CN110485197A - Biomass sizing agent - Google Patents
Biomass sizing agent Download PDFInfo
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- CN110485197A CN110485197A CN201810460606.1A CN201810460606A CN110485197A CN 110485197 A CN110485197 A CN 110485197A CN 201810460606 A CN201810460606 A CN 201810460606A CN 110485197 A CN110485197 A CN 110485197A
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- sizing agent
- methyl
- acid
- biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
Abstract
It is the aqueous dispersion as made of the copolymerization of lignin, alkali, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, acid, siloxanes, (methyl) acrylic ester monomer, (methyl) styrene and initiator the invention discloses a kind of biomass sizing agent.Biomass sizing agent of the invention is the product of a kind of high-performance for being able to satisfy paper for surface sizing, environmental protection.The product carries out top sizing to fluting medium together with starch, can not only improve the Cobb value of corrugated paper, accelerates curing speed, and can increase substantially the surface ring crush intensity of corrugated paper, adapts to the needs of highly intensified corrugated paper development.The lignin generated in paper-making process can be used as starting material in the Cypres simultaneously, significantly reduces production cost.
Description
Technical field
The present invention relates to paper surface-sizing agent fields, and in particular to a kind of biomass sizing agent.
Background technique
Paper, especially corrugated paper, paperboard development trend show:
1) just develop from high grammes per square metre to low grammes per square metre direction.
2) wood pulp is replaced using waste paper, but at the intensity difference of paper, hygroscopicity value is high.
3) internal sizing variable factor it is more caused by paper quality is unstable, class is difficult the problem of improving,
So that manufacturer uses or abandon less internal sizing, fashion trend is become using the technique that top sizing is made up.It applies on surface
The addition of jelly can improve page characteristic or increase surface property, intensity and the water-resistance of Paper or cardboard.
Sizing agent requirement for above-mentioned top sizing: ring crush intensity a) is improved；B) Cobb value (hygroscopicity value) is greatly reduced；
C) curing speed is fast, it is desirable that lower machine is with regard to ripe.
But though present Cypres can improve the certain ring crush intensity of corrugated paper, sizing agent dosage is big, at
This height.
A kind of sizing agent disclosed in Chinese patent CN107034730A, although rate of drying is fast, for corrugated paper
Ring crush intensity improves little.
Summary of the invention
The object of the present invention is to provide a kind of biomass sizing agents, to solve drawbacks described above existing for background technique.
The present invention realizes by the following technical solutions:
A kind of biomass sizing agent, be by lignin, alkali, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, acid, siloxanes,
Aqueous dispersion made of (methyl) acrylic ester monomer, (methyl) styrene and initiator copolymerization.
Further, the parts by weight of each component are as follows:
The alkali generally selects inorganic base, preferably at least one of sodium hydroxide, potassium hydroxide and ammonium hydroxide.
The acid can be organic acid or inorganic acid, preferably at least one of hydrochloric acid, acetic acid and sulfuric acid.
The siloxanes is selected from vinyltrimethoxysilane, vinyltriethoxysilane, (the 2- methoxyl group of vinyl three
Ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, (the β-front three of γ-methacryloxypropyl three
At least one of oxygroup Ethoxysilane).
(methyl) acrylic ester monomer is being selected from methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid just
Butyl ester, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, first
Base propyl acrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid are different
At least one of monooctyl ester.
The initiator is selected from least one of hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, tert-butyl hydroperoxide.
Water in component is as the dispersion solvent in reaction process, and dosage does not have considered critical, those skilled in the art
Member can need suitably to adjust amount of water according to real reaction, and preferred dosage is 150~2440 parts by weight.
Biomass sizing agent of the present invention, prepares with the following method:
(methyl) styrene, (methyl) acrylic ester monomer and siloxanes are mixed and are made into mix monomer by step 1；
Initiator is dissolved in suitable quantity of water and is made into initiator solution by step 2；
Lignin, alkali and suitable quantity of water is added in step 3 in the reactor, and the chloro- 2- hydroxypropyl three of 3- is added after completely dissolution
Ammonio methacrylate reaction；
Step 4 continuously adds acid, and the mix monomer is then added simultaneously and initiator solution carries out polymerization reaction,
Obtain the biomass sizing agent.
Preferably, the reaction temperature of step 3 is 45-70 DEG C；The reaction temperature of step 4 is 70-95 DEG C.
Biomass sizing agent of the present invention, the surface treatment for fluting medium.
The inventors discovered that by being modified to lignin in biomass sizing agent, it is unexpected, it can be significantly
The Cobb value of the ring crush intensity while corrugated paper that improve corrugated paper is decreased obviously.This may due in the present invention to lignin into
It is cationized after hydrophilic hydroxyl reaction in lignin during row etherificate cation modifying, cation group energy and fiber
The hydroxy combining of starch in a large amount of hydroxyl in surface and glue application solution plays the role of bridge formation, improves between fiber fines
Power.Siloxy group can also react with the hydroxyl on starch and fiber simultaneously simultaneously, play crosslinked action, improve glue application solution film forming
Closure improves the effect of sizing agent.The ring crush intensity for showing as corrugated paper improves, and the Cobb value of paper can significantly drop
It is low.
Biomass sizing agent of the invention is the product of a kind of high-performance for being able to satisfy paper for surface sizing, environmental protection.It should
Product carries out top sizing to fluting medium together with starch, can not only improve the Cobb value of corrugated paper, accelerates curing speed, and
The surface ring crush intensity that corrugated paper can be increased substantially adapts to the needs of highly intensified corrugated paper development.
Specific embodiment
The present invention is illustrated below by specific embodiment, but is not intended to limit the present invention.
Embodiment 1:
A) by 20 grams of styrene, 20 grams of n-butyl acrylates are uniformly mixed, spare.
B) 0.3 gram of ammonium persulfate is dissolved in 10 grams of deionized waters, it is spare.
C) in the four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 146.3 grams of deionizations are added
Water, 10 grams of potassium hydroxide, 100 grams of lignin are warming up to 45 DEG C after being completely dissolved, the chloro- 2- Hydroxyproyl Trimethyl chlorine of 5 grams of 3- is added dropwise
Change ammonium, time for adding 0.25 hour.Continue heat preservation 0.75 hour.70 DEG C are warming up to, 1 gram of hydrochloric acid is added.In 70 DEG C of a dropping steps
A the mix monomer in), time for adding 1 hour；Simultaneously a dropping step B) in initiator solution, time for adding 1 hour, be added dropwise
After continue at 70 DEG C heat preservation 1 hour, be cooled to 25 DEG C, pH=6.45.It is filtered through 100 mesh filter screens, obtained biomass is applied
Jelly, solid content 49.76wt%.
Embodiment 2
A) by 100 grams of methyl styrenes, 100 grams of Isooctyl acrylate monomers, 20 grams of vinyltrimethoxysilanes are uniformly mixed,
It is spare.
B) 10 grams of sodium peroxydisulfates are dissolved in 100 grams of deionized waters, it is spare.
C) in the four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 2337 grams of deionized waters are added,
40 grams of ammonium hydroxide, 100 grams of lignin, are warming up to 55 DEG C after being completely dissolved, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 40 grams of 3- is added dropwise
Ammonium, time for adding 1 hour.Continue heat preservation 2 hours.95 DEG C are warming up to, 20 grams of sulfuric acid are added.In 95 DEG C of a dropping step A) in it is mixed
Conjunction monomer, time for adding 3 hours；Simultaneously a dropping step B) in initiator solution, time for adding 3 hours, after completion of dropwise addition
95 DEG C are continued heat preservation 2 hours, are cooled to 25 DEG C, pH=1.13.It is filtered through 100 mesh filter screens, obtained biomass sizing agent, admittedly contain
Measure 15.28wt%.
Embodiment 3
A) by 60 grams of methyl styrenes, 50 grams of ethyl methacrylate, 10 grams of γ-methacryloxypropyl trimethoxy
Base silane is uniformly mixed, spare.
B) 6 grams of hydrogen peroxide are dissolved in 100 grams of deionized waters, it is spare.
C) in the four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 544 grams of deionized waters are added,
20 grams of sodium hydroxides, 100 grams of lignin, are warming up to 65 DEG C after being completely dissolved, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 20 grams of 3- is added dropwise
Ammonium, time for adding 2 hours.Continue heat preservation 1 hour.85 DEG C are warming up to, 10 grams of acetic acid are added.In 85 DEG C of a dropping step A) in it is mixed
Conjunction monomer, time for adding 1.5 hours；Simultaneously a dropping step B) in initiator solution, time for adding 2 hours, after completion of dropwise addition
Continue heat preservation 1 hour at 85 DEG C, is cooled to 25 DEG C, pH=3.67.It is filtered through 100 mesh filter screens, obtained biomass sizing agent, Gu
Content 29.78wt%.
Embodiment 4
A) by 10 grams of methyl styrenes, 20 grams of styrene, 20 grams of Isobutyl methacrylates, 20 grams of methyl methacrylates
Ester, 5 grams of vinyltriethoxysilane, 10 grams of vinyl three (2- methoxy ethoxy) silane mixtures are uniform, spare.
B) 4 grams of hydrogen peroxide are dissolved in 100 grams of deionized waters, it is spare.
C) in the four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 936 grams of deionized waters are added,
25 grams of sodium hydroxides, 100 grams of lignin, are warming up to 70 DEG C after being completely dissolved, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 30 grams of 3- is added dropwise
Ammonium, time for adding 1 hour.Continue heat preservation 1 hour.80 DEG C are warming up to, 15 grams of acetic acid are added.In 80 DEG C of a dropping step A) in it is mixed
Conjunction monomer, time for adding 2 hours；Simultaneously a dropping step B) in initiator solution, time for adding 3 hours, after completion of dropwise addition
80 DEG C are continued heat preservation 1 hour, are cooled to 25 DEG C, pH=4.56.It is filtered through 100 mesh filter screens, obtained biomass sizing agent, admittedly contain
Measure 20.09wt%.
Embodiment 5
A) by 40 grams of methyl styrenes, 30 grams of styrene, 50 grams of Tert-butyl Methacrylates, 5 grams of propyl methacrylates,
5 grams of γ-methacryloxypropyls three (β-trimethoxy Ethoxysilane) are uniformly mixed, spare.
B) 5 grams of hydrogen peroxide, 2 grams of sodium peroxydisulfates are dissolved in 100 grams of deionized waters, it is spare.
C) in the four-hole boiling flask for having condenser, Dropping feeder, blender, thermometer, 308 grams of deionized waters are added,
15 grams of sodium hydroxides, 100 grams of lignin, are warming up to 60 DEG C after being completely dissolved, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 15 grams of 3- is added dropwise
Ammonium, time for adding 1 hour.Continue heat preservation 0.5 hour.90 DEG C are warming up to, 5 grams of hydrochloric acid are added.In 90 DEG C of a dropping step A) in
Mix monomer, time for adding 2.5 hours；Simultaneously a dropping step B) in initiator solution, time for adding 2.5 hours, be added dropwise knot
Continue heat preservation 1 hour after beam at 90 DEG C, is cooled to 25 DEG C, pH=2.88.It is filtered through 100 mesh filter screens, obtained biomass sizing
Agent, solid content 39.56wt%.
Embodiment 6
It is glued in corrugated paper upper surface:
Comparative example: the sizing agent prepared by the method for Chinese patent CN107034730A embodiment 1, solid content are
15wt%.
Sizing agent prepared by Examples 1 to 5 formula is diluted to 15wt% with deionized water.
The preparation of glue application solution: preparing 500 grams of 10wt% oxidized starch aqueous solutions, is warming up to 90 DEG C, is gelatinized 20 minutes, cooling
To 40 DEG C, add comparative example and Examples 1 to 5 formula preparation sizing agent (oxidized starch (dry): sizing agent (wet)=50:
4) it, adds water and is diluted to 8wt%.
The measurement of Cobb value:
GB/T1540- suddenly can be pressed by absorbability analyzer using the XSH type of Hangzhou Qingtong Boke Automation Technology Co., Ltd.
1989 methods detect pattern to be measured.
Ring crush intensity measurement:
Pattern to be measured is detected using the CT300A compressive strength tester of Hangzhou Qingtong Boke Automation Technology Co., Ltd..
It is glued in corrugated paper upper surface:
The glue application solution prepared using comparative example and Examples 1 to 5 formula on 120 grams of fluting mediums with 10# spreading rod into
Row coating, coating weight 2g/m2, dried 30 seconds or 120 seconds in 110 DEG C of baking ovens respectively after coating, take out, be cooled to room temperature progress
Measurement.Criterion: Cobb value is the smaller the better, and ring crush index is the bigger the better.Measurement result is shown in Table 1.
1 product performance index of table
From it is above-mentioned using result it can be seen that using the embodiment of the present invention 1~5 prepare biomass sizing agent, with comparison
Example is compared, and can not only be increased substantially the ring crush intensity of paper, be significantly improved Cobb value, while the Cobb value of paper, ring after sizing
The pressure index different curing times are not much different, and curing speed is fast.
The above shows and describes the basic principle, main features and advantages of the invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of biomass sizing agent, which is characterized in that its be by lignin, alkali, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride,
Aqueous dispersion made of acid, siloxanes, (methyl) acrylic ester monomer, (methyl) styrene and initiator copolymerization.
2. biomass sizing agent as described in claim 1, which is characterized in that the parts by weight of each component are as follows:
3. biomass sizing agent as described in claim 1, which is characterized in that the alkali be selected from sodium hydroxide, potassium hydroxide and
At least one of ammonium hydroxide.
4. biomass sizing agent as described in claim 1, which is characterized in that the acid is in hydrochloric acid, acetic acid and sulfuric acid
It is at least one.
5. biomass sizing agent as described in claim 1, which is characterized in that (methyl) acrylic ester monomer is selected from third
E pioic acid methyl ester, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid
Different monooctyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, metering system
At least one of sour isobutyl ester, Tert-butyl Methacrylate, isooctyl methacrylate.
6. biomass sizing agent as described in claim 1, which is characterized in that the siloxanes is selected from vinyl trimethoxy silicon
Alkane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxy) silane, γ-methacryloxypropyl front three
Oxysilane, at least one of γ-methacryloxypropyl three (β-trimethoxy Ethoxysilane).
7. biomass sizing agent as described in claim 1, which is characterized in that the initiator is selected from hydrogen peroxide, persulfuric acid
At least one of ammonium, sodium peroxydisulfate, tert-butyl hydroperoxide.
8. the method for preparing any one of the claim 1-7 biomass sizing agent, which comprises the steps of:
(methyl) styrene, (methyl) acrylic ester monomer and siloxanes are mixed and are made into mix monomer by step 1；
Initiator is dissolved in suitable quantity of water and is made into initiator solution by step 2；
Lignin, alkali and suitable quantity of water is added in step 3 in the reactor, and the chloro- 2- Hydroxyproyl Trimethyl of 3- is added after completely dissolution
Ammonium chloride reaction；
Step 4 continuously adds acid, and the mix monomer is then added simultaneously and initiator solution carries out polymerization reaction, obtains
The biomass sizing agent.
9. method according to claim 8, which is characterized in that the reaction temperature of step 3 is 45-70 DEG C；The reaction of step 4
Temperature is 70-95 DEG C.
10. the application of any one of the claim 1-7 biomass sizing agent, which is characterized in that the surface for fluting medium
Processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460606.1A CN110485197A (en) | 2018-05-15 | 2018-05-15 | Biomass sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810460606.1A CN110485197A (en) | 2018-05-15 | 2018-05-15 | Biomass sizing agent |
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| CN110485197A true CN110485197A (en) | 2019-11-22 |
Family
ID=68545106
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| CN201810460606.1A Pending CN110485197A (en) | 2018-05-15 | 2018-05-15 | Biomass sizing agent |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787960A (en) * | 1987-07-23 | 1988-11-29 | Westvaco Corporation | Cationic and anionic lignin amine sizing agents |
| CN101148842A (en) * | 2007-06-28 | 2008-03-26 | 上海东升新材料有限公司 | Paper surface sizing agent and preparation method thereof |
| CN106351066A (en) * | 2016-08-29 | 2017-01-25 | 上海东升新材料有限公司 | A preparing method for surface sizing agent for corrugated paper and its products and application |
| CN106368062A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Novel surface sizing agent and preparation method thereof |
| CN106368059A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Preparing method of surface sizing agent for corrugated paper, product and application of surface sizing agent |
-
2018
- 2018-05-15 CN CN201810460606.1A patent/CN110485197A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787960A (en) * | 1987-07-23 | 1988-11-29 | Westvaco Corporation | Cationic and anionic lignin amine sizing agents |
| CN101148842A (en) * | 2007-06-28 | 2008-03-26 | 上海东升新材料有限公司 | Paper surface sizing agent and preparation method thereof |
| CN106351066A (en) * | 2016-08-29 | 2017-01-25 | 上海东升新材料有限公司 | A preparing method for surface sizing agent for corrugated paper and its products and application |
| CN106368062A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Novel surface sizing agent and preparation method thereof |
| CN106368059A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Preparing method of surface sizing agent for corrugated paper, product and application of surface sizing agent |
Non-Patent Citations (1)
| Title |
|---|
| 王晓红等: ""木质素季铵盐表面活性剂的合成"", 《中国造纸》 * |
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Application publication date: 20191122 |