CN112210021A - Cationic guar gum thickening agent and preparation method and application thereof - Google Patents
Cationic guar gum thickening agent and preparation method and application thereof Download PDFInfo
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- CN112210021A CN112210021A CN202011172354.6A CN202011172354A CN112210021A CN 112210021 A CN112210021 A CN 112210021A CN 202011172354 A CN202011172354 A CN 202011172354A CN 112210021 A CN112210021 A CN 112210021A
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- guar gum
- cationic guar
- cationic
- thickener
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 136
- 229920002907 Guar gum Polymers 0.000 title claims abstract description 103
- 239000000665 guar gum Substances 0.000 title claims abstract description 103
- 229960002154 guar gum Drugs 0.000 title claims abstract description 103
- 235000010417 guar gum Nutrition 0.000 title claims abstract description 103
- 239000002562 thickening agent Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- 238000006266 etherification reaction Methods 0.000 claims description 40
- 150000003138 primary alcohols Chemical class 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- -1 chloropropanol trimethyl ammonium chloride Chemical compound 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims 7
- 239000003845 household chemical Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 150000001768 cations Chemical class 0.000 abstract description 12
- 239000002453 shampoo Substances 0.000 abstract description 11
- 239000012530 fluid Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000008719 thickening Effects 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 26
- 244000303965 Cyamopsis psoralioides Species 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical group OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- RJQQOKKINHMXIM-UHFFFAOYSA-N 2-hydroxypropanoate;tris(2-hydroxyethyl)azanium Chemical compound CC(O)C(O)=O.OCCN(CCO)CCO RJQQOKKINHMXIM-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000002579 anti-swelling effect Effects 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- JUGRTVJQTFZHOM-UHFFFAOYSA-N 1,1,1-tribromo-2-methylpropan-2-ol Chemical compound CC(C)(O)C(Br)(Br)Br JUGRTVJQTFZHOM-UHFFFAOYSA-N 0.000 description 2
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920013750 conditioning polymer Polymers 0.000 description 2
- 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 2
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 2
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- DSKUSRPNKICWGY-UHFFFAOYSA-N 1-chloro-2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCC(O)Cl DSKUSRPNKICWGY-UHFFFAOYSA-N 0.000 description 1
- QTDIEDOANJISNP-UHFFFAOYSA-N 2-dodecoxyethyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOCCOS(O)(=O)=O QTDIEDOANJISNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical group [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical group [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Emergency Medicine (AREA)
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- Polymers & Plastics (AREA)
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a cationic guar gum thickening agent, and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The invention provides a cationic guar gum thickener which has the characteristics of quick dissolution (the thickening rate is more than or equal to 90% in 3min and more than or equal to 98% in 10 min), low-water insoluble substance (less than or equal to 2.5%), strong thickening capacity (apparent viscosity (1.0%, 25 ℃, 2#20rpm) and more than or equal to 800mPa & s), and can meet the requirement of transparency by forming strong complexing capacity between amino nitrogen atoms and hydroxyl oxygen in cations and metal ions such as zirconium, titanium and the like in a metal organic cross-linking agentThe preparation requirements of shampoo and neutral high-temperature resistant fracturing fluid.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a cationic guar gum thickening agent, and a preparation method and application thereof.
Background
Guar gum is a kind of polysaccharide extracted from guar bean, and its molecular structure is that galactose units are randomly grafted in a-1, 6 connection mode on a mannan backbone connected with beta-1, 4. The galactose units are distributed irregularly on the main chain, hair areas with dense grafting and smooth areas without grafting exist, and the molar ratio of the total mannose units to the galactose units is 1.6-2.1. Guar gum is widely used in oil field, daily chemical industry, printing and dyeing, pharmacy and other industries. Guar gum will be modified or processed differently depending on the final product. Cationic guar gum is an important functional natural polymer material, has direct conditioning effect on hair and skin, is widely used in hair care and skin care products, such as shampoo, hand sanitizer and bath lotion products, and can also be used as a thickening agent for fracturing in the oil and gas industry.
Since smooth regions without grafting exist in the guar molecule and smooth regions of each molecule are aggregated due to hydrogen bonding interactions, the hydrophilic properties of the region are deteriorated. Pure cationic substituted guar, because of the low substitution efficiency in the smooth zone, results in a high level of low substituted cationic product in the cationic guar, and a low degree of cationic substitution results in a high level of water insoluble material.
Disclosure of Invention
In view of the above, the present invention aims to provide a cationic guar gum thickener, a preparation method thereof and applications thereof. The cationic guar gum thickener provided by the invention has low content of water insoluble substances.
The invention provides a cationic guar gum thickener having a structure shown in formula I:
wherein ,
R1～R9independently selected from a substituent shown in formula a, a substituent shown in formula b or H:
and R is1～R9The structures which are not simultaneously represented by the formula b are also not simultaneously-H;
wherein z is 1 or 0,
(1) when z is 1, x is 0, y is 3-6 or x is 1, and y is 1-4;
(2) when z is 0, x is 2 to 3, y is 0 or x is 0, and y is 0
In the formula b z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0。
Preferably, the total substitution degree of the group shown in the formula a and the group shown in the formula b in the cationic guar gum thickener is 0.15-0.8.
Preferably, the total substitution degree of the group shown in the formula a and the group shown in the formula b in the cationic guar gum thickener is 0.15-0.5.
Preferably, the substitution degree of the group shown in the formula a in the cationic guar gum thickening agent is 0.05-0.6.
Preferably, the substitution degree of the structure shown in the formula a of the cationic guar gum thickener is 0.1-0.4.
Preferably, the percentage of the substituted number of the structures shown in the formula a in the cationic guar gum thickener in the sum of the numbers of the structures shown in the formula a and the structures shown in the formula b is 20-80%.
Preferably, the weight average molecular weight of the cationic guar gum thickener is 120 to 300 ten thousand.
The invention also provides a preparation method of the cationic guar gum thickener, which comprises the following steps:
curing the guar gum and the alkaline solution to obtain a cured material;
under the protective atmosphere, mixing the cured material with a primary alcohol etherifying agent with a structure shown in a formula II to carry out primary alcohol etherification reaction to obtain a primary alcohol etherified substance with a structure shown in a formula III;
in the formula II, X is Cl, Br or epoxy ethyl;
when X ═ Cl or Br, Ra＝-CH2-OH, and n-2-6 or Ra＝-CH2CH2O-, L-H, and n-2-3;
when X is epoxyethyl, Ra＝-CH2-OH and n is 1 to 4;
in the formula (III), the reaction solution is prepared,
R’1～R’9Independently selected from a substituent represented by formula b or-H:
and R'1～R’9Is not H at the same time;
in the formula c z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0；
Under a protective atmosphere, mixing the primary alcohol etherate with the structure shown in the formula III with a cationic etherifying agent aqueous solution to perform a cationic etherification reaction to obtain a cationic guar gum thickening agent with the structure shown in the formula I; the cationic etherifying agent in the cationic etherifying agent aqueous solution is epoxypropyl trimethyl ammonium chloride or chloropropanol trimethyl ammonium chloride.
Preferably, the temperature of the cation etherification reaction is 50-75 ℃.
The invention also provides the application of the cationic guar gum thickener in the technical scheme or the cationic guar gum thickener prepared by the preparation method in the technical scheme as a thickener and a fracturing thickener for daily chemical products.
The invention provides a cationic guar gum thickener which contains a group shown in a formula b, so that cationic substitution is easier and more efficient, cationic substitution is relatively uniform on a molecular chain, the stability of a solution is improved after the macromolecular chain is dissolved, and in addition, the larger substitution structural group of the group shown in the formula a and the ionic action of cations effectively weaken the hydrogen bond action among guar gum molecular chains, so that the macromolecular chain is easier to hydrate and dissolve, and the content of water-insoluble substances is effectively reduced. The cationic guar gum thickener provided by the invention has the characteristics of instant dissolution (the thickening rate is more than or equal to 90% in 3min and more than or equal to 98% in 10 min), low water insoluble substance (less than or equal to 2.5%), and strong thickening capacity (apparent viscosity (1.0%, 25 ℃, 2#20rpm) and more than or equal to 800mPa & s). When the cationic guar gum thickener provided by the invention is used, amino nitrogen atoms and hydroxyl oxygen in cations and zirconium and titanium metal ions in a metal organic cross-linking agent form stronger complexing ability to form a complex, the complexing mode of the complex is shown as formula IV, and the preparation requirements of transparent shampoo and neutral high-temperature-resistant fracturing fluid can be met.
In the formula IV, M is zirconium ion or titanium ion;
The invention also provides a preparation method of the cationic guar gum thickening agent, which comprises the steps of firstly carrying out primary alcoholization modification reaction on guar gum under an alkaline condition, and then carrying out cationic etherification modification on primary alcohol substituent groups. The preparation method provided by the invention has the advantages of simple process and low raw material cost, and effectively solves the problems of complex steps or high requirements and high cost of cation guar gum synthesis.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the cationic guar thickener obtained in example 1;
FIG. 2 is a comparison graph of wet combing tests on brown hair tresses with cationic guar thickener (cationic guar thickener as conditioning polymer), without cationic guar thickener (no polymer), conventionally synthesized cationic guar made in example 1 of the present invention;
FIG. 3 is a rheological curve of guar fracturing fluid prepared in example 2 at 180 ℃;
fig. 4 is a nuclear magnetic resonance hydrogen spectrum of the cationic guar thickener obtained in example 4.
Detailed Description
The invention provides a cationic guar gum thickening agent, which has a structure shown in a formula I:
wherein ,
R1～R9independently selected from a substituent shown in formula a, a substituent shown in formula b or H:
and R is1～R9The structures which are not simultaneously represented by the formula b are also not simultaneously-H;
wherein z is 1 or 0,
(1) when z is 1, x is 0, y is 3-6 or x is 1, and y is 1-4;
(2) when z is 0, x is 2 to 3, y is 0 or x is 0, and y is 0
In the formula b z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0。
According to the invention, the guar gum molecular chain structure in the cationic guar gum thickener is formed by randomly grafting 1,6 connection galactose units on a mannose unit in a 1,4 connection mode as a main chain, and the macromolecular chain of the cationic guar gum thickener is a nonrepeating structural unit.
In the invention, the total substitution degree of the group shown in the formula a and the group shown in the formula b in the cationic guar gum thickener is preferably 0.15-0.8, and more preferably 0.15-0.5.
In the invention, the substitution degree of the group shown in the formula a in the cationic guar gum thickener is preferably 0.05-0.6, and more preferably 0.1-0.4.
In the invention, the percentage of the substituted number of the structures shown in the formula a in the cationic guar gum thickener to the sum of the number of the structures shown in the formula a and the number of the structures shown in the formula b is preferably 20-80%, and more preferably 40-65%.
In the invention, the weight average molecular weight of the cationic guar gum thickener is preferably 120-300 ten thousand, and more preferably 160-270 ten thousand.
The invention also provides a preparation method of the cationic guar gum thickener, which comprises the following steps:
curing the guar gum and the alkaline solution to obtain a cured material;
under the protective atmosphere, mixing the cured material with a primary alcohol etherifying agent with a structure shown in a formula II to carry out primary alcohol etherification reaction to obtain a primary alcohol etherified substance with a structure shown in a formula III;
in the formula II, X is Cl, Br or epoxy ethyl;
when X ═ Cl or Br, Ra＝CH2Wherein L is OH, and n is 2-6 or R2＝CH2CH2O, L is H, and n is 2-3;
when X is epoxyethyl, Ra＝CH2Wherein L is OH and n is 1-4;
wherein ,
R’1～R’9selected from:
and R'1～R’9Is not H at the same time;
z1either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0；
Under a protective atmosphere, mixing the primary alcohol etherate with the structure shown in the formula III with a cationic etherifying agent aqueous solution to perform a cationic etherification reaction to obtain a cationic guar gum thickening agent with the structure shown in the formula I; the cationic etherifying agent in the cationic etherifying agent aqueous solution is epoxypropyl trimethyl ammonium chloride or chloropropanol trimethyl ammonium chloride.
In the present invention, the starting materials used are all commercially available ones unless otherwise specified.
According to the invention, guar gum and alkaline solution are cured to obtain cured material. In the present invention, the aging is preferably performed under a protective atmosphere, which is preferably nitrogen.
In the invention, the mass fraction of the alkaline solution is preferably 15-40%, more preferably 30%, and the mass ratio of the guar gum to the alkaline solution is preferably 100: 20-280, more preferably 100: 40-64, and most preferably 100: 50. In the present invention, the alkaline solution is preferably a sodium hydroxide solution. In the present invention, the guar gum is preferably guar splits. The source of the guar splits is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
According to the invention, the alkaline solution is preferably added to the guar gum by a pump, and the adding rate of the pump is preferably 50-75 mL/s.
In the present invention, physical swelling occurs during the ripening. In the invention, the curing time is preferably 30-60 min, and more preferably 30-40 min; the temperature is preferably normal temperature.
After the cured material is obtained, the cured material and a primary alcohol etherifying agent with a structure shown in a formula II are mixed to carry out primary alcohol etherification reaction under the protective atmosphere to obtain a primary alcohol etherified substance with a structure shown in a formula III,
wherein X is Cl, Br or epoxyethyl;
when X ═ Cl or Br, Ra＝CH2Wherein L is OH, and n is 2-6 or R2＝CH2CH2O, L is H, and n is 2-3;
when X is epoxyethyl, Ra＝CH2Wherein L is OH and n is 1-4;
in the formula (III), the reaction solution is prepared,
R’1～R’9independently selected from a substituent represented by formula b or-H:
and R'1～R’9Is not H at the same time;
in the formula c z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y12-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0。
In the present invention, the protective atmosphere is preferably nitrogen.
In the invention, the mass ratio of the guar gum to the primary alcohol etherifying agent with the structure shown in the formula II is preferably 100: 15-225, more preferably 100: 15-58, and most preferably 100: 25-42. In the present invention, the primary alcohol etherifying agent is preferably chloroethanol, chlorodiethylene glycol, epoxypropanol or bromobutanol. In the present invention, the primary alcohol etherifying agent is preferably added in the form of an aqueous solution of the primary alcohol etherifying agent, and the concentration of the primary alcohol etherifying agent solution is not particularly limited in the present invention.
According to the invention, the primary alcohol etherifying agent solution with the structure shown in the formula II is preferably added into the cured material by a pump, and the pumping rate is preferably 50-60 mL/s.
In the invention, the temperature of the primary alcohol etherification reaction is preferably 50-75 ℃, and more preferably 60-70 ℃; the time is preferably 90-360 min, and more preferably 120-240 min; the heating rate of heating to the temperature of the primary alcohol etherification reaction is preferably 5-7 ℃/min. In the present invention, the etherification reaction of the primary alcohol is preferably carried out under stirring conditions, and the parameters of the stirring are not particularly limited in the present invention.
After the primary alcohol etherification reaction is finished, the invention preferably carries out solid-liquid separation and washing on the obtained primary alcohol etherification reaction product in sequence, supplements alkaline solution and then carries out cation etherification reaction. In the present invention, the solid-liquid separation is preferably centrifugation, and the specific operation of the centrifugation is not particularly limited in the present invention. In the present invention, the detergent used for washing is preferably an alcohol-water mixed solution, the alcohol-water mixed solution is preferably an ethanol aqueous solution or an isopropanol aqueous solution, the mass fraction of the alcohol-water mixed solution is preferably 65% to 80%, and the washing is performed to remove impurities such as partial salts, unreacted or side-reacted etherifying agents, small molecular polymers, and the like. In the invention, the mass ratio of the guar gum to the supplemented alkaline solution is preferably 100: 6-160, more preferably 100:16, the mass fraction of the supplemented alkaline solution is preferably 15-40%, more preferably 30%, in the invention, the specific type of the supplemented alkaline solution is preferably consistent with the type of the alkaline solution added during curing, and the purpose of the supplemented alkaline solution is to alkalize the primary alcohol etherified guar gum derivative and provide chemical reaction conditions for the cationic etherifying agent.
After the primary alcohol etherate with the structure shown in the formula II is obtained, mixing the primary alcohol etherate with the structure shown in the formula II with a cationic etherifying agent aqueous solution under a protective atmosphere to carry out a cationic etherification reaction to obtain a cationic guar gum thickening agent with the structure shown in the formula I; the cationic etherifying agent in the cationic etherifying agent aqueous solution is epoxypropyl trimethyl ammonium chloride or chloropropanol trimethyl ammonium chloride.
In the present invention, the protective atmosphere is preferably nitrogen.
In the invention, the mass ratio of the guar gum to the cationic etherifying agent aqueous solution is preferably 100: 20-500, more preferably 100: 45-105, and more preferably 100:65, and the mass fraction of the cationic etherifying agent aqueous solution is preferably 40-70%, and more preferably 36%.
According to the invention, the cationic etherifying agent aqueous solution is preferably added to the primary alcohol etherified substance with the structure shown in the formula II by a pump, and the pumping rate is in a range of 50-70 ml/s. In the present invention, the pumping is preferably carried out at 25 ℃ or lower.
In the invention, the temperature of the cation etherification reaction is preferably 50-75 ℃, and more preferably 60-70 ℃; the time is preferably 90-360 min, and more preferably 120-240 min; the heating rate of the temperature rise to the temperature of the cation etherification reaction is preferably 5-7 ℃/min, and the time of the cation etherification reaction at the temperature of the cation etherification reaction is preferably calculated after the cation etherifying agent aqueous solution is added by a pump and stirred for 10-30 min.
After the cationic etherification reaction is finished, the obtained cationic etherification reaction product is preferably sequentially cooled, the pH value is adjusted to 7.0-8.0, alcohol is washed, solid-liquid separation is carried out, grinding and crushing are carried out, and airflow drying is carried out, so that the cationic guar gum thickening agent is obtained. In the present invention, the temperature reduction is preferably naturally cooled to room temperature. In the invention, the regulator for regulating the pH value preferably comprises hydrochloric acid, phosphoric acid, acetic acid, citric acid or carbon dioxide, and the dosage of the regulator is not particularly limited, so that the pH value can be regulated to 7.0-8.0. In the invention, the number of times of alcohol washing is preferably 2-3, the alcohol-water mixed solution used for alcohol washing is preferably an ethanol water solution or an isopropanol water solution, and the mass fraction of the alcohol-water mixed solution is preferably 65-80%. The specific modes of the solid-liquid separation, the roller compaction and the airflow drying are not particularly limited in the invention, and the modes known by the technicians in the field can be adopted. The invention also provides the application of the cationic guar gum thickener in the technical scheme or the cationic guar gum thickener prepared by the preparation method in the technical scheme as a daily chemical product thickener and a fracturing thickener.
The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
In the invention, the daily chemical product is preferably shampoo, and the shampoo preferably comprises the following components in percentage by mass: 12% of sodium lauryl ether sulfate, 1.6% of cocoyl amine propyl betaine, 0.25% of a cationic guar gum thickening agent, 1-3% of sodium chloride, 2% of silicone, 1-3% of essential oil, 1-2% of a humectant and the balance of water. In the present invention, the silicone is added in the form of an aqueous silicone polydimethylsiloxane dispersion, preferably at a concentration of 50% by mass.
The method for preparing the shampoo is not particularly limited, and the method known by the person skilled in the art can be adopted.
In the invention, the application preferably prepares the guar fracturing fluid, and the guar fracturing fluid preferably comprises the following components in percentage by mass: 0.65% of cationic guar gum thickener, 0.015% of anti-swelling agent, 0.015% of cleanup additive, 0.010% of bactericide, 0.060% of crosslinking accelerator, 0.012% of crosslinking agent, 0.2% of temperature stabilizer and the balance of water. The specific types of the anti-swelling agent, the excretion assistant, the bactericide, the crosslinking accelerator, the crosslinking agent and the temperature stabilizer are not particularly limited, and the types well known to those skilled in the art can be adopted. In the invention, the anti-swelling agent is preferably poly dimethyl diallyl ammonium chloride (PDMDAAC) or poly trimethyl allyl ammonium chloride (PTMAAC), the PDMDAAC and the PTMAAC are preferably added in the form of aqueous solution, the mass fraction of the aqueous solution is preferably 5%, the cleanup additive is preferably alkylphenol ethoxylate and/or fluorocarbon fatty acid surfactant, the cleanup additive is preferably added in the form of aqueous solution of cleanup additive, the mass fraction of the aqueous solution of cleanup additive is preferably 5%, the bactericide is preferably dodecyl dimethyl benzyl ammonium chloride, the dodecyl dimethyl benzyl ammonium chloride is preferably added in the form of aqueous solution of dodecyl dimethyl benzyl ammonium chloride, the mass fraction of the aqueous solution of dodecyl dimethyl benzyl ammonium chloride is preferably 10%, the crosslinking accelerator is preferably sodium hydroxide or a mixture of sodium hydroxide and sodium carbonate, the mass ratio of sodium hydroxide to sodium carbonate in the mixture is 3:1, the crosslinking accelerator is preferably added in the form of an aqueous solution, the mass fraction of the aqueous solution is preferably 20% sodium hydroxide solution or sodium hydroxide and sodium carbonate (3:1) mixed solution), the crosslinking agent is preferably triethanolamine zirconate lactate, the triethanolamine zirconate lactate is preferably added in the form of triethanolamine zirconate aqueous solution, the mass fraction of the triethanolamine zirconate lactate aqueous solution is preferably 20%, and the temperature stabilizer is preferably sodium sulfite or sodium thiosulfate.
To further illustrate the present invention, the cationic guar thickeners and methods of making and using the same provided herein are described in detail below with reference to the examples, which should not be construed as limiting the scope of the present invention.
Example 1
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, pumping 40 kg of 30 mass percent sodium hydroxide solution at low temperature (5-15 ℃), stirring and curing for half an hour, pumping 100 kg of 25 mass percent chloroethanol, heating to 70 ℃, stirring for primary alcohol etherification reaction for 2 hours, centrifuging, and washing the solid for 2 times by using alcohol water (70 percent isopropanol water solution). Adding 16 kg of 30 mass percent sodium hydroxide solution into a supplementary pump under the condition of introducing nitrogen, stirring for half an hour, adding 65 kg of 36 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with citric acid until the pH value is 7.0, centrifuging, washing the solid with alcohol water (80 percent isopropanol water solution) for 2 times, grinding and crushing, and drying by air flow (60 ℃ and the contact time is 10 seconds) to obtain the cationic guar gum thickening agent.
The cationic guar gum thickening agent obtained in example 1 is subjected to nuclear magnetic characterization, fig. 1 is a nuclear magnetic resonance hydrogen spectrum of the cationic guar gum thickening agent obtained in example 1, and as can be seen from fig. 1, the structure of the cationic guar gum thickening agent obtained in this example is shown as follows:
R1～R9independently selected from a substituent shown in a formula a, a substituent shown in a formula b or H;
the reason why x is 0,1,2, y and z are 0, x is 0,1 and 2 in the substituted structural formula is that the hydroxy group of the sugar ring in the molecule of the prepared cationic guar gum thickener is randomly substituted by 1 or 2 ethylene oxide structural units, and the average value of x is 1.3.
b is substituted for x in the structural formula1＝1,2，y1 and z1＝0，x1The reason for 2 is that the hydroxyl groups of the sugar ring in the molecule of the prepared cationic guar gum thickener are randomly substituted by 1 or 2 ethylene oxide structural units, and the average value of x is 1.3.
And R is1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total substitution degree of the propanol trimethyl ammonium chloride cation groups is 0.15,
wherein a degree of substitution of 0.10 is attached to the hydroxyethyl groups, and the total degree of substitution of the hydroxyethyl groups is 0.30.
The substitution degree of the substituent is obtained by detecting and analyzing a nuclear magnetic resonance spectrometer of the fully hydrolyzed guar gum derivative.
Application example 1
Preparing shampoo from the cationic guar gum thickening agent prepared in the example 1, wherein the shampoo comprises the following components in percentage by mass:
sodium lauryl ether sulphate (SLES; 2mo1 ethylene oxide containing) 12%
Cocoyl amine propyl betaine 1.6%
0.25 percent of cation guar gum thickening agent
3 percent of sodium chloride
2 percent of silicone (added in the form of silicone polydimethylsiloxane aqueous dispersion, the mass concentration of the silicone polydimethylsiloxane aqueous dispersion is 50 percent)
Essential oil (camellia oil) 3%
Humectant (trimethylglycine) 2%
The balance of water.
Mixing sodium lauryl ether sulfate, cocoyl amine propyl betaine, cationic guar gum, sodium chloride, silicone polydimethylsiloxane aqueous dispersion, essential oil, humectant and water to obtain shampoo.
Example 2
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, pumping 75 kg of 30 mass percent sodium hydroxide solution at low temperature (5-15 ℃), stirring and curing for half an hour, pumping 100 kg of 40 mass percent epoxy propanol, heating to 50 ℃, stirring for primary alcohol etherification reaction for 3 hours, centrifuging, and washing the solid for 2 times by using alcohol water (70 percent isopropanol water solution). Adding 21 kg of 30 mass percent sodium hydroxide solution into a supplementary pump under the condition of introducing nitrogen, stirring for half an hour, adding 105 kg of 30 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with acetic acid until the pH value is 8.0, centrifuging, washing the solid with alcohol water (80 percent isopropanol water solution) for 2 times, grinding and crushing, and drying by air flow to obtain the cationic guar gum thickener, wherein the structural formula is shown in formula I, wherein a substitution structure is shown in the specification, and a substitution structure is shown in the specification, wherein the substitution structure is a substitution structureWherein x is 2, y and z is 0, and b is substituted for x in the structural formula1＝2，y1 and z1Is equal to 0, and R1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total substitution degree of the propanol trimethyl ammonium chloride cation groups is 0.20;
wherein the degree of substitution is 0.13 to the glyceryl groups.
The total degree of glyceryl substitution was 0.35.
Application example 2
The cationic guar gum thickener prepared in example 2 is used to prepare shampoo, and the specific mass percentage composition and preparation method are the same as those in example 1.
The cationic guar gum thickeners (as conditioning polymers), cationic guar gum thickeners (without polymers) and conventionally synthesized cationic guar gums prepared in examples 1 and 2 were subjected to wet combing test on brown hair tresses using a TA-XTPlus texture analyzer, the conventionally synthesized cationic guar gums including conventionally synthesized cationic guar gums (DS 0.12-0.15) and conventionally synthesized cationic guar gums (DS 0.20-0.25), the specific steps of conventionally synthesized cationic guar gums (DS 0.12-0.15) were: the same as in example 1, except that primary alcohol etherification was not performed, cationic etherification was directly performed; the specific steps of conventionally synthesizing the cationic guar gum (DS 0.20-0.25) are as follows: the same as in example 2, except that primary alcohol etherification was not performed, cationic etherification was directly performed.
The wet carding test process is as follows: the straightened hair bundle is clamped at two ends by clamps and then wetted by water, different shampoos are kneaded quantitatively, the hair bundle is washed for a certain time by water after being treated for a certain time, a comb fixed on a texture analyzer is inserted, the combing force is tested, the average value is calculated by repeating the experiments for many times, and the result is shown in figure 2. As can be seen from fig. 2, the cationic guar thickeners prepared in examples 1 and 2 have a higher wet combing improvement rate of 50% than the same cationic etherification level and cationic etherification level, which indicates that the cationic guar synthesized by the present invention has better wet combing performance.
Example 3
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, pumping 40 kg of 30 mass percent sodium hydroxide solution at low temperature (5-15 ℃), stirring and curing for half an hour, pumping 100 kg of 25 mass percent chloroethanol, heating to 70 ℃, stirring for primary alcohol etherification reaction for 2 hours, centrifuging, and washing the solid for 2 times by using alcohol water (70 percent isopropanol water solution). Adding 30 kg of 30 mass percent sodium hydroxide solution into a supplementary pump under the condition of introducing nitrogen, stirring for half an hour, adding 110 kg of 36 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with citric acid until the pH value is 7.0, centrifuging, washing the solid with alcohol water (80 percent isopropanol water solution) for 2 times, grinding and crushing, and drying with air flow (60 ℃ for 10s) to obtain the cationic guar gum thickening agent
The structural formula is shown as follows, wherein
The reason why x is 1,2, y and z is 0 in the substituted structural formula, x is 1,2, y and z are 0 in the substituted structural formula, and x is 1,2 is that the hydroxyl group of the sugar ring in the molecule of the prepared cationic guar gum thickener is randomly substituted by 1 or 2 ethylene oxide structural units, wherein the average value of x is 1.35.
b is substituted for x in the structural formula1＝1,2，y1 and z 10, wherein x is 1,2, y and z is 0, x1The reason for 2 is that the hydroxyl groups of the sugar ring in the molecule of the prepared cationic guar gum thickener are randomly substituted by 1 or 2 ethylene oxide structural units, and the average value of x is 1.35.
And R is1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total degree of substitution of the cationic group of propanol trimethyl ammonium chloride was 0.30, wherein the degree of substitution of 0.18 was attached to the hydroxyethyl group, and the total degree of substitution of the hydroxyethyl group was 0.30.
Application example 3
The cationic guar gum thickener prepared in the example 3 is used for preparing guar gum fracturing fluid, and the guar gum fracturing fluid specifically comprises the following components: 0.65% of cationic guar gum thickener prepared in example 3, 0.015% of polydimethyldiallylammonium chloride, 0.015% of alkylphenol polyoxyethylene, 0.010% of dodecyl dimethyl benzyl ammonium chloride, 0.060% of sodium hydroxide, 0.012% of lactic acid triethanolamine zirconate, 0.2% of sodium sulfite and the balance of water. Wherein the poly dimethyl diallyl ammonium chloride is added in the form of aqueous solution, and the mass fraction is 5%; adding alkylphenol polyoxyethylene into the solution in the form of aqueous solution, wherein the mass fraction of the aqueous solution is 5%; the dodecyl dimethyl benzyl ammonium chloride is preferably added in the form of aqueous solution, and the mass fraction of the aqueous solution is 10%; adding sodium hydroxide in the form of aqueous solution, wherein the mass fraction of the aqueous solution is 20%; adding the lactic acid triethanolamine zirconate in the form of a lactic acid triethanolamine zirconate aqueous solution, wherein the mass fraction of the aqueous solution is 20%; the temperature stabilizer is preferably sodium thiosulfate.
FIG. 3 is the rheological curve of the guar fracturing fluid of example 3 at 180 deg.C, as can be seen from FIG. 3, at 180 deg.C and 170s-1The final viscosity after 2 hours is above 100mpa.s, which shows that the jelly has good rheological property and high temperature resistance.
Example 4
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, adding 45 kg of 25 mass percent sodium hydroxide solution into a pump under the condition of low temperature (15 ℃), stirring and curing for half an hour, heating to 60 ℃, introducing 100 kg of ethylene oxide, stirring and reacting for 3 hours, centrifuging, and washing the solid for 2 times by using alcohol water (75 percent isopropanol water solution). Adding 16 kg of 30 mass percent sodium hydroxide solution into a supplementary pump under the condition of introducing nitrogen, stirring for half an hour, adding 65 kg of 36 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with carbon dioxide until the pH value is 8.0, centrifuging, washing a solid with alcohol water (75 percent isopropanol water solution) for 2 times, grinding and crushing, and drying by air flow to obtain the cationic guar gum thickening agent with a structural formula shown in formula I, wherein x is 1,2, y and z are 0 in a substituted structural formula, and x is 0 in a substituted structural formula1＝1,2，y1 and z1＝0，x＝1.37。 R1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total substitution degree of the propanol trimethyl ammonium chloride cation groups is 0.15;
in which a degree of substitution of 0.09 is attached to the hydroxyethyl group.
The total degree of substitution by hydroxyethyl groups was 0.25.
Example 5
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, adding 32 kg of 30 mass percent sodium hydroxide solution into a pump under the condition of low temperature (10 ℃), stirring and curing for half an hour, adding 110 kg of 42 mass percent bromobutanol into the pump, heating to 70 ℃, stirring for primary alcohol etherification reaction for 2 hours, centrifuging, and washing the solid for 2 times by using alcohol water (70 percent isopropanol water solution). Under the condition of introducing nitrogen, adding 16 kg of 30 mass percent sodium hydroxide solution into a supplementary pump, stirring for half an hour, adding 65 kg of 36 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with acetic acid until the pH value is 8.0, centrifuging, washing the solid with alcohol water (70 percent isopropanol water solution) for 2 times, grinding and crushing, and drying by air flow to obtain the cationic guar gum thickening agent.
The cationic guar gum thickening agent obtained in example 4 is subjected to nuclear magnetic characterization, fig. 4 is a nuclear magnetic resonance hydrogen spectrum of the cationic guar gum thickening agent obtained in example 4, and as can be seen from fig. 4, the structure of the cationic guar gum thickening agent obtained in this example is shown as follows:
R1～R9independently selected from a substituent shown in a formula a, a substituent shown in a formula b or H;
a is substituted where x is 0, y is 4 and z is 1, or x is 0, y is 0 and z is 0
b is substituted for x in the structural formula1＝0，y1＝4 and z1＝1
And R is1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total substitution degree of the propanol trimethyl ammonium chloride cation groups is 0.15,
wherein a degree of substitution of 0.10 is attached to the hydroxybutyl group.
The total degree of substitution of hydroxybutyl was 0.27.
Example 6
Introducing nitrogen into 100 kg of guar gum pieces for 30 minutes, adding 64 kg of 30 mass percent sodium hydroxide solution into a pump under the condition of low temperature (10 ℃), stirring and curing for half an hour, adding 100 kg of 42 mass percent chloroethanol into the pump, heating to 70 ℃, stirring for carrying out primary alcohol etherification reaction for 2 hours, centrifuging, and washing the solid for 2 times by using alcohol water (80 percent isopropanol water solution). Adding 27 kg of 30 mass percent sodium hydroxide solution into a supplementary pump under the condition of introducing nitrogen, stirring for half an hour, adding 45 kg of 42 mass percent chloropropanol trimethyl ammonium chloride solution into the pump, heating to 70 ℃, stirring for carrying out cationic etherification reaction for 2 hours, naturally cooling to room temperature, neutralizing with acetic acid until the pH value is 8.0, centrifuging, washing the solid with alcohol water (75 percent isopropanol water solution) for 2 times, grinding and crushing, and drying by air flow to obtain the cationic guar gum thickening agent with the structural formula shown in formula I, wherein the structural formula is shown in the specification, and the structural formula is shown in the specification
The reason why x is 1,2, y and z is 0 in the substituted structural formula, x is 1,2, y and z are 0 in the substituted structural formula, and x is 1,2 is that the hydroxyl group of the sugar ring in the molecule of the prepared cationic guar gum thickener is randomly substituted by 1 or 2 ethylene oxide structural units, wherein the average value of x is 1.4.
b is substituted for x in the structural formula1＝1,2，y1 and z 10, wherein x is 1,2, y and z is 0, x11 and 2 are due toThe hydroxyl groups of the sugar ring in the molecule of the prepared cationic guar gum thickener are randomly substituted by 1 or 2 ethylene oxide structural units, and the average value of x is 1.4.
And R is1～R9Structures which are not simultaneously represented by formula a or formula b are also not simultaneously-H;
degree of substitution: the total substitution degree of the propanol trimethyl ammonium chloride cation group is 0.25
In which a degree of substitution of 0.18 is attached to the hydroxyethyl group.
The total degree of substitution by hydroxyethyl groups was 0.49.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A cationic guar thickener having the structure of formula I:
wherein ,
R1～R9independently selected from a substituent shown in formula a, a substituent shown in formula b or H:
and R is1～R9The structures which are not simultaneously represented by the formula b are also not simultaneously-H;
wherein z is 1 or 0,
(1) when z is 1, x is 0, y is 3-6 or x is 1, and y is 1-4;
(2) when z is 0, x is 2 to 3, y is 0 or x is 0, and y is 0
In the formula b z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1, x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0。
2. The cationic guar gum thickener according to claim 1, wherein the total degree of substitution of the group of formula a and the group of formula b in the cationic guar gum thickener is 0.15 to 0.8.
3. The cationic guar thickener according to claim 1 or 2, wherein the total degree of substitution of the group of formula a and the group of formula b in the cationic guar thickener is 0.15 to 0.5.
4. The cationic guar gum thickener according to claim 1, wherein the degree of substitution of the group of formula a in the cationic guar gum thickener is 0.05 to 0.6.
5. The cationic guar gum thickener according to claim 1 or 4, wherein the substitution degree of the structure represented by the formula a in the cationic guar gum thickener is 0.1-0.4.
6. The cationic guar thickener according to claim 1, wherein the percentage of the number of structural substitutions represented by formula a in the cationic guar thickener to the sum of the number of structures represented by formula a and b is 20% to 80%.
7. The cationic guar thickener according to claim 1, wherein the cationic guar thickener has a weight average molecular weight of 120 to 300 ten thousand.
8. The method for preparing the cationic guar gum thickener according to any one of claims 1 to 7, comprising the following steps:
curing the guar gum and the alkaline solution to obtain a cured material;
under the protective atmosphere, mixing the cured material with a primary alcohol etherifying agent with a structure shown in a formula II to carry out primary alcohol etherification reaction to obtain a primary alcohol etherified substance with a structure shown in a formula III;
in the formula II, X is Cl, Br or epoxy ethyl;
when X ═ Cl or Br, Ra＝-CH2-OH, and n-2-6 or Ra＝-CH2CH2O-, L-H, and n-2-3;
when X is epoxyethyl, Ra＝-CH2-OH and n is 1 to 4;
in the formula (III), the reaction solution is prepared,
R’1～R’9independently selected from a substituent represented by formula b or-H:
and R'1～R’9Is not H at the same time;
in the formula c z1Either 1 or 0, or a combination thereof,
(1) when z is1When 1 is true，x1＝0，y13-6 or x1＝1，y1＝1～4；
(2) When z is1When equal to 0, x1When 2-3, y1＝0；
Under a protective atmosphere, mixing the primary alcohol etherate with the structure shown in the formula III with a cationic etherifying agent aqueous solution to perform a cationic etherification reaction to obtain a cationic guar gum thickening agent with the structure shown in the formula I; the cationic etherifying agent in the cationic etherifying agent aqueous solution is epoxypropyl trimethyl ammonium chloride or chloropropanol trimethyl ammonium chloride.
9. The preparation method according to claim 8, wherein the temperature of the cationic etherification reaction is 50 to 75 ℃.
10. Use of the cationic guar gum thickener according to any one of claims 1 to 7 or the cationic guar gum thickener prepared by the preparation method according to claim 8 or 9 as a thickener for household chemical products and a fracturing thickener.
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| CN116554853A (en) * | 2023-07-10 | 2023-08-08 | 克拉玛依市正诚有限公司 | Modified fracturing fluid thickener and preparation method thereof |
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| US5756720A (en) * | 1996-10-25 | 1998-05-26 | Rhodia Inc. | Derivatized guar gum composition including nonionic and cationic groups which demonstrate excellent solution clarity properties |
| US20150098921A1 (en) * | 2013-10-07 | 2015-04-09 | Hercules Incorporated | Dihydroxyalkyl substituted polygalactomannan, and methods for producing and using the same |
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| JP2019099752A (en) * | 2017-12-06 | 2019-06-24 | 花王株式会社 | Polysaccharide derivative |
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| US5756720A (en) * | 1996-10-25 | 1998-05-26 | Rhodia Inc. | Derivatized guar gum composition including nonionic and cationic groups which demonstrate excellent solution clarity properties |
| US20150098921A1 (en) * | 2013-10-07 | 2015-04-09 | Hercules Incorporated | Dihydroxyalkyl substituted polygalactomannan, and methods for producing and using the same |
| CN107629139A (en) * | 2017-11-02 | 2018-01-26 | 山东广浦生物科技有限公司 | A kind of transparent guar gum and preparation method thereof |
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| CN116554853A (en) * | 2023-07-10 | 2023-08-08 | 克拉玛依市正诚有限公司 | Modified fracturing fluid thickener and preparation method thereof |
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