CN102220728B - High-performance sizing agent emulsion and preparation method and application thereof - Google Patents
High-performance sizing agent emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance sizing agent emulsion and a preparation method and an application thereof, and the preparation method comprises the following steps: mixing a cationic polymer and water, adding a molten alkyl ketene dimmer, stirring for homogenization to obtain the high-performance sizing agent emulsion, wherein the cationic polymer is prepared by allowing a cationic monomer, chitosan, hydrogen peroxide, silane and sulfuric acid to react under the action of an initiator. The high-performance sizing agent emulsion of the invention is a high-performance environment-friendly product which meets requirements of papermaking coatings. The product is applicable to the internal sizing of paper, and can significantly improve the hydrophobicity of paper, and decrease the Cobb value.
Description
Technical field
The present invention relates to a kind of sizing agent emulsion, be applied to the plasm-glue-blending in the paper production process.
Background technology
Along with the development of neutral and alkali paper technology,, have characteristics such as applying glue efficient is high, consumption is few and in papermaking, be widely used as a kind of neutral and alkali sizing agent of response type.The tradition sizing agent emulsion uses cationic starch as emulsifying agent and stabilizing agent, but the retention of this emulsion on fiber is lower, and slower with the reaction of fiber, the applying glue curing time is long.In recent years; Use along with coated broke, deinked waste paper, high yield pulp; The raising of paper machine white water circulation degree of closure and the use of other paper making additives make the aggregate concentration of the interfering anionic impurity of wet end of machine increasingly high, and be increasing to the harm of wet end of machine operation.For better solving anionic impurity to the problem that applying glue brought, especially improve the effect of sizing agent neutral and alkali applying glue, should adopt the higher polymer of charge density to replace cationic starch that anionic impurity is caught.Shitosan is a kind of natural polymer that self is cationic, has similar in appearance to cellulosic structure, and it is different that difference is the group that is connected on the two C2 atom; On this position, what fibre bundle linked is a hydroxyl, and the shitosan link is amino or acylamino-.
Chinese patent CN200710150369.0 discloses the method that a kind of cationic polymer emulsification sizing agent that adopts the natural polymer glycerol polymerization obtains sizing agent emulsion, the sizing agent emulsion applying glue slaking rapid speed that obtains, but sizing agent large usage quantity.
Summary of the invention
The objective of the invention is to propose a kind of high-performance sizing agent emulsion, overcoming the defective of prior art.
The preparation method of described high-performance sizing agent emulsion comprises the steps:
Cationic polymer and water are mixed, and at 70～75 ℃, mixing speed is 8000～10000rpm/min; Add the alkyl ketene dimer (being called for short AKD wax) of fusion, mixing time is 10～15 minutes, homogeneous under 10～15Mpa condition; It is the availability sizing agent emulsion; 15～25%, 25 ℃ of viscosity of weight solid content are intact to be 5～30mPa.s, and pH is 3～5;
Said cationic polymer obtains with cationic monomer, shitosan, hydrogen peroxide solution, silane and sulfuric acid prepared in reaction under action of evocating.
Each ingredients weight parts is:
100 parts in AKD wax
5～25 parts of cationic polymers
300～590 parts in water.
The preparation method of said cationic polymer comprises the steps:
(a) under 60～70 ℃, hydrogen peroxide solution is added the mixture of shitosan and water, be incubated 1～3 hour, using sulfuric acid adjustment pH is 3～5;
(b) be warming up to 70～90 ℃ again, with the product of the initiator solution step (a) of gross weight 20～30%, insulation
5～10 minutes; Drip the initiator solution of cationic monomer and surplus more simultaneously, 1～3 hour dropping time, then drip silane again; The dropping time is 5～15 minutes, and 70～90 ℃ are incubated 0.5～1 hour, adds the entry dilution; The adjustment solid content; Obtain cationic polymer, the weight solid content is 20～25%, and weight average molecular weight is 10000～100000g/mol;
The weight portion of each component is:
Described cationic monomer is selected from least a in dimethyl diallyl ammonium chloride or the methacrylic acid acyl-oxygen ethyl-trimethyl salmiac;
Described silane is selected from least a in vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane or the VTES;
Described initator is selected from least a in potassium peroxydisulfate, sodium peroxydisulfate or the ammonium persulfate;
Described sizing agent emulsion is mainly used in the plasm-glue-blending of paper.
The inventor finds; The cationic polymer of grafting cationic monomer, the suitable molecular weight gained of adjustment on shitosan; Can use as the sizing agent emulsifying agent; Can obviously improve the application performance of sizing agent emulsion; This possibly be owing to have a large amount of amidos and a large amount of cationic monomer of grafting on the chitosan molecule amount, under acid condition, is cationic and improves the cationic of whole sizing agent emulsion system, when being applied to plasm-glue-blending, can increase sizing agent and fiber bonding point and improves application performance.The inventor finds; Unexpectedly; In system, add the application performance that a spot of silane can improve sizing agent emulsion, this maybe since silane can with the hydroxyl reaction on the shitosan, the hydrophilic hydroxyl of part is by end-blocking; End-blocking combines with the hydroxyl reaction of fiber easily again and improves the hydrophobicity of paper, reduction Cobb value when plasm-glue-blending.
High-performance sizing agent emulsion of the present invention is a kind of product that can satisfy papermaking paint with high-performance, environmental protection.This product is being applied to the plasm-glue-blending of paper, can obviously improve the hydrophobicity of paper, reduces the Cobb value.
The specific embodiment
Among the embodiment, the chemical name of said AKD wax is an alkyl ketene dimer, can adopt the product of Shanghai dongsheng New Materials Co., Ltd;
Embodiment 1
Synthesizing of cationic polymer:
A) the 0.3g potassium peroxydisulfate is dissolved in the 10g deionized water dissolving and becomes initiator solution, subsequent use;
B) 100g shitosan, 300g deionized water are added in the 1000ml four-hole boiling flask, dissolving is warming up to 60 ℃;
C) under 60 ℃ of situation, the 1g hydrogen peroxide solution is added in the four-hole boiling flask, 60 ℃ are incubated 1 hour; With 1g sulfuric acid adjustment pH=3.02.
D) be warming up to 70 ℃ again, the 2.06g initiator solution is added rapidly in the four-hole boiling flask, 70 ℃ are incubated 10 minutes; Drip the initiator solution of 10g dimethyl diallyl ammonium chloride and surplus simultaneously, 1 hour dropping time; Then drip 0.1g vinyl silane triisopropoxide, 15 minutes dropping time again.
E) 70 ℃ are incubated 1 hour; Add the 130.1g deionized water; Be cooled to 25 ℃ of filtrations; Obtain cationic polymer: the weight solid content is 20.2wt%, and molecular weight is 99850g/mol (the multi-angle dynamic laser light scattering molecular weight apparatus that uses U.S. Wyatt Technology Corp company to produce is measured).
The preparation of high-performance sizing agent emulsion:
1) with 100gAKD wax (Shanghai dongsheng New Materials Co., Ltd) 70 ℃ of fusions, subsequent use;
2) 5g cationic polymer (embodiment 1 scheme makes), 303g deionized water are mixed, under agitation be warming up to 65 ℃, improve mixing speed to 10000rpm/min, stir the sizing agent wax liquid that adds fusion down, mixing time is 5 minutes.Homogeneous once under 65 ℃, 10Mpa condition.
3) be cooled to 25 ℃ rapidly, 100 eye mesh screens filter discharging.The sizing agent emulsion of gained, weight solid content 25.1wt%, viscosity 28.5mPa.s (NDJ-1 rotary viscosity design determining), pH=3.08 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 2
Synthesizing of cationic polymer:
A) the 3g sodium peroxydisulfate is dissolved in the 10g deionized water dissolving and becomes initiator solution.Subsequent use;
B) 100g shitosan, 300g deionized water are added in the 1000ml four-hole boiling flask, dissolving is warming up to 70 ℃;
C) under 70 ℃ of situation, the 5g hydrogen peroxide solution is added in the four-hole boiling flask, 70 ℃ are incubated 3 hours; With 0.1g sulfuric acid adjustment pH=4.91.
D) be warming up to 90 ℃ again, the 3.9g initiator solution is added rapidly in the four-hole boiling flask, 90 ℃ are incubated 5 minutes; Drip the initiator solution of 30g methacrylic acid acyl-oxygen ethyl-trimethyl salmiac and surplus simultaneously, 3 hours dropping time; Then drip 1g γ-methacryloxypropyl trimethoxy silane, 5 minutes dropping time again.
E) 90 ℃ are incubated 0.5 hour; Add the 92.08g deionized water; Be cooled to 25 ℃ of filtrations; Obtain cationic polymer: the weight solid content is 25.05wt%, and molecular weight is 10025g/mol (the multi-angle dynamic laser light scattering molecular weight apparatus that uses U.S. Wyatt Technology Corp company to produce is measured).
The preparation of high-performance sizing agent emulsion:
1) with 100gAKD wax (Shanghai dongsheng New Materials Co., Ltd) 70 ℃ of fusions, subsequent use;
2) 25g cationic polymer (embodiment 2 schemes make), 583.3g deionized water are mixed, under agitation be warming up to 75 ℃, improve mixing speed to 8000rpm/min, stir the sizing agent wax liquid that adds fusion down, mixing time is 15 minutes.Homogeneous once under 75 ℃, 15Mpa condition.
3) be cooled to 25 ℃ rapidly, 100 eye mesh screens filter discharging.The sizing agent emulsion of gained, weight solid content 14.96wt%, viscosity 8.3mPa.s (NDJ-1 rotary viscosity design determining), pH=4.89 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 3
Synthesizing of cationic polymer:
A) the 2g ammonium persulfate is dissolved in the 10g deionized water dissolving and becomes initiator solution.Subsequent use;
B) 100g shitosan, 300g deionized water are added in the 1000ml four-hole boiling flask, dissolving is warming up to 65 ℃;
C) under 65 ℃ of situation, the 3g hydrogen peroxide solution is added in the four-hole boiling flask, 65 ℃ are incubated 2 hours; With 0.5g sulfuric acid adjustment pH=4.12.
D) be warming up to 80 ℃ again, the 3g initiator solution is added rapidly in the four-hole boiling flask, 80 ℃ are incubated 8 minutes; Drip the initiator solution of 20g methacrylic acid acyl-oxygen ethyl-trimethyl salmiac and surplus simultaneously, 2 hours dropping time; Then drip 0.5g VTES, 10 minutes dropping time again.
E) 80 ℃ are incubated 0.7 hour; Add the 108.67g deionized water; Be cooled to 25 ℃ of filtrations; Obtain cationic polymer: the weight solid content is 22.58wt%, and molecular weight is 50125g/mol (the multi-angle dynamic laser light scattering molecular weight apparatus that uses U.S. Wyatt Technology Corp company to produce is measured).
The preparation of high-performance sizing agent emulsion:
1) with 100gAKD wax (Shanghai dongsheng New Materials Co., Ltd) 70 ℃ of fusions, subsequent use;
2) 15g cationic polymer (embodiment 3 schemes make), 401.9g deionized water are mixed, under agitation be warming up to 70 ℃, improve mixing speed to 9000rpm/min, stir the sizing agent wax liquid that adds fusion down, mixing time is 10 minutes.Homogeneous once under 70 ℃, 13Mpa condition.
3) be cooled to 25 ℃ rapidly, 100 eye mesh screens filter discharging.The sizing agent emulsion of gained, weight solid content 20.15wt%, viscosity 12.8mPa.s (NDJ-1 rotary viscosity design determining), pH=3.87 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 4
Synthesizing of cationic polymer:
A) the 1g ammonium persulfate is dissolved in the 10g deionized water dissolving and becomes initiator solution.Subsequent use;
B) 100g shitosan, 300g deionized water are added in the 1000ml four-hole boiling flask, dissolving is warming up to 63 ℃;
C) under 63 ℃ of situation, the 2g hydrogen peroxide solution is added in the four-hole boiling flask, 63 ℃ are incubated 2.5 hours; With 0.4g sulfuric acid adjustment pH=4.25.
D) be warming up to 85 ℃ again, the 3.08g initiator solution is added rapidly in the four-hole boiling flask, 85 ℃ are incubated 7 minutes; Drip the initiator solution of 10g dimethyl diallyl ammonium chloride, 5g methacrylic acid acyl-oxygen ethyl-trimethyl salmiac and surplus simultaneously, 1.5 hours dropping time; Then drip 0.1g VTES, 0.6g vinyl silane triisopropoxide, 12 minutes dropping time again.
E) 85 ℃ are incubated 0.8 hour; Add the 57.32g deionized water; Be cooled to 25 ℃ of filtrations; Obtain cationic polymer: the weight solid content is 24.08wt%, and molecular weight is 67581g/mol (the multi-angle dynamic laser light scattering molecular weight apparatus that uses U.S. Wyatt Technology Corp company to produce is measured).
The preparation of high-performance sizing agent emulsion:
1) with 100gAKD wax (Shanghai dongsheng New Materials Co., Ltd) 70 ℃ of fusions, subsequent use;
2) 10g cationic polymer (embodiment 4 schemes make), 458.9g deionized water are mixed, under agitation be warming up to 72 ℃, improve mixing speed to 8500rpm/min, stir the sizing agent wax liquid that adds fusion down, mixing time is 12 minutes.Homogeneous once under 72 ℃, 14Mpa condition.
3) be cooled to 25 ℃ rapidly, 100 eye mesh screens filter discharging.The sizing agent emulsion of gained, weight solid content 18.32wt%, viscosity 10.98mPa.s (NDJ-1 rotary viscosity design determining), pH=4.26 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 5
Synthesizing of cationic polymer:
A) 1g potassium peroxydisulfate, 0.5g sodium peroxydisulfate are dissolved in the 10g deionized water dissolving and become initiator solution.Subsequent use;
B) 100g shitosan, 300g deionized water are added in the 1000ml four-hole boiling flask, dissolving is warming up to 63 ℃;
C) under 67 ℃ of situation, the 1.5g hydrogen peroxide solution is added in the four-hole boiling flask, 67 ℃ are incubated 1.5 hours; With 0.8g sulfuric acid adjustment pH=3.53.
D) be warming up to 75 ℃ again, the 2.53g initiator solution is added rapidly in the four-hole boiling flask, 75 ℃ are incubated 6 minutes; Drip the initiator solution of 15g dimethyl diallyl ammonium chloride, 10g methacrylic acid acyl-oxygen ethyl-trimethyl salmiac and surplus simultaneously, 2.5 hours dropping time; Then drip 0.3g γ-methacryloxypropyl trimethoxy silane, 0.5g vinyl silane triisopropoxide, 8 minutes dropping time again.
E) 75 ℃ are incubated 0.6 hour; Add the 155.16g deionized water; Be cooled to 25 ℃ of filtrations; Obtain cationic polymer: the weight solid content is 21.56wt%, and molecular weight is 34251g/mol (the multi-angle dynamic laser light scattering molecular weight apparatus that uses U.S. Wyatt Technology Corp company to produce is measured).
The preparation of high-performance sizing agent emulsion:
1) with 100gAKD wax (Shanghai dongsheng New Materials Co., Ltd) 70 ℃ of fusions, subsequent use;
2) 20g cationic polymer (embodiment 5 schemes make), 458.9g deionized water are mixed, under agitation be warming up to 68 ℃, improve mixing speed to 9500rpm/min, stir the sizing agent wax liquid that adds fusion down, mixing time is 8 minutes.Homogeneous once under 68 ℃, 12Mpa condition.
3) be cooled to 25 ℃ rapidly, 100 eye mesh screens filter discharging.The sizing agent emulsion of gained, weight solid content 22.10wt%, viscosity 13.54mPa.s (NDJ-1 rotary viscosity design determining), pH=3.61 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 6
Comparative Examples: the sizing agent emulsion of pressing the method preparation of CN200710150369.0
With embodiment 1～5 and Comparative Examples, carry out application experiment by following technology
Experiment condition
Slurry: needle slurry (40 ° of SR): broad-leaved slurry (40 ° of SR)=20: 80 (doing/do) laboratory making beating
Beating degree: 40.0 ° of SR weight in wet base: 3.6g
Sizing agent addition: 1.0 ‰, 1.3 ‰, 1.6 ‰, 1.9 ‰ (doing/dried paper)
The process program design
Quantitative 50g/m manufactures paper with pulp
2
Technology: slurry 100%+ sizing agent emulsion
By above-mentioned technology, take by weighing slurry, add sizing agent emulsion and stir; Take off the slurry for preparing, copy sheet, after the squeezing of 73-50 standard page squeezer with the semi-automatic sheet forming apparatus of 73-62; Natural air drying detects the 1min Cobb value of pattern behind 105 ℃ of baking oven slaking 1.5min and 3min then.
Criterion: the low more effect of Cobb value is good more
Handsheet pattern Cobb value index (temperature/humidity 10 ℃/37%)
Can find out from above-mentioned application result: use the sizing agent emulsion of the embodiment of the invention 1～5 preparation, compare with Comparative Examples, be applied to the plasm-glue-blending in the paper manufacture process, the Cobb value of gained paper is low, and effect is good.
Claims (4)
1. the preparation method of high-performance sizing agent emulsion; It is characterized in that, comprise the steps: cationic polymer and water are mixed, at 70～75 ℃; Mixing speed is 8000～10000rpm/min; Add the alkyl ketene dimer of fusion, mixing time is 10～15 minutes, homogeneous under 10～15Mpa condition; Can obtain the high-performance sizing agent emulsion, said cationic polymer obtains with cationic monomer, shitosan, hydrogen peroxide solution, silane and sulfuric acid prepared in reaction under action of evocating;
Ingredients weight parts is: 100 parts of alkyl ketene dimers, 5～25 parts of cationic polymers, 300～590 parts in water;
The preparation method of said cationic polymer comprises the steps:
(a) under 60～70 ℃, hydrogen peroxide solution is added the mixture of shitosan and water, be incubated 1～3 hour, using sulfuric acid adjustment pH is 3～5;
(b) be warming up to 70～90 ℃ again, the initiator solution of gross weight 20～30% is added the product of step (a), be incubated 5～10 minutes; Drip the initiator solution of cationic monomer and surplus more simultaneously, 1～3 hour dropping time, then drip silane again; The dropping time is 5～15 minutes, and 70～90 ℃ are incubated 0.5～1 hour, adds the entry dilution; The adjustment solid content; Obtain cationic polymer, described cationic polymer weight solid content is 20～25wt%, and weight average molecular weight is 10000～100000g/mol;
The weight portion of each component is:
100 parts of shitosans
Weight concentration is 1～5 part in 30% hydrogen peroxide solution
10～30 parts of cationic monomers
Weight concentration is 0.1～1 part in 10% sulfuric acid
0.1～1 part in silane
0.3～3 part of initator
395～450 parts in water
Described cationic monomer is selected from least a in dimethyl diallyl ammonium chloride or the methacrylic acid acyl-oxygen ethyl-trimethyl salmiac;
Described silane is selected from least a in vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane or the VTES;
Described initator is selected from least a in potassium peroxydisulfate, sodium peroxydisulfate or the ammonium persulfate.
2. method according to claim 1 is characterized in that, 15～25%, 25 ℃ of viscosity of sizing agent emulsion weight solid content are 5～30mPa.s, and pH is 3～5.
3. the sizing agent emulsion for preparing according to each described method of claim 1～2.
4. the application of sizing agent emulsion according to claim 3 is characterized in that being applied to the plasm-glue-blending of paper.
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| CN102719208B (en) * | 2012-06-29 | 2014-10-01 | 上海东升新材料有限公司 | High polymer binder and preparation method thereof |
| CN102852034A (en) * | 2012-09-29 | 2013-01-02 | 上海东升新材料有限公司 | Internal sizing agent emulsion and preparation method and application of same |
| CN103015261A (en) * | 2012-12-19 | 2013-04-03 | 青岛汉河药业有限公司 | Sizing agent emulsion |
| CN103410052A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Preparation method for surface sizing agent emulsion |
| CN110409217A (en) * | 2018-04-27 | 2019-11-05 | 上海东升新材料有限公司 | A kind of strong paper surface sizing agent of high table |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1936178A (en) * | 2006-10-19 | 2007-03-28 | 上海东升新材料有限公司 | High-curing modified-guar-gum-contained aqueous solution and preparing method |
| CN101173026A (en) * | 2007-11-26 | 2008-05-07 | 天津科技大学 | AKD emulsion and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005003457A1 (en) * | 2003-07-07 | 2005-01-13 | Nippon Paper Industries Co., Ltd. | Newsprint paper treated with cationic surface-sizing agent |
| JP4864418B2 (en) * | 2005-10-27 | 2012-02-01 | ハリマ化成株式会社 | Method for producing newsprint for offset printing and method for preventing plate smear in offset printing |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1936178A (en) * | 2006-10-19 | 2007-03-28 | 上海东升新材料有限公司 | High-curing modified-guar-gum-contained aqueous solution and preparing method |
| CN101173026A (en) * | 2007-11-26 | 2008-05-07 | 天津科技大学 | AKD emulsion and method for producing the same |
Non-Patent Citations (2)
| Title |
|---|
| 赵青等.阳离子壳聚糖衍生物的合成及其在中性施胶中的应用.《天津科技大学学报》.2008,第23卷(第3期),第42-44，第86页. |
| 阳离子壳聚糖衍生物的合成及其在中性施胶中的应用;赵青等;《天津科技大学学报》;20080930;第23卷(第3期);第42-44，第86页 * |
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