * | 1983-05-09 | 1984-11-14 | Pluss Stauffer Ag | Calcium carbonate |
| CN1556154A (en) * | 2004-01-08 | 2004-12-22 | 上海交通大学 | Method of inorganic whisker surface treatment |
| CN101967309A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing active calcium carbonate |
| CN102337703A (en) * | 2011-10-08 | 2012-02-01 | 长沙理工大学 | Method for preparing modified calcium sulfate crystal whisker papermaking filler |
| CN103408823A (en) * | 2013-07-18 | 2013-11-27 | 华南师范大学 | Highly-calcium-carbonate-filled highly-resilient soft foamed polyethylene material and preparation method thereof |
-
2014
- 2014-05-09 CN CN201410195681.1A patent/CN103952760A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2139606A (en) * | 1983-05-09 | 1984-11-14 | Pluss Stauffer Ag | Calcium carbonate |
| CN1556154A (en) * | 2004-01-08 | 2004-12-22 | 上海交通大学 | Method of inorganic whisker surface treatment |
| CN101967309A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing active calcium carbonate |
| CN102337703A (en) * | 2011-10-08 | 2012-02-01 | 长沙理工大学 | Method for preparing modified calcium sulfate crystal whisker papermaking filler |
| CN103408823A (en) * | 2013-07-18 | 2013-11-27 | 华南师范大学 | Highly-calcium-carbonate-filled highly-resilient soft foamed polyethylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李运涛等: "铝钛偶联剂的合成及其对碳酸钙表面性能的影响", 《化工进展》 * |
| 王丽丽: "铝钛偶联剂的合成及其应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592839A (en) * | 2014-12-30 | 2015-05-06 | 成都新柯力化工科技有限公司 | Special coating liquid for stone paper coating and preparation method thereof |
| CN104592839B (en) * | 2014-12-30 | 2017-01-25 | 成都新柯力化工科技有限公司 | Special coating liquid for stone paper coating and preparation method thereof |
| CN110075555A (en) * | 2019-04-19 | 2019-08-02 | 贺州学院 | A kind of method of modified heavy calcium carbonate microwave intermittently drying |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102206395B (en) | Preparation method and application of nano-montmorillonite/polyacrylate composite material | |
| CN102702795B (en) | Preparation method of special nano calcium carbonate for polyurethane adhesives | |
| CN101591414B (en) | Organic montmorillonite/acrylic acid size and preparation method thereof | |
| WO2006048280A1 (en) | Cellulose-containing filling material for paper, tissue, or cardboard products, method for the production thereof, paper, tissue, or cardboard product containing such a filling material, or dry mixture used therefor | |
| CN102249530B (en) | Wollastonite fiber with large length-diameter ratio and preparation method thereof | |
| Xu et al. | Dialdehyde modified cellulose nanofibers enhanced the physical properties of decorative paper impregnated by aldehyde-free adhesive | |
| Nandiyanto et al. | Domestic waste (eggshells and banana peels particles) as sustainable and renewable resources for improving resin-based brakepad performance: Bibliometric literature review, techno-economic analysis, dual-sized reinforcing experiments, to comparison... | |
| CN107524043B (en) | A kind of enhancing paper base and the preparation method and application thereof of stacking assembling | |
| CN106832425A (en) | High performance Graphene composite nano fiber element and preparation method thereof, application | |
| CN110670407B (en) | Pulp molding product modifying additive, preparation method and application | |
| CN104231676A (en) | Modified attapulgite packing and preparation method thereof | |
| Zhu et al. | Effect of amphoteric grafting branch on the adhesion of starch to textile fibers | |
| CN108503892A (en) | A kind of sericite composite material and preparation method in plastic, transparent masterbatch | |
| CN102704338A (en) | Sizing reinforcing agent and preparation process and application thereof | |
| Shen et al. | Preparation and characterization of oxidized sesbania gum and evaluation of its warp sizing performance for fine cotton yarns | |
| CN105985601A (en) | Polymethyl methacrylate-carboxylated carbon nanotube composite based on charge conjugation synergism and preparation method thereof | |
| CN103952760A (en) | Preparation method of modified calcium carbonate whisker for papermaking coating | |
| CN102719208B (en) | High polymer binder and preparation method thereof | |
| CN105061774A (en) | Papermaking enhancer and preparation method thereof | |
| CN104194056A (en) | Anti-ultraviolet modified attapulgite and preparation method thereof | |
| CN107385984B (en) | A kind of waterproof paper and preparation method thereof | |
| CN105175800B (en) | A kind of imitative mineral bridges high mechanical properties film and preparation method thereof | |
| CN103145139A (en) | Viscosity reducer for improving viscosity of kaolin, and its preparation method | |
| CN114230867A (en) | High-wet-strength cellulose composite material and preparation method thereof | |
| CN105220492A (en) | One becomes more meticulous, and nano modified acrylic class is non-knits by slurry and manufacture method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140730 |
|
| RJ01 | Rejection of invention patent application after publication |