CN110373941A - A kind of corrugated paper Cypres and preparation method thereof of the acrylate of grafted epoxy containing lignin - Google Patents
A kind of corrugated paper Cypres and preparation method thereof of the acrylate of grafted epoxy containing lignin Download PDFInfo
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- CN110373941A CN110373941A CN201910737173.4A CN201910737173A CN110373941A CN 110373941 A CN110373941 A CN 110373941A CN 201910737173 A CN201910737173 A CN 201910737173A CN 110373941 A CN110373941 A CN 110373941A
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- lignin
- epoxy
- acrylic acid
- carboxylated
- 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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- Epoxy Resins (AREA)
Abstract
The present invention discloses a kind of corrugated paper Cypres and preparation method thereof of acrylate of grafted epoxy containing lignin, including following weight percent composition: lignin grafted epoxy acrylic acid ester emulsion 23-49%, cationic rosin size 10-15%, cationic peach gum 10-15%, cation cassava starch 10-15%, emulsifier 1-2%, water 20-30%；The lignin grafted epoxy acrylic acid ester emulsion is formed by carboxylated epoxy acrylate and alkali lignin copolymerized grafting.The present invention is first with the esterification between acrylic acid and carboxylated epoxy monomer, acrylic acid long flexible chain molecule is introduced into epoxy resin structural, improve toughness, esterification and etherification reaction between products therefrom and alkali lignin is recycled to produce lignin grafted epoxy acrylate, cross-link intensity and crosslink density are higher, the sizing agent adhesion strength prepared is high, toughness is high, compatibility is good, good heat stability, environmentally friendly, waterproof and dampproof.
Description
Technical field
The invention belongs to corrugated paper field of material technology, and in particular to a kind of acrylate of grafted epoxy containing lignin
Corrugated paper Cypres and preparation method thereof.
Background technique
Aqueous epoxy resins Cypres are shown as because containing the functional groups such as phenyl, epoxy group, secondary hydroxyl in its structure
Excellent mechanical performance and dimensional stability, meanwhile, there is excellent waterproof performance, but the poor toughness of epoxy resin, anti-folding is strong
Degree and impact resistance lesion capability are lower, meanwhile, identical as other most of thermosetting resins, there is also thermo-oxidative ageings for epoxy resin
The poor problem of performance, in 150 DEG C or more of air, quality and bending strength begin to constantly reduce, i.e. generation aging
Phenomenon, but the stupefied temperature that rises of corrugating medium is up to 180 DEG C, at this temperature, epoxy resin surface sizing agent accelerated ageing.Using
Flexible acrylic acid long-chain molecule can be grafted in epoxy resin structural epoxy resin modification by acrylic acid, reduce epoxy resin
Brittleness；Epoxy resin is modified using lignin, the thermal-oxidative aging property and environment phase of epoxy resin can be significantly improved
Capacitive, but there is poor compatibility in physical doping method, and lignin particles are easily precipitated, and the modified method of traditional chemical mainly passes through ether
Oxygen key connects lignin and epoxy resin, cross-link intensity and crosslink density are low.
In conclusion developing the lignin grafting ring that a kind of toughness is high, Environmental compatibility and thermo oxidative aging performance are excellent
Oxypropylene acid esters is of great significance for the performance and quality that improve corrugation paper gluing agents.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of acrylic acid of grafted epoxy containing lignin
Corrugated paper Cypres of ester and preparation method thereof.
Technical solution of the present invention is summarized as follows:
A kind of corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, including following weight percent at
Point: lignin grafted epoxy acrylic acid ester emulsion 23-49%, cationic rosin size 10-15%, cationic peach gum 10-15%, sun
Ion tapioca 10-15%, emulsifier 1-2%, water 20-30%；
The lignin grafted epoxy acrylic acid ester emulsion is by carboxylated epoxy acrylate and alkali lignin copolymerized grafting
It forms.
Preferably, the emulsifier includes sodium lignin sulfonate, lauryl sodium sulfate, fatty acid polyethylene glycol ester
It is one or more.
A kind of preparation method of the corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, including following step
It is rapid:
S1: lignin grafted epoxy acrylic acid ester emulsion is prepared:
A. press (1-2): (0.5-1): (2-3): 15 weight ratio is by maleic anhydride, octenyl succinic acid anhydride, dichloro
Acetic acid is dissolved in dehydrated alcohol, obtains carboxylated activating agent；
B. 1:(3-7 is pressed): the hybrid epoxidized propane of the weight ratio of (0.05-0.2), epoxychloropropane, carboxylated activating agent obtain
Carboxylated epoxy monomer；
C. 1:(3-5 is pressed): (0.01-0.1): the weight ratio of (0.01-0.1) mixes carboxylated epoxy monomer, metering system
Acid, polymerization inhibitor, catalyst, 75-80 DEG C is stirred to react 3-5h and obtains carboxylated epoxy FRP pipe；
D. alkali lignin monomer is added to the water, sufficiently after swelling, the alkali lignin solution that concentration is 20-25% is made,
Press (1-2) again: (3-5): the weight ratio of (0.01-0.1) is by itself and carboxylated epoxy FRP pipe, boron trifluoride ether
Mixing, and it is 3-5 that the concentrated sulfuric acid, which is added dropwise, to adjust PH, in 85-95 DEG C of polycondensation reaction 1-3h, to get lignin grafted epoxy after neutralization
Acrylic acid ester emulsion；
S2: Cypres are prepared: mixing lignin grafted epoxy acrylic acid ester emulsion, cation pine by weight percentage
Balosam, cationic peach gum, cation cassava starch, emulsifier, water, to get the Cypres after 60 DEG C of ultrasonic disperses.
Beneficial effects of the present invention:
(1) Cypres adhesion strength of the present invention is high, compatibility is good, not stratified, do not fall off, toughness and tensile strength
Height, good heat stability are environmentally friendly.
(2) present invention is utilized respectively acrylic acid, alkali lignin is modified epoxy resin, first passes through acrylic acid and carboxyl
Change the esterification between epoxy monomer, acrylic acid long flexible chain molecule is introduced into epoxy resin structural, it is soft to improve epoxy resin
Toughness and elasticity recycle esterification and etherification reaction between alkali lignin and carboxylated epoxy FRP pipe to prepare
Lignin grafted epoxy acrylate is handed over that is, using ester bond and ether oxygen key connection alkali lignin and epoxy FRP pipe
Join intensity and crosslink density is higher, chemical property is stablized, and improves the thermal-oxidative aging property and Environmental compatibility of epoxy resin.
(3) subject cationic gum rosin, cationic peach gum, cation cassava starch are weakened hydrophilic using cation group
The effect of hydroxyl is improved waterproof and dampproof performance, and is improved and be glued with the ionic bond that corrugated paper surface fiber fines are formed using it
The adhesion strength of agent complements each other with lignin grafted epoxy acrylic acid ester emulsion, synergistic, improves sizing efficiency.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
Embodiment 1
A kind of corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, including following weight percent at
Point: lignin grafted epoxy acrylic acid ester emulsion 23%, cationic rosin size 15%, cationic peach gum 15%, cationic tapioca
Starch 15%, sodium lignin sulfonate 2%, water 30%.
Preparation method, comprising the following steps:
S1: lignin grafted epoxy acrylic acid ester emulsion is prepared:
A. maleic anhydride, octenyl succinic acid anhydride, dichloroacetic acid are dissolved in by the weight ratio of 1:0.5:2:15 anhydrous
In ethyl alcohol, carboxylated activating agent is obtained；
B. the hybrid epoxidized propane of weight ratio, epoxychloropropane, the carboxylated activating agent for pressing 1:3:0.05, obtain carboxylated epoxy
Monomer；
C. carboxylated epoxy monomer, methacrylic acid, polymerization inhibitor, catalyst are mixed by the weight ratio of 1:3:0.01:0.01,
75 DEG C are stirred to react 3h and obtain carboxylated epoxy FRP pipe；
D. alkali lignin monomer is added to the water, sufficiently after swelling, concentration is made and is 20% alkali lignin solution, then presses
The weight ratio of 1:3:0.01 mixes it with carboxylated epoxy FRP pipe, boron trifluoride ether, and the concentrated sulfuric acid is added dropwise
Adjusting PH is 3, in 85 DEG C of polycondensation reaction 1h, to get lignin grafted epoxy acrylic acid ester emulsion after neutralization；
S2: Cypres are prepared: mixes gained lignin grafted epoxy acrylic acid ester emulsion and its by weight percentage
His ingredient, to get the Cypres after 60 DEG C of ultrasonic disperses.
Embodiment 2
A kind of corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, including following weight percent at
Point: lignin grafted epoxy acrylic acid ester emulsion 36%, cationic rosin size 12.5%, cationic peach gum 12.5%, cation
Tapioca 12.5%, lauryl sodium sulfate 1.5%, water 25%.
The preparation method is the same as that of Example 1, and difference is:
S1: lignin grafted epoxy acrylic acid ester emulsion is prepared:
A. maleic anhydride, octenyl succinic acid anhydride, dichloroacetic acid, dehydrated alcohol weight ratio be 1.5:0.75:
2.5:15；
B. propylene oxide, epoxychloropropane, carboxylated activating agent weight ratio be 1:5:0.12；
C. carboxylated epoxy monomer, methacrylic acid, polymerization inhibitor, catalyst weight ratio be 1:4:0.05:0.05, stirring
Reaction temperature and time are respectively 78 DEG C, 4h；
D.20-25% alkali lignin solution, carboxylated epoxy FRP pipe, boron trifluoride ether weight ratio be
1.5:4:0.05, PH are adjusted to 4, and polycondensation reaction temperature and time is respectively 90 DEG C, 2h.
Embodiment 3
A kind of corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, including following weight percent at
Point: lignin grafted epoxy acrylic acid ester emulsion 23%, cationic rosin size 15%, cationic peach gum 15%, cationic tapioca
Starch 15%, fatty acid polyethylene glycol ester 2%, water 30%.
The preparation method is the same as that of Example 1, and difference is:
S1: lignin grafted epoxy acrylic acid ester emulsion is prepared:
A. maleic anhydride, octenyl succinic acid anhydride, dichloroacetic acid, dehydrated alcohol weight ratio be 2:1:3:15；
B. propylene oxide, epoxychloropropane, carboxylated activating agent weight ratio be 1:7:0.2；
C. carboxylated epoxy monomer, methacrylic acid, polymerization inhibitor, catalyst weight ratio be 1:5:0.1:0.1, stirring is anti-
Answering temperature and time is respectively 80 DEG C, 5h；
D.20-25% alkali lignin solution, carboxylated epoxy FRP pipe, boron trifluoride ether weight ratio be
2:5): 0.1, PH is adjusted to 5, and polycondensation reaction temperature and time is respectively 95 DEG C, 3h.
The 110g/m that embodiment 1-3 manufactures paper with pulp to 100% domestic waste paper is respectively adopted2Fluting medium is glued, 1t paper
Resin added is 2kg, and is tested for the property, and test result is as follows shown in table:
As seen from the above table, the present invention significantly improves the ring crush intensity and water resistant humidity resistance of fluting medium.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (3)
1. a kind of corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, which is characterized in that including following weight
Percent composition: lignin grafted epoxy acrylic acid ester emulsion 23-49%, cationic rosin size 10-15%, cationic peach gum
10-15%, cation cassava starch 10-15%, emulsifier 1-2%, water 20-30%；
The lignin grafted epoxy acrylic acid ester emulsion is formed by carboxylated epoxy acrylate and alkali lignin copolymerized grafting.
2. the corrugated paper Cypres of a kind of Graft Epoxy Resin containing lignin according to claim 1, which is characterized in that
The emulsifier include sodium lignin sulfonate, lauryl sodium sulfate, fatty acid polyethylene glycol ester it is one or more.
3. a kind of preparation method of the corrugated paper Cypres of the acrylate of grafted epoxy containing lignin, which is characterized in that packet
Include following steps:
S1: lignin grafted epoxy acrylic acid ester emulsion is prepared:
A. press (1-2): (0.5-1): (2-3): 15 weight ratio is by maleic anhydride, octenyl succinic acid anhydride, dichloroacetic acid
It is dissolved in dehydrated alcohol, obtains carboxylated activating agent；
B. 1:(3-7 is pressed): the hybrid epoxidized propane of the weight ratio of (0.05-0.2), epoxychloropropane, carboxylated activating agent obtain carboxyl
Change epoxy monomer；
C. 1:(3-5 is pressed): (0.01-0.1): the weight ratio of (0.01-0.1) mixes carboxylated epoxy monomer, methacrylic acid, resistance
Poly- agent, catalyst, 75-80 DEG C is stirred to react 3-5h and obtains carboxylated epoxy FRP pipe；
D. alkali lignin monomer is added to the water, sufficiently after swelling, concentration is made and is the alkali lignin solution of 20-25%, then presses
(1-2): (3-5): the weight ratio of (0.01-0.1) mixes it with carboxylated epoxy FRP pipe, boron trifluoride ether
It closes, and it is 3-5 that the concentrated sulfuric acid, which is added dropwise, to adjust PH, in 85-95 DEG C of polycondensation reaction 1-3h, to get lignin grafted epoxy third after neutralization
Olefin(e) acid ester lotion；
S2: Cypres are prepared: mixing lignin grafted epoxy acrylic acid ester emulsion, cation colophony by weight percentage
Glue, cationic peach gum, cation cassava starch, emulsifier, water, to get the Cypres after 60 DEG C of ultrasonic disperses.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910737173.4A CN110373941B (en) | 2019-08-11 | 2019-08-11 | Corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and preparation method thereof |
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| CN201910737173.4A CN110373941B (en) | 2019-08-11 | 2019-08-11 | Corrugated paper surface sizing agent containing lignin grafted epoxy acrylate and preparation method thereof |
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| CN110373941A true CN110373941A (en) | 2019-10-25 |
| CN110373941B CN110373941B (en) | 2021-10-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232260A (en) * | 2022-08-09 | 2022-10-25 | 江西安德力高新科技有限公司 | Water-based epoxy modified acrylate emulsion for gravure ink and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| 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 |
-
2019
- 2019-08-11 CN CN201910737173.4A patent/CN110373941B/en active Active
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232260A (en) * | 2022-08-09 | 2022-10-25 | 江西安德力高新科技有限公司 | Water-based epoxy modified acrylate emulsion for gravure ink and preparation method thereof |
| CN115232260B (en) * | 2022-08-09 | 2023-12-01 | 江西安德力高新科技有限公司 | Water-based epoxy modified acrylate emulsion for gravure ink and preparation method thereof |
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| CN110373941B (en) | 2021-10-29 |
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