CN103408700A - Preparation method of amphoteric dry strength agent - Google Patents
Preparation method of amphoteric dry strength agent Download PDFInfo
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- CN103408700A CN103408700A CN2013102876595A CN201310287659A CN103408700A CN 103408700 A CN103408700 A CN 103408700A CN 2013102876595 A CN2013102876595 A CN 2013102876595A CN 201310287659 A CN201310287659 A CN 201310287659A CN 103408700 A CN103408700 A CN 103408700A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- 229920002472 Starch Polymers 0.000 claims abstract description 18
- 239000008107 starch Substances 0.000 claims abstract description 18
- 235000019698 starch Nutrition 0.000 claims abstract description 18
- 230000001678 irradiating effect Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract 3
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- -1 (methyl) acrylyl Chemical group 0.000 claims description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 8
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229940123457 Free radical scavenger Drugs 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- SGZOTQPYJLDQRT-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC=CC=C1C=C SGZOTQPYJLDQRT-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 150000004054 benzoquinones Chemical class 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229960004194 lidocaine Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000010893 paper waste Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000000123 paper Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920002401 polyacrylamide Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 5
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- XUIKGJQOQAHGQE-UHFFFAOYSA-N CC(=CC)[Na] Chemical compound CC(=CC)[Na] XUIKGJQOQAHGQE-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000274582 Pycnanthus angolensis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 229920006320 anionic starch Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Paper (AREA)
Abstract
The invention provides a preparation method of an amphoteric dry strength agent, which is characterized by comprising the following steps: mixing cationic starch and water, gelatinizing by heating, sequentially adding water, acrylamide, anionic monomer, crosslinkable monomer, chain transfer agent, other functional monomers and photoinitiator, heating to 70-95 DEG C in an oxygen-free environment, irradiating ultraviolet light on the reaction system to react for 1-2 hours, taking samples and carrying out viscosity testing at set intervals, stopping irradiating the ultraviolet light when the viscosity reaches 4000-9000 mP*s, adding a pH regulator to regulate the pH value to 4-6, and adding a free radical trapper to obtain the dry strength agent. The dry strength agent synthesized by the method has the characteristics of low consumption, favorable effect and low cost. The dry strength agent can be used in producing box making paper, corrugated base paper, enamelled paper, cone paper, special-type paper and many other types of paper, has the function of increasing the dry strength of paper, and especially has more obvious effect when using recovered wastepaper pulp as a paper making raw material.
Description
Technical field
The present invention relates to a kind of preparation method of both sexes Dry Strength Resin.
Background technology
Dry Strength Resin is in paper industry, to increase a class important chemical of paper strength, is generally used for the decline that filler or the caused paper intensity of low-grade fiber (as regenerated fibre) are added in compensation.Many water miscible, the superpolymer that can form hydrogen bonded with fiber can become Dry Strength Resin.
In recent years, China's waste paper resource utilization rises year by year, and development potentiality is huge.But the raising of the utilization ratio of waste paper means waste paper and recycles the increase of number of times, can cause declining to a great extent of paper strength index, so need, add Dry Strength Resin and strengthen paper strength.Along with constantly rising to the paper and Board demand in consumption market, pulled the rapid growth of Dry Strength Resin demand.Study of Paper-Strengthening Agent Based has been widely used in the production process of all kinds of paper and cardboard, in order to the dry strength of remarkable increase paper and cardboard, reduces high-quality raw material consumption, reduces production costs; Perhaps improve product specification, the more and more higher specification of quality constantly proposed to meet the user.
Dry Strength Resin commonly used has natural polymer such as starch and modifier (cationic starch, anionic starch, cross-linking starch etc.), synthetic polymer such as polyacrylamide, polyvinyl alcohol etc. and other water-soluble natural product type Dry Strength Resin (as guar gum and derivative thereof etc.).In most of the cases, only add such material of massfraction 0.1%-0.75% just can reach effectively dry potent fruit.
Current effect Dry Strength Resin preferably is polyacrylamide and multipolymer thereof, comprises anion-polyacrylamide, cationic-type polyacrylamide and amphiprotic polyacrylamide.Wherein amphiprotic polyacrylamide shows best effect.Polyacrylamide is from also dividing direct linkage type and branched chain type in view of structure.The polyacrylamide that the degree of branching is high has better effect.According to the literature, molecular weight is in the application performance preferably that has of 500,000 left and right.
The main flow of current synthesized high-performance Dry Strength Resin and the branched chain type amphiphilic polymers that trend is synthetic molecular weight and modest viscosity.This Dry Strength Resin can play the dry enhancement of good paper in the situation that do not add Tai-Ace S 150.The normal employing adds the method for linking agent to obtain the branched chain type Dry Strength Resin, but often has a common problem, is exactly reaction process control problem, and the viscosity of resulting polymers often there will be excessive or too small problem, controls the improper gelation that also often there will be.Because various monomer prices used are higher, the cost of synthesis type Dry Strength Resin is relatively high at present.Starch is carried out to graft modification and both can reduce the cost of product, can also obtain close with modified starch series Dry Strength Resin performance with existing polyacrylamide or better Dry Strength Resin by suitable composition and engineering.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of both sexes Dry Strength Resin, the above-mentioned defect existed to overcome prior art.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of both sexes Dry Strength Resin, it is characterized in that, comprise the steps: cationic starch and water are mixed, be heated to 75～95 ℃ of gelatinizations, form uniform liquid, add successively again water, acrylamide, anionic monomer, cationic monomer, cross-linkable monomer, chain-transfer agent, other functional monomers and photoinitiator, under oxygen-free environment (for example, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, continue logical nitrogen after 30～60 minutes, temperature of reaction kettle is risen to 70～95 ℃, maintain logical nitrogen), temperature is risen to 70-95 ℃, to reaction system irradiating ultraviolet light reaction 1-2 hour, viscosity test is carried out in (for example 20 minutes) sampling at set intervals afterwards, viscosity stops irradiating ultraviolet light after reaching 4000-9000mP*s, add pH adjusting agent to regulate pH to 4-6, and add free radical scavenger, obtain described Dry Strength Resin.
The weight ratio of above each component following (calculating with effective content 100%):
Wherein:
Described cationic starch, can select according to practical situation the product of different cationic degrees, to adapt to the demand of actual use;
Described acrylamide can add with solid form, and also used water solution form adds, and if with aqueous solution form, added, need carry out effective content calculating and guarantee its effective content, and should be according to the add-on of water in practical situation adjustment system.
Described anionic monomer is one or more in the monomers such as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride, sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium, sodium allyl sulfonate and methallylsulfonic acid sodium or its esters.
Described cationic monomer is (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, diallyldimethylammonium chloride, dimethylamino propyl acrylamide etc. with one or more in tertiary amino monomers or quaternary ammonium salt monomer.
Described cross-linkable monomer is one or more in di-vinyl monomers (as methylene-bisacrylamide etc.), trivinyl monomer (as N, N-diallyl acrylamide etc.) or the activated monomer of other tools (as N,N-DMAA etc.).The participation of cross-linkable monomer, can make polymkeric substance produce side chain at an easy rate.
Described other functional monomers can be one or more in some soft monomers (as Hydroxyethyl acrylate, Propylene glycol monoacrylate), hard monomer (as vinylbenzene, methyl methacrylate), hydrophobic monomer (as alkyl acrylate, alkyl methacrylate etc.).Various functional monomers are in order to adjust the performance of Dry Strength Resin in some special aspects.Soft monomer can improve the performance of Dry Strength Resin aspect the paper folding endurance, and hard monomer can be strengthened Dry Strength Resin in the performance of improving on the paper ring crush index, and hydrophobic monomer can improve the dispersiveness of Dry Strength Resin in water.
Described photoinitiator is benzophenone, benzophenone soluble derivative, st-yrax analog derivative, fluorescein and eosin etc.
Described chain-transfer agent can be for inorganic chain-transfer agent (as sodium bisulfite, Sodium Pyrosulfite and Sulfothiorine etc.), organic chain transfer agent (as positive Dodecyl Mercaptan, tert-dodecyl mercaptan, Thiovanic acid, mercaptoethanol, with other materials of sulfydryl, Virahol etc.) with one or more in the monomer of allyl group or methylpropenyl.
Described free radical scavenger is the material (as sodium bisulfite, xitix etc.) that various water-soluble stoppers (as Resorcinol, benzoquinones, iron(ic) chloride, neutralized verdigris etc.) maybe can consume free radical.
Described pH adjusting agent determines as the case may be, when before the system pH regulator higher than 6 the time, pH adjusting agent is acids (example hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid etc.); When before the system pH regulator lower than 4 the time, pH adjusting agent is bases (as NaOH, ammoniacal liquor etc.).
Described ultraviolet source is high voltage mercury lamp, and its wavelength is 100～1000nm, and its power is according to the size adjustment of reaction vessel.
The present invention adopts UV-irradiation photoinitiator initiated polymerization to prepare starch grafting type both sexes Dry Strength Resin: the cationic starch aqueous solution of take is basis, take acrylamide, anionic monomer, cationic starch, cross-linkable monomer, chain-transfer agent and other functional monomers is the grafting raw material, under the existence of photoinitiator, in nitrogen atmosphere with the UV-irradiation Inducing Graft Polymerization, viscosity stops irradiating ultraviolet light after reaching target zone, finishes polyreaction.Due to light-initiated characteristics, free radical can produce in a short period of time, also can disappear in a short period of time, therefore the method is compared conventional synthetic method and is had simple to operate, viscosity is easy to control, the advantages such as gelation can be effectively prevented, all moderate Dry Strength Resins of molecular weight, the degree of branching and viscosity can be obtained.
By grafted polyacrylamide chain in cationic starch, make gained graftomer type Dry Strength Resin have the advantage of starch based Dry Strength Resin and polyacrylamide Dry Strength Resin concurrently, both also show synergy.In synthetic, introduce cross-linkable monomer, make grafted chain itself also have branched structure, this gives its unique performance.The introducing of anionic monomer and cationic monomer make resulting polymers on grafted chain with the yin, yang ion, with the positively charged ion on main chain, form together the both sexes structure, make it in use can effectively avoid system excessively oxygen ionized, and have better adaptive capacity to environment.Moreover, by adjusting the ratio of soft or hard monomer, make Dry Strength Resin have suitable hard and soft property and adhesive property.The performances such as the above ring pressure that these make such Dry Strength Resin add after paper pulp can to improve into well paper, folding, anti-broken, anti-tensile, paper internal bond strength.In addition, the branched structure that this Dry Strength Resin has and suitable hydrophilic and hydrophobic matter, make it have less viscosity, in water, has good dispersiveness, can dilute at an easy rate, the convenient use.
With the synthetic Dry Strength Resin of present method, have easy dispersion, wide adaptability, consumption is few, effective, cost is low characteristics.Can in the production of the multiple paper kinds such as boxboard, Corrugating Base Paper, enamelled paper, cop tube paper, speciality paper, use, play the effect that increases the paper dry strength, especially when with reclaimed waste paper, starching as paper making raw material, effect is more remarkable.Such Dry Strength Resin can have the dry reinforced effects of outstanding paper in the situation that do not add Tai-Ace S 150.
Embodiment
In embodiment, the consumption of component is weight part.
Embodiment 1
In reactor, add water 350g, under stirring, add the 35g cationic starch, be heated to 75 ℃ and carried out gelatinization 2 hours, then add successively acrylamide 85g, methylene-succinic acid 2g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 16g, DMAA 1g, sodium allyl sulfonate 0.6g, Propylene glycol monoacrylate 3g, ethyl propenoate 1.5g and benzophenone 0.6g stir, add 55g water and rinse charging opening, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, then maintain logical nitrogen, temperature of reaction kettle is risen to 85 ℃, to the reaction system irradiating ultraviolet light, in the situation of basic maintenance constant temperature, reaction is 1.5 hours, start afterwards to carry out viscosity test every sampling in 20 minutes, viscosity stops irradiating ultraviolet light after reaching 7000mP*s, add liquid caustic soda (32%) 1g to regulate pH to 4～6, finally add Resorcinol 0.01g, add water and regulate solid content to 20 ± 1%, be the finished product.
Embodiment 2
In reactor, add water 350g, under stirring, add the 58g cationic starch, be heated to 85 ℃ and carried out gelatinization 1 hour, then add successively acrylamide 58g, maleic anhydride 1g, (methyl) dimethylaminoethyl acrylate 5g, methylene-bisacrylamide 0.08g, methylpropenyl sodium sulfonate 0.8g, Propylene glycol monoacrylate 15g, vinylbenzene 5g and benzophenone 0.5g stir, with 50g water, rinse charging opening, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, then maintain logical nitrogen, temperature of reaction kettle is risen to 75 ℃, to the reaction system irradiating ultraviolet light, in the situation of basic maintenance constant temperature, reaction is 2 hours, start afterwards to carry out viscosity test every sampling in 20 minutes, viscosity stops irradiating ultraviolet light after reaching 5000mP*s, add liquid caustic soda (32%) 1g to regulate pH to 4～6, finally add sodium bisulfite 2g, add water and regulate solid content to 20 ± 1%, be the finished product.
Embodiment 3
In reactor, add water 450g, under stirring, add the 40g cationic starch, be heated to 95 ℃ and carried out gelatinization 0.5 hour, then add successively acrylamide 50g, vinylformic acid 1g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 5g, methylene-bisacrylamide 0.03g, sodium allyl sulfonate 0.2g, methyl methacrylate 4g, Propylene glycol monoacrylate 1g, ethyl propenoate 1g and benzophenone 0.5g stir, with 70g water, rinse charging opening, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, then maintain logical nitrogen, temperature of reaction kettle is risen to 85 ℃, to the reaction system irradiating ultraviolet light, in the situation of basic maintenance constant temperature, reaction is 1.5 hours, start afterwards to carry out viscosity test every sampling in 20 minutes, viscosity stops irradiating ultraviolet light after reaching 6500mP*s, regulate pH to 4～6, finally add para benzoquinone 0.01g, add water and regulate solid content to 15 ± 1%, be the finished product.
Embodiment 4
In reactor, add water 400g, under stirring, add the 110g cationic starch, be heated to 95 ℃ and carried out gelatinization 1 hour, then add successively acrylamide 52g, vinylformic acid 1g, dimethyl diallyl ammonium chloride 8g, DMAA 1g, ethyl thioglycolate 0.6g, Dodecyl Mercaptan 0.002g, Propylene glycol monoacrylate 4g, vinylbenzene 2g and benzoin methyl ether 0.5g stir, add 20g water and rinse charging opening, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, then maintain logical nitrogen, temperature of reaction kettle is risen to 82 ℃, to the reaction system irradiating ultraviolet light, in the situation of basic maintenance constant temperature, reaction is 2 hours, start afterwards to carry out viscosity test every sampling in 20 minutes, viscosity stops irradiating ultraviolet light after reaching 8500mP*s, regulate pH to 4～6, finally add Dichlorodiphenyl Acetate copper 0.01g, add water and regulate solid content to 30 ± 1%, be the finished product.
Comparative example 1
In reactor, add successively water 405g, acrylamide 120g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 16g, methylene-bisacrylamide 0.08g, mercaptoethanol 1g, Propylene glycol monoacrylate 4g, ethyl propenoate 2g and benzophenone 1g stir, reactor is vacuumized to logical nitrogen 2～3 times repeatedly, then maintain logical nitrogen, temperature of reaction kettle is risen to 85 ℃, to the reaction system irradiating ultraviolet light, in the situation of basic maintenance constant temperature, reaction is 1.5 hours, start afterwards to carry out viscosity test every sampling in 20 minutes, viscosity stops irradiating ultraviolet light after reaching 4500mP*s, add liquid caustic soda (32%) 1.5g to regulate pH to 4～6, finally add Resorcinol 0.02g, add water and regulate solid content to 20 ± 1%.
Comparative example 2
In reactor, add successively water 550g, acrylamide 83g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 9g, DMAA 0.8g, sodium allyl sulfonate 0.2g stirs, logical nitrogen drove oxygen 60 minutes, be warmed up to 60 ℃, add ammonium persulphate 0.5g(to be dissolved in 20g water), temperature of reaction kettle is risen to 82 ℃, react after 1 hour and start sampling detection viscosity.Viscosity adds the stopper stopped reaction after reaching 3500mPa*s.Regulate pH to 4～6, adding water move to solid content is 15 ± 1%.
Application Example
Adopt the reclaimed waste paper case to pull an oar as raw material, beating degree adds Dry Strength Resin to stir 5 minutes after reaching 35 ° of SR, after being shaped, adopts by semi-automatic sheet-former the squeezing of standard page squeezing machine, natural air drying, then detect the index such as tensile strength, ring crush intensity, bursting strength, folding endurance, internal bond strength of paper.The Dry Strength Resin add-on is 4.5～7.5 ‰ (dry/oven dry stocks).Table 2 has provided the application data of the prepared Dry Strength Resin of aforesaid method.
Table 1. adds the handsheet intensity index (dry/oven dry stock) of Dry Strength Resin
As can be known by above-described embodiment, Comparative Examples and application examples, the synthetic Dry Strength Resin of method therefor of the present invention has good application performance, on effect, compares and approaches or certain advantage arranged with the cationic Dry Strength Resin of polyacrylamide.And wherein part material is cheap cationic starch, can be significantly reduced to this.
Claims (10)
1. the preparation method of a both sexes Dry Strength Resin, it is characterized in that, comprise the steps: cationic starch and water are mixed, the heating gelatinization, add successively again water, acrylamide, anionic monomer, cationic monomer, cross-linkable monomer, chain-transfer agent, other functional monomers and photoinitiator, under oxygen-free environment, temperature is risen to 70-95 ℃, to reaction system irradiating ultraviolet light reaction 1-2 hour, viscosity test is carried out in sampling at set intervals afterwards, viscosity stops irradiating ultraviolet light after reaching 4000-9000mP*s, add pH adjusting agent to regulate pH to 4-6, and add free radical scavenger, obtain described Dry Strength Resin.
2. method according to claim 1, is characterized in that, the parts by weight of each component are as follows:
3. method according to claim 2, it is characterized in that, described anionic monomer is selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid or their salt, more than one in maleic anhydride, sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium, sodium allyl sulfonate and methallylsulfonic acid sodium; Described cationic monomer is selected from more than one in (methyl) acrylyl oxy-ethyl-trimethyl salmiac, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, diallyldimethylammonium chloride, dimethylamino propyl acrylamide.
4. method according to claim 2, is characterized in that, described cross-linkable monomer is selected from more than one in di-vinyl monomers, trivinyl monomer.
5. method according to claim 2, is characterized in that, described cross-linkable monomer is methylene-bisacrylamide, N, more than one in N-diallyl acrylamide, N,N-DMAA.
6. method according to claim 2, is characterized in that, described other functional monomers are selected from more than one in soft monomer, hard monomer, hydrophobic monomer.
7. method according to claim 6, is characterized in that, described other functional monomers are more than one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylbenzene, methyl methacrylate, alkyl acrylate, alkyl methacrylate.
8. method according to claim 2, is characterized in that, described photoinitiator is more than one of benzophenone, benzophenone soluble derivative, st-yrax analog derivative, fluorescein and eosin.
9. method according to claim 2, is characterized in that, described chain-transfer agent is more than one of sodium bisulfite, Sodium Pyrosulfite and Sulfothiorine etc., positive Dodecyl Mercaptan, tert-dodecyl mercaptan, Thiovanic acid, mercaptoethanol, Virahol.
10. method according to claim 2, is characterized in that, described free radical scavenger is Resorcinol, benzoquinones, iron(ic) chloride, neutralized verdigris, sodium bisulfite, xitix.
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