CN104164805B - A method of enhancing papermaking wet-end paper strength by applying betaine amphoteric cellulose - Google Patents
A method of enhancing papermaking wet-end paper strength by applying betaine amphoteric cellulose Download PDFInfo
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- CN104164805B CN104164805B CN201410309208.1A CN201410309208A CN104164805B CN 104164805 B CN104164805 B CN 104164805B CN 201410309208 A CN201410309208 A CN 201410309208A CN 104164805 B CN104164805 B CN 104164805B
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 83
- 239000001913 cellulose Substances 0.000 title claims abstract description 83
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229960003237 betaine Drugs 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 20
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims abstract description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 235000010980 cellulose Nutrition 0.000 claims description 76
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 50
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001450 anions Chemical group 0.000 abstract description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 abstract 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 abstract 1
- 230000009172 bursting Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- -1 betaine structure compound Chemical class 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 5
- PMNYTGAGAKEGJE-UHFFFAOYSA-N ethane-1,2-diamine;sodium Chemical compound [Na].[Na].NCCN PMNYTGAGAKEGJE-UHFFFAOYSA-N 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 241001044369 Amphion Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010016590 Fibrin deposition on lens postoperative Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 108700003601 dimethylglycine Proteins 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Paper (AREA)
Abstract
A method of enhancing papermaking wet-end paper strength by applying betaine amphoteric cellulose is provided. The betaine amphoteric cellulose is a special cellulose derivative side chains of which containing strictly matched anion groups and kation groups. The method includes: synthesizing a betaine amphoteric functional monomer 3-(N,N-dimethylammonium propyl acrylamide) propanesulfonate (DMAPAAS); subjecting the monomer and cellulose to a homogenous reaction in a DMAc/LiCl solvent system under conditions of a ceric ammonium nitrate (CAN)/disodium ethylenediaminetetraacetate dihydrate (EDTA) composite initiating system to synthesize a sulfonic acid-containing betaine/side-group cellulose grafted copolymer; and adding a small amount of the betaine amphoteric cellulose in a paper handsheet experiment, then the bursting strength, the tensile strength and the tearing strength of paper are enhanced to a certain degree. When the adding amount is 0.5%, the tear index of the paper is increased by 10.3%, the burst index is increased by 10.7%, the folding strength is increased by 42.9%, and the fracture length is increased by 15.5%.
Description
Technical field
The present invention relates to a kind of Homogeneous synthesis betaine type amphoteric cellulose apply and be used for strengthening paper with paper making wet part
The method of intensity, belongs to field of papermaking.
Background technology
Cellulose is natural organic matter the abundantest in the world, accounts for more than the 50% of plant kingdom's carbon content.Estimate according to scientist
Meter, the earth reaches 100,000,000,000 tons by biosynthesis cellulose every year, consumption is roughly equal therewith or slightly more.Cellulose
It is important paper making raw material (consuming 1.0 hundred million tons every year) and textile raw material (consuming 0.12 hundred million tons every year), additionally, also extensively being made
For the raw material of the aspects such as plastics, explosive, electrician and Scientific Research Equipments, it is greatly also as fuel or building log
Use.The content of cellulose of cotton, close to 100%, is the natural source of pure cellulose.In general timber, cellulose accounts for 40～
50%, additionally, fiber crops, straw, rice bagasse etc., it is all the abundant source of cellulose.Cellulose is a kind of the linear of polydispersity
High molecular polymer, the polysaccharide being formed by connecting with β-Isosorbide-5-Nitrae-glycosidic bond each other by d- glucopyranose units.Have on glucosyl group
Three hydroxyls being freely present, wherein 2,3 is secondary hydroxyl, 6 upper primary hydroxyls.Although the factor of impact fibrin reaction is very
Many, but as a rule, the respond of primary hydroxyl is higher than secondary hydroxyl, particularly when reacting with macoradical, due to
Three-dimensional effect, the respond of primary hydroxyl is higher than secondary hydroxyl seems.Due to the presence of great amount of hydroxy group in cellulose macromolecule,
It is not a letter that cellulose is readily formed very strong intramolecular and intermolecular hydrogen bonding, the therefore dissolving of cellulose and homogeneous reaction
Single problem.
With the decline of the irreplaceable energy such as reserves such as oil, coal, the soaring and various countries of oil price are to environment
The increasingly raising requiring, as reproducible green resource, the application in industry-by-industry is also increasingly subject to scientific research to cellulose
The attention of worker.
Amphoteric cellulose is exactly a kind of cellulose-derived products of high added value.It is that the water miscible cellulose of a class derives
Thing.Similar with common ampholytes, it has special SOLUTION PROPERTIES and rheological property, has thickening, fall resistance, flocculation, hangs
The function such as floating, on the other hand also has the advantages of macromolecule polysaccharide abundance, easily biological-degradable it is expected in oilfield exploitation, ring
The neighborhoods such as guarantor, papermaking, weaving, turbulent flow drag reduction, medicine, colloid protection obtain important application.Fine with cationic cellulose, anion
Dimension element is compared, and amphoteric cellulose has wider array of range of application, and its serviceability is also superior to both other.Amphoteric cellulose is permissible
It is divided into two kinds according to the distribution of positive and negative group:
1) positive and negative charge of amphoteric cellulose is on different chain links, such as accompanying drawing 1a.At present, most amphoteric fibers
Element broadly falls into this structure.
2) positive and negative charge of amphoteric cellulose is on same chain link, commonly referred to as betaine structure compound, also known as
Be inner salt compound, its result such as accompanying drawing 1b.At present, only only a few amphoteric cellulose is belonging to this inner salt compound knot
Structure.
The preparation method of betaine type cellulosic material has:
1) etherification method: burghard et al. selects hydroxyethyl cellulose and the chloro- 2- hydroxypropyl two of amphion etherifying agent 3-
First ammonium acetic acid reactant salt is obtained the amphoteric cellulose of betaine type.Cellulose ether agent is by epoxychloropropane and n, n- bis-
Methylglycine reacts under certain condition and to obtain.But n in this method, n- dimethylglycine is expensive, reclaims
Rate is relatively low.In addition might have some accessory substances, the chloro- 2- propyl alcohol of such as 1,3- bis-, bi-quaternary ammonium salt etc..Unreacted epoxy chloropropionate
Alkane and the chloro- 2- propyl alcohol of 1,3- bis- are difficult to get rid of from reaction system.These materials are during preparing hydroxyethyl cellulose
It is likely to make hydroxyethyl cellulose produce crosslinking.Identical raw material dry process two under base catalysis such as Liang Yaqin
Property cellulose, with DMAA, sodium chloroacetate and hypochlorous acid are Material synthesis both sexes etherifying agent.
2) Graft Method: Zhang Liming etc., with ammonium ceric nitrate/ethylenediamine tetra-acetic acid as initiator system, causes hydroxyethyl cellulose to connect
Branch glycine betaine monomer n- methylacryoyloxyethyl-n, n- dimethylamino acetate obtains amphoteric cellulose.Chen Liqiong etc. is with nitre
Sour cerium ammonium/disodium EDTA is initiator system, causes hydroxyethyl cellulose graft copolymerization sulphonic acid betaine monomer to obtain
To amphoteric cellulose.
In this patent, we adopt acrylamide propyl-dimethyl amine (dmapaa) in acetone soln with 1,3- propyl group sulphur
Lactone (ps) reacts generation both sexes function monomer 3- (acrylamide propyl-dimethyl amine) propane sulfonic acid salt at 55 DEG C
(dmapaas).Its reaction equation is shown in accompanying drawing 2.Then in the dmac/licl solution of cellulose, in ammonium ceric nitrate/tetraacethyl
Under ethylenediamine disodium salt initiator system, reacted with the dmapaas monomer synthesizing above, by controlling the concentration of monomer and molten
The ph of liquid, to control the reaction mechanism mechanism of reaction, finally obtains betaine type amphoteric cellulose.Its reaction mechanism is shown in accompanying drawing 3.Finally also to it
Strengthening for paper effect is assessed.
Content of the invention
1. a kind of application betaine type amphoteric cellulose strengthens the method for paper strength it is characterised in that wrapping in paper making wet part
Include following step:
Step (1): it is former that betaine type amphoteric monomer adopts acrylamide propyl-dimethyl amine and 1,3- propyl group sultone
Material；
Step (2): acrylamide propyl-dimethyl amine is added equipped with the container of acetone soln, then by 1,3- propyl group
The acetone soln of sultone is added dropwise in reaction vessel in 2-5 hour, and reaction temperature is 40-70 DEG C；Keeping temperature afterwards
Reaction 2-24 hour；3- (acrylamide propyl-dimethyl amine) propane sulfonic acid salt is separated out with white crystal, finally with a large amount of volume ratios 3
: 1 acetone and the mixed liquor of ether rinse repeatedly to remove unreacting material；Finally vacuum drying obtains betaine type amphoteric list
Body product；
Step (3): it is raw material that cellulose adopts microcrystalline cellulose or bleached hardwood pulp；
Step (4): cellulosic material profit under the conditions of 0 DEG C of temperature in 17.5wt%naoh solution rises 1-5 hour, uses water
Wash respectively repeatedly until filtrate ph is neutral with ethanol；Cellulose after profit is risen under the conditions of 25 DEG C, in dimethylacetylamide
The inside is continued profit and is risen 2-10 hour；
Step (5): prepare the dimethylacetamide solution of the lithium chloride of 8w/v%, then the solution prepared is first to heat to
120-130 DEG C, then it is cooled to 60-80 DEG C, the cellulose then step (4) being processed is gradually added under conditions of stirring
Inside solution, until being completely dissolved, time 2-5 hour, finally obtain transparent homogeneous cellulose solution；
Step (6): the homogeneous cellulose solution that step (5) is obtained adds initiator nitre under blanket of nitrogen and stirring condition
The betaine type amphoteric monomer 3- (acrylamide that sour cerium ammonium/EDTA disodium salting liquid and a certain amount of step (2) synthesize
Propyl-dimethyl amine) propane sulfonic acid salt, stop reaction after reaction 2-8 hour, carry out precipitate and separate with acetone, be dried to constant weight, obtain
Amphoteric cellulose product to betaine type；
Step (7): bleached sulphate broad-leaved pulpboard is discongested and pull an oar about 39 ° of sr, the paper pulp laboratory after process
Quick handsheet machine, quickly manufactures paper with pulp into the page of a diameter of 200mm using wet method and is dried, add a certain amount of during manufacturing paper with pulp
The betaine type amphoteric cellulose product prepared of step (6), obtain paper, and test paper performance；When a small amount of step of interpolation
After the amphoteric cellulose product of the betaine type that (6) synthesize suddenly, the intensity of paper just has obvious increase；When addition be based on
During oven dry stock mass percent 0.5%, the tear-proof index of paper improves 10.3%, and burst index lifts 10.7%, and folding strength carries
Rise 42.9%, fracture length strengthens 15.5%.
Brief description
Accompanying drawing 1: the amphoteric cellulose schematic diagram of different chains nodal pattern (a) and betaine type (b) structure.
Accompanying drawing 2: the synthetic reaction equation of dish alkaline monomer dmapaas
Accompanying drawing 3: the reaction mechanism of betaine type monomer dmapaas and cellulose
The infrared spectrogram of accompanying drawing 4:dmapaa, PS and dmapaas
Accompanying drawing 5: beet alkali ampholytic cellulose and mcc infrared spectrogram
Specific embodiment
Referring specifically to accompanying drawing 1-5:
1. the synthesis of betaine type amphoteric cellulose:
The acrylamide propyl-dimethyl amine of 0.11mol is added in 50ml acetone soln, adds 0.1% polymerization inhibitor
MEHQ；Then 1, the 3- propyl group sultone of 0.1mol and 15ml acetone soln are added in dropping funel, little in 2-5
When interior be added dropwise in flask, reaction temperature be 40-70 DEG C；The 2-24 hour of keeping temperature reaction afterwards.3- (acrylamide propyl
Dimethyl amine) propane sulfonic acid salt with white crystal separate out, finally repeatedly rushed with a large amount of acetone of volume ratio 3: 1 and the mixed liquor of ether
Wash to remove unreacting material；Finally it is dried to obtain product in vacuum drying chamber.Betaine type amphoteric monomer 3- (acrylamide
Propyl-dimethyl amine) propane sulfonic acid salt (dmapaas) and reaction raw materials acrylamide propyl-dimethyl amine (dmapaa) and 1,3-
The infrared spectrogram of propyl group sultone is shown in accompanying drawing 4.
Cellulosic material profit under the conditions of 0 DEG C of temperature in 17.5wt%naoh solution rises 1-5 hour, is washed with water and ethanol
Wash and wash respectively repeatedly until filtrate ph is neutral；The cellulose obtaining after profit is risen, under the conditions of 25 DEG C, continues inside dmac
Continue profit to rise 2-10 hour；Prepare the licl/dmac solution of 8w/v%, then the solution prepared be first to heat to 120-130 DEG C,
Then it is cooled to 60-80 DEG C, the cellulose being then passed through activating is gradually added into inside solution, under agitation until completely molten
Solution, time 2-5 hour, finally obtain the homogeneous phase solution of cellulose.
Homogeneous cellulose solution is added under blanket of nitrogen and stirring condition 5x10-3Initiator ammonium ceric nitrate/tetra- of mol/l
Acetic ethylenediamine disodium salting liquid and 0.1% (w/v) MEHQ polymerization inhibitor, are subsequently adding the betaine type above synthesizing
Ampholytic monomer 3- (acrylamide propyl-dimethyl amine) propane sulfonic acid salt (dmapaas), regulation system ph value, after reaction certain time
Stop reaction, carry out precipitate and separate with acetone, be dried to constant weight amount, obtain the amphoteric cellulose product of betaine type.It is infrared
Spectral signature is shown in accompanying drawing 5.
2. the application in paper making wet part of the method for betaine type amphoteric cellulose is it is characterised in that comprise the steps:
Bleached sulphate broad-leaved pulpboard is discongested and pulls an oar about 39 ° of sr, the quick handsheet in the paper pulp laboratory after process
Machine is copied into paper, quickly manufactures paper with pulp into the page of a diameter of 200mm using wet method and is dried, adds a certain amount of during manufacturing paper with pulp
Betaine type amphoteric cellulose product, and last test paper performance.
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
This.
Embodiment 1
The acrylamide propyl-dimethyl amine of 0.11mol is added in 50ml acetone soln, adds 0.1% polymerization inhibitor
MEHQ；Then 1, the 3- propyl group sultone of 0.1mol and 15ml acetone soln are added in dropping funel, at 2 hours
Inside it is added dropwise in flask, reaction temperature is 40 DEG C；Keeping temperature is reacted 2 hours afterwards.3- (acrylamide propyl-dimethyl
Amine) propane sulfonic acid salt with white crystal separate out, finally repeatedly rinsed with the acetone of a large amount of volume ratios 3: 1 and the mixed liquor of ether to remove
Remove unreacting material；Finally obtain product in 55 DEG C of vacuum drying.
Cellulosic material moistens under the conditions of 0 DEG C of temperature in 17.5wt%naoh solution and rises 5 hours, is washed with water and ethanol
Wash respectively repeatedly until filtrate ph is neutral；The cellulose obtaining after profit is risen, under the conditions of 25 DEG C, is continuing inside dmac
Continue profit to rise 10 hours；Prepare the licl/dmac solution of 8w/v%, then the solution prepared is first to heat to 130 DEG C, Ran Houleng
But to 80 DEG C, then weigh the cellulose through overactivation and be gradually added under agitation inside solution, until being completely dissolved, when
Between 5 hours, finally obtain the homogeneous phase solution of 5wt% cellulose.
Homogeneous cellulose solution is added under blanket of nitrogen and stirring condition 5x10-3Initiator ammonium ceric nitrate/tetra- of mol/l
Acetic ethylenediamine disodium salting liquid and 0.1% (w/v) MEHQ polymerization inhibitor, are subsequently adding with respect to plain with bone dry fiber
Betaine type amphoteric monomer 3- (acrylamide propyl-dimethyl amine) the propane sulfonic acid salt synthesizing before equal quality, regulation system
Ph value, reaction stopped reaction after 5 hours, carried out precipitate and separate with acetone, is dried to permanent quality, obtains the amphoteric fibers of betaine type
Plain product, is 1.3 with respect to the yield of cellulose.The a small amount of water soluble of product of changing products.
In the handsheet of copy paper is tested, add the product obtaining being equivalent to oven dry stock 0.5%, with respect to blank sample
Product, tear index increase is inconspicuous, and folding strength lifts 5% than blank sample, and burst index lifts 5%, and fracture length increases by 8%.
Embodiment 2
The acrylamide propyl-dimethyl amine of 0.11mol is added in 50ml acetone soln, adds 0.1% polymerization inhibitor
MEHQ；Then 1, the 3- propyl group sultone of 0.1mol and 15ml acetone soln are added in dropping funel, at 5 hours
Inside it is added dropwise in flask, reaction temperature is 70 DEG C；Keeping temperature is reacted 24 hours afterwards.3- (acrylamide propyl-dimethyl
Amine) propane sulfonic acid salt with white crystal separate out, finally repeatedly rinsed with the acetone of a large amount of volume ratios 3: 1 and the mixed liquor of ether to remove
Remove unreacting material；Finally in 55 DEG C of vacuum drying chambers, it is dried to obtain product.
Cellulosic material moistens under the conditions of 0 DEG C of temperature in 17.5wt%naoh solution and rises 2 hours, is washed with water and ethanol
Wash respectively repeatedly until filtrate ph is neutral；The cellulose obtaining after profit is risen, under the conditions of 25 DEG C, is continuing inside dmac
Continue profit to rise 5 hours；Prepare the licl/dmac solution of 8w/v%, then the solution prepared is first to heat to 120 DEG C, Ran Houleng
But to 70 DEG C, then weigh the cellulose through overactivation and be gradually added under agitation inside solution, until being completely dissolved, when
Between 3 hours, finally obtain the homogeneous phase solution of 3wt% cellulose.
Homogeneous cellulose solution is added under blanket of nitrogen and stirring condition 5x10-3Initiator ammonium ceric nitrate/tetra- of mol/l
Acetic ethylenediamine disodium salting liquid and 0.1% (w/v) MEHQ polymerization inhibitor, are subsequently adding with respect to plain with bone dry fiber
Betaine type amphoteric monomer 3- (acrylamide propyl-dimethyl amine) the propane sulfonic acid salt synthesizing before equal quality, reaction 2 is little
When after stop reaction, carry out precipitate and separate with acetone, be dried to permanent quality, obtain the amphoteric cellulose product of betaine type, relatively
In cellulose yield be 1.5.Changing solubility in water for the sample is 68%.
In the handsheet of copy paper is tested, add the product obtaining being equivalent to oven dry stock mass percent 0.5%, relatively
In blank sample, tear index increase is inconspicuous, and folding strength lifts 10% than blank sample, and burst index lifts 8%, fracture length
Increase by 10%.
Embodiment 3
The acrylamide propyl-dimethyl amine of 0.11mol is added in 50ml acetone soln, adds 0.1% polymerization inhibitor
MEHQ；Then 1, the 3- propyl group sultone of 0.1mol and 15ml acetone soln are added in dropping funel, at 5 hours
Inside it is added dropwise in flask, reaction temperature is 60 DEG C；Keeping temperature is reacted 8 hours afterwards.3- (acrylamide propyl-dimethyl
Amine) propane sulfonic acid salt with white crystal separate out, finally repeatedly rinsed with the acetone of a large amount of volume ratios 3: 1 and the mixed liquor of ether to remove
Remove unreacting material；Finally in 55 DEG C of vacuum drying chambers, it is dried to obtain product.
Cellulosic material moistens under the conditions of 0 DEG C of temperature in 17.5wt%naoh solution and rises 1 hour, is washed with water and ethanol
Wash respectively repeatedly until filtrate ph is neutral；The cellulose obtaining after profit is risen, under the conditions of 25 DEG C, is continuing inside dmac
Continue profit to rise 2 hours；Prepare the licl/dmac solution of 8w/v%, then the solution prepared is first to heat to 130 DEG C, Ran Houleng
But to 60 DEG C, then weigh the cellulose through overactivation and be gradually added under agitation inside solution, until being completely dissolved, when
Between 6 hours, finally obtain the homogeneous phase solution of 1wt% cellulose.
Homogeneous cellulose solution is added under blanket of nitrogen and stirring condition 5x10-3Initiator ammonium ceric nitrate/tetra- of mol/l
Acetic ethylenediamine disodium salting liquid and 0.1% (w/v) MEHQ polymerization inhibitor, are subsequently adding with respect to plain with bone dry fiber
Betaine type amphoteric monomer 3- (acrylamide propyl-dimethyl amine) the propane sulfonic acid salt synthesizing before equal quality, regulation system
Ph value, reaction stopped reaction after 8 hours, carried out precipitate and separate with acetone, is dried to permanent quality, obtains the amphoteric fibers of betaine type
Plain product, is 1.8 with respect to the yield of cellulose.Changing solubility in water for the sample is 83%.
With respect to blank sample, addition is that the tear-proof index of paper during oven dry stock mass percent 0.5% improves
10.3%, burst index lifting 10.7%, folding strength lifting 42.9%, fracture length strengthens 15.5%.
Technique effect
The present invention passes through the betaine type amphoteric monomer of synthesis, carries out anti-in the homogeneous licl/dmac solution of cellulose
Should, thus having prepared the amphoteric cellulose based high molecular of betaine type, this chemicals can not only be used in paper making wet part
Enhancing effect on it is also possible to the function such as there is thickening, fall resistance, flocculation, suspend, on the other hand also there is macromolecule polysaccharide
Source is enriched, it is expected in oilfield exploitation, papermaking, weaving, medicine, environmental protection, turbulent flow drag reduction, colloid protection the advantages of easily biological-degradable
Etc. aspect obtain important application.
In addition declare, be only presently preferred embodiments of the present invention in specific embodiment, not the present invention made any
Pro forma restriction is although the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any familiar
Professional and technical personnel, in the range of without departing from technical solution of the present invention, when the technology contents of available the disclosure above do
Go out a little Equivalent embodiments changing or be modified to equivalent variations, as long as being without departing from technical solution of the present invention content, according to this
Any simple modification, equivalent variations and modification that the technical spirit of invention is made to above embodiment, all still fall within the present invention
In the range of technical scheme.
Claims (1)
1. a kind of application betaine type amphoteric cellulose is under the method for paper making wet part enhancing paper strength is it is characterised in that include
State step:
Step (1): it is raw material that betaine type amphoteric monomer adopts acrylamide propyl-dimethyl amine and 1,3- propyl group sultone；
Step (2): acrylamide propyl-dimethyl amine is added equipped with the container of acetone soln, then by 1,3- propyl group sulphur
The acetone soln of ester is added dropwise in reaction vessel in 2-5 hour, and reaction temperature is 40-70 DEG C；Keeping temperature reaction afterwards
2-24 hour；3- (acrylamide propyl-dimethyl amine) propane sulfonic acid salt is separated out with white crystal, finally with a large amount of volume ratios 3: 1
The mixed liquor of acetone and ether rinses repeatedly to remove unreacting material；Finally vacuum drying obtains betaine type amphoteric monomer and produces
Thing；
Step (3): it is raw material that cellulose adopts microcrystalline cellulose or bleached hardwood pulp；
Step (4): cellulosic material profit under the conditions of 0 DEG C of temperature in 17.5wt% naoh solution rises 1-5 hour, with water and
Ethanol washs respectively repeatedly until filtrate ph is neutral；Cellulose after profit is risen under the conditions of 25 DEG C, in dimethylacetylamide
Face is continued profit and is risen 2-10 hour；
Step (5): prepare the dimethylacetamide solution of the lithium chloride of 8w/v%, then the solution prepared is first to heat to 120-
130 DEG C, then it is cooled to 60-80 DEG C, the cellulose then step (4) being processed is gradually added into solution under conditions of stirring
The inside, until being completely dissolved, time 2-5 hour, finally obtain transparent homogeneous cellulose solution；
Step (6): the homogeneous cellulose solution that step (5) is obtained adds initiator cerous nitrate under blanket of nitrogen and stirring condition
The betaine type amphoteric monomer 3- (acrylamide propyl that ammonium/EDTA disodium salting liquid and a certain amount of step (2) synthesize
Dimethyl amine) propane sulfonic acid salt, stop reaction after reaction 2-8 hour, carry out precipitate and separate with acetone, be dried to constant weight, obtain sweet
The amphoteric cellulose product of dish alkaline；
Step (7): bleached sulphate broad-leaved pulpboard is discongested and pull an oar 39 ° of sr, quickly the copying of the paper pulp laboratory after process
Piece machine, quickly manufactures paper with pulp into the page of a diameter of 200mm using wet method and is dried, add a certain amount of step during manufacturing paper with pulp
(6) the betaine type amphoteric cellulose product prepared, obtains paper, and tests paper performance；Close when adding a small amount of step (6)
After the amphoteric cellulose product of betaine type becoming, the intensity of paper just has obvious increase；Addition is based on fiber quality
During percentage 0.5%, the tear-proof index of paper improves 10.3%, and burst index lifts 10.7%, and folding strength lifts 42.9%,
Fracture length strengthens 15.5%.
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| CN112876716B (en) * | 2021-01-20 | 2022-01-18 | 华南理工大学 | Method for rapidly preparing high-strength bacterial cellulose paper in large area |
| CN113605136B (en) * | 2021-08-18 | 2022-08-09 | 浙江金励环保纸业有限公司 | Method for recycling waste paper pulp |
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| CN103145857B (en) * | 2013-03-28 | 2016-08-17 | 东华大学 | A kind of method utilizing solidago canadesis to prepare amphoteric cellulose |
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