CN110373941B - Corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and preparation method thereof - Google Patents
Corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and preparation method thereof Download PDFInfo
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- CN110373941B CN110373941B CN201910737173.4A CN201910737173A CN110373941B CN 110373941 B CN110373941 B CN 110373941B CN 201910737173 A CN201910737173 A CN 201910737173A CN 110373941 B CN110373941 B CN 110373941B
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- epoxy acrylate
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- 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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Abstract
The invention discloses a corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and a preparation method thereof, wherein the corrugated paper surface sizing agent comprises the following components in percentage by weight: 23-49% of lignin grafted epoxy acrylate emulsion, 10-15% of cationic rosin gum, 10-15% of cationic peach gum, 10-15% of cationic tapioca starch, 1-2% of emulsifier and 20-30% of water; the lignin grafted epoxy acrylate emulsion is formed by copolymerization and grafting of carboxylated epoxy acrylate and alkali lignin. According to the invention, the esterification reaction between acrylic acid and a carboxylated epoxy monomer is firstly utilized to introduce flexible long-chain molecules of acrylic acid into an epoxy resin structure, so that the toughness is improved, then the esterification reaction and the etherification reaction between the obtained product and alkali lignin are utilized to produce lignin grafted epoxy acrylate, the crosslinking strength and the crosslinking density are higher, and the prepared sizing agent has the advantages of high bonding strength, high toughness, good compatibility, excellent thermal stability, environmental friendliness, water resistance and moisture resistance.
Description
Technical Field
The invention belongs to the technical field of materials for corrugated paper, and particularly relates to a corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and a preparation method thereof.
Background
The water-based epoxy resin surface sizing agent has excellent mechanical property and dimensional stability due to the fact that the structure of the water-based epoxy resin surface sizing agent contains functional groups such as phenyl, epoxy, secondary hydroxyl and the like, and meanwhile, the water-based epoxy resin surface sizing agent has excellent waterproof performance, but the epoxy resin has poor toughness, lower breaking strength and impact damage resistance, and has the problem of poor thermo-oxidative aging performance like most other thermosetting resins, the quality and bending strength of the epoxy resin surface sizing agent begin to be reduced continuously in air with the temperature of more than 150 ℃, namely, the aging phenomenon occurs, but the corrugating temperature of corrugated core paper is as high as 180 ℃, and the epoxy resin surface sizing agent is accelerated to age at the temperature. The epoxy resin is modified by adopting acrylic acid, so that flexible acrylic acid long-chain molecules can be grafted to the epoxy resin structure, and the brittleness of the epoxy resin is reduced; the lignin is adopted to modify the epoxy resin, so that the thermo-oxidative aging performance and the environmental compatibility of the epoxy resin can be obviously improved, but the physical doping method has the problem of poor compatibility, lignin particles are easy to separate out, the traditional chemical modification method is mainly used for connecting the lignin and the epoxy resin through ether-oxygen bonds, and the crosslinking strength and the crosslinking density are low.
In conclusion, the development of the lignin grafted epoxy acrylate with high toughness, environmental compatibility and thermal-oxidative-aging resistance has important significance for improving the performance and quality of the corrugated paper sizing agent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
a corrugated paper surface sizing agent containing lignin grafted epoxy acrylate comprises the following components in percentage by weight: 23-49% of lignin grafted epoxy acrylate emulsion, 10-15% of cationic rosin gum, 10-15% of cationic peach gum, 10-15% of cationic tapioca starch, 1-2% of emulsifier and 20-30% of water;
the lignin grafted epoxy acrylate emulsion is formed by copolymerization and grafting of carboxylated epoxy acrylate and alkali lignin.
Preferably, the emulsifier comprises one or more of sodium lignosulfonate, sodium lauryl sulfate, and fatty acid polyglycol ester.
A preparation method of a corrugated paper surface sizing agent containing lignin grafted epoxy acrylate comprises the following steps:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. according to the formula (1-2): (0.5-1): (2-3): 15, dissolving maleic anhydride, octenyl succinic anhydride and dichloroacetic acid in absolute ethyl alcohol to obtain a carboxylation active agent;
b. according to the following steps: (3-7): (0.05-0.2) mixing epoxypropane, epichlorohydrin and a carboxylation active agent in a weight ratio to obtain a carboxylated epoxy monomer;
c. according to the following steps: (3-5): (0.01-0.1): (0.01-0.1) mixing a carboxylated epoxy monomer, methacrylic acid, a polymerization inhibitor and a catalyst in a weight ratio, and stirring and reacting at 75-80 ℃ for 3-5h to obtain a carboxylated epoxy acrylate prepolymer;
d. adding alkali lignin monomer into water, fully swelling to prepare alkali lignin solution with the concentration of 20-25%, and then adding the alkali lignin monomer into the water according to the proportion of (1-2): (3-5): (0.01-0.1), mixing the lignin grafted epoxy acrylate emulsion with the carboxylated epoxy acrylate prepolymer and boron trifluoride diethyl etherate, dropwise adding concentrated sulfuric acid to adjust the pH to 3-5, carrying out polycondensation reaction at 85-95 ℃ for 1-3h, and neutralizing to obtain the lignin grafted epoxy acrylate emulsion;
s2: preparing a surface sizing agent: mixing lignin grafted epoxy acrylate emulsion, cationic rosin size, cationic peach gum, cationic tapioca starch, emulsifier and water according to weight percentage, and performing ultrasonic dispersion at 60 ℃ to obtain the surface sizing agent.
The invention has the beneficial effects that:
(1) the surface sizing agent has the advantages of high bonding strength, good compatibility, no delamination and no falling off, high toughness and tensile strength, excellent thermal stability and environmental friendliness.
(2) According to the invention, acrylic acid and alkali lignin are respectively utilized to modify epoxy resin, firstly, flexible long-chain molecules of acrylic acid are introduced into an epoxy resin structure through esterification reaction between acrylic acid and a carboxylated epoxy monomer, so that the flexibility and elasticity of the epoxy resin are improved, and then lignin grafted epoxy acrylate is prepared through esterification reaction and etherification reaction between the alkali lignin and a carboxylated epoxy acrylate prepolymer, namely, the alkali lignin and the epoxy acrylate prepolymer are connected by ester bonds and ether oxygen bonds, so that the crosslinking strength and the crosslinking density are higher, the chemical property is stable, and the thermo-oxidative aging performance and the environmental compatibility of the epoxy resin are improved.
(3) The cationic rosin size, the cationic peach size and the cationic tapioca starch improve the waterproof and moistureproof performance by weakening the action of hydrophilic hydroxyl groups by using cationic groups, improve the bonding strength of the sizing agent by using ionic bonds formed by the cationic rosin size, the cationic peach size and the cationic tapioca starch, supplement each other with the lignin grafted epoxy acrylate emulsion, realize synergistic interaction and improve the sizing effect.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
A corrugated paper surface sizing agent containing lignin grafted epoxy acrylate comprises the following components in percentage by weight: 23% of lignin grafted epoxy acrylate emulsion, 15% of cationic rosin size, 15% of cationic peach gum, 15% of cationic tapioca starch, 2% of sodium lignosulfonate and 30% of water.
The preparation method comprises the following steps:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. according to the following steps: 0.5: 2: 15, dissolving maleic anhydride, octenyl succinic anhydride and dichloroacetic acid in absolute ethyl alcohol to obtain a carboxylation active agent;
b. according to the following steps: 3: mixing 0.05 weight percent of epoxypropane, epichlorohydrin and carboxylation active agent to obtain a carboxylation epoxy monomer;
c. according to the following steps: 3: 0.01: mixing 0.01 weight percent of carboxylated epoxy monomer, methacrylic acid, polymerization inhibitor and catalyst, stirring and reacting for 3 hours at 75 ℃ to obtain a carboxylated epoxy acrylate prepolymer;
d. adding alkali lignin monomer into water, fully swelling to prepare an alkali lignin solution with the concentration of 20%, and then mixing the alkali lignin monomer with the alkali lignin monomer according to the proportion of 1: 3: mixing the lignin grafted epoxy acrylate emulsion with 0.01 weight ratio of the carboxyl epoxy acrylate prepolymer and boron trifluoride diethyl etherate, dropwise adding concentrated sulfuric acid to adjust the pH to 3, carrying out polycondensation reaction at 85 ℃ for 1h, and neutralizing to obtain lignin grafted epoxy acrylate emulsion;
s2: preparing a surface sizing agent: mixing the obtained lignin grafted epoxy acrylate emulsion and other components according to the weight percentage, and performing ultrasonic dispersion at 60 ℃ to obtain the surface sizing agent.
Example 2
A corrugated paper surface sizing agent containing lignin grafted epoxy acrylate comprises the following components in percentage by weight: 36% of lignin grafted epoxy acrylate emulsion, 12.5% of cationic rosin size, 12.5% of cationic peach gum, 12.5% of cationic tapioca starch, 1.5% of sodium dodecyl sulfate and 25% of water.
The preparation method is the same as that of example 1, except that:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. the weight ratio of the maleic anhydride to the octenyl succinic anhydride to the dichloroacetic acid to the absolute ethyl alcohol is 1.5: 0.75: 2.5: 15;
b. the weight ratio of the epoxypropane to the epichlorohydrin to the carboxylation activator is 1: 5: 0.12;
c. the weight ratio of the carboxylated epoxy monomer to the methacrylic acid to the polymerization inhibitor to the catalyst is 1: 4: 0.05: 0.05, stirring and reacting at 78 ℃ for 4 hours;
d, the weight ratio of 20-25% alkali lignin solution, carboxylated epoxy acrylate prepolymer and boron trifluoride diethyl etherate is 1.5: 4: 0.05, adjusting the pH to 4, and respectively controlling the polycondensation reaction temperature and time to 90 ℃ and 2 h.
Example 3
A corrugated paper surface sizing agent containing lignin grafted epoxy acrylate comprises the following components in percentage by weight: 23% of lignin grafted epoxy acrylate emulsion, 15% of cationic rosin size, 15% of cationic peach gum, 15% of cationic tapioca starch, 2% of fatty acid polyethylene glycol ester and 30% of water.
The preparation method is the same as that of example 1, except that:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. the weight ratio of maleic anhydride, octenyl succinic anhydride, dichloroacetic acid and absolute ethyl alcohol is 2: 1: 3: 15;
b. the weight ratio of the epoxypropane to the epichlorohydrin to the carboxylation activator is 1: 7: 0.2;
c. the weight ratio of the carboxylated epoxy monomer to the methacrylic acid to the polymerization inhibitor to the catalyst is 1: 5: 0.1: 0.1, stirring and reacting at the temperature and time of 80 ℃ for 5 hours respectively;
d, the weight ratio of 20-25% alkali lignin solution, carboxylated epoxy acrylate prepolymer and boron trifluoride diethyl etherate is 2: 5): 0.1, adjusting the pH value to 5, and respectively keeping the polycondensation reaction temperature and time at 95 ℃ for 3 h.
The paper is made into 110g/m of 100 percent domestic waste paper by adopting the paper making method of the examples 1 to 3 respectively2The corrugated base paper is sized, the sizing amount of 1t of paper is 2kg, and performance tests are carried out, and the test results are shown in the following table:
as can be seen from the above table, the invention obviously improves the ring crush strength and the water and moisture resistance of the corrugated base paper.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (3)
1. The corrugated paper surface sizing agent containing lignin grafted epoxy acrylate is characterized by comprising the following components in percentage by weight: 23-49% of lignin grafted epoxy acrylate emulsion, 10-15% of cationic rosin gum, 10-15% of cationic peach gum, 10-15% of cationic tapioca starch, 1-2% of emulsifier and 20-30% of water;
the lignin grafted epoxy acrylate emulsion is formed by copolymerization and grafting of carboxylated epoxy acrylate and alkali lignin;
the preparation method of the corrugated paper surface sizing agent containing the lignin grafted epoxy acrylate is characterized by comprising the following steps:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. according to the formula (1-2): (0.5-1): (2-3): 15, dissolving maleic anhydride, octenyl succinic anhydride and dichloroacetic acid in absolute ethyl alcohol to obtain a carboxylation active agent;
b. according to the following steps: (3-7): (0.05-0.2) mixing epoxypropane, epichlorohydrin and a carboxylation active agent in a weight ratio to obtain a carboxylated epoxy monomer;
c. according to the following steps: (3-5): (0.01-0.1): (0.01-0.1) mixing a carboxylated epoxy monomer, methacrylic acid, a polymerization inhibitor and a catalyst in a weight ratio, and stirring and reacting at 75-80 ℃ for 3-5h to obtain a carboxylated epoxy acrylate prepolymer;
d. adding alkali lignin monomer into water, fully swelling to prepare alkali lignin solution with the concentration of 20-25%, and then adding the alkali lignin monomer into the water according to the proportion of (1-2): (3-5): (0.01-0.1), mixing the lignin grafted epoxy acrylate emulsion with the carboxylated epoxy acrylate prepolymer and boron trifluoride diethyl etherate, dropwise adding concentrated sulfuric acid to adjust the pH to 3-5, carrying out polycondensation reaction at 85-95 ℃ for 1-3h, and neutralizing to obtain the lignin grafted epoxy acrylate emulsion;
s2: preparing a surface sizing agent: mixing lignin grafted epoxy acrylate emulsion, cationic rosin size, cationic peach gum, cationic tapioca starch, emulsifier and water according to weight percentage, and performing ultrasonic dispersion at 60 ℃ to obtain the surface sizing agent.
2. The corrugated paper surface sizing agent containing lignin-grafted epoxy resin as claimed in claim 1, wherein the emulsifier comprises one or more of sodium lignosulfonate, sodium lauryl sulfate, and fatty acid polyglycol ester.
3. The preparation method of the corrugated paper surface sizing agent containing the lignin grafted epoxy acrylate is characterized by comprising the following steps:
s1: preparing lignin grafted epoxy acrylate emulsion:
a. according to the formula (1-2): (0.5-1): (2-3): 15, dissolving maleic anhydride, octenyl succinic anhydride and dichloroacetic acid in absolute ethyl alcohol to obtain a carboxylation active agent;
b. according to the following steps: (3-7): (0.05-0.2) mixing epoxypropane, epichlorohydrin and a carboxylation active agent in a weight ratio to obtain a carboxylated epoxy monomer;
c. according to the following steps: (3-5): (0.01-0.1): (0.01-0.1) mixing a carboxylated epoxy monomer, methacrylic acid, a polymerization inhibitor and a catalyst in a weight ratio, and stirring and reacting at 75-80 ℃ for 3-5h to obtain a carboxylated epoxy acrylate prepolymer;
d. adding alkali lignin monomer into water, fully swelling to prepare alkali lignin solution with the concentration of 20-25%, and then adding the alkali lignin monomer into the water according to the proportion of (1-2): (3-5): (0.01-0.1), mixing the lignin grafted epoxy acrylate emulsion with the carboxylated epoxy acrylate prepolymer and boron trifluoride diethyl etherate, dropwise adding concentrated sulfuric acid to adjust the pH to 3-5, carrying out polycondensation reaction at 85-95 ℃ for 1-3h, and neutralizing to obtain the lignin grafted epoxy acrylate emulsion;
s2: preparing a surface sizing agent: mixing lignin grafted epoxy acrylate emulsion, cationic rosin size, cationic peach gum, cationic tapioca starch, emulsifier and water according to weight percentage, and performing ultrasonic dispersion at 60 ℃ to obtain the surface sizing agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031108A (en) * | 2011-10-08 | 2013-04-10 | 中国科学院青岛生物能源与过程研究所 | Method for preparing lignin-based adhesive |
| CN104910335A (en) * | 2015-07-03 | 2015-09-16 | 长春工业大学 | Lignin-based epoxy acrylate resin and preparation method thereof |
| CN108625224A (en) * | 2018-05-09 | 2018-10-09 | 上海昶法新材料有限公司 | A kind of lignin-base epoxy phenolics class sizing agent and its preparation method and application |
| CN108912306A (en) * | 2018-06-07 | 2018-11-30 | 华东理工大学 | A kind of preparation method of water-base epoxy type wet strength agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031108A (en) * | 2011-10-08 | 2013-04-10 | 中国科学院青岛生物能源与过程研究所 | Method for preparing lignin-based adhesive |
| CN104910335A (en) * | 2015-07-03 | 2015-09-16 | 长春工业大学 | Lignin-based epoxy acrylate resin and preparation method thereof |
| CN108625224A (en) * | 2018-05-09 | 2018-10-09 | 上海昶法新材料有限公司 | A kind of lignin-base epoxy phenolics class sizing agent and its preparation method and application |
| CN108912306A (en) * | 2018-06-07 | 2018-11-30 | 华东理工大学 | A kind of preparation method of water-base epoxy type wet strength agent |
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Effective date of registration: 20230322 Address after: 519000 l area, room 321, bee+ maker space, living area, No. 1, Software Park Road, Tangjiawan Town, high tech Zone, Zhuhai, Guangdong Province (centralized office area) Patentee after: Zhuhai Bonnie Environmental Protection Technology Co.,Ltd. Address before: 235143 No. 10, A District, industrial park, Lin Huan Town, Suixi County, Huaibei, Anhui. Patentee before: HUAIBEI SHUOHUA MACHINERY EQUIPMENT Co.,Ltd. |