CN108642959A - A kind of lignin Cypres and preparation method thereof - Google Patents
A kind of lignin Cypres and preparation method thereof Download PDFInfo
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- CN108642959A CN108642959A CN201810439611.4A CN201810439611A CN108642959A CN 108642959 A CN108642959 A CN 108642959A CN 201810439611 A CN201810439611 A CN 201810439611A CN 108642959 A CN108642959 A CN 108642959A
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- Prior art keywords
- lignin
- cypres
- methyl
- acid
- grams
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- 229920005610 lignin Polymers 0.000 title claims abstract description 66
- 235000004258 Cordia alliodora Nutrition 0.000 title claims abstract description 53
- 244000085692 Cordia alliodora Species 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 27
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004494 ethyl ester group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 claims description 4
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- XSQNOFMFKVYSNL-UHFFFAOYSA-N ethene;toluene Chemical group C=C.CC1=CC=CC=C1 XSQNOFMFKVYSNL-UHFFFAOYSA-N 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 238000004513 sizing Methods 0.000 abstract description 16
- 239000011436 cob Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 7
- 229920002472 Starch Polymers 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 235000019698 starch Nutrition 0.000 abstract description 3
- 239000008107 starch Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 21
- 238000010792 warming Methods 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- 235000005078 Chaenomeles speciosa Nutrition 0.000 description 2
- 240000000425 Chaenomeles speciosa Species 0.000 description 2
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical class CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- JDBYOFONDXFLQH-UHFFFAOYSA-N n-methylmethanamine;2-methylprop-2-enamide Chemical class CNC.CC(=C)C(N)=O JDBYOFONDXFLQH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The present invention provides the preparation methods of a kind of lignin Cypres and the lignin Cypres.The lignin Cypres are the aqueous dispersions made of lignin, alkali, trimethylamine, epoxychloropropane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) styrene, initiator copolymerization.The lignin Cypres are very suitable for the surface treatment of fluting medium.The product can carry out top sizing together with starch to fluting medium, can not only improve the Cobb values of corrugated paper, accelerate curing speed, and can increase substantially the surface ring crush intensity of corrugated paper, adapt to the needs of highly intensified corrugated paper development；In addition, the preparation method of the lignin Cypres, for the lignin generated using in paper-making process as starting material, cost is relatively low, and operating procedure is simple, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to papermaking chemical product manufacturing field, more particularly to a kind of lignin Cypres and described
The preparation method of lignin Cypres.
Background technology
Currently, the development trend of paper, especially corrugated paper, paperboard shows the following aspects：
1) just develop from high grammes per square metre to low grammes per square metre direction；
2) waste paper is used to replace wood pulp, but at the intensity difference of paper, hygroscopicity value is high；
3) the problem of paper quality is unstable caused by internal sizing variable factor is more, class is difficult raising,
So that manufacturer uses or abandon less internal sizing, fashion trend is become using the technique that top sizing is made up.
In addition, for above-mentioned top sizing sizing agent generally require meet it is claimed below：A) ring crush intensity is improved；B) big
Width reduces Cobb values (hygroscopicity value)；C) curing speed is fast, it is desirable that lower machine is with regard to ripe.
Although existing Cypres can improve the ring crush intensity of corrugated paper to a certain extent on the market, apply
Jelly dosage is excessive, high so as to cause cost.For example, Chinese patent application CN107034730A in the prior art is public
A kind of moisture-proof quick-dry type Cypres are opened, quickly, but it improves not the ring crush intensity of corrugated paper to rate of drying
Greatly.
Therefore, it is urgent to provide a kind of completely new corrugated paper Cypres, make it that Cobb values can either be greatly reduced, quickly
Curing, and the ring crush intensity of corrugated paper can be significantly improved.
Invention content
In order to overcome many technological deficiencies existing in the prior art, the present invention is intended to provide a kind of being suitable for industrialized production
Cypres synthesis technology and be made a kind of new Cypres, main application is in the top sizing of corrugated paper, no
But Cobb values can be greatly reduced, it is basic to realize that lower machine is just ripe, and can significantly be carried in the case where sizing agent dosage is constant
The ring crush intensity of high corrugated paper.
Therefore, first aspect present invention provides a kind of lignin Cypres, and it includes following components：Lignin,
Alkali, trimethylamine, epoxychloropropane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) styrene, initiator with
And water.In fact, the lignin Cypres are by lignin, alkali, trimethylamine, epoxychloropropane, acid, cation mono
Aqueous dispersion made of body, (methyl) acrylic ester monomer, (methyl) styrene, initiator copolymerization.It applies on the lignin surface
Jelly is very suitable for the surface treatment of fluting medium.
Preferably, in above-mentioned lignin Cypres, the weight of each component is as follows：
It is further preferred that in above-mentioned lignin Cypres, the alkali is selected from following any one or more：Hydrogen-oxygen
Change sodium, potassium hydroxide and ammonium hydroxide.
It is further preferred that in above-mentioned lignin Cypres, the acid is selected from following any one or more：Salt
Acid, acetic acid and dilute sulfuric acid.
It is further preferred that in above-mentioned lignin Cypres, the cationic monomer be selected from it is following any or
It is a variety of：Acrylic acid-N, TMSDMA N dimethylamine base ethyl ester, dimethylaminopropyl methacrylamide.
It is further preferred that in above-mentioned lignin Cypres, (methyl) acrylic ester monomer be selected from
Under it is any one or more：Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, third
Enoic acid ter-butyl ester, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, metering system
Sour N-butyl, Isobutyl methacrylate, Tert-butyl Methacrylate, isooctyl methacrylate.
It is further preferred that in above-mentioned lignin Cypres, the initiator is selected from following any one or more：
Hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, tert-butyl hydroperoxide.
Meanwhile second aspect of the present invention additionally provides a kind of preparation side of the lignin Cypres described in first aspect
Method comprising following steps：By lignin, alkali, trimethylamine, epoxychloropropane, acid, cationic monomer, (methyl) acrylate
Class monomer, (methyl) styrene, initiator and water mixing, add up reaction 3~10 hours under 45~95 DEG C of reaction temperature,
Aqueous dispersion is copolymerized into get the lignin Cypres, solid content is 15~50wt%, pH=1~7.
In addition, being worth supplementary explanation, the lignin added in the lignin Cypres unexpectedly can
The ring crush intensity of corrugated paper is enough increased substantially, and simultaneously so that the Cobb values of the corrugated paper are remarkably decreased.This may due to
The hydrophilic hydroxy group in cation-modified lignin in the process is carried out in the present invention to lignin to be shielded, while cation
Cation group in polymer can with the hydroxy combining of the starch in a large amount of hydroxyl in lignin fibre surface and glue application solution, and
It is combined by ionic bond, plays the role of bridge formation, to improve the active force between fiber fines and to enhance corrugated paper apparent
Ring crush intensity, while the Cobb values for realizing paper decline.
In short, lignin Cypres provided by the present invention are a kind of high-performance that can meet paper for surface sizing
Environment-friendly products.The product can carry out top sizing together with starch to fluting medium, can not only improve the Cobb values of corrugated paper,
Accelerate curing speed, and the surface ring crush intensity of corrugated paper can be increased substantially, adapts to the needs of highly intensified corrugated paper development；
In addition, the preparation method of the lignin Cypres provided by the present invention, wooden using what is generated in paper-making process
Element is used as starting material, and cost is relatively low, and operating procedure is simple, is suitable for large-scale industrial production.
Specific implementation mode
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
Lignin Cypres according to a first aspect of the present invention, including following components：Lignin, alkali, trimethylamine, ring
Oxygen chloropropane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) styrene, initiator and water.
In a preferred embodiment, the weight of each component of lignin Cypres is as follows：
In a further preferred embodiment, the alkali is selected from following any one or more：Sodium hydroxide, hydroxide
Potassium and ammonium hydroxide.
In a further preferred embodiment, the acid is selected from following any one or more：Hydrochloric acid, acetic acid and dilute sulphur
Acid.
In a further preferred embodiment, the cationic monomer is selected from following any one or more：Acrylic acid-
N, TMSDMA N dimethylamine base ethyl ester, dimethylaminopropyl methacrylamide.
In a further preferred embodiment, (methyl) acrylic ester monomer is selected from following any or more
Kind：Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, third
The different monooctyl ester of olefin(e) acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, methyl
Isobutyl acrylate, Tert-butyl Methacrylate, isooctyl methacrylate.
In a further preferred embodiment, the initiator is selected from following any one or more：Hydrogen peroxide, mistake
Ammonium sulfate, sodium peroxydisulfate, tert-butyl hydroperoxide.
The preparation method of lignin Cypres according to a second aspect of the present invention, includes the following steps：By lignin,
Alkali, trimethylamine, epoxychloropropane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) styrene, initiator with
And water mixing, add up reaction 3~10 hours under 45~95 DEG C of reaction temperature, is copolymerized into aqueous dispersion to get described wooden
Plain Cypres.
Embodiment 1
Lignin Cypres are prepared according to the following steps 1.：
Step A)：By 20 grams of styrene, 20 grams of n-butyl acrylates, 5 grams of acrylic acid-N, the mixing of TMSDMA N dimethylamine base ethyl ester is
It is even, it is spare；
Step B)：0.3 gram of ammonium persulfate is dissolved in 10 grams of deionized waters, it is spare；
Step C)：With condenser, Dropping feeder, blender, thermometer four-hole boiling flask in, be added 148.3 grams go
Ionized water, 10 grams of potassium hydroxide, 1 gram of trimethylamine, 100 grams of lignin are warming up to 45 DEG C after being completely dissolved, 1 gram of epoxy chlorine is added dropwise
Propane, 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 mix monomer made from), time for adding 1 hour；A dropping step B simultaneously) made from initiator solution, time for adding 1 is small
When；Continue insulation reaction 1 hour after completion of dropwise addition at 70 DEG C, is subsequently cooled to 25 DEG C, pH=5.91；It is filtered through 100 mesh filter screens,
Lignin Cypres are made 1., solid content 49.95wt%.
Embodiment 2
Lignin Cypres are prepared according to the following steps 2.：
Step A)：By 100 grams of methyl styrenes, 100 grams of Isooctyl acrylate monomers, 100 grams of Methacrylamide dimethylamines
Base amine is uniformly mixed, spare；
Step B)：10 grams of sodium peroxydisulfates are dissolved in 100 grams of deionized waters, it is spare；
Step C)：With condenser, Dropping feeder, blender, thermometer four-hole boiling flask in, be added 2960 grams go from
Sub- water, 40 grams of ammonium hydroxide, 25 grams of trimethylamines, 100 grams of lignin are warming up to 55 DEG C after being completely dissolved, 25 grams of epoxy chlorine are added dropwise
Propane, time for adding 1 hour continue heat preservation 2 hours；95 DEG C are warming up to, 40 grams of dilute sulfuric acids are added；In 95 DEG C of a dropping step A) system
The mix monomer obtained, time for adding 3 hours；Simultaneously a dropping step B) made from initiator solution, time for adding 3 hours；Drop
Continue insulation reaction 2 hours after adding at 95 DEG C, is subsequently cooled to 25 DEG C, pH=1.09；It filters, is made through 100 mesh filter screens
Lignin Cypres 2., solid content 15.16wt%.
Embodiment 3
Lignin Cypres are prepared according to the following steps 3.：
Step A)：By 60 grams of methyl styrenes, 50 grams of ethyl methacrylate, 50 grams of Methacrylamide propyl-dimethyls
Amine is uniformly mixed, spare；
Step B)：6 grams of hydrogen peroxide are dissolved in 100 grams of deionized waters, it is spare；
Step C)：With condenser, Dropping feeder, blender, thermometer four-hole boiling flask in, be added 684 grams go from
Sub- water, 20 grams of sodium hydroxides, 15 grams of trimethylamines, 100 grams of lignin are warming up to 65 DEG C after being completely dissolved, 15 grams of epoxy chlorine are added dropwise
Propane, time for adding 2 hours continue heat preservation 1 hour；85 DEG C are warming up to, 20 grams of acetic acid are added；In 85 DEG C of a dropping step A) it is made
Mix monomer, time for adding 1.5 hours；Simultaneously a dropping step B) made from initiator solution, time for adding 2 hours；Drop
Continue insulation reaction 1 hour after adding at 85 DEG C, is subsequently cooled to 25 DEG C, pH=4.16；It filters, is made through 100 mesh filter screens
Lignin Cypres 3., solid content 30.18wt%.
Embodiment 4
Lignin Cypres are prepared according to the following steps 4.：
Step A)：By 10 grams of methyl styrenes, 20 grams of styrene, 20 grams of Isobutyl methacrylates, 20 grams of metering systems
Sour methyl esters, 30 grams of dimethylaminopropyl methacrylamides are uniformly mixed, spare；
Step B)：4 grams of hydrogen peroxide are dissolved in 100 grams of deionized waters, it is spare；
Step C)：With condenser, Dropping feeder, blender, thermometer four-hole boiling flask in, be added 976 grams go from
Sub- water, 25 grams of sodium hydroxides, 10 grams of trimethylamines, 100 grams of lignin are warming up to 70 DEG C after being completely dissolved, 18 grams of epoxy chlorine are added dropwise
Propane, time for adding 1 hour continue heat preservation 1 hour；80 DEG C are warming up to, 12 grams of acetic acid are added；In 80 DEG C of a dropping step A) it is made
Mix monomer, time for adding 2 hours；Simultaneously a dropping step B) made from initiator solution, time for adding 3 hours；It is added dropwise
After continue insulation reaction 1 hour at 80 DEG C, be subsequently cooled to 25 DEG C, pH=5.01；It is filtered through 100 mesh filter screens, wood is made
Quality Cypres 4., solid content 20.34wt%.
Embodiment 5
Lignin Cypres are prepared according to the following steps 5.：
Step A)：By 40 grams of methyl styrenes, 30 grams of styrene, 50 grams of Tert-butyl Methacrylates, 5 grams of methacrylic acids
Propyl ester, 15 grams of dimethylaminopropyl methacrylamides are uniformly mixed, spare；
Step B)：5 grams of hydrogen peroxide, 2 grams of tert-butyl hydroperoxide are dissolved in 100 grams of deionized waters, it is spare；
Step C)：With condenser, Dropping feeder, blender, thermometer four-hole boiling flask in, be added 383 grams go from
Sub- water, 15 grams of sodium hydroxides, 22 grams of trimethylamines, 100 grams of lignin are warming up to 60 DEG C after being completely dissolved, 13 grams of epoxy chlorine are added dropwise
Propane, time for adding 1 hour continue heat preservation 0.5 hour；90 DEG C are warming up to, 25 grams of hydrochloric acid are added；In 90 DEG C of a dropping step A) system
The mix monomer obtained, time for adding 2.5 hours；A dropping step B simultaneously) made from initiator solution, time for adding 2.5 is small
When；Continue insulation reaction 1 hour after completion of dropwise addition at 90 DEG C, is subsequently cooled to 25 DEG C, pH=3.11；It is filtered through 100 mesh filter screens,
Lignin Cypres are made 5., solid content 40.12wt%.
Embodiment 6
The sizing agent prepared in the method described in Chinese patent application CN107034730A (its solid content is 15wt%)
As a comparison case, with lignin Cypres made from Examples 1 to 5 1.~5. (be diluted to solid content with deionized water
15wt%) it is used as experimental group, inventor also to carry out a series of key index detections.
The preparation of glue application solution：500 grams of 10wt% oxidized starch aqueous solutions are prepared, are warming up to 90 DEG C, gelatinization after twenty minutes, is dropped
Temperature to 40 DEG C, then be separately added into comparative example sizing agent and lignin Cypres 1.~5. (oxidized starch (dry)：Sizing agent
(wet)=50：4) it, adds water and is diluted to solid content 8wt%.
Include in the step of corrugated paper upper surface is glued：
Will by comparative example sizing agent, lignin Cypres 1.~5. 6 kinds of glue application solutions obtained use 10# spreading rods respectively
It is coated on 120 grams of fluting mediums, coating weight is 2g/m2, after coating, dried 30 seconds or 120 seconds in 110 DEG C of baking ovens respectively,
After taking-up, it is cooled to room temperature and measures Cobb values and ring crush intensity.
Cobb values measure：It can vigorous absorbability analyzer using the XSH types of Hangzhou Qingtong Boke Automation Technology Co., Ltd.
And detect pattern to be measured by GB/T 1540-1989 methods.
Ring crush intensity measures：Using the CT300A compressive strength testers of Hangzhou Qingtong Boke Automation Technology Co., Ltd.
Detect pattern to be measured.
General estimation standard：Cobb values are the smaller the better, and ring crush index is the bigger the better.
Specifically, testing result is as shown in table 1 below：
1 Cobb values of table are compared with ring crush intensity testing result
By analyzing upper table data it is found that relative to comparative example, according to lignin top sizing made from Examples 1 to 5
Agent 1.~5. can be obviously improved the ring crush intensity of paper and be obviously improved Cobb values, meanwhile, under the different curing times, sizing
The Cobb values of paper afterwards, ring crush index are not much different, and cure very fast, satisfaction actual needs.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by impartial conversion and
Modification, all should be contained within the scope of the invention.
Claims (8)
1. a kind of lignin Cypres, which is characterized in that include following components：Lignin, alkali, trimethylamine, epoxy chloropropionate
Alkane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) styrene, initiator and water.
2. lignin Cypres according to claim 1, which is characterized in that the weight of each component is as follows：
3. lignin Cypres according to claim 2, which is characterized in that the alkali is selected from following any or more
Kind：Sodium hydroxide, potassium hydroxide and ammonium hydroxide.
4. lignin Cypres according to claim 2, which is characterized in that the acid is selected from following any or more
Kind：Hydrochloric acid, acetic acid and dilute sulfuric acid.
5. lignin Cypres according to claim 2, which is characterized in that the cationic monomer is selected from following
It is one or more：Acrylic acid-N, TMSDMA N dimethylamine base ethyl ester, dimethylaminopropyl methacrylamide.
6. lignin Cypres according to claim 2, which is characterized in that (methyl) acrylic ester monomer
Selected from following any one or more：Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl
Ester, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, first
Base n-butyl acrylate, Isobutyl methacrylate, Tert-butyl Methacrylate, isooctyl methacrylate.
7. lignin Cypres according to claim 2, which is characterized in that the initiator is selected from following any
Or it is a variety of：Hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, tert-butyl hydroperoxide.
8. a kind of preparation method of lignin Cypres according to claim 1, which is characterized in that including following step
Suddenly：By lignin, alkali, trimethylamine, epoxychloropropane, acid, cationic monomer, (methyl) acrylic ester monomer, (methyl) benzene
Ethylene, initiator and water mixing, add up reaction 3~10 hours under 45~95 DEG C of reaction temperature, are copolymerized into aqueous dispersion,
Up to the lignin Cypres.
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| CN110067146A (en) * | 2019-05-09 | 2019-07-30 | 南京林业大学 | A method of addition compounding lignin is manufactured paper with pulp high strength paper |
| CN112760089A (en) * | 2021-01-28 | 2021-05-07 | 重庆化工职业学院 | Lignin-based gemini surfactant and preparation method thereof |
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