CN108285938A - A kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt and preparation method thereof - Google Patents
A kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt and preparation method thereof Download PDFInfo
- Publication number
- CN108285938A CN108285938A CN201810179306.6A CN201810179306A CN108285938A CN 108285938 A CN108285938 A CN 108285938A CN 201810179306 A CN201810179306 A CN 201810179306A CN 108285938 A CN108285938 A CN 108285938A
- Authority
- CN
- China
- Prior art keywords
- gelatin
- modified
- retanning agent
- acid orange
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 151
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 119
- 229920000159 gelatin Polymers 0.000 title claims abstract description 119
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 119
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 119
- 239000008273 gelatin Substances 0.000 title claims abstract description 118
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 title claims abstract description 57
- 239000004593 Epoxy Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003115 biocidal effect Effects 0.000 claims abstract description 44
- 239000000975 dye Substances 0.000 claims abstract description 36
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 27
- 239000010985 leather Substances 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 15
- 238000005034 decoration Methods 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- NDTCWHJPYLGPSK-UHFFFAOYSA-M diethyl-methyl-(oxiran-2-ylmethyl)azanium;chloride Chemical class [Cl-].CC[N+](C)(CC)CC1CO1 NDTCWHJPYLGPSK-UHFFFAOYSA-M 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 13
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229940050176 methyl chloride Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 72
- 108010025899 gelatin film Proteins 0.000 description 60
- 230000008719 thickening Effects 0.000 description 23
- 241000588724 Escherichia coli Species 0.000 description 12
- 241000295644 Staphylococcaceae Species 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000010802 sludge Substances 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 ammonium salt compound Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- JXHZVHFODJSANQ-UHFFFAOYSA-N n-ethyl-n-methylethanamine;hydrochloride Chemical compound Cl.CCN(C)CC JXHZVHFODJSANQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical class CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JCZUIEHTNMQCRK-VHEBQXMUSA-O Cc(cc1)ccc1/[NH+]=N/c(c1ccccc1cc1)c1O Chemical compound Cc(cc1)ccc1/[NH+]=N/c(c1ccccc1cc1)c1O JCZUIEHTNMQCRK-VHEBQXMUSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000991 leather dye Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/26—Chemical tanning by organic agents using other organic substances, containing halogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Epoxy Resins (AREA)
- Paper (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses composite modified gelatin retanning agents of a kind of acid orange/mono- epoxy quaternary ammonium salt and preparation method thereof, using 2,3 glycidyl ethyl-methyl ethylammonium chlorides are modified at least one amino in gelatin, and are modified at least one carboxyl in gelatin using acid orange；Wherein, it is to carry out ring-opening reaction using the amino in the epoxy group and gelatin in 2,3 glycidyl ethyl-methyl ethylammonium chlorides to be modified to amino, and it is carboxyl progress esterification in phenolic hydroxyl group and gelatin using acid orange to be modified to carboxyl.The retanning agent has the characteristics that good penetrability, dye-uptake are high, significantly thickens hide contracting line effect, and has many advantages, such as to increase dyestuff absorption and fixation, antibiotic property, improves leather tearing toughness, a kind of new dye use is can be used as, be especially suitable for decoration leather, the retanning agent of suitcase leather, clothing leather or car decoration leather.
Description
Technical field
The present invention relates to technical field of leather dye, and in particular to a kind of acid orange/mono- epoxy quaternary ammonium salt is composite modified bright
Glue retanning agent and preparation method thereof.
Background technology
In numerous anti-biotic materials such as inorganic salts, organic metal, heterocyclic compound with anion, quarternary ammonium salt compound with
Nontoxic, the features such as antimicrobial efficiency is strong, is widely accepted.Epoxide is often used to change with high ring strain and strain energy
Property collagen.This project will synthesize quaternary epoxide, and opening using primary amino group under alkaline condition and epoxy group
Ring reacts, and quaternary ammonium salt is introduced on protein molecular, cationic protein is prepared.Cationic protein can be used as leather composite tanning agent, to change
The antibiotic property and fillibility of kind hide, and play the role of adsorbing dyestuff.On the other hand, more work is contained in hide glue original molecule
Property group (such as-NH2,-COOH ,-OH etc.) can be well compatible with cationic protein, to improve resistance to elution and the rub resistance of leather
Ability.About the synthesis of organic carbon quaternaries cation albumen, from the point of view of the synthetic method of report, mainly there is unsaturated quaternary ammonium
The graft reaction and cationic monomer of salt are directly reacted with amino in albumen, obtain corresponding cationic protein product, but this
A little products are indefinite in structure, illustrate the performance in some aspects of product simply by application, if carrying out industrial metaplasia
Production, then be difficult to carry out controllable quantitative reaction, and also you can't get the products that performance is stablized.It is currently reported to utilize primary amino group
Quaternary ammonium salt is grafted on collagen polypeptide molecule by determination techniques, determines conversion ratio, but is limited to quaternary ammonium salt molecular structure,
It is limited with the primary amino group reaction efficiency on gelatin molecule, and quaternization degree is relatively low, it is difficult to give full play to cationic protein
Effect.Also, in leather industry, addition dyestuff is painted to hide, comprising free dye molecule in the sewage discharged, is held
Easily cause water pollution.
Invention content
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of acid orange/mono- epoxy quaternary ammonium salt
Composite modified gelatin retanning agent, the retanning agent have the characteristics that good penetrability, dye-uptake are high, significantly thicken hide contracting line effect,
And have many advantages, such as to increase dyestuff and absorb and fixation, antibiotic property, raising leather tearing toughness, can be used as a kind of new dye makes
Be especially suitable for decoration leather, the retanning agent of suitcase leather, clothing leather or car decoration leather.
To achieve the goals above, the technical scheme is that：
A kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt, using 2,3- glycidyl ethyl-methyl chlorine
Change ethamine to be modified at least one amino in gelatin, and at least one carboxyl in gelatin is changed using acid orange
Property；
Wherein, amino is modified be using in 2,3- glycidyl ethyl-methyl ethylammonium chlorides epoxy group with it is bright
Amino in glue carries out ring-opening reaction, and it is carboxyl progress ester in phenolic hydroxyl group and gelatin using acid orange to be modified to carboxyl
Change reaction；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The acid orange (No. CAS：Chemical structural formula 633-96-5) is：
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
The second object of the present invention is to provide a kind of composite modified gelatin retanning agent solution of acid orange/mono- epoxy quaternary ammonium salt,
For the aqueous solution of above-mentioned retanning agent, which is less than 700 centipoises in 50 DEG C of viscosity, and solid content is 10~60%.
The third object of the present invention is to provide a kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt or acidity
The preparation method of orange/mono- composite modified gelatin retanning agent solution of epoxy quaternary ammonium salt,
2,3- glycidyl ethyl-methyl ethylammonium chlorides are added into aqueous gelatin solution, 2,3- glycidyl ethyl first is made
Amino in epoxy group and gelatin in base ethylammonium chloride carries out ring-opening reaction and obtains the molten of the quaternary ammonium salt-modified gelatin of monocycle oxygen
Then acid orange is added in liquid, the carboxyl in the phenolic hydroxyl group and gelatin of acid orange is made to carry out esterification；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The chemical structural formula of the acid orange is：(No. CAS：633-96-5)
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
What the fourth object of the present invention was to provide prepared by a kind of above-mentioned retanning agent, retanning agent solution, above-mentioned preparation method answers
Tanning agent or retanning agent solution are applied in processing decoration leather, suitcase leather, clothing leather or car decoration leather.
Beneficial effects of the present invention are：
1. retanning agent prepared by the present invention has the characteristics that good penetrability, dye-uptake are high, significantly thickens hide contracting line effect.
Increase dyestuff absorption and fixation 2. retanning agent prepared by the present invention has, antibiotic property, improve leather tearing toughness
The advantages that.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the infrared spectrum of 2,3- glycidyl ethyl-methyl ethylammonium chlorides；
Fig. 2 is 2,3- glycidyl ethyl-methyl ethylammonium chlorides1H NMR spectras；
Fig. 3 is the infrared spectrum of the quaternary ammonium salt-modified gelatin of monocycle oxygen；
Fig. 4 is the quaternary ammonium salt-modified gelatin of monocycle oxygen1H NMR spectras；
Fig. 5 is gelatin13C NMR spectras；
Fig. 6 is the quaternary ammonium salt-modified gelatin of monocycle oxygen13C NMR spectras；
Fig. 7 is the infrared spectrum of acid orange/composite modified gelatin of mono- epoxy quaternary ammonium salt.
Specific implementation mode
It is noted that described further below be all exemplary, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As background technology is introduced, the dye molecule that leather industry sewage effluent includes free exists in the prior art
It is insufficient to pollute environment, in order to solve technical problem as above, changes present applicant proposes a kind of acid orange/mono- epoxy quaternary ammonium salt is compound
Property gelatin retanning agent and preparation method thereof.
It is multiple to provide a kind of acid orange/composite modified gelatin of mono- epoxy quaternary ammonium salt for a kind of exemplary embodiment of the application
Tanning agent is modified at least one amino in gelatin using 2,3- glycidyl ethyl-methyl ethylammonium chlorides, and using acid
Property orange is modified at least one carboxyl in gelatin；
Wherein, amino is modified be using in 2,3- glycidyl ethyl-methyl ethylammonium chlorides epoxy group with it is bright
Amino in glue carries out ring-opening reaction, and it is carboxyl progress ester in phenolic hydroxyl group and gelatin using acid orange to be modified to carboxyl
Change reaction；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The chemical structural formula of the acid orange is：(No. CAS：633-96-5)
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
Preferably, glass transition temperature is 195~225 DEG C, and tearing toughness is 0.15~0.25MPa, antibiotic rate
It is 40~90%, absorption dyestuff rate is 70~85%, thickens rate 110~180%.
Another embodiment of the invention provides a kind of composite modified gelatin retanning of acid orange/mono- epoxy quaternary ammonium salt
Agent solution is the aqueous solution of above-mentioned retanning agent, which is less than 700 centipoises in 50 DEG C of viscosity, and solid content is 10~60%.
The present invention the third embodiment there is provided a kind of composite modified gelatin retannings of acid orange/mono- epoxy quaternary ammonium salt
The preparation method of agent or the composite modified gelatin retanning agent solution of acid orange/mono- epoxy quaternary ammonium salt,
2,3- glycidyl ethyl-methyl ethylammonium chlorides are added into aqueous gelatin solution, 2,3- glycidyl ethyl first is made
Amino in epoxy group and gelatin in base ethylammonium chloride carries out ring-opening reaction and obtains the molten of the quaternary ammonium salt-modified gelatin of monocycle oxygen
Then acid orange is added in liquid, the carboxyl in the phenolic hydroxyl group and gelatin of acid orange is made to carry out esterification；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The chemical structural formula of the acid orange is：
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
Preferably, the step of progress ring-opening reaction is：The pH for adjusting aqueous gelatin solution is 8~11, and 2,3- epoxies third are added
Base ethyl-methyl ethylammonium chloride reacts 6~14h in 40~70 DEG C.It is further preferred that 2,3- glycidyl ethyl-methyl chlorinations
The addition mole of ethamine is 0.5~3 times of amino mole in gelatin molecule.Gelatin is adjusted using the sodium hydroxide of 2mol/L
The pH of aqueous solution.
Preferably, the step of progress esterification is：The pH for adjusting the solution of the quaternary ammonium salt-modified gelatin of monocycle oxygen is 3~6,
Acid orange is added, reacts 12~20h in 40~70 DEG C.It is further preferred that the addition mole of acid orange is in gelatin molecule
0.1~1.5 times of carboxyl mole.The pH of the solution of the quaternary ammonium salt-modified gelatin of monocycle oxygen is adjusted using the hydrochloric acid of 2mol/L.
Preferably, the mass fraction of gelatin is 2~25% in aqueous gelatin solution.
Preferably, the mass fraction of the quaternary ammonium salt-modified gelatin of monocycle oxygen is 12 in the solution of the quaternary ammonium salt-modified gelatin of monocycle oxygen
~57%.
Preferably, the quality of acid orange/composite modified gelatin of mono- epoxy quaternary ammonium salt point in the solution obtained after esterification
Number is 12~57%.
Preferably, it is dried after esterification and can be obtained retanning agent film, dry process is：In 2~10 DEG C/min
Heating rate under be warming up to 40~80 DEG C and dried.
The synthetic method of the middle 2,3- glycidyl ethyl-methyl ethylammonium chlorides used of the application for：By ethamine and epoxy
Chloropropane obtains 2,3- glycidyl ethamine using the alkylated reaction of primary amino group, then by 2,3- glycidyl ethamine and a chlorine
Methane carries out reaction and obtains 2,3- glycidyl ethyl-methyl ethylammonium chlorides.
It is further preferred that the condition of the alkylated reaction of primary amino group is：Reaction temperature is 50~55 DEG C, is with potassium sulfate
The mixture of catalyst, water and methanol is as solvent.It is further preferred that the molar ratio of ethamine and epoxychloropropane is 1:1.
Embodiment there is provided a kind of above-mentioned retanning agent, retanning agent solution, above-mentioned preparation method systems for the 4th kind of the application
Standby retanning agent or retanning agent solution is applied in processing decoration leather, suitcase leather, clothing leather or car decoration leather.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Content of primary amine group in gelatin molecule is measured [method for using patent CN102393466A] with primary amine groups analyzer；
6.8×10-4mol/g
Bis-epoxy cationic protein is synthesized with nucleophilic displacement of fluorine polymerization technique；
Product flows back 48 hours in acetone solvent, removes unreacted two (2,3- glycidyl) tetraethyl chlorinations second two
Amine, ethylenediamine, epoxychloropropane and acid orange；
Polymer architecture with it is infrared,1H NMR、13C NMR characterizations；
Contact angle is measured with contact angle instrument；
Elongation at break and 100% elasticity modulus are measured by mechanical stretching instrument；
Glass transition temperature (Tg) measured with differential thermal calorimetric scan instrument；
Antibiotic rate；
Adsorb dyestuff rate；
Thicken rate；
Viscosity is with rotary viscosity design determining.
The weight average molecular weight of the gelatin used in following embodiment is 1.8 × 104。
Embodiment 1：
9.45 grams of epoxy chloropropionates are added in three mouthfuls of reaction bulbs equipped with thermometer socket, sample tap and condenser socket
Alkane, 4.75 grams of ethamine, 0.178 gram of potassium sulfate, 17 ml methanols and 22 ml deionized waters, are heated with stirring to 50 DEG C, with perseverance
It presses and 4.75 grams of ethamine is added dropwise in funnel half an hour, after continuing stirring 1.5 hours, acquired solution is evaporated under reduced pressure, obtains 2,
3- glycidyl ethamine.
9.45 grams of monochloro methanes are added in three mouthfuls of reaction bulbs equipped with thermometer socket, sample tap and condenser socket,
Acquired solution is evaporated under reduced pressure in 50 DEG C of agitating and heatings 2 hours, obtains 2,3- rings by 4.75 grams of 2,3- glycidyl ethamine
Oxygen propyl group ethyl-methyl ethylammonium chloride, structural characterization are as shown in Figure 1,3.
10 grams of gelatin are added in three mouthfuls of reaction bulbs equipped with thermometer socket, sample tap and condenser socket and (account for total matter
The 5% of amount, the structural characterization of gelatin is as shown in Figure 5), 190 grams of deionized waters are heated with stirring to 50 DEG C, wait for that gelatin is completely dissolved
Afterwards, the sodium hydroxide of 2 mol/Ls of 0.65mL is added, it is 8 to adjust reaction pH, with 2,3- glycidyl ethyl-methyl ethylammonium chlorides
The molar ratio of epoxy group and the primary amino group in gelatin molecule is (1：1) 2,3- glycidyl ethyl-methyl ethylammonium chlorides, are added,
Reaction starts, and the primary amino group content after 12 hours in system no longer changes, and stops stirring and heating, obtains 2,3- epoxies third
Base ethyl-methyl ethylammonium chloride modified gelatin solution.Acquired solution viscosity is 700 centipoises (50 DEG C).10mL solution is taken out, is carried out
Low temperature lyophilization then carries out cable-styled purification, obtains two (2,3 glycidyl) tetraethyl chlorination ethylenediamine modified gelatins, knot
Structure is characterized as shown in Fig. 2,4,6.
In remaining 2,3- glycidyl ethyl-methyl ethylammonium chloride modified gelatin solution, 2 mol/Ls of 0.58mL are added
Salt acid for adjusting pH to 3, be added acid orange, the additions mole of acid orange is 0.8 times of carboxyl mole in gelatin molecule, in
60 DEG C of reaction 20h, obtain the composite modified gelatin solution of acid orange/2,3- glycidyl ethyl-methyl ethylammonium chloride.By solution 2
It is warming up to 80 DEG C under the heating rate of~10 DEG C/min to be dried, the glycidyl ethyl-methyl chlorination of acid orange/2,3- is obtained
The film of the composite modified gelatin of ethamine (acid orange/composite modified gelatin of mono- epoxy quaternary ammonium salt), as retanning agent film, structural characterization
As shown in Figure 7.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, and the contact angle increase of modified retanning agent film is
76 °, illustrate that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and 100% elasticity modulus point
Not Wei 1mm and 0.05MPa, the elongation at break and 100% elasticity modulus of modified retanning agent film are respectively 11mm, 0.13MPa；
Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to 212 DEG C, illustrates Modified Membrane
Flexibility improve；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified retanning agent film increases to
82%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 85%, and antibiotic property obviously increases；
The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 75%, and Dye Adsorption rate significantly improves；
The rate that thickens for making hide of raw material gelatin film reaches 10%, and the rate that thickens for making hide of modified retanning agent film reaches 119%,
Play the role of significantly thickening.
Embodiment 2：
Described method is consistent with embodiment 1, is not both uniquely, mole of epoxy group and the primary amino group in gelatin molecule
Than being (1.5：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (1.0：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 12mm, 0.19MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
207 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 63%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 65%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 85%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 140%, plays the role of significantly thickening.
Embodiment 3：
Described method is consistent with embodiment 1, is not both uniquely, mole of epoxy group and the primary amino group in gelatin molecule
Than being (2.0：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (1.1：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 12mm, 0.19MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
207 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 63%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 65%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 85%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 140%, plays the role of significantly thickening.
Embodiment 4：
Described method is consistent with embodiment 1, is not both uniquely, mole of epoxy group and the primary amino group in gelatin molecule
Than being (2.5：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (1.0：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 12mm, 0.19MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
207 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 63%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 65%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 85%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 140%, plays the role of significantly thickening.
Embodiment 5：
Described method is consistent with embodiment 1, is not both uniquely, the molar ratio of epoxy group and the primary amino group in gelatin molecule
It is (2.5：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (1.5：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 73 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly reduces；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 17mm, 0.25MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
198 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 75%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 78%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 65%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 180%, plays the role of significantly thickening.
Embodiment 6：
Described method is consistent with embodiment 1, is not both uniquely, the molar ratio of epoxy group and the primary amino group in gelatin molecule
It is (3.0：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (1.0：1).
Gained viscosity of sludge is 675 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 73 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 14mm, 0.18MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
206 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 56%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 58%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 67%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 135%, plays the role of significantly thickening.
Embodiment 7：
Described method is consistent with embodiment 1, is not both uniquely, the molar ratio of epoxy group and the primary amino group in gelatin molecule
It is (3.0：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (0.5：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 73 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly reduces；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 11mm, 0.13MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
217 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 38%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 41%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 43%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 105%, plays the role of significantly thickening.
Embodiment 8：
Described method is consistent with embodiment 1, is not both uniquely, mole of epoxy group and the primary amino group in gelatin molecule
Than being (2.5：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (0.5：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 18mm, 0.22MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
201 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 65%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 67%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 61%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 145%, plays the role of significantly thickening.
Embodiment 9：
Described method is consistent with embodiment 1, is not both uniquely, mole of epoxy group and the primary amino group in gelatin molecule
Than being (2.5：1), the molar ratio of acid orange and the carboxyl in gelatin molecule is (0.8：1).
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 73 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 13mm, 0.18MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
187 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 66%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 68%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 55%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 120%, plays the role of significantly thickening.
Embodiment 10：
Described method is consistent with embodiment 1, and not being both uniquely that 2,3- glycidyl ethyl-methyl ethylammonium chlorides are compound changes
The pH of property gelatin solution is adjusted to 5.
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 13mm, 0.16MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
212 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 58%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 44%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 47%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 103%, plays the role of significantly thickening.
Embodiment 11：
Described method is consistent with embodiment 1, and not being both uniquely that 2,3- glycidyl ethyl-methyl ethylammonium chlorides are compound changes
The pH of property gelatin solution is adjusted to 4.
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 73 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 13mm, 0.15MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
213 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 58%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 60%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 64%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 115%, plays the role of significantly thickening.
Embodiment 12：
Described method is consistent with embodiment 1, and not being both uniquely that 2,3- glycidyl ethyl-methyl ethylammonium chlorides are compound changes
The pH of property gelatin solution is adjusted to 6.
Gained viscosity of sludge is 665 centipoises (50 DEG C), and solution is warming up to 80 DEG C under the heating rate of 2~10 DEG C/min
It is dried, obtains retanning agent film.Contact angle test shows that the contact angle of raw material gelatin film is 74 °, modified retanning agent film
It is 75 ° that contact angle, which increases, illustrates that the hydrophobicity of modified retanning agent film slightly improves；The elongation at break of raw material gelatin film and
100% elasticity modulus is respectively 1mm and 0.05MPa, and the elongation at break of modified retanning agent film and 100% elasticity modulus are distinguished
For 12mm, 0.13MPa；Glass transition temperature (the T of raw material gelatin filmg) it is 224 DEG C, the T of modified retanning agent filmgDrop to
222 DEG C, illustrate that the flexibility of Modified Membrane improves；Raw material gelatin film is 18.3% to the antibiotic rate of Escherichia coli, and modified answers
Tanning agent film increases to 34%；Antibiotic rate to gold-coloured staphylococci is 0%, and modified retanning agent film increases to 35%,
Antibiotic property obviously increases；The absorption dyestuff rate of raw material gelatin film is 5%, and modified retanning agent film increases to 45%, dyestuff
Adsorption rate significantly improves；The rate that thickens for making hide of raw material gelatin film reaches 10%, and modified retanning agent film makes hide
The rate of thickening reaches 105%, plays the role of significantly thickening.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt, characterized in that use 2,3- glycidyl ethyls
Methyl chloride ethamine is modified at least one amino in gelatin, and using acid orange at least one carboxyl in gelatin into
Row is modified；
Wherein, be modified to amino is using in the epoxy group and gelatin in 2,3- glycidyl ethyl-methyl ethylammonium chlorides
Amino carry out ring-opening reaction, be modified that be that carboxyl in phenolic hydroxyl group and gelatin using acid orange be esterified anti-to carboxyl
It answers；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The chemical structural formula of the acid orange is：
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
2. retanning agent as described in claim 1, characterized in that its glass transition temperature is 195~225 DEG C, and tear-proof is strong
Degree is 0.15~0.25MPa, and antibiotic rate is 40~90%, and absorption dyestuff rate is 70~85%, thickens rate 110~180%.
3. a kind of composite modified gelatin retanning agent solution of acid orange/mono- epoxy quaternary ammonium salt, characterized in that for claims 1 or 2 institute
The aqueous solution of retanning agent is stated, which is less than 700 centipoises in 50 DEG C of viscosity, and solid content is 10~60%.
4. a kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt or acid orange/mono- epoxy quaternary ammonium salt are composite modified
The preparation method of gelatin retanning agent solution, characterized in that
2,3- glycidyl ethyl-methyl ethylammonium chlorides are added into aqueous gelatin solution, 2,3- glycidyl ethyl-methyl chlorine is made
Change the amino in the epoxy group and gelatin in ethamine and carry out the solution that ring-opening reaction obtains the quaternary ammonium salt-modified gelatin of monocycle oxygen, so
After acid orange is added, so that carboxyl in the phenolic hydroxyl group and gelatin of acid orange is carried out esterification；
The chemical structural formula of the 2,3- glycidyl ethyl-methyl ethylammonium chloride is：
The chemical structural formula of the acid orange is：
The weight average molecular weight of the gelatin is (1.5~2.0) × 104。
5. preparation method as claimed in claim 4, characterized in that carry out ring-opening reaction the step of be：Adjust aqueous gelatin solution
PH be 8~11, be added 2,3- glycidyl ethyl-methyl ethylammonium chlorides, in 40~70 DEG C react 6~14h；Preferably, 2,3-
The addition mole of glycidyl ethyl-methyl ethylammonium chloride is 0.5~3 times of amino mole in gelatin molecule.
6. preparation method as claimed in claim 4, characterized in that carry out esterification the step of be：Adjust monocycle oxygen quaternary ammonium
The pH of the solution of salt modified gelatin is 3~6, and acid orange is added, and reacts 12~20h in 40~70 DEG C；Preferably, acid orange plus
Enter 0.1~1.5 times that mole is carboxyl mole in gelatin molecule.
7. preparation method as claimed in claim 4, characterized in that the mass fraction of gelatin is 2~25% in aqueous gelatin solution；
Or, the mass fraction of the quaternary ammonium salt-modified gelatin of monocycle oxygen is 12~57% in the solution of the quaternary ammonium salt-modified gelatin of monocycle oxygen；
Or, in the solution obtained after esterification acid orange/composite modified gelatin of mono- epoxy quaternary ammonium salt mass fraction be 12~
57%.
8. preparation method as claimed in claim 4, characterized in that it is dried after esterification and can be obtained retanning agent film,
Dry process is：40~80 DEG C are warming up under the heating rate of 2~10 DEG C/min to be dried.
9. preparation method as claimed in claim 4, characterized in that the synthesis side of 2,3- glycidyl ethyl-methyl ethylammonium chlorides
Method is：Ethamine and epoxychloropropane are obtained into 2,3- glycidyl ethamine using the alkylated reaction of primary amino group, then by 2,3-
Glycidyl ethamine, which with monochloro methane react, obtains 2,3- glycidyl ethyl-methyl ethylammonium chlorides；
Preferably, the condition of the alkylated reaction of primary amino group is：Reaction temperature is 50~55 DEG C, using potassium sulfate as catalyst, water
Mixture with methanol is as solvent；It is further preferred that the molar ratio of ethamine and epoxychloropropane is 1:1.
10. retanning agent solution, claim 4~9 times described in a kind of retanning agent as claimed in claim 1 or 2, claim 3
Retanning agent or retanning agent solution prepared by the preparation method described in one is in processing decoration leather, suitcase leather, clothing leather or car decoration leather
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810179306.6A CN108285938B (en) | 2018-03-05 | 2018-03-05 | Acid orange/single-epoxy quaternary ammonium salt composite modified gelatin retanning agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810179306.6A CN108285938B (en) | 2018-03-05 | 2018-03-05 | Acid orange/single-epoxy quaternary ammonium salt composite modified gelatin retanning agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108285938A true CN108285938A (en) | 2018-07-17 |
| CN108285938B CN108285938B (en) | 2020-05-12 |
Family
ID=62833416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810179306.6A Active CN108285938B (en) | 2018-03-05 | 2018-03-05 | Acid orange/single-epoxy quaternary ammonium salt composite modified gelatin retanning agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108285938B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436169A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane and quaternary ammonium salt-containing antibacterial gelatin leather finishing agent and preparation method |
| CN103436167A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and preparation method |
| CN107312110A (en) * | 2017-07-06 | 2017-11-03 | 山东师范大学 | A kind of N thiosemicarbazides O quaternary ammonium salts chitosan oligosaccharide and preparation method and application |
-
2018
- 2018-03-05 CN CN201810179306.6A patent/CN108285938B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436169A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane and quaternary ammonium salt-containing antibacterial gelatin leather finishing agent and preparation method |
| CN103436167A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and preparation method |
| CN107312110A (en) * | 2017-07-06 | 2017-11-03 | 山东师范大学 | A kind of N thiosemicarbazides O quaternary ammonium salts chitosan oligosaccharide and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108285938B (en) | 2020-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108219162A (en) | A kind of retanning agent for significantly improving leather tearing toughness and preparation method thereof | |
| CN108384906A (en) | One kind dramatically increasing dyestuff absorption and fixed leather composite tanning agent and preparation method thereof | |
| Hashem et al. | Preparation and characterization of cationized cellulose for the removal of anionic dyes | |
| CN108285938A (en) | A kind of composite modified gelatin retanning agent of acid orange/mono- epoxy quaternary ammonium salt and preparation method thereof | |
| JP2003055454A (en) | Modified polyalkylene imine | |
| US3795657A (en) | Epoxy resin compositions containing aromatic biguanides as latent curing agents therefor | |
| CN108384905A (en) | It is a kind of have thicken and the leather composite tanning agent and preparation method thereof of contracting line effect | |
| JP2020100810A (en) | Composite materials comprising chemically linked fluorographite-derived nanoparticles | |
| CN108864422A (en) | A kind of preparation method for the polyethylene glycol that high-purity both ends are amino-terminated | |
| Shimizu et al. | Synthesis of novel crosslinked chitosans with a higher fatty diacid diglycidyl and their adsorption abilities towards acid dyes | |
| CN109535770B (en) | Functionalized graphene oxide and preparation method and application thereof | |
| US4167623A (en) | Pullulan aminoalkyl ether | |
| Kim et al. | Synthesis and characterization of water-soluble phthalocyanine Copper (II) complex and its coloration on acrylic fibers | |
| CN115368694B (en) | Biomass-based reinforced polyvinyl alcohol composite material and preparation method thereof | |
| JP4547620B2 (en) | Method for producing crosslinked allylamine polymers | |
| JPH02216297A (en) | Resin for coating paper and paper-coating composition utilizing the same resin | |
| CN113788933B (en) | Nonionic water-based epoxy curing agent and preparation method and application thereof | |
| JPS61152731A (en) | Production of paper-coating resin | |
| US7728072B2 (en) | Epichlorohydrin amine polymers used for treating the surface of leather | |
| JP2636530B2 (en) | Paper coating resin and paper coating composition | |
| CN109867799A (en) | A kind of heat sensitive compounds and preparation method thereof | |
| JPH04142326A (en) | Epoxy resin and its production | |
| JPH0482996A (en) | Resin for paper coating and composition for paper coating | |
| JP3982103B2 (en) | Surface treatment agent for inkjet printing paper and inkjet printing paper | |
| JPS61195124A (en) | Production of paper-coating resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211124 Address after: 250303 2-3-2a039, second floor, building 3, zone 2, Hexin 2025, Jinan innovation Valley, Changqing District, Jinan City, Shandong Province Patentee after: Shandong Shanke Meigu Technology Development Co.,Ltd. Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee before: Qilu University of Technology |
|
| TR01 | Transfer of patent right |