CN117186501A - Preparation method and application of waxy polysaccharide modified material containing cellulose component - Google Patents
Preparation method and application of waxy polysaccharide modified material containing cellulose component Download PDFInfo
- Publication number
- CN117186501A CN117186501A CN202310894558.8A CN202310894558A CN117186501A CN 117186501 A CN117186501 A CN 117186501A CN 202310894558 A CN202310894558 A CN 202310894558A CN 117186501 A CN117186501 A CN 117186501A
- Authority
- CN
- China
- Prior art keywords
- waxy
- amylopectin
- crosslinking
- polysaccharide
- modified material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 88
- 150000004676 glycans Chemical class 0.000 title claims abstract description 68
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 68
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002678 cellulose Polymers 0.000 title claims abstract description 10
- 239000001913 cellulose Substances 0.000 title claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 67
- 229920000945 Amylopectin Polymers 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 37
- 238000006266 etherification reaction Methods 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000000853 adhesive Substances 0.000 claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011243 crosslinked material Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- -1 hydroxypropyl Chemical group 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000000047 product Substances 0.000 description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 17
- 229920002472 Starch Polymers 0.000 description 16
- 239000008107 starch Substances 0.000 description 16
- 235000019698 starch Nutrition 0.000 description 16
- 239000003292 glue Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 14
- 206010016807 Fluid retention Diseases 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 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 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 240000006394 Sorghum bicolor Species 0.000 description 5
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 229960002598 fumaric acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- GWCPZQLAAJBPMC-UHFFFAOYSA-N acetyl acetate;hexanedioic acid Chemical compound CC(=O)OC(C)=O.OC(=O)CCCCC(O)=O GWCPZQLAAJBPMC-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229960000250 adipic acid Drugs 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 229940074360 caffeic acid Drugs 0.000 description 3
- 235000004883 caffeic acid Nutrition 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229960004365 benzoic acid Drugs 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 229940089960 chloroacetate Drugs 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical group OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 235000011087 fumaric acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229940099690 malic acid Drugs 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229940116315 oxalic acid Drugs 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229960001367 tartaric acid Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical compound CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005113 hydroxyalkoxy group Chemical group 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the field of waxy polysaccharide materials, in particular to a preparation method and application of a waxy polysaccharide modified material containing a cellulose component. The preparation method comprises the following steps: dispersing nanocellulose in water to obtain a dispersion; taking the dispersion and the amylopectin as raw materials, carrying out crosslinking reaction of the nanocellulose and the amylopectin under the action of a crosslinking agent, and separating out a product to obtain a primary modified crosslinking material; and (3) carrying out etherification treatment on the primary modified crosslinked material to obtain the waxy polysaccharide modified material. The waxy polysaccharide modified material obtained by the preparation method has better water retention capacity, and can endow the tile adhesive with longer open time and higher bonding strength when being used in the tile adhesive.
Description
Technical Field
The invention relates to the field of waxy polysaccharide materials, in particular to a preparation method and application of a waxy polysaccharide modified material containing a cellulose component.
Background
The ceramic tile is used as a decorative material, has a wide market, and the ceramic tile adhesive matched with the ceramic tile is widely applied to decorative places such as ceramic tiles, wall tiles, floor tiles and the like as a matched product with the ceramic tile adhesive and having high cost performance. The special ceramic tile adhesive has the main characteristics of high adhesive strength, water resistance, freeze thawing resistance, good ageing resistance and convenient construction, can save more space than cement, effectively reduces waste materials, has no toxic additives, meets the environmental requirements, and is rapidly developed as a novel special ceramic tile adhesive with excellent performance and cost performance advantages.
At present, the common ceramic tile adhesive in the market is mainly prepared by mixing cement, river sand, hydroxypropyl methyl cellulose (HPMC), EVA (vinyl acetate-ethylene copolymer) emulsion powder, calcium formate, polyvinyl alcohol (PVA), styrene-butadiene rubber powder and the like according to a certain proportion. The starch ether obtained after the modification of the polysaccharide starch material is a high cost performance product which can replace part of HPMC and has more stable performance, can be used as an additive for cement-based products, gypsum-based products and gray calcium products in the field of construction, has good compatibility with other building materials and additives, and is particularly suitable for building dry mixing materials such as mortar, adhesive, plastering, roll-on materials and the like. However, the existing starch ether is prepared by introducing mono-functional and di-functional group etherification (such as hydroxypropyl etherification and carboxymethyl etherification) on the basis of corn starch or tapioca starch, and when the starch ether is applied to tile adhesives, the water retention of the starch ether is insufficient, so that the opening time (open time) is too short, and the bonding strength is low.
Disclosure of Invention
The invention provides a preparation method and application of a waxy polysaccharide modified material containing a cellulose component, and aims to solve the technical problems that the existing starch ether has too short opening time and lower bonding strength when used for tile glue. The waxy polysaccharide modified material obtained by the preparation method has better water retention capacity, and can endow the tile adhesive with longer open time and higher bonding strength when being used in the tile adhesive.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for preparing a waxy polysaccharide modified material comprising a cellulosic component, comprising the steps of:
(1) Dispersing nanocellulose in water to obtain a dispersion;
(2) Taking the dispersion and the amylopectin as raw materials, carrying out crosslinking reaction of the nanocellulose and the amylopectin under the action of a crosslinking agent, and separating out a product to obtain a primary modified crosslinking material;
(3) And (3) carrying out etherification treatment on the primary modified crosslinked material to obtain the waxy polysaccharide modified material.
According to the invention, the nanocellulose and the amylopectin are compounded and crosslinked, and then etherification is carried out, so that the obtained waxy polysaccharide modified material has better water retention, and when the waxy polysaccharide modified material is used in the tile adhesive, the tile adhesive has longer open time and higher bonding strength.
Specifically:
1) Amylopectin is a hyperbranched polymer in which D-glucopyranose units are linked by alpha-1, 4-glycosidic bonds to form a linear chain, which in turn can form side chains by alpha-1, 6-glycosidic bonds, on which side chains a further branched side chain is present. The use of a highly branched structure in amylopectin gives it better binding, water retention than amylose.
2) Amylopectin has poor shear stability, the starch chain is easy to be destroyed under the action of shear force, the viscosity is reduced, and the water retention is weakened. According to the invention, the amylopectin is crosslinked, so that a network structure with wider and higher crosslinking degree is formed among starch molecules, the structural stability is improved, the shearing resistance of the amylopectin is improved, the amylopectin can keep better stability under the action of shearing force, and meanwhile, the formation of the network structure is favorable for further improving the water-retaining property of the amylopectin.
3) The nano cellulose has the characteristics of high surface area and high water retention, and can be mixed with the amylopectin for cross-linking, so that the nano cellulose can be stably dispersed in an amylopectin network, the network cohesion of the molecular group end of the nano cellulose is improved, and the water retention and anti-slip performance of the amylopectin network can be improved to a greater extent.
Preferably, in step (2): before the crosslinking reaction, adding a salt stabilizer, wherein the mass ratio of the amylopectin to the salt stabilizer is 100:1.0-1.5; the process of separating out the product is to remove water from filter residues after filtering, and washing is not performed.
By adding a certain amount of salt stabilizer before the crosslinking reaction, the crosslinking agent can be protected from rapid hydrolysis, resulting in reduced crosslinking efficiency. .
During the crosslinking reaction, since electrons of the outermost layer of the ionic crystal are usually already obtained or lost, and it is difficult to obtain new electrons again, the salt stabilizer can exist stably in the system without reacting with other additive phase substances. After the crosslinking reaction is finished, products are separated in a filtering and dewatering mode, washing is not carried out in the process, and the materials obtained after filtering and dewatering are directly etherified in the step (3), so that a large amount of salt stabilizers can be remained in the primary modified crosslinking materials, the acceleration effect is achieved for the subsequent etherification reaction, the etherification degree of waxy polysaccharide modified materials is improved, and the method is beneficial to prolonging the open time of the tile glue when the method is used in the tile glue.
Further, the salt stabilizer comprises one or more of hydroxyethylthiol, sodium thiosulfate, sodium chloride, sodium borohydride, sodium metabisulfite, disodium hydrogen phosphate, disodium ethylenediamine tetraacetate, sodium dithionite, sodium aliphatic alcohol polyether sulfate and potassium iodide. Further preferred are one or more of sodium thiosulfate, sodium chloride, disodium hydrogen phosphate and sodium fatty alcohol polyether sulfate. More preferably one or more of sodium thiosulfate, sodium chloride and disodium hydrogen phosphate.
Preferably, the specific process of step (2) comprises the following steps: mixing the dispersion, the amylopectin and the salt stabilizer, regulating the pH value to 10.6-11.5, then adding the cross-linking agent, carrying out a cross-linking reaction for 1-5 h at 20-50 ℃ with the mass ratio of the amylopectin to the cross-linking agent being 100:0.0005-0.001, and separating out the product to obtain the primary modified cross-linked material.
In a certain range, the pH of the crosslinking reaction is improved, the crosslinking degree can be improved, and the water-retaining property of the waxy polysaccharide modified material is improved; however, when the pH of the crosslinking reaction is too high, the crosslinking degree is too high, the expansion performance of the amylopectin is inhibited, the open time of the tile adhesive is shortened, and the bonding strength is weakened.
In a certain range, the increase of the dosage of the cross-linking agent can improve the cross-linking degree, but when the dosage is too large, the cross-linking bond in a cross-linking reaction system is obviously increased, a more compact reticular molecular structure is easy to form, the cross-linking bond energy on a starch molecular group is increased, the thermal expansion potential energy of starch is inhibited, the viscosity is obviously insufficient, the bonding strength is low, and the application effect is poor.
After the experimental study is combined on the basis of the theoretical analysis, the pH value of a reaction system is regulated before the crosslinking reaction, the pH value is controlled within the range of 10.6-11.5, the dosage of the crosslinking agent is controlled within the range of 0.0005-0.001 wt% of amylopectin, and the waxy polysaccharide modified material can be endowed with better performance, so that the waxy polysaccharide modified material can realize longer open time and higher bonding strength when being used for tile adhesives.
Further, the temperature of the crosslinking reaction is 23-48 ℃. More preferably, the temperature of the crosslinking reaction is 25 to 45 ℃ and the time is 1 to 4 hours.
Further, the crosslinking agent includes one or more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate, acetaldehyde, acetic anhydride-adipic acid mixture, acrolein, carbonyl chloride, dichlorobutene, aliphatic dihalide, cyanuric chloride, and sodium tetraborate. Further preferred are one or more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate, acetaldehyde, acetic anhydride-adipic acid mixture, acrolein, aliphatic dihalides, cyanuric chloride and sodium tetraborate. More preferably one or more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate and sodium tetraborate.
Further, the adjustment of the pH to 10.6 to 11.5 is achieved by adding a crosslinking catalyst.
Further, the crosslinking catalyst includes one or more of calcium oxide, sodium peroxide, magnesium oxide, sodium metaaluminate, sodium hydroxide, calcium hydroxide, sodium metasilicate, sodium ethoxide, and potassium hydroxide. Further preferred are one or more of calcium oxide, sodium metaaluminate, sodium hydroxide, calcium hydroxide and potassium hydroxide. More preferably one or more of sodium metaaluminate, sodium hydroxide and potassium hydroxide.
Preferably, the waxy polysaccharide modified material has a 5wt% aqueous dispersion viscosity of > 6500mpa.s.
Preferably, in step (2): the mass ratio of the amylopectin to the nano cellulose in the dispersion is 100:0.003-0.01.
Preferably, in step (1): the content of nanocellulose in the dispersion is 0.0035-0.005 wt%.
The content of the nanocellulose in the dispersion is controlled to be 0.0035-0.005 wt%, so that the solid content of the system in the crosslinking reaction in the step (2) is prevented from being too low, the high collision probability between the crosslinking agent, the nanocellulose and the amylopectin is ensured, the prepared primary modified crosslinking material can reach a proper crosslinking degree, and the waxy polysaccharide modified material is endowed with better water retention performance.
Preferably, in step (2): the water content of the primary modified crosslinking material is 10-14 wt%.
Preferably, in step (3): the etherification treatment comprises carboxymethyl etherification treatment; after etherification treatment, adding an acid regulator, wherein the mass ratio of the amylopectin to the acid regulator is 100:1.0-1.8, and obtaining the waxy polysaccharide modified material.
The acid regulator is added after etherification, so that the acid-base performance of the etherified material can be better maintained and changed, the PH value of the system is reduced by adding the acid regulator, the system can be better stabilized, the stabilizing period and the shelf life of the system are prolonged, and the comprehensive function of improving the color of the material can be achieved. However, because the carboxymethyl groups introduced after the carboxymethyl etherification treatment have the characteristics of alkali resistance and acid resistance, if the addition amount of the acid regulator is too large, the viscosity of the aqueous dispersion of the waxy polysaccharide modified material is too low, so that the open time of the tile adhesive is too short and the bonding strength is too low when the aqueous dispersion is used in the tile adhesive.
Further, the acid regulator comprises one or more of citric acid, adipic acid, malic acid, ascorbic acid, fumaric acid, succinic acid, citric acid, tartaric acid, glacial acetic acid, oxalic acid, benzoic acid, salicylic acid and caffeic acid. Further preferred is one or more of citric acid, fumaric acid, citric acid, glacial acetic acid, salicylic acid and caffeic acid. More preferably one or more of fumaric acid, glacial acetic acid and salicylic acid.
Preferably, in the step (3), the specific process of the etherification treatment comprises the following steps: mixing the primary modified crosslinking material, the hydroxypropyl etherifying agent and the carboxymethyl etherifying agent, wherein the mass ratio of the amylopectin to the hydroxypropyl etherifying agent to the carboxymethyl etherifying agent is 100:10-30:10-15, etherifying under the protection of alcohol, and then removing the alcohol.
The invention adopts a hydroxypropyl and carboxymethyl synchronous semi-dry etherification method, and theories that the anionic and nonionic etherification reactions are carried out under alkaline conditions, and the hydroxyl groups on Starch molecules are utilized to carry out ionization reaction (Starch-ONa) and then attack the added etherification reagent to carry out bimolecular nucleophilic substitution reaction. The two etherifying agents are adopted to carry out etherification modification treatment on the crosslinked amylopectin and nano cellulose composite material, so that the comprehensive performance of the composite material can be improved, and longer open time and higher bonding strength can be realized when the composite material is applied to ceramic tile adhesives.
Further, the hydroxypropyl etherifying agent is ethylene oxide and/or propylene oxide; the carboxymethyl etherifying agent is chloroacetic acid and/or chloroacetate.
Further, the etherification temperature is 20-70 ℃ and the etherification time is 2.0-5.0 h.
Further, the volume fraction of the alcohol is 70-80%, and the mass ratio of the amylopectin to the alcohol is 100:5-30.
Preferably, in step (3): in the waxy polysaccharide modified material, the content of hydroxypropyl is 14.0-16.5% and the substitution degree of carboxymethyl is 0.15-0.30.
Preferably, in step (1): the average diameter of the nanocellulose is 10-100 nm, and the average length is 2000-20000 nm.
Preferably, in step (2): the branched chain content of the amylopectin is more than 95.0 percent.
The adoption of the nanocellulose with larger length-diameter ratio and the amylopectin with higher branched chain content can endow the waxy polysaccharide modified material with better water retention and anti-slip performance.
Preferably, in step (2): the amylopectin is obtained by processing and extracting sorghum, corn, cassava or potato.
In a second aspect, the present invention provides a waxy polysaccharide modified material prepared by the method.
In a third aspect, the invention provides the use of the waxy polysaccharide modified material in tile adhesives.
Preferably, the tile adhesive comprises the following raw materials in parts by weight: 320-380 parts of cement, 600-650 parts of fine silica sand, 10-15 parts of hydroxypropyl methyl cellulose, 0.5-1.5 parts of EVA emulsion powder and 2-5 parts of waxy polysaccharide modified material.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts nanocellulose and amylopectin to compound and crosslink, and then carries out etherification treatment, and the prepared waxy polysaccharide modified material has better water retention, so that when the waxy polysaccharide modified material is used in ceramic tile glue, the waxy polysaccharide modified material can endow the ceramic tile glue with longer open time and higher bonding strength.
(2) According to the invention, a certain amount of salt stabilizer is added before the crosslinking reaction, and a specific method is adopted to separate the product of the crosslinking reaction, so that the salt stabilizer remains in the product, the subsequent etherification reaction can be promoted, the etherification degree of the waxy polysaccharide modified material is improved, and the tile glue has longer open time.
(3) The invention can control the crosslinking degree to be at a proper level by controlling the content of nanocellulose in the dispersion, the dosage of the crosslinking agent and the pH value of the crosslinking reaction system, thereby endowing the waxy polysaccharide modified material with better water retention property, and realizing longer open time and higher bonding strength when the waxy polysaccharide modified material is used for ceramic tile glue.
Detailed Description
The invention is further described below with reference to examples.
General examples
A method for preparing a waxy polysaccharide modified material containing a cellulose component, comprising the steps of:
(1) Dispersing nanocellulose in water to obtain a dispersion;
(2) Taking the dispersion and the amylopectin as raw materials, carrying out crosslinking reaction of the nanocellulose and the amylopectin under the action of a crosslinking agent, and separating out a product to obtain a primary modified crosslinking material;
(3) And (3) carrying out etherification treatment on the primary modified crosslinked material to obtain the waxy polysaccharide modified material.
As a specific embodiment, in step (1): the content of nanocellulose in the dispersion is 0.0035-0.005 wt%.
As a specific embodiment, in step (1): the average diameter of the nanocellulose is 10-100 nm, and the average length is 2000-20000 nm.
As a specific embodiment, in step (1): the amylopectin is obtained by processing and extracting sorghum, corn, cassava or potato, and the content of the branched chain is more than 95.0%.
As a specific embodiment, the specific process of step (2) includes the following steps: mixing the dispersion, the amylopectin and the salt stabilizer, wherein the mass ratio of the amylopectin to the nano cellulose in the dispersion to the salt stabilizer is 100:0.003-0.01:1.0-1.5, adding a crosslinking catalyst to adjust the pH value to 10.6-11.5, then adding the crosslinking agent, performing a crosslinking reaction for 1-5 h at 20-50 ℃, filtering, and removing water from filter residues without washing to obtain the primary modified crosslinking material with the water content of 10-14 wt%.
In the above specific embodiments, optionally:
the salt stabilizer comprises one or more of hydroxyethylthiol, sodium thiosulfate, sodium chloride, sodium borohydride, sodium metabisulfite, disodium hydrogen phosphate, disodium ethylenediamine tetraacetate, sodium dithionite, sodium aliphatic alcohol polyether sulfate and potassium iodide;
the cross-linking agent comprises one or more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate, acetaldehyde, acetic anhydride-adipic acid mixture, acrolein, phosgene, butylene dichloride, aliphatic dihalide, cyanuric chloride and sodium tetraborate;
the crosslinking catalyst comprises one or more of calcium oxide, sodium peroxide, magnesium oxide, sodium metaaluminate, sodium hydroxide, calcium hydroxide, sodium metasilicate, sodium ethoxide and potassium hydroxide.
As a specific embodiment, the specific process of step (3) includes the following steps: mixing the primary modified crosslinking material, the hydroxypropyl etherifying agent and the carboxymethyl etherifying agent, wherein the mass ratio of the amylopectin to the hydroxypropyl etherifying agent to the carboxymethyl etherifying agent is 100:10-30:10-15, etherification is carried out under the protection of alcohol with the volume fraction of 70-80%, the temperature is 20-70 ℃ and the time is 2.0-5.0 h, the mass ratio of the amylopectin to the alcohol is 100:5-30, then alcohol is removed, and then an acid regulator is added, wherein the mass ratio of the amylopectin to the acid regulator is 100:1.0-1.8, so that the waxy polysaccharide modified material with the hydroxypropyl content of 14.0-16.5%, the carboxymethyl substitution degree of 0.15-0.30 and the aqueous dispersion viscosity of 5wt% of more than 6500mpa.s is obtained.
In the above specific embodiments, optionally:
the hydroxypropyl etherifying agent is ethylene oxide and/or propylene oxide;
the carboxymethyl etherifying agent is chloroacetic acid and/or chloroacetate;
the acid regulator comprises one or more of citric acid, adipic acid, malic acid, ascorbic acid, fumaric acid, succinic acid, citric acid, tartaric acid, glacial acetic acid, oxalic acid, benzoic acid, salicylic acid and caffeic acid.
The waxy polysaccharide modified material prepared by the preparation method is prepared.
The waxy polysaccharide modified material is applied to tile adhesives.
As a specific embodiment, the tile adhesive comprises the following raw materials in parts by weight: 320-380 parts of cement, 600-650 parts of fine silica sand, 10-15 parts of hydroxypropyl methyl cellulose, 0.5-1.5 parts of EVA emulsion powder and 2-5 parts of waxy polysaccharide modified material.
Example 1
The waxy polysaccharide modified material containing cellulose component is prepared by the following steps (the dosage of each substance is calculated in parts by weight): (1) 1 part of a nanocellulose aqueous dispersion having a concentration of 0.5wt%, an average d=50nm, an average l=9000 nm, and an aspect ratio of 180 was added to 140 parts of deionized water by using a disperser, and dispersed at 25000rpm/min for 5 minutes, to obtain a dispersion.
(2) Transferring the dispersion into a conventional stirring reaction kettle, adding 100 parts of amylopectin (obtained by processing and extracting sorghum, with the branched chain content of 95.5%) and 1.2 parts of stabilizer (disodium hydrogen phosphate) under stirring, mixing and pulping, adding 1.0 part of crosslinking catalyst (sodium hydroxide) to adjust the pH value to 11.0, adding 0.0005 part of crosslinking agent (sodium trimetaphosphate) at 30 ℃, carrying out crosslinking reaction for 2 hours at 30 ℃, and carrying out suction filtration, dehydration and drying on the product to obtain the product with the water content of 13.25wt%, namely the primary modified crosslinked material.
(3) Adding 20 parts of 75vol% alcohol protection, 20.0 parts of hydroxypropyl etherifying agent (propylene oxide) and 12.0 parts of carboxymethyl etherifying agent (sodium chloroacetate) into the primary modified crosslinking material, finishing semi-dry etherification treatment in a high-pressure reaction kettle, controlling the temperature to be 50 ℃, the pressure to be 0.4MPa, and the time to be 3.0h, adding 1.5 parts of acid regulator (citric acid) into the product after removing the alcohol, mixing and stirring, sieving the product, and packaging the product to obtain the waxy polysaccharide modified material.
Examples 2 to 12 and comparative examples 1 to 5
Waxy polysaccharide modified materials of examples 2 to 12 and comparative examples 1 to 5 were prepared according to the procedure in example 1. Examples 2 to 12 and comparative examples 1 to 5 differ from example 1 only in that: the amounts of the respective raw materials, as well as the pH value, the crosslinking reaction temperature and the time in the step (2), were changed according to Table 1. In Table 1, the amounts of the respective materials are parts by weight, the unit of temperature is the unit of DEG C, and the unit of time is the unit of h.
TABLE 1
Comparative example 6
The waxy polysaccharide modified material containing cellulose component is prepared by the following steps (the dosage of each substance is calculated in parts by weight): (1) 140 parts of deionized water is added into a conventional stirring reaction kettle, 100 parts of amylopectin (which is obtained by processing and extracting sorghum, and has the branched chain content of 95.5%) and 1.2 parts of stabilizer (disodium hydrogen phosphate) are added under stirring to mix and pulp, then 1.0 part of crosslinking catalyst (sodium hydroxide) is added to adjust the pH value to 11.0, 0.0005 part of crosslinking agent (sodium trimetaphosphate) is added at 30 ℃, then the crosslinking reaction is carried out at 30 ℃ for 2 hours, and the product with the water content of 13.25 weight percent is obtained by suction filtration, dehydration and drying, namely the primary modified crosslinked material.
(2) 1 part of nano cellulose aqueous dispersion with the concentration of 0.5 weight percent, the average d=50 nm, the average L=9000 nm and the length-diameter ratio of 180 is taken, and the nano cellulose with the water content of 13.60 weight percent is obtained after suction filtration, dehydration and drying.
(3) After the nanocellulose and the primary modified cross-linked material are uniformly mixed, 20 parts of 75vol% alcohol protection, 20.0 parts of hydroxypropyl etherifying agent (propylene oxide) and 12.0 parts of carboxymethyl etherifying agent (sodium chloroacetate) are added into the mixture, semi-dry etherification treatment is completed in a high-pressure reaction kettle, the temperature is controlled to be 50 ℃, the time is 3.0h, after the alcohol is removed, 1.5 parts of acid regulator (citric acid) is added into the product, the mixture is mixed and stirred, and the product is sieved and packaged to obtain the waxy polysaccharide modified material.
Comparative example 7
The waxy polysaccharide modified material containing cellulose component is prepared by the following steps (the dosage of each substance is calculated in parts by weight): (1) 1 part of a nanocellulose aqueous dispersion having a concentration of 0.5wt%, an average d=50nm, an average l=9000 nm, and an aspect ratio of 180 was added to 140 parts of deionized water by using a disperser, and dispersed at 25000rpm/min for 5 minutes, to obtain a dispersion.
(2) Transferring the dispersion into a conventional stirring reaction kettle, adding 100 parts of amylopectin (obtained by processing and extracting sorghum, with the branched chain content of 95.5%) and 1.2 parts of stabilizer (sodium dihydrogen phosphate) under stirring, mixing and pulping, adding 1.0 part of crosslinking catalyst (sodium hydroxide) to adjust the pH value to 11.0, adding 0.0005 part of crosslinking agent (sodium trimetaphosphate) at 30 ℃, carrying out crosslinking reaction for 2 hours at 30 ℃, carrying out suction filtration on the product, washing 3 times with deionized water, and dehydrating and drying to obtain the product with the water content of 13.25wt%, namely the primary modified crosslinked material.
(3) Adding 20 parts of 75vol% alcohol protection, 20.0 parts of hydroxypropyl etherifying agent (propylene oxide) and 12.0 parts of carboxymethyl etherifying agent (sodium chloroacetate) into the primary modified crosslinking material, finishing semi-dry etherification treatment in a high-pressure reaction kettle, controlling the temperature to be 50 ℃ for 3.0h, adding 1.5 parts of acid regulator (citric acid) into the product after removing the alcohol, mixing and stirring, sieving the product, and packaging the product to obtain the waxy polysaccharide modified material.
Application examples 1 to 12 and comparative application examples 1 to 7
The waxy polysaccharide modified materials prepared in examples 1 to 12 and comparative examples 1 to 7 were used to prepare tile adhesives of application examples 1 to 12 and comparative application examples 1 to 7 according to the following formulation: 42.5R cement 350g, fine silica sand 633g,HPMC 13g,EVA latex powder 1g, waxy polysaccharide modified material 3g and tap water 260g. And strictly according to the technical requirement specified by 6.1 and the stirring method specified by 7.4.1 in the standard JC/T547-2017 ceramic tile adhesive.
Test example 1: properties of waxy polysaccharide modified materials
The waxy polysaccharide modified materials prepared in each of examples and comparative examples were examined for moisture and ash content, whiteness, viscosity of a 5wt% aqueous dispersion, hydroxypropyl content, and carboxymethyl substitution (DS). Wherein:
(1) The carboxymethyl substitution (DS) detection method comprises the following steps:
firstly, fully washing a sample until no Cl < - > exists, drying the sample, slowly heating the sample in a muffle furnace, gradually heating the sample to 700 ℃, burning the sample for 1h to completely ash the sample, and quantitatively converting the sample into Na 2 O, dissolving ashes by using a quantitative sulfuric acid standard solution, and titrating excessive sulfuric acid by using a NaOH standard solution, wherein the substitution degree of carboxymethyl of starch ether is calculated according to the following formula:
wherein B is 1/2H consumed per gram of sample 2 SO 4 The value of which is calculated according to the following formula:
wherein,the unit is mol/L of the molar concentration of the sulfuric acid; />The volume of sulfuric acid is mL; c (C) NaOH The unit is mol/L of the molar concentration of the sodium hydroxide; v (V) NaOH The volume of sodium hydroxide is mL; w is the mass of the starch ether sample baked to constant weight, and the unit is g.
(2) The hydroxypropyl content detection method is to quantitatively cleave substituted alkoxy and hydroxyalkoxy groups through hydroiodic acid under the catalysis of adipic acid according to the detection method of the content of cellulose ether groups in appendix D of JC/T2190-2013 cellulose ether for building dry-mixed mortar, and then to detect the hydroxypropyl content through gas chromatography.
(3) The viscosity of the 5wt% aqueous dispersion was measured with an NDJ-1 type viscometer and the temperature was 20 ℃.
The physical and chemical property detection results of the waxy polysaccharide modified material are shown in Table 2. In Table 2, the 5wt% viscosity refers to the 5wt% aqueous dispersion viscosity of the waxy polysaccharide modified material.
TABLE 2
Test example 2: performance of tile glue
The tile adhesives prepared in each application example and comparative application example were used to determine open time, tensile bond strength and slip according to the standard JC/T547-2017 ceramic tile adhesive, and the results are shown in Table 3.
TABLE 3 Table 3
Analysis of the performance test results of the waxy polysaccharide modified materials and tile adhesives in tables 2 and 3 shows that:
(1) Compared with example 1, the dosage of deionized water is increased in the process of dispersing nano cellulose in comparative example 1, the viscosity of 5wt% of the prepared waxy polysaccharide modified material is obviously reduced, the open time of the tile glue is shortened, the tensile bonding strength is weakened, and the slip is increased, which is probably due to the fact that the solid content of a crosslinking reaction system is reduced, the collision probability between a crosslinking agent and amylopectin and nano cellulose molecules is reduced, the crosslinking efficiency is reduced, and the crosslinking degree in the prepared primary modified crosslinked material and the waxy polysaccharide modified material is reduced.
(2) Compared with example 1, examples 5 and 9 increased the pH of the crosslinking reaction system, the open time of the tile glue was significantly prolonged, and the tensile bond strength of example 5 was improved, probably because the water retention of the waxy polysaccharide modified material could be improved by increasing the pH of the crosslinking reaction system in a certain range, by appropriately increasing the crosslinking degree. While comparative examples 2 and 4 have further improved pH, the time required for suction filtration is greatly prolonged during the suction filtration of the crosslinked product in step (2), the surface of the filter cake has a problem of gelatinization, the whiteness is reduced, and the yield of the primary modified crosslinked material is reduced from 98.5% of example 1 to 88% (comparative example 2) and 84% (comparative example 4), and the sieving of the etherified product in the subsequent step (3) is also difficult, the fineness is poor, and the viscosity of the waxy polysaccharide modified material is significantly reduced by 5wt%, and furthermore, the open time of the tile glue is significantly shortened to decrease the tensile bond strength and increase the slip, which may be due to the excessive degree of crosslinking, causing inhibition of the swelling properties of pullulan, leading to a shortened open time of the waxy polysaccharide modified material and decreased bond strength.
(3) Compared with the embodiment 1, the comparative example 3 increases the amount of the cross-linking agent, the viscosity of the prepared waxy polysaccharide modified material of 5wt% is obviously reduced, the open time of the tile glue is shortened, the tensile bonding strength is weakened, and the slip is increased, which is probably due to the fact that when the amount of the cross-linking agent is too large, the cross-linking bond in a cross-linking reaction system is obviously increased, a more compact reticular molecular structure is easily formed, the cross-linking bond energy on starch molecular groups is increased, the thermal expansion potential energy of starch is inhibited, the viscosity is obviously insufficient, and the application effect is poor.
(4) Compared with the embodiment 1, the comparative example 1 increases the addition amount of the acid regulator, the viscosity of the prepared waxy polysaccharide modified material of 5wt percent is obviously reduced, the open time of the tile glue is shortened, the tensile bonding strength is weakened, and the slip is increased, which is probably due to the fact that carboxymethyl groups introduced during etherification have some characteristic problems of alkali resistance but acid resistance, and therefore, when the pH value of a system is too low after the acid regulating amount of the system is increased, the paste viscosity is obviously reduced. Compared with the embodiment 1, the comparative example 6 only carries out crosslinking on the amylopectin, the amylopectin and the nanocellulose are not crosslinked, the open time of the tile adhesive is obviously shortened, the tensile bonding strength is weakened, and the slip is increased, which is probably due to the fact that the nanocellulose is not effectively crosslinked before the nanocellulose is mixed with the amylopectin, the network cohesive force of the molecular group end of the nanocellulose is insufficient, the problem of insufficient water-retaining property is caused, the comprehensive network stretching degree is not required to a larger extent, and the comprehensive performance of the tile adhesive is influenced.
(6) Compared with the embodiment 1, the embodiment 7 has the advantages that the salt stabilizer is remained in the primary modified cross-linked material in a greatly reduced amount by washing for a plurality of times in the process of separating the cross-linked product, better catalysis can not be exerted in the subsequent etherification reaction, the etherification efficiency and the modification depth of the waxy polysaccharide modified material can not be improved, and the airing time of the tile glue can be prolonged when the catalyst is used in the tile glue.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a waxy polysaccharide modified material containing a cellulose component, comprising the steps of:
(1) Dispersing nanocellulose in water to obtain a dispersion;
(2) Taking the dispersion and the amylopectin as raw materials, carrying out crosslinking reaction of the nanocellulose and the amylopectin under the action of a crosslinking agent, and separating out a product to obtain a primary modified crosslinking material;
(3) And (3) carrying out etherification treatment on the primary modified crosslinked material to obtain the waxy polysaccharide modified material.
2. The method of claim 1, wherein in step (2): before the crosslinking reaction, adding a salt stabilizer, wherein the mass ratio of the amylopectin to the salt stabilizer is 100:1.0-1.5; the process of separating out the product is to remove water from filter residues after filtering, and washing is not performed.
3. The preparation method according to claim 2, wherein the specific process of step (2) comprises the steps of: mixing the dispersion, the amylopectin and the salt stabilizer, regulating the pH to 10.6-11.5, then adding the cross-linking agent, carrying out a cross-linking reaction for 1-5 h at 20-50 ℃ with the mass ratio of the amylopectin to the cross-linking agent being 100:0.0005-0.001, and separating out the product to obtain the primary modified cross-linked material.
4. The method of claim 1, wherein the waxy polysaccharide modified material has a viscosity of > 6500mpa.s in a 5 wt.% aqueous dispersion.
5. The method of claim 1, wherein in step (2): the mass ratio of the amylopectin to the nanocellulose in the dispersion is 100:0.003-0.01.
6. A method according to claim 1 or 3, wherein in step (1): the content of nanocellulose in the dispersion is 0.0035-0.005 wt%.
7. The method of claim 1, wherein in step (3): the etherification treatment comprises carboxymethyl etherification treatment; and after etherification treatment, adding an acid regulator, wherein the mass ratio of the amylopectin to the acid regulator is 100:1.0-1.8, and obtaining the waxy polysaccharide modified material.
8. The method according to claim 1 or 7, wherein in the step (3), the specific process of the etherification treatment comprises the steps of: mixing the primary modified crosslinking material, the hydroxypropyl etherifying agent and the carboxymethyl etherifying agent, wherein the mass ratio of the amylopectin to the hydroxypropyl etherifying agent to the carboxymethyl etherifying agent is 100:10-30:10-15, etherifying under the protection of alcohol, and then removing the alcohol.
9. A waxy polysaccharide modified material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a waxy polysaccharide modified material according to claim 9 in tile adhesives.
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| CN202310894558.8A CN117186501A (en) | 2023-07-20 | 2023-07-20 | Preparation method and application of waxy polysaccharide modified material containing cellulose component |
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