CN103436167B - A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method - Google Patents

A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method Download PDF

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CN103436167B
CN103436167B CN201310369025.4A CN201310369025A CN103436167B CN 103436167 B CN103436167 B CN 103436167B CN 201310369025 A CN201310369025 A CN 201310369025A CN 103436167 B CN103436167 B CN 103436167B
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gelatin
gelatin film
solution
modified gelatin
film
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CN103436167A (en
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许静
李天铎
唐晓龙
姜青伟
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Shandong Shanke Meigu Technology Development Co.,Ltd.
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Qilu University of Technology
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Abstract

The present invention relates to a kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method, Gelatin being mixed with in water mass concentration is 2 ~ 20% aqueous solution, 40 ~ 70 DEG C, under pH is the condition of 6 ~ 12, add epoxy quaternary ammonium salt in 1st reaction flask, obtain solution 1; Add Racemic glycidol in 2nd reaction flask, obtain solution 2; Add tensio-active agent in 3rd reaction flask, add the epoxy polysiloxane containing Si-O-Si repeating unit simultaneously in batches or continuously, obtain solution 3.Solution 1,2,3 is mixed in varing proportions, take the mould that 15-20g is placed in tetrafluoroethylene, add single or three, four mixed solvents of 5-10mL ethanol, tetrahydrofuran (THF), acetone, methyl alcohol, in 40-80 DEG C of normal pressure drying in oven, obtain multifunctional type gelatin hide finishes.This finishing agent has the feature such as hydrophobic, film is pliable and tough, antibacterial, high heat is steady, organic solvent-resistant, resistance to wet rubbing by force.

Description

A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method
Technical field
The present invention relates to gelatin hide finishes, particularly one is containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method.This hide finishes has that film is pliable and tough, the feature such as hydrophobic, antibacterial, heat-resisting, anti-oxidant, organic solvent-resistant, resistance to wet rubbing by force, is especially suitable for use as the finishing agent of suitcase leather, clothing leather or car dressing leather.
Background technology
Gelatin film is used to the biology such as covering with paint, packaging, leather tanning, regenerative medicine, organizational project, drug delivery, chemical field, and the conventional strategy improving gelatin film performance is exactly chemically modified.The modification of gelatin has multiple method, wherein plasticization and modification mainly uses some polyvalent alcohols, containing a large amount of hydroxyls in its molecule, intermolecular hydrogen bonding can be formed with the polar group on gelatin molecule, weaken the interactions such as gelatin molecule interchain hydrogen bond, electrostatic, thus reduce tensile strength and the Young's modulus of gelatin film, increase elongation at break (FoodHydrocolloids, 2005,19:899 ~ 907; JFoodEng, 2000,43:25 ~ 30; , but while the toughness of gelatin film is increased, intensity, thermostability all decrease East China University of Science's journal (natural science edition), 2006,32 (10), 50 ~ 54.).
Gelatin is collagen hydrolysate, has become the important raw and processed materials preparing protein film, as other natural macromolecular materials, after this kind of protein material film forming, has that plastic sense is strong, a problem such as water resisting property and rotproofness difference.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, there is provided a kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method, invention preparation has the feature multifunctional type gelatin hide finishess such as height is hydrophobic, film is pliable and tough, antibacterial, high heat is steady, organic solvent-resistant, resistance to wet rubbing.
The technical scheme that the present invention takes is:
A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt and preparation method, comprise step as follows:
A kind of containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, by epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A), α-butyl-ω-[3-(2,3-glycidoxy) propyl group] polydimethylsiloxane grafted gelatin polymkeric substance (B) and Racemic glycidol grafted gelatin polymkeric substance (C) composition, wherein A account for that 20 ~ 40%, B of gross weight accounts for that 10 ~ 50%, C of gross weight accounts for gross weight 30 ~ 50%.The viscosity of this mixing solutions is less than 1200 centipoises (60 DEG C), and solid content is 20 ~ 50%.
A kind of containing polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt, by above-mentioned containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt is placed in the normal pressure drying in oven of 50 DEG C, obtain gelatin film, measuring its second-order transition temperature is 20 ~ 238 DEG C, and swelling ratio is in deionized water 20 ~ 160X, Young's modulus 2 ~ 65MPa, contact angle is 85 ~ 122 o.
Wherein, epoxy quaternary ammonium salt and glycidyl monomer are bought by Aladdin Reagent Company, and epoxy quaternary ammonium salt is for epoxy quaternary ammonium salt, and its structural formula is , molecular weight Mw=151.63.The structure of glycidyl monomer , molecular weight Mw=74.2.α-butyl-ω-[3-(2,3-glycidoxy) propyl group] polydimethylsiloxane structural formula is , conventionally synthesize, see document (ColloidsandSurfacesB:Biointerfaces2013,103,375 – 380).
Wherein polymer A, the molecular formula of B, C is shown below
Epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A)
Wherein, n=1 ~ 9
The molecular weight (Mw) 10000 ~ 10000 of A, viscosity 300 centipoise (60 DEG C), second-order transition temperature 235 DEG C, swelling capacity is in deionized water greater than 400X, contact angle 20 o.Epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A) synthesizes according to prior art, reference literature (QingweiJiang, JingXu, TianduoLi*, CongdeQiaoandYulongLi.Synthesisandantibacterialactivitie sofquaternaryammoniumsaltofgelatin. jMacromolecularSciB, InPressing).
Epoxy polysiloxane grafted gelatin polymkeric substance (B)
Wherein, m=4 ~ 40
The molecular weight (Mw) 10000 ~ 10000 of B, viscosity 550 centipoise (60 DEG C), second-order transition temperature 135 and 189 DEG C, swelling capacity is in deionized water less than 60X, contact angle 119 o.α ~ butyl ~ ω ~ [3 ~ (2,3 ~ glycidoxy) propyl group] polydimethylsiloxane adopts art methods synthesis, see document ColloidsandSurfacesB:Biointerfaces2013, and 103,375 – 380.Synthesizing according to existing method of α-butyl-ω-[3-(2,3-glycidoxy) propyl group] polydimethylsiloxane grafted gelatin polymkeric substance (B), referenced patent ZL201310012166.0 .
Racemic glycidol grafted gelatin polymkeric substance (C)
The molecular weight (Mw) 10000 ~ 10000 of C, viscosity 270 centipoise (60 DEG C), second-order transition temperature 85 DEG C, swelling capacity is in deionized water greater than 1200X, and contact angle is less than 20 o.Racemic glycidol grafted gelatin polymkeric substance (C) adopts art methods to synthesize, see document ColloidsandSurfacesB:Biointerfaces2012, and 95,201 – 207.
The present invention also provides described containing polysiloxane, and the preparation method of the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, comprises the steps:
(1) by Gelatin in water, prepare aqueous gelatin solution;
(2) prepare the aqueous solution of epoxy quaternary ammonium salt grafted gelatin polymkeric substance, be called solution 1, strength of solution is 2 ~ 22%;
(3) prepare the aqueous solution of Racemic glycidol grafted gelatin polymkeric substance, be called solution 2, strength of solution is 2 ~ 22%;
(4) prepare the aqueous solution of epoxy polysiloxane grafted gelatin polymkeric substance, be called solution 3, strength of solution is 2 ~ 28%;
(5) by solution 1, solution 2 and solution 3 are (1 ~ 6) with mass ratio: (2 ~ 6): after the mixing of (1 ~ 5) ratio, mix, and obtain described containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt.
The present invention also provides described containing polysiloxane, and the preparation method of the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt, comprises the steps:
(1) by Gelatin in water, prepare aqueous gelatin solution;
(2) prepare the aqueous solution of epoxy quaternary ammonium salt grafted gelatin polymkeric substance, be called solution 1, strength of solution is 2 ~ 22%;
(3) prepare the aqueous solution of Racemic glycidol grafted gelatin polymkeric substance, be called solution 2, strength of solution is 2 ~ 22%;
(4) prepare the aqueous solution of epoxy polysiloxane grafted gelatin polymkeric substance, be called solution 3, strength of solution is 2 ~ 28%;
(5) by solution 1, solution 2 and solution 3 are (1 ~ 6) with mass ratio: (2 ~ 6): after the mixing of (1 ~ 5) ratio, mix, and obtain described containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt;
(6) 15-20g is taken above-mentioned containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, be placed in the mould of tetrafluoroethylene, add solvent in a mold, under the temperature rise rate of 2 ~ 10 DEG C, in normal pressure baking oven, be warming up to 40 ~ 80 DEG C of oven dry, obtain the gelatin film containing epoxy quaternary ammonium salt, Racemic glycidol and polysiloxane.
Preferably, the aqueous gelatin solution of preparing described in step (1) is that Gelatin is mixed with the aqueous solution in water, regulates its temperature at 40-70 DEG C, and regulation system pH is 6-12;
Preferably, preparation epoxy quaternary ammonium salt grafted gelatin polymkeric substance described in step (2) is, by the solution stirring that step (1) obtains, after the pH value of system is stable, epoxy quaternary ammonium salt is added in reaction flask, the consumption of epoxy quaternary ammonium salt is 0.2-8 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtains the solution 1 of polymer A;
Preferably, Racemic glycidol grafted gelatin polymkeric substance of preparing described in step (3) is, by the solution stirring that step (1) obtains, after the pH value of system is stable, Racemic glycidol is added in reaction flask, the consumption of Racemic glycidol is 0.1-10 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtains the solution 2 of polymkeric substance C;
Preferably, epoxy polysiloxane grafted gelatin polymkeric substance of preparing described in step (4) is, by the solution stirring that step (1) obtains, after the pH value of system is stable, in reaction flask, add tensio-active agent and the epoxy polysiloxane containing Si-O-Si repeating unit, dosage of surfactant is 0.5 ~ 20% of gelatin quality, and the consumption of epoxy polysiloxane is 0.2 ~ 8 times of primary amine groups molar weight in gelatin molecule in batches, in 40 ~ 70 DEG C of reaction 12 ~ 24h, obtain polymer B solution 3.
Preferably, add tensio-active agent described in step (3), for point 1 ~ 4 batch adds, the weight often criticized is identical, every minor tick 30 minutes in batches.
Preferably, solvent described in step (6) is the mixed solvent of a kind of in ethanol, tetrahydrofuran (THF), acetone, methyl alcohol or three kinds, four kinds, mixed solvent proportioning is ethanol: tetrahydrofuran (THF): acetone: methyl alcohol=(1 ~ 10): (0 ~ 10): (0 ~ 10): (0 ~ 10), volume ratio.
Tensio-active agent described in above-mentioned steps (3) is alkyl-sulphate, alkylbenzene sulfonate and EPE polyol EPE compatibility, and proportion compatibility is (6 ~ 8): (1 ~ 3): 1, weight ratio.
Solution 1 described in above-mentioned steps (5), the proportioning of solution 2 and solution 3 is 1:(2 ~ 6): any one proportioning in (1 ~ 5), weight ratio.
In above-mentioned steps (1), the mass concentration of gelatin solution is 2 ~ 16%.
The viscosity of this hide finishes is less than 1200 centipoises (60 DEG C), and containing a certain amount of tensio-active agent, with the emulsion particle of polymer formation nucleocapsid structure, under certain condition, breakdown of emulsion can impel polymer formation continuous print film, and therefore this product is without the need to further emulsification.
The present invention utilizes epoxy quaternary ammonium salt, and Racemic glycidol and polysiloxane-modified gelatin have following remarkable advantage.First, first, quaternary ammonium salt has significant germ resistance, can improve anti-corruption and the antibacterial ability of gelatin film.Secondly, after on each Racemic glycidol molecule and gelatin molecule, primary amine groups is reacted, by generation 3-OH.-OH can form intermolecular hydrogen bonding with the polar group on gelatin molecule, plays plastification to gelatin materials.Again, the polysiloxane-modified gelatin that molecule segment is longer, can form micro phase separation structure with gelatin molecule.Interacted by intermolecular hydrogen bonding and supramolecule between quaternary ammonium salt, Racemic glycidol, polysiloxane block and gelatin molecule, impel material bodies to reveal excellence, special performance.Add a certain amount of tensio-active agent in present method implementation process, can participate in gelatin molecule, polysiloxane and quaternary ammonium salt block and form nucleocapsid structure, under certain condition, breakdown of emulsion can impel polymer formation continuous print film, and therefore this product is without the need to further emulsification.The more former gelatin film of Young's modulus of multi-functional gelatin film prepared by the present invention improves 2 ~ 65MPa, occur glass temperature, and numerical value is little compared with former gelatin film, illustrates that film snappiness is improved; Contact angle is from 72 obe increased to 122 o, swelling ratio is reduced to 60X, illustrates that film water resisting property obviously increases; Bacteriostasis rate is increased to 86.2%, illustrates that film has obvious germ resistance.
Can see from structural formula 1-3, quaternary ammonium salt group, Racemic glycidol are grafted to after on gelatin molecule, form poly-hydroxy type polymkeric substance, and the introducing of atom N will strengthen the intermolecular hydrogen bonding of polar group on atom N and hydroxyl, gelatin molecule, effectively weaken the interactions such as gelatin molecule interchain hydrogen bond, electrostatic, thus make gelatin film show excellent mechanical property.Polysiloxane itself has special construction, and its main chain-Si-O-Si-belongs to " inorganic structure ", and the bond energy of Si-O key is 462.0kJm/ol, far above the bond energy 346.9kJm/ol of C-C key, thus bond polarity is large, serves shielding effect, improve oxidative stability to connected alkyl.Therefore, it is generally acknowledged that it has two-fold advantage that is organic and inorganic materials concurrently, as Heat stability is good, second-order transition temperature is low, ventilation property is high, dielectricity is excellent, with the feature such as advantage and low surface property such as good biocompatibility, meet the high-end demand of suitcase leather, clothing leather or car dressing leather.While exploitation superior performance, cheap hybrid protein finishing agent, make the waste of tanning industry obtain high level and transform.
One of the present invention is containing polysiloxane, and the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt can be used as luggage leather, and dress ornament is removed from office, car dressing leather, decoration leather, and physical culture leather is covered with paint, lacquer, colour wash, etc.
Wherein, polymer A, B, C and the contrast of described product performance are as shown in the table:
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of gelatin;
Fig. 2 is the nuclear magnetic spectrogram of gelatin and the nuclear magnetic spectrogram of Racemic glycidol modified gelatin of the present invention;
Fig. 3 is the infrared spectrum of epoxy quaternary ammonium salt modified gelatin;
Fig. 4 is the infrared spectrum of epoxy polysiloxane modified gelatin of the present invention;
Fig. 5 is for containing polysiloxane, the Infrared Characterization spectrogram of the multifunctional type gelatin hide finishes product of Racemic glycidol and quaternary ammonium salt.
embodiment:
The present invention will be described in detail below by specific embodiment:
Content of primary amine group in gelatin molecule measures [method adopting patent CN102393466A] with primary amine groups determinator;
Epoxy polysiloxane synthesizes with anionic polymerization;
Product refluxes 48 hours in chloroform solvent, removes unreacted Racemic glycidol and epoxy polysiloxane;
Polymer architecture is with nuclear-magnetism, infrared, x-ray photoelectron spectroscopy sign;
Contact angle measures with contact angle instrument;
Elongation at break and 100% Young's modulus are measured by mechanical stretching instrument;
Second-order transition temperature ( tg) measure with differential thermal calorimetric scan instrument;
Thermostability measures with thermogravimeter;
Viscosity is with rotary viscosity design determining.
embodiment 1:
In 250ml tri-mouthfuls of reaction flasks that thermometer socket, thief hole and condenser socket are housed, add 12 grams of gelatin (account for 11.76% of total mass, its molecular structure is verified by infrared spectrum, see Fig. 1), 85 grams of deionized waters, be heated with stirring to 50 DEG C, after gelatin dissolves completely, add the sodium hydroxide of 0.25mL3 mol/L, reaction pH is regulated to be 10.0, add epoxy quaternary ammonium salt 13g, question response thing continues stirring 8 hours, prepares epoxy quaternary ammonium salt graft modification gelatin copolymer solution (solution 1) after dissolving without safety.
In the infrared spectrogram (Fig. 3) of epoxy quaternary ammonium salt modified gelatin, former 1643cm -1n ~ H absorption peak of place's primary amino disappears, simultaneously at 1475cm -1there is-N (CH in place 3) 3the new absorption peak of C-H.Disappeared by 1 the N-H absorption peak occurred in spectrogram, 1 ~ N (CH 3) 3the charateristic avsorption band of upper C-H, illustrates that the epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide there occurs reaction.
In 250ml tri-mouthfuls of reaction flasks that thermometer socket, thief hole and condenser socket are housed, add 12 grams of gelatin (account for 11.76% of total mass, its molecular structure is verified by infrared spectrum, see Fig. 1), 85 grams of deionized waters, be heated with stirring to 50 DEG C, after gelatin dissolves completely, add the sodium hydroxide of 0.25mL3 mol/L, reaction pH is regulated to be 10.0, add Racemic glycidol 10g, question response thing continues stirring 8 hours, prepares Racemic glycidol graft modification gelatin copolymer solution (solution 2) after dissolving without safety.
Racemic glycidol modified gelatin 1in H nuclear magnetic spectrum figure (Fig. 2), in the triatomic ring near former δ=2.8ppm, on two carbon, the peak of hydrogen disappears, and occur new multiplet at δ=3.6ppm, may be-C simultaneously h oH-and-C h 2the peak of OH.Disappeared by 2 the C-H absorption peaks occurred in spectrogram, the formation of the charateristic avsorption band of 1 C-H, illustrates that the epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide there occurs reaction.
Thermometer socket is being housed, 12 grams of gelatin (accounting for 11.76% of total mass) are added in 250ml tri-mouthfuls of reaction flasks of thief hole and condenser socket, 85 grams of deionized waters, be heated with stirring to 50 DEG C, after gelatin dissolves completely, add the sodium hydroxide of 0.25mL3 mol/L, reaction pH is regulated to be 10.0, add 5.0g sodium lauryl sulphate, sodium laurylsulfonate and sorbyl alcohol mixed surfactant, wherein sodium lauryl sulphate is 55%(w/w), sodium laurylsulfonate is 20%(w/w), sorbyl alcohol is 25%(w/w) make emulsifying agent (accounting for 4.90% of total mass), after continuing to be stirred to dissolving completely, add epoxy polysiloxane (M continuously or in batches w=1000), reaction starts, and the content of primary amine group of reacting in 24 hours systems no longer changes, and stops stirring and heating, obtains epoxy polysiloxane modified gelatin solution (solution 3).
Occurred the new bands of a spectrum do not had in 3 collagen polypeptide infrared spectrograms in the infrared spectrogram (Fig. 4) of epoxy polysiloxane modified gelatin, their ownership is as follows: (1) 802cm -1the peak that place occurs is the rocking vibration absorption peak of C-H in Si-CH3, and this is one of characteristic peak of polydimethylsiloxane; (2) 1261cm -1the peak that place occurs is the symmetric deformation flexural vibration absorption peak of C-H in Si-CH3, and this is also one of characteristic peak of polydimethylsiloxane; (3) 2963cm -1the peak that place occurs is the stretching vibration absorption peak of C-H.By the charateristic avsorption band of 3 Si-CH3 occurred in spectrogram, illustrate that the epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide there occurs reaction.
By solution 1,2 and 3 in mass ratio 1:1:1 ratio mixing, wherein the quality of solution 1 is 6g, solution 2 is 6g, solution 3 is 6g, gained viscosity of sludge is ~ 560 centipoises (50 DEG C), add the mixed solvent of ethanol that volume ratio is 1:1:1, tetrahydrofuran (THF), methyl alcohol, be positioned over the normal pressure drying in oven 6 hours of 45 DEG C, form snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 137 DEG C and 209 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 820%, and tensile strength is increased to 3.6MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 66.6%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 99 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 243 o, illustrate that the thermostability of modified gelatin film improves.
Not only-N (CH has been there is at 1475cm-1 place in the infrared spectrogram (Fig. 5) of product 3) 3the new absorption peak of C-H, also at 802cm -1there is the rocking vibration absorption peak of C-H on Si-CH3 in polydimethylsiloxane group in place, at 1261cm -1the peak that place occurs is the symmetric deformation flexural vibration absorption peak of C-H in Si-CH3, at 2963cm -1the peak that place occurs is the stretching vibration absorption peak of C-H.Illustrate that the epoxide group in epoxy polysiloxane, epoxy quaternary ammonium salt and the primary amino on collagen polypeptide there occurs reaction.In addition, also there is the stretching vibration peak of C-O-C at 1191cm-1 place, illustrate with water glyceryl ether and its reaction.
embodiment 2:
Described method is consistent with embodiment 1, and the proportioning not uniquely being both solution 1,2,3 is replaced by mass ratio 2:1:1, and wherein the quality of solution 1 is 9g, and solution 2 is 4.5g, and solution 3 is 4.5g.
Gained viscosity of sludge is ~ 620 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 142 DEG C and 185 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 320%, and tensile strength is increased to 13.4MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 86.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 76.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 88 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 248 o, illustrate that the thermostability of modified gelatin film improves.
Wherein, polymer A, B, C and the contrast of described product performance are as shown in the table:
Polymer A Polymer B Polymkeric substance C Product
Viscosity ~ 300 centipoises (60 DEG C) ~ 550 centipoises (60 DEG C) ~ 270 centipoises (60 DEG C) ~ 560 centipoises (60 DEG C)
Second-order transition temperature 235℃ 137 and 189 DEG C 85℃ 142 and 185 DEG C
To colibacillary bacteriostasis rate >75% —— —— 86.2%
To the bacteriostasis rate of gold-coloured staphylococci >72% —— —— 76.1%
embodiment 3:
Described method is consistent with embodiment 1, and be not both gelatin quality and be replaced by 3 grams (accounting for 2.83% of total mass), pH is replaced by 6.0, and heated and stirred is to 40 DEG C.
Gained viscosity of sludge is ~ 480 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 126 DEG C and 175 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 375%, and tensile strength is increased to 3.4MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 89.4%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 83.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 108 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 262 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 4:
Described method is consistent with embodiment 1, and be not both gelatin quality and be replaced by 16 grams (accounting for 15.09% of total mass), pH is replaced by 12.0, and heated and stirred is to 40 DEG C.
Gained viscosity of sludge is ~ 730 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 165 DEG C and 198 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 320%, and tensile strength is increased to 42.64MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 64.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 85 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 242 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 5:
Described method is consistent with embodiment 1, is not both heated and stirred to 70 DEG C.
Gained viscosity of sludge is ~ 450 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 132 DEG C and 185 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 240%, and tensile strength is increased to 2.8MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 71.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.4%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 78 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 236 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 6:
Described method is consistent with embodiment 1, and be not both epoxy quaternary ammonium salt and be replaced by 1 gram, pH is replaced by 12, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 560 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 186 DEG C and 209 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 104%, and tensile strength is increased to 1.6MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 65.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 60.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 112 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 251 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 7:
Described method is consistent with embodiment 1, is not both epoxy quaternary ammonium salt and is replaced by 20 grams, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 440 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 134 DEG C and 198 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 430%, and tensile strength is increased to 6.1MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 93.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 84.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 101 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 246 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 8:
Described method is consistent with embodiment 1, is not both epoxy quaternary ammonium salt and is replaced by 1 gram, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 330 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 150 DEG C and 186 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 30%, and tensile strength is increased to 0.98MPa, shows that the ductility of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 61.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 56.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 92 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 222 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 9:
Described method is consistent with embodiment 1, and be not both epoxy quaternary ammonium salt and be replaced by 22 grams, pH is replaced by 6, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 350 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 132 DEG C and 170 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 20%, and tensile strength is increased to 5.4MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 96.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 87.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 115 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 242 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 10:
Described method is consistent with embodiment 1, and be not both Racemic glycidol and be replaced by 1.5 grams, pH is replaced by 12, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 650 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 15 DEG C and 112 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 1140%, and tensile strength is increased to 12.8MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 65.4%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 115 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 252 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 11:
Described method is consistent with embodiment 1, is not both Racemic glycidol and is replaced by 24 grams, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 710 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 5 DEG C and 84 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 690%, and tensile strength is increased to 1.5MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 45.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 36.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 105 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 246 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 12:
Described method is consistent with embodiment 1, is not both Racemic glycidol and is replaced by 1.5 grams, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 560 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 20 DEG C and 96 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 1040%, and tensile strength is increased to 56.2MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 56.8%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 42.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 114 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 253 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 13:
Described method is consistent with embodiment 1, and be not both Racemic glycidol and be replaced by 26 grams, pH is replaced by 6, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 780 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 3 DEG C and 72 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 460%, and tensile strength is increased to 1.8MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 85.4%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 72.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 82 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 235 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 14:
Described method is consistent with embodiment 1, be not both ethanol, tetrahydrofuran (THF), methanol mixed solvent proportioning be replaced by 4:1:1.
Gained viscosity of sludge is ~ 630 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 139 DEG C and 176 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 300%, and tensile strength is increased to 12.9MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 56.3%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 40.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 80 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 256 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 15:
Described method is consistent with embodiment 8, be not both ethanol, tetrahydrofuran (THF), methanol mixed solvent proportioning be replaced by 8:6:0.
Gained viscosity of sludge is ~ 560 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 130 DEG C and 176 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 860%, and tensile strength is increased to 2.9MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 58.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 46.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 81 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 252 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 16:
Described method is consistent with embodiment 11, be not both ethanol, tetrahydrofuran (THF), methanol mixed solvent proportioning be replaced by 3:0:6.
Gained viscosity of sludge is ~ 620 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gbe 183 DEG C and 226 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 36%, and tensile strength is increased to 89.4MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 73.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 59.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 77 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 258 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 17:
Described method is consistent with embodiment 13, be not both ethanol, tetrahydrofuran (THF), methanol mixed solvent proportioning be replaced by 5:5:2.Gained viscosity of sludge is ~ 620 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 85 DEG C and 221 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 410%, and tensile strength is increased to 35.1MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 74.9%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 68.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 105 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 251 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 18:
Described method is consistent with embodiment 1, and the proportioning not uniquely being both solution 1,2,3 is replaced by mass ratio 1:1:3, and wherein the quality of solution 1 is 3.6g, and solution 2 is 3.6g, solution, and 3 is 10.8g.
Gained viscosity of sludge is ~ 580 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 132 DEG C and 216 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 480%, and tensile strength is increased to 64.5MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 58.3%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 49.5%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 122 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 253 o, illustrate that the thermostability of modified gelatin film improves.
Wherein, polymer A, B, C and the contrast of described product performance are as shown in the table:
Polymer A Polymer B Polymkeric substance C Product
Contact angle 20 O~30 O 95 O~119 O <20 O 88 O
Young's modulus 1.3Mpa 36.2MPa 0.62MPa 64.5MPa
embodiment 19:
Described method is consistent with embodiment 18, and be not both epoxy quaternary ammonium salt and be replaced by 22 grams, pH is replaced by 6, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 430 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 20 DEG C and 60 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 210%, and tensile strength is increased to 0.86MPa, shows that the ductility of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 86.6%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 48.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 73 o, illustrate that the hydrophobicity of modified gelatin film slightly improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 240 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 20:
Described method is consistent with embodiment 18, and be not both epoxy quaternary ammonium salt and be replaced by 1 gram, pH is replaced by 12, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 740 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 76 DEG C and 140 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 65%, and tensile strength is increased to 14.2MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 72.9%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 96 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 251 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 21:
Described method is consistent with embodiment 18, is not both epoxy quaternary ammonium salt and is replaced by 1 gram, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 425 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 65 DEG C and 142 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 5%, and tensile strength is increased to 0.83MPa, shows that the ductility of modified gelatin slightly strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 52.6%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 35.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 72 o; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 231 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 22:
Described method is consistent with embodiment 21, is not both and only uses ethanol to be solvent.
Gained viscosity of sludge is ~ 660 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 34 DEG C and 102 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 410%, and tensile strength is increased to 8.3MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 50.1%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 35.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 116 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 253 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 23:
Described method is consistent with embodiment 1, and the proportioning not uniquely being both solution 1,2,3 is replaced by mass ratio 1:2:1, and wherein the quality of solution 1 is 4.5g, and solution 2 is 9g, solution, and 3 is 4.5g.
Gained viscosity of sludge is ~ 690 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 131 DEG C and 167 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 1560%, and tensile strength is increased to 1.3MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 60.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 53.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 114 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 248 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 24:
Described method is consistent with embodiment 23, is not both Racemic glycidol and is replaced by 24 grams, stirs and is warmed up to 40 DEG C.
Gained viscosity of sludge is ~ 620 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 40 DEG C and 100 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 280%, and tensile strength is increased to 2.1MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 70.6%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 61.9%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 113 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 235 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 25:
Described method is consistent with embodiment 23, is not both Racemic glycidol and is replaced by 1.5 grams, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 310 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 126 DEG C and 188 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 310%, and tensile strength is increased to 9.6MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 85.4%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 73.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 116 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 253 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 26:
Described method is consistent with embodiment 23, and be not both Racemic glycidol and be replaced by 26 grams, pH is replaced by 6, stirs and is warmed up to 70 DEG C.
Gained viscosity of sludge is ~ 540 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 20 DEG C and 90 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 1120%, and tensile strength is increased to 2.3MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 70.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 53.6%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 96 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 241 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 27:
Described method is consistent with embodiment 13, is not both and only uses tetrahydrofuran (THF) to be solvent.
Gained viscosity of sludge is ~ 780 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gbe 186 DEG C and 235 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 53%, and tensile strength is increased to 31.6MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 70.8%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 63.2%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 118 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 251 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 28:
Described method is consistent with embodiment 14, is not uniquely both tensio-active agent and is replaced by sodium lauryl sulphate, the mixture of sodium laurylsulfonate.
Gained viscosity of sludge is ~ 490 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 131 DEG C and 170 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 2130%, and tensile strength is increased to 5.8MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 88.6%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 81.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 85 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 242 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 29:
Described method is consistent with embodiment 28, and be not both gelatin quality and be replaced by 3 grams (accounting for 2.83% of total mass), pH is replaced by 6.0, and heated and stirred is to 40 DEG C.
Gained viscosity of sludge is ~ 350 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 189 DEG C and 226 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 230%, and tensile strength is increased to 4.2MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 68.9%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 54.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 102 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 244 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 30:
Described method is consistent with embodiment 28, and be not both gelatin quality and be replaced by 16 grams (accounting for 15.09% of total mass), pH is replaced by 12.0, and heated and stirred is to 40 DEG C.
Gained viscosity of sludge is ~ 750 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gbe 198 DEG C and 234 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 30%, and tensile strength is increased to 35.2MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 86.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 76.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 77 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 231 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 31:
Described method is consistent with embodiment 28, and be not both dosage of surfactant and be replaced by 1 gram (accounting for 0.69% of total mass), epoxy quaternary ammonium salt is replaced by 1 gram, and Racemic glycidol is replaced by 24 grams, and the reaction times is replaced by 18 hours.
Gained viscosity of sludge is ~ 610 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 139 DEG C and 186 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 280%, and tensile strength is increased to 3.5MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 81.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 65.4%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 118 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 252 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 32:
Described method is consistent with embodiment 28, and be not both dosage of surfactant and be replaced by 18 grams (accounting for 17.32% of total mass), epoxy quaternary ammonium salt is replaced by 20 grams, and Racemic glycidol is replaced by 1.5 grams, and the reaction times is replaced by 12 hours.
Gained viscosity of sludge is ~ 540 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 138 DEG C and 197 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 260%, and tensile strength is increased to 8.9MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 86.2%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 76.1%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 82 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 251 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 33:
Described method is consistent with embodiment 23, is not uniquely both tensio-active agent and is replaced by sodium lauryl sulphate, the mixture of sodium laurylsulfonate.
Gained viscosity of sludge is ~ 560 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film gdrop to 142 DEG C and 219 DEG C, occur obvious microphase-separated; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 260%, and tensile strength is increased to 52.5MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 64.5%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 58.7%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 118 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 250 o, illustrate that the thermostability of modified gelatin film improves.
embodiment 34:
Described method is consistent with embodiment 33, is not both and only uses methyl alcohol to be solvent.
Gained viscosity of sludge is ~ 300 centipoises (50 DEG C), is positioned over the normal pressure drying in oven 6 hours of 45 DEG C, forms snappiness comparatively strong film.Second-order transition temperature (the T of raw material gelatin film g) be 224 DEG C, the T of modified gelatin film git is 238 DEG C; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and the elongation at break of modified gelatin film is increased to 5%, and tensile strength is increased to 50.2MPa, shows that the snappiness of modified gelatin obviously strengthens; Raw material gelatin film is 18.3% to colibacillary antibiotic rate, modified gelatin film be increased to 60.1%; Be 0% to the antibiotic rate of gold-coloured staphylococci, modified gelatin film be increased to 62.3%, germ resistance obviously increases. 13cNMR to show in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and 63ppm place there is new peak, in epoxide modified collagen polypeptide- c the peak of HOH-group; 69 and 72ppm occur new peak for- c h 2the peak of OH group; 13cNMR to show in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C is formed; XPS shows that the chemical shift of N moves to 399.87, shows that C-N is formed; Contact angle test shows, the contact angle of raw material gelatin film is 72 o, the contact angle of modified gelatin film increases to 94 o, illustrate that the hydrophobicity of modified gelatin film improves; The heat decomposition temperature of raw material gelatin film is 218 o, the heat decomposition temperature of modified gelatin film brings up to 252 o, illustrate that the thermostability of modified gelatin film improves.

Claims (6)

1. one kind contains polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, by the aqueous solution of epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A), α-butyl-ω-[3-(2,3-glycidoxy) propyl group] aqueous solution composition of the aqueous solution of polydimethylsiloxane grafted gelatin polymkeric substance (B) and Racemic glycidol grafted gelatin polymkeric substance (C), wherein A accounts for 20 ~ 40% of gross weight, B account for that 10 ~ 50%, C of gross weight accounts for gross weight 30 ~ 50%; This mixing solutions is less than 1200 centipoises the viscosity of 60 DEG C, and solid content is 20 ~ 50%.
2. one kind contains polysiloxane, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt, by according to claim 1 containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt is placed in the normal pressure drying in oven of 50 DEG C, obtain gelatin film, its second-order transition temperature is 20 ~ 238 DEG C, and swelling ratio is in deionized water 20 ~ 160X, Young's modulus 2 ~ 65MPa, contact angle is 85 ~ 122 °.
3. as claimed in claim 1 containing polysiloxane, the preparation method of the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, comprises the steps:
(1) Gelatin is mixed with the aqueous solution in water, regulates its temperature at 40-70 DEG C, regulation system pH is 6-12;
(2) by solution stirring that step (1) obtains, after the pH value of system is stable, epoxy quaternary ammonium salt is added in reaction flask, the consumption of epoxy quaternary ammonium salt is 0.2-8 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtain solution 1, wherein strength of solution is 2 ~ 22%;
(3) by solution stirring that step (1) obtains, after the pH value of system is stable, glycidyl ether is added in reaction flask, the consumption of glycidyl ether is 0.1-10 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtain solution 2, wherein strength of solution is 2 ~ 22%;
(4) by solution stirring that step (1) obtains, after the pH value of system is stable, add tensio-active agent and the epoxy polysiloxane containing Si-O-Si repeating unit in reaction flask in batches, dosage of surfactant is 0.5 ~ 20% of gelatin quality, the consumption of epoxy polysiloxane is 0.2 ~ 8 times of primary amine groups molar weight in gelatin molecule, in 40 ~ 70 DEG C of reaction 12 ~ 24h, obtain solution 3, wherein strength of solution is 2 ~ 28%;
(5) by solution 1, solution 2 and solution 3 are (1 ~ 6) with mass ratio: (2 ~ 6): after the mixing of (1 ~ 5) ratio, mix, obtain described containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt:
Described tensio-active agent is alkyl-sulphate, alkylbenzene sulfonate and EPE polyol EPE compatibility, and proportion compatibility is (6 ~ 8): (1 ~ 3): 1, weight ratio;
Epoxy quaternary ammonium salt structural formula is the structure of epoxy quaternary ammonium salt grafted gelatin polymkeric substance is racemic glycidol ether structure is the structure of Racemic glycidol grafted gelatin polymkeric substance is the structure of epoxy polysiloxane is the structure of epoxy polysiloxane grafted gelatin polymkeric substance is wherein m=4 ~ 40.
4. as claimed in claim 2 containing polysiloxane, the preparation method of the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt, comprises the steps:
(1) Gelatin is mixed with the aqueous solution in water, regulates its temperature at 40-70 DEG C, regulation system pH is 6-12;
(2) by solution stirring that step (1) obtains, after the pH value of system is stable, epoxy quaternary ammonium salt is added in reaction flask, the consumption of epoxy quaternary ammonium salt is 0.2-8 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtain solution 1, wherein strength of solution is 2 ~ 22%;
(3) by solution stirring that step (1) obtains, after the pH value of system is stable, glycidyl ether is added in reaction flask, the consumption of glycidyl ether is 0.1-10 times of primary amine groups molar weight in gelatin molecule, in 40-70 DEG C of reaction 6-12h, obtain solution 2, wherein strength of solution is 2 ~ 22%;
(4) by solution stirring that step (1) obtains, after the pH value of system is stable, add tensio-active agent and the epoxy polysiloxane containing Si-O-Si repeating unit in reaction flask in batches, dosage of surfactant is 0.5 ~ 20% of gelatin quality, the consumption of epoxy polysiloxane is 0.2 ~ 8 times of primary amine groups molar weight in gelatin molecule, in 40 ~ 70 DEG C of reaction 12 ~ 24h, obtain solution 3, wherein strength of solution is 2 ~ 28%;
(5) by solution 1, solution 2 and solution 3 are (1 ~ 6) with mass ratio: (2 ~ 6): after the mixing of (1 ~ 5) ratio, mix, obtain described containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt:
Described tensio-active agent is alkyl-sulphate, alkylbenzene sulfonate and EPE polyol EPE compatibility, and proportion compatibility is (6 ~ 8): (1 ~ 3): 1, weight ratio;
Epoxy quaternary ammonium salt structural formula is the structure of epoxy quaternary ammonium salt grafted gelatin polymkeric substance is racemic glycidol ether structure is the structure of Racemic glycidol grafted gelatin polymkeric substance is the structure of epoxy polysiloxane is the structure of epoxy polysiloxane grafted gelatin polymkeric substance is wherein m=4 ~ 40;
(6) 15-20g is taken above-mentioned containing polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, be placed in the mould of tetrafluoroethylene, add solvent in a mold, under the temperature rise rate of 2 ~ 10 DEG C, in normal pressure baking oven, be warming up to 40 ~ 80 DEG C of oven dry, obtain the gelatin film containing epoxy quaternary ammonium salt, Racemic glycidol and polysiloxane.
5. method as claimed in claim 3, is characterized in that, adds tensio-active agent described in step (4) in batches, and for point 1 ~ 4 batch adds, the weight often criticized is identical, every minor tick 30 minutes.
6. method as claimed in claim 4, it is characterized in that, solvent described in step (6) is the mixed solvent of a kind of in ethanol, tetrahydrofuran (THF), acetone, methyl alcohol or three kinds, four kinds, mixed solvent proportioning is ethanol: tetrahydrofuran (THF): acetone: methyl alcohol=(1 ~ 10): (0 ~ 10): (0 ~ 10): (0 ~ 10), volume ratio.
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