CN117820652B - Biodegradable modified rosin resin and preparation method and application thereof - Google Patents
Biodegradable modified rosin resin and preparation method and application thereof Download PDFInfo
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- CN117820652B CN117820652B CN202410233892.3A CN202410233892A CN117820652B CN 117820652 B CN117820652 B CN 117820652B CN 202410233892 A CN202410233892 A CN 202410233892A CN 117820652 B CN117820652 B CN 117820652B
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- tannic acid
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- rosin
- chitin
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 126
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 123
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920002101 Chitin Polymers 0.000 claims abstract description 99
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 95
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 95
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 95
- 229940033123 tannic acid Drugs 0.000 claims abstract description 95
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 95
- 229920002258 tannic acid Polymers 0.000 claims abstract description 95
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 69
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims abstract description 67
- 108010022355 Fibroins Proteins 0.000 claims abstract description 51
- 239000001530 fumaric acid Substances 0.000 claims abstract description 46
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000004365 Protease Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 25
- 108091005804 Peptidases Proteins 0.000 claims description 22
- 235000019419 proteases Nutrition 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 108090000526 Papain Proteins 0.000 claims description 12
- 235000019834 papain Nutrition 0.000 claims description 12
- 229940055729 papain Drugs 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 11
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 10
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 9
- 108090000145 Bacillolysin Proteins 0.000 claims description 8
- 102000035092 Neutral proteases Human genes 0.000 claims description 8
- 108091005507 Neutral proteases Proteins 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 7
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940088598 enzyme Drugs 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 230000000415 inactivating effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 6
- 239000003607 modifier Substances 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 102000035195 Peptidases Human genes 0.000 description 16
- 230000006872 improvement Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 101000693530 Staphylococcus aureus Staphylokinase Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012738 dissolution medium Substances 0.000 description 1
- 125000000567 diterpene group Chemical group 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KQKPFRSPSRPDEB-UHFFFAOYSA-N sumatriptan Chemical compound CNS(=O)(=O)CC1=CC=C2NC=C(CCN(C)C)C2=C1 KQKPFRSPSRPDEB-UHFFFAOYSA-N 0.000 description 1
- 229960003708 sumatriptan Drugs 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- -1 welding aid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- C09K3/00—Materials not provided for elsewhere
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a biodegradable modified rosin resin and a preparation method and application thereof, and belongs to the technical field of chemical industry. The 2-hydroxyethyl chitin reacts with tannic acid to prepare a 2-hydroxyethyl chitin/tannic acid modified substance, the 2-hydroxyethyl chitin/tannic acid modified substance reacts with rosin in an esterification mode, and then reacts with fumaric acid and silk fibroin peptide to prepare the biodegradable modified rosin resin. The prepared biodegradable modified rosin resin has good water solubility and degradability, and simultaneously has good tackifying, thickening and emulsifying properties, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a biodegradable modified rosin resin and a preparation method and application thereof.
Background
Rosin is known as petroleum growing on trees as a renewable natural resin, and is commonly used in the fields of paint, ink, paint, adhesive, welding aid, rubber, paper making, food additives, biological products and the like. The main component in the rosin is rosin resin acid (a compound shown in a formula I) with a tricyclic diterpene structure and two types of active groups (carbon-carbon double bonds and carboxyl groups), wherein the rosin resin acid mainly comprises abietic acid, neoabietic acid, palustric acid, levopimaric acid and other compounds, and under a certain temperature condition (t is more than or equal to 120 ℃), other resin acids except for the levopimaric acid can be converted into the levopimaric acid (the compound shown in a formula IV) through tautomerism, and the levopimaric acid can react with other compounds with conjugated double bonds through Diels-Alder addition. In order to widen the application path of rosin, rosin is generally modified, and carboxyl and double bonds in the rosin can be used for esterification and addition reaction to prepare rosin resins with different physical and chemical properties.
The water-soluble rosin resin takes rosin as a raw material, utilizes conjugated double bonds in a rosin structure to carry out addition reaction, then carries out esterification reaction with polyol, introduces hydrophilic groups or solubilising groups into the resin, and enables the resin to take water as a dissolution medium, thereby having stronger initial viscosity and being widely applied to industries such as water-based adhesives, water-based coatings, water-based ink and the like. At present, water-soluble rosin resin is often used as a tackifier of an aqueous adhesive, the requirements on production technology and equipment are high, the rosin resin is required to be subjected to emulsification treatment, and the problem of low storage stability is generally solved.
Chinese patent No. 113913114B discloses a preparation method of degradable rosin resin, which belongs to the field of rosin deep processing. The method comprises the following steps: melting rosin under the protection of inert gas; unsaturated acid is added for reaction; adding a catalyst and mixed alcohol to react; removing water generated by the reaction, cooling, adding an antioxidant and a degradation promoter, and uniformly mixing to obtain the rosin resin. The prepared rosin resin is degradable, has good appearance, good stability and good viscosity when being applied to degradable hot melt adhesive, and has good application prospect.
However, the degradable rosin resin prepared by the patent has the problems of easy crystallization, easy oxidative discoloration, low softening point and the like.
Disclosure of Invention
The invention aims to provide a biodegradable modified rosin resin, a preparation method and application thereof, which have better water solubility and degradability, and simultaneously have good tackifying, thickening and emulsifying properties, high softening point, abundant raw material sources, low price, environmental protection and cleanness, can be widely applied to industries such as medicines, foods, textiles, papermaking and the like, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of biodegradable modified rosin resin, which comprises the steps of reacting 2-hydroxyethyl chitin with tannic acid to obtain 2-hydroxyethyl chitin/tannic acid modified substance, esterifying the 2-hydroxyethyl chitin/tannic acid rosin ester with rosin to obtain 2-hydroxyethyl chitin/tannic acid rosin ester, and reacting the 2-hydroxyethyl chitin/tannic acid rosin ester with fumaric acid to obtain fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, and reacting the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester with silk fibroin peptide to obtain biodegradable modified rosin resin;
the mass ratio of the 2-hydroxyethyl chitin to the tannic acid is 20-25:2-4;
The mass ratio of the rosin to the 2-hydroxyethyl chitin to the tannic acid is 100:22-27;
The mass ratio of the 2-hydroxyethyl chitin/tannic acid rosin ester to the fumaric acid is 100:12-15;
The mass ratio of the fumaric acid modified 2-hydroxyethyl chitin to the tannic acid rosin ester to the silk fibroin peptide is 100:25-30.
As a further improvement of the invention, the method comprises the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 2-hydroxyethyl chitin in water, adding tris (hydroxymethyl) aminomethane and tannic acid, regulating the pH value of the solution, heating, stirring, reacting, dialyzing, and drying to obtain 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding rosin and the 2-hydroxyethyl chitin/tannic acid modified substance prepared in the step S1 into toluene, stirring and dissolving, dropwise adding concentrated sulfuric acid, heating and refluxing for reaction, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding fumaric acid into the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, and heating and stirring for reaction to prepare fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
S4, hydrolysis of silk fibroin: dissolving silk fibroin in water, adding protease, performing enzymolysis, inactivating enzyme, filtering, and freeze drying the filtrate to obtain silk fibroin peptide;
s5, reaction with silk fibroin peptide: adding fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide which are prepared in the step S3 into water, performing an activation reaction, adding silk fibroin peptide prepared in the step S4, and performing a heating reaction to prepare the biodegradable modified rosin resin.
As a further improvement of the invention, in the step S1, the mass ratio of the 2-hydroxyethyl chitin to the tris (hydroxymethyl) aminomethane to the tannic acid is 20-25:3-5:2-4, the pH value of the solution is adjusted to 8-8.5, the temperature of the heating and stirring reaction is 40-50 ℃ for 5-7h, the aperture of a dialysis bag used for dialysis is 3-5kDa, and the dialysis time is 2-4h.
As a further improvement of the invention, the mass ratio of the rosin to the 2-hydroxyethyl chitin/tannic acid modified matter to the concentrated sulfuric acid in the step S2 is 100:22-27:3-5, and the heating reflux reaction time is 7-10h.
As a further improvement of the invention, the mass ratio of the 2-hydroxyethyl chitin to the tannic acid rosin ester to the fumaric acid in the step S3 is 100:12-15, the temperature of the heating and stirring reaction is 190-220 ℃, and the time is 1-3h.
As a further improvement of the invention, the mass ratio of the silk fibroin to the protease in the step S4 is 100:2-3, the protease is a mixture of neutral protease and papain, the mass ratio is 7-10:3-5, the enzymolysis temperature is 45-55 ℃, and the enzymolysis time is 1-3h.
As a further improvement of the invention, in the step S5, the mass ratio of the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the N-hydroxysuccinimide and the silk fibroin peptide is 100:15-18:36-42:25-30, the temperature of the activation reaction is 0-4 ℃ for 20-30min, the temperature of the heating reaction is 35-45 ℃ for 6-8h.
As a further improvement of the invention, the method specifically comprises the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 20-25 parts by weight of 2-hydroxyethyl chitin in 200 parts by weight of water, adding 3-5 parts by weight of tris (hydroxymethyl) aminomethane and 2-4 parts by weight of tannic acid, regulating the pH value of the solution to 8-8.5, heating to 40-50 ℃, stirring for reacting for 5-7 hours, dialyzing for 2-4 hours by using a dialysis bag with the aperture of 3-5kDa, and drying to obtain a 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding 100 parts by weight of rosin and 22-27 parts by weight of the 2-hydroxyethyl chitin/tannic acid modified product prepared in the step S1 into 500 parts by weight of toluene, stirring and dissolving, dropwise adding 3-5 parts by weight of concentrated sulfuric acid, heating and refluxing for reaction for 7-10 hours, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding 12-15 parts by weight of fumaric acid into 100 parts by weight of the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, heating to 190-220 ℃, and stirring for reacting for 1-3 hours to prepare the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
S4, hydrolysis of silk fibroin: dissolving 100 parts by weight of silk fibroin in 500 parts by weight of water, adding 2-3 parts by weight of protease, carrying out enzymolysis for 1-3 hours at 45-55 ℃, inactivating enzyme, filtering, and freeze-drying filtrate to obtain silk fibroin peptide;
the protease is a mixture of neutral protease and papain, and the mass ratio of the protease to the papain is 7-10:3-5;
S5, reaction with silk fibroin peptide: 100 parts by weight of fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S3, 15-18 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 36-42 parts by weight of N-hydroxysuccinimide are added into 500 parts by weight of water, activated and reacted for 20-30min at 0-4 ℃, 25-30 parts by weight of silk fibroin peptide prepared in the step S4 are added, heated to 35-45 ℃, and stirred and reacted for 6-8h, so that the biodegradable modified rosin resin is prepared.
The invention further protects the biodegradable modified rosin resin prepared by the preparation method.
The invention further protects application of the biodegradable modified rosin resin in preparation of tackifiers and thickeners.
The invention has the following beneficial effects:
the traditional rosin resin is usually used for producing products such as printing ink, adhesives, coatings and the like, contains a large amount of solvents, can generate a large amount of Volatile Organic Compounds (VOC), can seriously harm the environment and the health of constructors in the production and construction processes, and has the problems of easy crystallization, easy oxidative discoloration, low softening point and the like.
The chitin and the silk fibroin have good biodegradability and environmental protection, the 2-hydroxyethyl chitin is taken as a raw material, the 2-hydroxyethyl chitin is a water-soluble chitin derivative, and reacts with tannic acid under alkaline conditions to form a macromolecular 2-hydroxyethyl chitin/tannic acid modified substance, the structure of the modified substance is provided with abundant hydroxyl groups, and the modified substance can be subjected to esterification reaction with carboxyl groups on rosin molecules to prepare 2-hydroxyethyl chitin/tannic acid rosin ester, and further, after the 2-hydroxyethyl chitin/tannic acid rosin ester with a levopimaric acid structure and fumaric acid undergo Diels-Alder addition reaction, the product is provided with carboxyl groups again. After the activation of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, carboxyl reacts with the exposed amino groups on the silk fibroin peptide, wherein the silk fibroin peptide is a protein peptide produced by partial hydrolysis of silk fibroin by protease, so that more amino groups are exposed on the protein peptide chain, and the dehydration condensation reaction with fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester is completed.
The prepared biodegradable modified rosin resin has good water solubility and degradability, good tackifying, thickening and emulsifying properties, high softening point, abundant raw material sources, low price, environmental protection and cleanness, can be widely applied to industries such as medicines, foods, textiles, papermaking and the like, and has wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Rosin is masson pine rosin (first grade) purchased from megaperil forest company limited in northern Guangxi city; silk fibroin, molecular weight >100KDa, purchased from sumatriptan biotechnology limited.
Neutral proteinase, 10 ten thousand U/g, purchased from Chongqing Tianrun biological products Co., ltd., papain, 10 ten thousand U/g, purchased from Nanning Dong Henghua biological technology Co., ltd.
Example 1
The embodiment provides a preparation method of biodegradable modified rosin resin, which specifically comprises the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 20 parts by weight of 2-hydroxyethyl chitin in 200 parts by weight of water, adding 3 parts by weight of tris (hydroxymethyl) aminomethane and 2 parts by weight of tannic acid, adjusting the pH value of the solution to 8, heating to 40 ℃, stirring and reacting for 5 hours, dialyzing for 4 hours by using a dialysis bag with the aperture of 3kDa, and drying to obtain a 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding 100 parts by weight of rosin and 22 parts by weight of the 2-hydroxyethyl chitin/tannic acid modified product prepared in the step S1 into 500 parts by weight of toluene, stirring and dissolving, dropwise adding 3 parts by weight of concentrated sulfuric acid, heating and refluxing for reaction for 7 hours, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding 12 parts by weight of fumaric acid into 100 parts by weight of the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, heating to 190 ℃, and stirring for reacting for 1h to prepare the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
s4, hydrolysis of silk fibroin: dissolving 100 parts by weight of silk fibroin in 500 parts by weight of water, adding 2 parts by weight of protease, carrying out enzymolysis for 1h at 45 ℃, inactivating enzyme, filtering, and freeze-drying filtrate to obtain silk fibroin peptide;
the protease is a mixture of neutral protease and papain, and the mass ratio of the protease to the papain is 7:3;
S5, reaction with silk fibroin peptide: 100 parts by weight of fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S3, 15 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 36 parts by weight of N-hydroxysuccinimide are added into 500 parts by weight of water, activated and reacted for 30min at 0 ℃, 25 parts by weight of silk fibroin peptide prepared in the step S4 are added, heated to 35 ℃, and stirred and reacted for 6h, so that the biodegradable modified rosin resin is prepared.
Example 2
The embodiment provides a preparation method of biodegradable modified rosin resin, which specifically comprises the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 25 parts by weight of 2-hydroxyethyl chitin in 200 parts by weight of water, adding 5 parts by weight of tris (hydroxymethyl) aminomethane and 4 parts by weight of tannic acid, adjusting the pH value of the solution to 8.5, heating to 50 ℃, stirring and reacting for 7 hours, dialyzing for 2 hours by using a dialysis bag with the aperture of 5kDa, and drying to obtain a 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding 100 parts by weight of rosin and 27 parts by weight of the 2-hydroxyethyl chitin/tannic acid modified product prepared in the step S1 into 500 parts by weight of toluene, stirring and dissolving, dropwise adding 5 parts by weight of concentrated sulfuric acid, heating and refluxing for reaction for 10 hours, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding 15 parts by weight of fumaric acid into 100 parts by weight of the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, heating to 220 ℃, and stirring for reaction for 3 hours to prepare the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
s4, hydrolysis of silk fibroin: dissolving 100 parts by weight of silk fibroin in 500 parts by weight of water, adding 3 parts by weight of protease, carrying out enzymolysis for 3 hours at 55 ℃, inactivating enzyme, filtering, and freeze-drying filtrate to obtain silk fibroin peptide;
the protease is a mixture of neutral protease and papain, and the mass ratio is 10:5;
s5, reaction with silk fibroin peptide: 100 parts by weight of fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S3, 18 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 42 parts by weight of N-hydroxysuccinimide are added into 500 parts by weight of water, activated and reacted for 30min at 0 ℃, 30 parts by weight of silk fibroin peptide prepared in the step S4 are added, heated to 45 ℃, and stirred and reacted for 8h, so that the biodegradable modified rosin resin is prepared.
Example 3
The embodiment provides a preparation method of biodegradable modified rosin resin, which specifically comprises the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 22 parts by weight of 2-hydroxyethyl chitin in 200 parts by weight of water, adding 4 parts by weight of tris (hydroxymethyl) aminomethane and 3 parts by weight of tannic acid, adjusting the pH value of the solution to 8.2, heating to 45 ℃, stirring and reacting for 6 hours, dialyzing for 3 hours by using a dialysis bag with the aperture of 4kDa, and drying to obtain a 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding 100 parts by weight of rosin and 25 parts by weight of the 2-hydroxyethyl chitin/tannic acid modified product prepared in the step S1 into 500 parts by weight of toluene, stirring and dissolving, dropwise adding 4 parts by weight of concentrated sulfuric acid, heating and refluxing for reaction for 8 hours, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding 13 parts by weight of fumaric acid into 100 parts by weight of the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, heating to 210 ℃, and stirring for reacting for 2 hours to prepare the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
s4, hydrolysis of silk fibroin: dissolving 100 parts by weight of silk fibroin in 500 parts by weight of water, adding 2.5 parts by weight of protease, carrying out enzymolysis for 2 hours at 50 ℃, inactivating enzyme, filtering, and freeze-drying filtrate to obtain silk fibroin peptide;
The protease is a mixture of neutral protease and papain, and the mass ratio is 9:4;
S5, reaction with silk fibroin peptide: 100 parts by weight of fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S3, 16 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 40 parts by weight of N-hydroxysuccinimide are added into 500 parts by weight of water, activated and reacted for 30min at 0 ℃, 27 parts by weight of silk fibroin peptide prepared in the step S4 are added, heated to 40 ℃, and stirred and reacted for 7h, so that the biodegradable modified rosin resin is prepared.
Example 4
The difference compared to example 3 is that the protease is a single neutral protease.
Example 5
The difference compared to example 3 is that the protease is a single papain.
Comparative example 1
The difference compared to example 3 is that step S1 is not performed and the 2-hydroxyethyl chitin/tannic acid modification in step S2 is replaced by an equivalent amount of 2-hydroxyethyl chitin.
Comparative example 2
In comparison with example 3, the difference is that step S4 is not performed, and the silk fibroin peptide is replaced with an equivalent amount of silk fibroin in step S5.
Comparative example 3
In comparison with example 3, the difference is that steps S3 to S5 are not performed.
Comparative example 4
In comparison with example 3, the difference is that steps S4 to S5 are not performed.
Comparative example 5
In comparison with example 3, the difference is that steps S1 and S2 are not carried out, and the 2-hydroxyethyl chitin/tannic acid rosin ester in step S3 is replaced with an equal amount of rosin.
Test example 1
The biodegradable modified rosin resins obtained in examples 1 to 5 and comparative examples 1 to 5 of the present invention were subjected to the following performance test, and the results are shown in Table 1.
Softening point: testing according to GB/T8146-2022 standard;
Viscosity: testing according to GB/T1723-1993 standard;
Solubility: the test was performed according to HG/T2710-1995 standard.
TABLE 1
As shown in the table above, the biodegradable modified rosin resin prepared in the examples 1-3 of the invention has good water solubility, proper viscosity and high softening point.
Test example 2
The biodegradable modified rosin resins obtained in examples 1 to 5 and comparative examples 1 to 5 of the present invention were subjected to the following performance test, and the results are shown in Table 2
Stability: weighing a certain mass of sample, preparing into an aqueous solution with the mass concentration of 1%, gelatinizing in a boiling water bath, preserving heat for 20min, cooling to room temperature, pouring into a cylinder with a stopper, shaking uniformly, standing, and recording the volume of sediment at the bottom after 24 h.
Biodegradability: the sample is weighed m 1 by adopting a soil burying method, buried in moist soil, taken out every 1 week, dried and weighed m 2, and the degradation time to the biodegradation rate of >99% is tested to characterize the degradation performance.
Biodegradation rate (%) = (m 1-m2）/m1 ×100%
Volatile organic compound content (volatile organic compound content, VOC) determination: the test was carried out according to the GB 18582-2020 standard.
TABLE 2
As can be seen from the above table, the biodegradable modified rosin resins prepared in examples 1 to 3 of the present invention have good stability, good biodegradability and low VOC content.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A preparation method of biodegradable modified rosin resin is characterized in that 2-hydroxyethyl chitin is reacted with tannic acid to prepare 2-hydroxyethyl chitin/tannic acid modified substance, esterification reaction is carried out on the 2-hydroxyethyl chitin/tannic acid modified substance and rosin to obtain 2-hydroxyethyl chitin/tannic acid rosin ester, then fumaric acid is reacted with fumaric acid to obtain fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, and the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester is reacted with silk fibroin peptide to prepare biodegradable modified rosin resin;
the mass ratio of the 2-hydroxyethyl chitin to the tannic acid is 20-25:2-4;
The mass ratio of the rosin to the 2-hydroxyethyl chitin to the tannic acid is 100:22-27;
The mass ratio of the 2-hydroxyethyl chitin/tannic acid rosin ester to the fumaric acid is 100:12-15;
The mass ratio of the fumaric acid modified 2-hydroxyethyl chitin to the tannic acid rosin ester to the silk fibroin peptide is 100:25-30;
The method comprises the following steps:
s1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 2-hydroxyethyl chitin in water, adding tris (hydroxymethyl) aminomethane and tannic acid, regulating the pH value of the solution, heating, stirring, reacting, dialyzing, and drying to obtain 2-hydroxyethyl chitin/tannic acid modified substance; the mass ratio of the 2-hydroxyethyl chitin to the tris (hydroxymethyl) aminomethane to the tannic acid is 20-25:3-5:2-4, the pH value of the solution is adjusted to 8-8.5, the temperature of the heating and stirring reaction is 40-50 ℃, the time is 5-7h, the aperture of a dialysis bag used for dialysis is 3-5kDa, and the time of dialysis is 2-4h;
S2, reaction with rosin: adding rosin and the 2-hydroxyethyl chitin/tannic acid modified substance prepared in the step S1 into toluene, stirring and dissolving, dropwise adding concentrated sulfuric acid, heating and refluxing for reaction, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding fumaric acid into the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, and heating and stirring for reaction to prepare fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
S4, hydrolysis of silk fibroin: dissolving silk fibroin in water, adding protease, performing enzymolysis, inactivating enzyme, filtering, and freeze drying the filtrate to obtain silk fibroin peptide;
s5, reaction with silk fibroin peptide: adding fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide which are prepared in the step S3 into water, performing an activation reaction, adding silk fibroin peptide prepared in the step S4, and performing a heating reaction to prepare the biodegradable modified rosin resin.
2. The preparation method according to claim 1, wherein the mass ratio of rosin, 2-hydroxyethyl chitin/tannic acid modifier and concentrated sulfuric acid in step S2 is 100:22-27:3-5, and the heating reflux reaction time is 7-10h.
3. The preparation method according to claim 1, wherein the mass ratio of the 2-hydroxyethyl chitin to the tannic acid rosin ester to the fumaric acid in the step S3 is 100:12-15, and the temperature of the heating and stirring reaction is 190-220 ℃ for 1-3h.
4. The preparation method according to claim 1, wherein in the step S4, the mass ratio of the silk fibroin to the protease is 100:2-3, the protease is a mixture of neutral protease and papain, the mass ratio is 7-10:3-5, the enzymolysis temperature is 45-55 ℃, and the enzymolysis time is 1-3h.
5. The preparation method according to claim 1, wherein in the step S5, the mass ratio of the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and silk fibroin peptide is 100:15-18:36-42:25-30, the activation reaction temperature is 0-4 ℃ for 20-30min, the heating reaction temperature is 35-45 ℃ for 6-8h.
6. The preparation method according to claim 1, characterized by comprising the following steps:
S1.2-preparation of hydroxyethyl chitin/tannic acid modified matter: dissolving 20-25 parts by weight of 2-hydroxyethyl chitin in 200 parts by weight of water, adding 3-5 parts by weight of tris (hydroxymethyl) aminomethane and 2-4 parts by weight of tannic acid, regulating the pH value of the solution to 8-8.5, heating to 40-50 ℃, stirring for reacting for 5-7 hours, dialyzing for 2-4 hours by using a dialysis bag with the aperture of 3-5kDa, and drying to obtain a 2-hydroxyethyl chitin/tannic acid modified substance;
S2, reaction with rosin: adding 100 parts by weight of rosin and 22-27 parts by weight of the 2-hydroxyethyl chitin/tannic acid modified product prepared in the step S1 into 500 parts by weight of toluene, stirring and dissolving, dropwise adding 3-5 parts by weight of concentrated sulfuric acid, heating and refluxing for reaction for 7-10 hours, washing with water, and removing the solvent under reduced pressure to prepare 2-hydroxyethyl chitin/tannic acid rosin ester;
S3, reaction with fumaric acid: adding 12-15 parts by weight of fumaric acid into 100 parts by weight of the 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S2, heating to 190-220 ℃, and stirring for reacting for 1-3 hours to prepare the fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester;
S4, hydrolysis of silk fibroin: dissolving 100 parts by weight of silk fibroin in 500 parts by weight of water, adding 2-3 parts by weight of protease, carrying out enzymolysis for 1-3 hours at 45-55 ℃, inactivating enzyme, filtering, and freeze-drying filtrate to obtain silk fibroin peptide;
the protease is a mixture of neutral protease and papain, and the mass ratio of the protease to the papain is 7-10:3-5;
S5, reaction with silk fibroin peptide: 100 parts by weight of fumaric acid modified 2-hydroxyethyl chitin/tannic acid rosin ester prepared in the step S3, 15-18 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 36-42 parts by weight of N-hydroxysuccinimide are added into 500 parts by weight of water, activated and reacted for 20-30min at 0-4 ℃, 25-30 parts by weight of silk fibroin peptide prepared in the step S4 are added, heated to 35-45 ℃, and stirred and reacted for 6-8h, so that the biodegradable modified rosin resin is prepared.
7. A biodegradable modified rosin resin produced by the production process according to any one of claims 1 to 6.
8. Use of the biodegradable modified rosin resin according to claim 7 for the preparation of tackifiers and thickeners.
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| CN101443426A (en) * | 2006-05-09 | 2009-05-27 | 阿利桑那化学公司 | Water-soluble rosin acid esters |
| CN108219676A (en) * | 2016-12-22 | 2018-06-29 | 谭海剑 | A kind of special modified rosin resin, preparation method and its application |
| CN112106975A (en) * | 2020-09-30 | 2020-12-22 | 郑州轻工业大学 | Chitin tannin composite colloidal particle emulsifier and preparation method and application thereof |
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|---|---|---|---|---|
| CN101443426A (en) * | 2006-05-09 | 2009-05-27 | 阿利桑那化学公司 | Water-soluble rosin acid esters |
| CN108219676A (en) * | 2016-12-22 | 2018-06-29 | 谭海剑 | A kind of special modified rosin resin, preparation method and its application |
| CN112106975A (en) * | 2020-09-30 | 2020-12-22 | 郑州轻工业大学 | Chitin tannin composite colloidal particle emulsifier and preparation method and application thereof |
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