CN103436167A - Polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and preparation method - Google Patents
Polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and preparation method Download PDFInfo
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Abstract
The invention relates to a polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and a preparation method. The preparation method comprises the following steps: dissolving gelatin in water to prepare aqueous solution with mass concentration of 2-20 percent; adding epoxy quaternary ammonium salt into a first reaction flask under the conditions of temperature of 40-70 DEG C and pH of 6-12 to obtain solution 1; adding glycidol into a second reaction flask to obtain solution 2; adding a surfactant into a third reaction flask, and meanwhile adding Si-O-Si repetitive unit-containing epoxypolysiloxane in batches or continuously to obtain solution 3; mixing the solution 1, the solution 2 and the solution 3 in different proportions, weighing 15-20 g of the mixed solution to be placed in a mold of polytetrafluoroethylene, adding 5-10 mL of one or three or four of ethanol, tetrahydrofuran, acetone and methanol and drying in a normal pressure drying oven at the temperature of 40-80 DEG C to obtain the multifunctional gelatin leather finishing agent. The finishing agent has the characteristics of strong hydrophobicity, flexible film, antibacterial property, high heat stability, organic solvent resistance, wet scrubbing resistance and the like.
Description
Technical field
The present invention relates to the gelatin hide finishes, particularly a kind of containing polysiloxane, multifunctional type gelatin hide finishes and the preparation method of Racemic glycidol and quaternary ammonium salt.This hide finishes has that film is pliable and tough, characteristics such as hydrophobic, antibiotic, heat-resisting, anti-oxidant, organic solvent-resistant, moisture-proof wiping 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 biology, the chemical fields such as covering with paint, packing, leather tanning, regenerative medicine, organizational project, drug delivery, and the conventional strategy that improves the gelatin film performance is exactly chemically modified.The modification of gelatin has several different methods, wherein plasticization and modification is mainly to use some polyvalent alcohols, contain a large amount of hydroxyls in its molecule, can with gelatin molecule on polar group form intermolecular hydrogen bonding, weaken the interactions such as gelatin molecule interchain hydrogen bond, static, thereby reduce tensile strength and the Young's modulus of gelatin film, increase elongation at break (Food Hydrocolloids, 2005,19:899～907; J Food Eng, 2000,43:25～30; East China University of Science's journal (natural science edition), 2006,32 (10), 50～54.), yet when the toughness of gelatin film is increased, intensity, thermostability all decrease.
Gelatin is collagen hydrolysate, has become the important raw and processed materials for preparing protein film, as other natural macromolecular materials, after this proteinoid material filming, has that plastic sense is strong, water resisting property and a problem such as rotproofness is poor.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide a kind of containing polysiloxane, multifunctional type gelatin hide finishes and the preparation method of Racemic glycidol and quaternary ammonium salt, the invention preparation has high hydrophobic, the characteristics multifunctional type gelatin hide finishess such as film is pliable and tough, antibiotic, high heat is steady, organic solvent-resistant, moisture-proof wiping.
The technical scheme that the present invention takes is:
A kind of containing polysiloxane, multifunctional type gelatin hide finishes and the preparation method of Racemic glycidol and quaternary ammonium salt comprise that step is 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, the 3-glycidoxy) propyl group] polydimethylsiloxane grafted gelatin polymkeric substance (B) and Racemic glycidol grafted gelatin polymkeric substance (C) composition, wherein A accounts for 20～40% of gross weight, and B accounts for 10～50% of gross weight, and C accounts for 30～50% of gross weight.The viscosity of this mixing solutions is less than 1200 centipoises (60 ℃), 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 the above-mentioned polysiloxane that contains, 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 ℃, obtain gelatin film, measuring its second-order transition temperature is 20～238 ℃, and the swelling ratio in deionized water is 20～160X, Young's modulus 2～65MPa, contact angle is 85～122
o.
Wherein, epoxy quaternary ammonium salt and Racemic glycidol monomer are bought by Aladdin reagent company, and the epoxy quaternary ammonium salt be take the epoxypropyl trimethyl quaternary ammonium salt as example, and its structural formula is
, molecular weight Mw=151.63.The structure of Racemic glycidol monomer
, molecular weight Mw=74.2.α-butyl-ω-[3-(2,3-glycidoxy) propyl group] polydimethylsiloxane structural formula is
, synthetic according to prior art, referring to document (Colloids and Surfaces B:Biointerfaces 2013,103,375 – 380).
Polymer A wherein, B, the molecular formula of C is shown below
Epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A)
Wherein, n=1～9
The molecular weight of A (Mw) 10000～10000, viscosity 300 centipoises (60 ℃), 235 ℃ of second-order transition temperatures, the swelling capacity in deionized water is greater than 400X, contact angle 20
o.Epoxy quaternary ammonium salt grafted gelatin polymkeric substance (A) is synthetic according to prior art, reference literature (Qingwei Jiang, Jing Xu, Tianduo Li*, Congde Qiao and Yulong Li. Synthesis and antibacterial activities of quaternary ammonium salt of gelatin.
j Macromolecular Sci B, In Pressing).
Epoxy polysiloxane grafted gelatin polymkeric substance (B)
Wherein, m=4～40
The molecular weight of B (Mw) 10000～10000, viscosity 550 centipoises (60 ℃), second-order transition temperature 135 and 189 ℃, the swelling capacity in deionized water is less than 60X, contact angle 119
o.α～butyl～ω～[3～(2,3～glycidoxy) propyl group] polydimethylsiloxane adopts art methods synthetic, referring to document Colloids and Surfaces B:Biointerfaces 2013,103,375 – 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 of C (Mw) 10000～10000, viscosity 270 centipoises (60 ℃), 85 ℃ of second-order transition temperatures, the swelling capacity in deionized water is greater than 1200X, and contact angle is less than 20
o.Racemic glycidol grafted gelatin polymkeric substance (C) adopts art methods synthetic, referring to document Colloids and Surfaces B:Biointerfaces 2012,95,201 – 207.
It is described containing polysiloxane that the present invention also provides, and the preparation method of the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt, comprise the steps:
(1) gelatin is dissolved in to water, prepares 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 be take mass ratio as (1 ~ 6): (2～6): (1～5) ratio mixes after mixing, and obtains described polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt of containing.
It is described containing polysiloxane that the present invention also provides, and the preparation method of the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt, comprise the steps:
(1) gelatin is dissolved in to water, prepares 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 be take mass ratio as (1 ~ 6): (2～6): (1～5) ratio mixes after mixing, and obtains described polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt of containing;
(6) take the above-mentioned polysiloxane that contains of 15-20g, 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 mould, under the temperature rise rate of 2～10 ℃, be warming up to 40～80 ℃ of oven dry in the normal pressure baking oven, obtain the gelatin film that contains epoxy quaternary ammonium salt, Racemic glycidol and polysiloxane.
Preferably, the described aqueous gelatin solution for preparing of step (1) is, gelatin is dissolved in the water and is mixed with the aqueous solution, regulates its temperature at 40-70 ℃, and regulation system pH is 6-12;
Preferably, the described epoxy quaternary ammonium salt grafted gelatin polymkeric substance for preparing of step (2) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, add the epoxy quaternary ammonium salt in reaction flask, the 0.2-8 that the consumption of epoxy quaternary ammonium salt is primary amine groups molar weight in gelatin molecule doubly, in 40-70 ℃ of reaction 6-12h, obtains the solution 1 of polymer A;
Preferably, the described Racemic glycidol grafted gelatin polymkeric substance for preparing of step (3) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, add Racemic glycidol in reaction flask, the 0.1-10 that the consumption of Racemic glycidol is primary amine groups molar weight in gelatin molecule doubly, in 40-70 ℃ of reaction 6-12h, obtains the solution 2 of polymkeric substance C;
Preferably, the described epoxy polysiloxane grafted gelatin polymkeric substance for preparing of step (4) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, to add tensio-active agent in reaction flask and, containing the epoxy polysiloxane of Si-O-Si repeating unit, dosage of surfactant is 0.5～20% of gelatin quality in batches, the consumption of epoxy polysiloxane is 0.2～8 times of primary amine groups molar weight in gelatin molecule, in 40～70 ℃ of reaction 12～24h, obtain polymer B solution 3.
Preferably, the described tensio-active agent that in batches adds of step (3), add for dividing 1～4 batch, and the weight of every batch is identical, every minor tick 30 minutes.
Preferably, the mixed solvent that the described solvent of step (6) is a kind of in ethanol, tetrahydrofuran (THF), acetone, methyl alcohol or three kinds, four kinds, the mixed solvent proportioning is ethanol: tetrahydrofuran (THF): acetone: methyl alcohol=(1 ~ 10): (0～10): (0～10): (0～10), volume ratio.
The described tensio-active agent of above-mentioned steps (3) is alkyl-sulphate, alkylbenzene sulfonate and EPE polyol EPE compatibility, and proportion compatibility is (6 ~ 8): (1 ~ 3): 1, and weight ratio.
The described solution 1 of 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 ℃), and contained a certain amount of tensio-active agent, with the emulsion particle of polymer formation nucleocapsid structure, under certain condition, breakdown of emulsion can impel continuous the filming of polymer formation, so this product is without further emulsification.
The present invention utilizes the epoxy quaternary ammonium salt, and Racemic glycidol and polysiloxane-modified gelatin have following remarkable advantage.At first, at first, quaternary ammonium salt has significant germ resistance, can improve anti-corruption and the antibacterial ability of gelatin film.Secondly, each Racemic glycidol molecule, with after primary amine groups on gelatin molecule is reacted, will produce 3-OH.-OH can with gelatin molecule on polar group form intermolecular hydrogen bonding, gelatin materials is played to plastification.Again, the polysiloxane-modified gelatin that molecule segment is long, can form micro phase separation structure with gelatin molecule.Interact 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 continuous the filming of polymer formation, so this product is without further emulsification.The more former gelatin film of the Young's modulus of multi-functional gelatin film prepared by the present invention improves 2～65MPa, glass temperature occurs, and numerical value is little than former gelatin film, and the improvement of film snappiness is described; 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.
From structural formula 1-3, can see, after quaternary ammonium salt group, Racemic glycidol are grafted on gelatin molecule, form poly-hydroxy type polymkeric substance, and the introducing of N atom will strengthen the intermolecular hydrogen bonding of polar group on N atom and hydroxyl, gelatin molecule, effectively weaken the interactions such as gelatin molecule interchain hydrogen bond, static, thereby make gelatin film show excellent mechanical property.Itself has special construction polysiloxane, and its main chain-Si-O-Si-belongs to " inorganic structure ", and the bond energy of Si-O key is 462.0kJm/ol, bond energy 346.9kJm/ol far above the C-C key, thereby bond polarity is large, connected alkyl has been played to shielding effect, improved oxidative stability.Therefore, it is generally acknowledged that it has organic and two-fold advantage inorganic materials concurrently, as Heat stability is good, second-order transition temperature is low, ventilation property is high, dielectricity is good, with the characteristics such as the advantage such as good biocompatibility and low surface property, met the high-end demand of suitcase leather, clothing leather or car dressing leather.In exploitation superior performance, cheap hybrid protein finishing agent, make the waste of tanning industry obtain high value conversion.
A kind of polysiloxane that contains of the present invention, the multifunctional type gelatin hide finishes of Racemic glycidol and quaternary ammonium salt can be used as luggage leather, the dress ornament leather, the car dressing leather, decorate leather, and physical culture is covered with paint, lacquer, colour wash, etc. with removing from office.
Wherein, polymer A, B, C and the contrast of described product performance are as shown in the table:
the accompanying drawing explanation
The infrared spectrum that Fig. 1 is gelatin;
The nuclear magnetic spectrogram of the nuclear magnetic spectrogram that Fig. 2 is gelatin and Racemic glycidol modified gelatin of the present invention;
The infrared spectrum that Fig. 3 is the quaternary ammonium salt-modified gelatin of epoxy;
The infrared spectrum that Fig. 4 is 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:
Below will describe the present invention in detail by specific embodiment:
Primary amine groups content in gelatin molecule is measured [method that adopts patent CN102393466A] with the primary amine groups determinator;
Epoxy polysiloxane is synthetic 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 is measured with contact angle instrument;
Elongation at break and 100% Young's modulus are measured by the mechanical stretching instrument;
Second-order transition temperature (
tg) with differential thermal calorimetric scanner, measure;
Thermostability is measured with thermogravimeter;
Viscosity is with rotary viscosity design determining.
embodiment 1:
In tri-mouthfuls of reaction flasks of the 250ml that thermometer socket, thief hole and condenser socket are housed, add 12 gram gelatin (to account for 11.76% of total mass, its molecular structure is verified by infrared spectrum, see Fig. 1), 85 gram deionized waters, be heated with stirring to 50 ℃, after gelatin dissolves fully, the sodium hydroxide that adds the 0.25mL3 mol/L, conditioned reaction pH is 10.0, add epoxy quaternary ammonium salt 13g, the question response thing continues to stir 8 hours after dissolving without safety, prepares epoxy quaternary ammonium salt graft modification gelatin copolymer solution (solution 1).
In the infrared spectrogram of the quaternary ammonium salt-modified gelatin of epoxy (Fig. 3), former 1643cm
-1the N of place's primary amino～H absorption peak disappears, simultaneously at 1475cm
-1occurred-N (the CH of place
3)
3the new absorption peak of C-H.By 1 the N-H absorption peak occurred in spectrogram, disappear, 1～N (CH
3)
3the charateristic avsorption band of upper C-H, illustrate that reaction has occurred for epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide.
In tri-mouthfuls of reaction flasks of the 250ml that thermometer socket, thief hole and condenser socket are housed, add 12 gram gelatin (to account for 11.76% of total mass, its molecular structure is verified by infrared spectrum, see Fig. 1), 85 gram deionized waters, be heated with stirring to 50 ℃, after gelatin dissolves fully, the sodium hydroxide that adds the 0.25mL3 mol/L, conditioned reaction pH is 10.0, add Racemic glycidol 10g, the question response thing continues to stir 8 hours after dissolving without safety, prepares Racemic glycidol graft modification gelatin copolymer solution (solution 2).
The Racemic glycidol modified gelatin
1in H nuclear magnetic spectrum figure (Fig. 2), near the triatomic ring former δ=2.8ppm on two carbon the peak of hydrogen disappear, at δ=3.6ppm, new multiplet appears simultaneously, may be-C
h oH-and-C
h 2the peak of OH.By 2 C-H absorption peaks that occur in spectrogram, disappear, the formation of the charateristic avsorption band of 1 C-H, illustrate that reaction has occurred for epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide.
The thermometer socket is being housed, add 12 gram gelatin (account for total mass 11.76%) in tri-mouthfuls of reaction flasks of the 250ml of thief hole and condenser socket, 85 gram deionized waters, be heated with stirring to 50 ℃, after gelatin dissolves fully, the sodium hydroxide that adds the 0.25mL3 mol/L, conditioned reaction pH is 10.0, add the 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 (account for total mass 4.90%), after continuing to be stirred to dissolving fully, add continuously or in batches epoxy polysiloxane (M
w=1000), reaction starts, and reacts the 24 hours primary amine groups content in system and no longer changes, and stops stirring and heating, obtains epoxy polysiloxane modified gelatin solution (solution 3).
Occurred the new bands of a spectrum that do not have in 3 collagen polypeptide infrared spectrograms in the infrared spectrogram of epoxy polysiloxane modified gelatin (Fig. 4), their ownership is as follows: (1) 802 cm
-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) 1261 cm
-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) 2963 cm
-1the stretching vibration absorption peak that the peak that place occurs is C-H.By the charateristic avsorption band of 3 Si-CH3 occurring in spectrogram, illustrate that reaction has occurred for epoxide group in epoxy polysiloxane and the primary amino on collagen polypeptide.
By solution 1, the 2 and 3 ratio mixing of 1:1:1 in mass ratio, wherein the quality of solution 1 is 6g, solution 2 is 6g, solution 3 is 6g, the gained viscosity of sludge is～560 centipoises (50 ℃), the mixed solvent that adds 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 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 137 ℃ and 209 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 820%, and tensile strength is increased to 3.6 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 66.6%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 243
o, illustrate that the thermostability of modified gelatin film improves.
In the infrared spectrogram of product (Fig. 5) not only at the occurred-N (CH of 1475cm-1 place
3)
3the new absorption peak of C-H, also at 802 cm
-1the rocking vibration absorption peak of the upper C-H of Si-CH3 in the polydimethylsiloxane group appears in place, at 1261 cm
-1the peak that place occurs is the symmetric deformation flexural vibration absorption peak of C-H in Si-CH3, at 2963 cm
-1the stretching vibration absorption peak that the peak that place occurs is C-H.Illustrate that reaction has occurred for epoxide group in epoxy polysiloxane, epoxy quaternary ammonium salt and the primary amino on collagen polypeptide.In addition, the stretching vibration peak that C-O-C also occurs at 1191 cm-1 places, illustrate with the water glyceryl ether and react with it.
embodiment 2:
Institute's described method is consistent with embodiment 1, and unique proportioning that is not 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.
The gained viscosity of sludge is～620 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 142 ℃ and 185 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 320%, and tensile strength is increased to 13.4 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 86.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 76.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of 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 ℃) | ~ 550 centipoises (60 ℃) | ~ 270 centipoises (60 ℃) | ~ 560 centipoises (60 ℃) |
| Second-order transition temperature | 235℃ | 137 and 189 ℃ | 85℃ | 142 and 185 ℃ |
| To colibacillary bacteriostasis rate | >75% | —— | —— | 86.2% |
| Bacteriostasis rate to gold-coloured staphylococci | >72% | —— | —— | 76.1% |
embodiment 3:
Institute's described method is consistent with embodiment 1, is not both the gelatin quality and is replaced by 3 grams (account for total mass 2.83%), and pH is replaced by 6.0, heated and stirred to 40 ℃.
The gained viscosity of sludge is～480 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 126 ℃ and 175 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 375%, and tensile strength is increased to 3.4 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 89.4%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 83.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 262
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 4:
Institute's described method is consistent with embodiment 1, is not both the gelatin quality and is replaced by 16 grams (account for total mass 15.09%), and pH is replaced by 12.0, heated and stirred to 40 ℃.
The gained viscosity of sludge is～730 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 165 ℃ and 198 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 320%, and tensile strength is increased to 42.64 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 64.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 242
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 5:
Institute's described method is consistent with embodiment 1, is not both heated and stirred to 70 ℃.
The gained viscosity of sludge is～450 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 132 ℃ and 185 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 240%, and tensile strength is increased to 2.8 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 71.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.4%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 236
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 6:
Institute's described method is consistent with embodiment 1, is not both the epoxy quaternary ammonium salt and is replaced by 1 gram, and pH is replaced by 12, stirs and is warmed up to 40 ℃.
The gained viscosity of sludge is～560 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 186 ℃ and 209 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 104%, and tensile strength is increased to 1.6 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 65.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 60.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 251
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 7:
Institute's described method is consistent with embodiment 1, is not both the epoxy quaternary ammonium salt and is replaced by 20 grams, stirs and is warmed up to 40 ℃.
The gained viscosity of sludge is～440 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 134 ℃ and 198 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 430%, and tensile strength is increased to 6.1 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 93.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 84.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 246
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 8:
Institute's described method is consistent with embodiment 1, is not both the epoxy quaternary ammonium salt and is replaced by 1 gram, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～330 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 150 ℃ and 186 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 30%, and tensile strength is increased to 0.98 MPa, shows that the ductility of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 61.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 56.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 222
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 9:
Institute's described method is consistent with embodiment 1, is not both the epoxy quaternary ammonium salt and is replaced by 22 grams, and pH is replaced by 6, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～350 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 132 ℃ and 170 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 20%, and tensile strength is increased to 5.4 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 96.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 87.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 242
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 10:
Institute's described method is consistent with embodiment 1, is not both Racemic glycidol and is replaced by 1.5 grams, and pH is replaced by 12, stirs and is warmed up to 40 ℃.
The gained viscosity of sludge is～650 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 15 ℃ and 112 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 1140%, and tensile strength is increased to 12.8 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 65.4%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 252
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 11:
Institute's 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 ℃.
The gained viscosity of sludge is～710 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 5 ℃ and 84 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 690%, and tensile strength is increased to 1.5 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 45.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 36.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 246
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 12:
Institute's 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 ℃.
The gained viscosity of sludge is～560 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 20 ℃ and 96 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 1040%, and tensile strength is increased to 56.2 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 56.8%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 42.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 253
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 13:
Institute's described method is consistent with embodiment 1, is not both Racemic glycidol and is replaced by 26 grams, and pH is replaced by 6, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～780 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 3 ℃ and 72 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 460%, and tensile strength is increased to 1.8 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 85.4%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 72.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 235
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 14:
Institute's described method is consistent with embodiment 1, and the proportioning that is not both ethanol, tetrahydrofuran (THF), methanol mixed solvent is replaced by 4:1:1.
The gained viscosity of sludge is～630 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 139 ℃ and 176 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 300%, and tensile strength is increased to 12.9 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 56.3%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 40.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 256
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 15:
Institute's described method is consistent with embodiment 8, and the proportioning that is not both ethanol, tetrahydrofuran (THF), methanol mixed solvent is replaced by 8:6:0.
The gained viscosity of sludge is～560 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 130 ℃ and 176 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 860%, and tensile strength is increased to 2.9 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 58.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 46.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 252
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 16:
Institute's described method is consistent with embodiment 11, and the proportioning that is not both ethanol, tetrahydrofuran (THF), methanol mixed solvent is replaced by 3:0:6.
The gained viscosity of sludge is～620 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gbe 183 ℃ and 226 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 36%, and tensile strength is increased to 89.4 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 73.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 59.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 258
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 17:
Institute's described method is consistent with embodiment 13, and the proportioning that is not both ethanol, tetrahydrofuran (THF), methanol mixed solvent is replaced by 5:5:2.The gained viscosity of sludge is～620 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 85 ℃ and 221 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 410%, and tensile strength is increased to 35.1 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 74.9%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 68.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 251
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 18:
Institute's described method is consistent with embodiment 1, and unique proportioning that is not 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.
The gained viscosity of sludge is～580 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 132 ℃ and 216 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 480%, and tensile strength is increased to 64.5 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 58.3%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 49.5%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of 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 | |
| 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:
Institute's described method is consistent with embodiment 18, is not both the epoxy quaternary ammonium salt and is replaced by 22 grams, and pH is replaced by 6, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～430 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 20 ℃ and 60 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 210%, and tensile strength is increased to 0.86 MPa, shows that the ductility of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 86.6%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 48.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of gelatin film increases to 73
o, illustrate that the hydrophobicity of modified gelatin film slightly is improved; The heat decomposition temperature of raw material gelatin film is 218
o, after modification, the heat decomposition temperature of gelatin film brings up to 240
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 20:
Institute's described method is consistent with embodiment 18, is not both the epoxy quaternary ammonium salt and is replaced by 1 gram, and pH is replaced by 12, stirs and is warmed up to 40 ℃.
The gained viscosity of sludge is～740 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 76 ℃ and 140 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 65%, and tensile strength is increased to 14.2MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 72.9%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 251
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 21:
Institute's described method is consistent with embodiment 18, is not both the epoxy quaternary ammonium salt and is replaced by 1 gram, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～425 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 65 ℃ and 142 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 5%, and tensile strength is increased to 0.83 MPa, shows that the ductility of modified gelatin slightly strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 52.6%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 35.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of gelatin film increases to 72
o; The heat decomposition temperature of raw material gelatin film is 218
o, after modification, the heat decomposition temperature of gelatin film brings up to 231
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 22:
Institute's described method is consistent with embodiment 21, is not both and only uses ethanol for solvent.
The gained viscosity of sludge is～660 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 34 ℃ and 102 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 410%, and tensile strength is increased to 8.3 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 50.1%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 35.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 253
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 23:
Institute's described method is consistent with embodiment 1, and unique proportioning that is not 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.
The gained viscosity of sludge is～690 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 131 ℃ and 167 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 1560%, and tensile strength is increased to 1.3 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 60.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 53.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 248
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 24:
Institute's 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 ℃.
The gained viscosity of sludge is～620 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 40 ℃ and 100 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 280%, and tensile strength is increased to 2.1 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 70.6%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 61.9%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 235
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 25:
Institute's 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 ℃.
The gained viscosity of sludge is～310 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 126 ℃ and 188 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 310%, and tensile strength is increased to 9.6 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 85.4%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 73.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 253
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 26:
Institute's described method is consistent with embodiment 23, is not both Racemic glycidol and is replaced by 26 grams, and pH is replaced by 6, stirs and is warmed up to 70 ℃.
The gained viscosity of sludge is～540 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 20 ℃ and 90 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 1120%, and tensile strength is increased to 2.3 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 70.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 53.6%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 241
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 27:
Institute's described method is consistent with embodiment 13, is not both and only uses tetrahydrofuran (THF) for solvent.
The gained viscosity of sludge is～780 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gbe 186 ℃ and 235 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 53%, and tensile strength is increased to 31.6 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 70.8%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 63.2%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 251
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 28:
Institute's described method is consistent with embodiment 14, and unique tensio-active agent that is not both is replaced by sodium lauryl sulphate, the mixture of sodium laurylsulfonate.
The gained viscosity of sludge is～490 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 131 ℃ and 170 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 2130%, and tensile strength is increased to 5.8 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 88.6%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 81.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 242
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 29:
Institute's described method is consistent with embodiment 28, is not both the gelatin quality and is replaced by 3 grams (account for total mass 2.83%), and pH is replaced by 6.0, heated and stirred to 40 ℃.
The gained viscosity of sludge is～350 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 189 ℃ and 226 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 230%, and tensile strength is increased to 4.2 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 68.9%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 54.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 244
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 30:
Institute's described method is consistent with embodiment 28, is not both the gelatin quality and is replaced by 16 grams (account for total mass 15.09%), and pH is replaced by 12.0, heated and stirred to 40 ℃.
The gained viscosity of sludge is～750 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gbe 198 ℃ and 234 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 30%, and tensile strength is increased to 35.2 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 86.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 76.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 231
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 31:
Institute's described method is consistent with embodiment 28, is not both dosage of surfactant and is replaced by 1 gram (account for total mass 0.69%), and the 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.
The gained viscosity of sludge is～610 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 139 ℃ and 186 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 280%, and tensile strength is increased to 3.5 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 81.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 65.4%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 252
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 32:
Institute's described method is consistent with embodiment 28, is not both dosage of surfactant and is replaced by 18 grams (account for total mass 17.32%), and the 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.
The gained viscosity of sludge is～540 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 138 ℃ and 197 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 260%, and tensile strength is increased to 8.9MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 86.2%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 76.1%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 251
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 33:
Institute's described method is consistent with embodiment 23, and unique tensio-active agent that is not both is replaced by sodium lauryl sulphate, the mixture of sodium laurylsulfonate.
The gained viscosity of sludge is～560 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
gdrop to 142 ℃ and 219 ℃, obvious microphase-separated occurs; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 260%, and tensile strength is increased to 52.5MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 64.5%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 58.7%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 250
o, illustrate that the thermostability of modified gelatin film improves.
embodiment 34:
Institute's described method is consistent with embodiment 33, is not both and only uses methyl alcohol for solvent.
The gained viscosity of sludge is～300 centipoises (50 ℃), is positioned over the normal pressure drying in oven 6 hours of 45 ℃, forms snappiness than strong film.Second-order transition temperature (the T of raw material gelatin film
g) be 224 ℃, the T of gelatin film after modification
git is 238 ℃; The extension at break 0 of raw material gelatin film, tensile strength is 1.3MPa, and after modification, the elongation at break of gelatin film is increased to 5%, and tensile strength is increased to 50.2 MPa, shows that the snappiness of modified gelatin obviously strengthens; The raw material gelatin film is 18.3% to colibacillary antibiotic rate, the gelatin film after modification be increased to 60.1%; Antibiotic rate to gold-coloured staphylococci is 0%, the gelatin film after modification be increased to 62.3%, germ resistance obviously increases.
13c NMR shows in Racemic glycidol modified gelatin product on gelatin molecule γ-C blackout on Methionin, arginine molecule, 61 and the 63ppm place new peak appears, 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;
13c NMR shows in epoxy polysiloxane modified gelatin product γ-C blackout on Methionin, arginine molecule, and the fignal center of organosilicon Si-C forms; XPS shows that the chemical shift of N moves to 399.87, shows that C-N forms; Contact angle is tested and is shown, the contact angle of raw material gelatin film is 72
o, after modification, the contact angle of 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, after modification, the heat decomposition temperature of gelatin film brings up to 252
o, illustrate that the thermostability of modified gelatin film improves.
Claims (10)
1. one kind contains 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, the 3-glycidoxy) propyl group] polydimethylsiloxane grafted gelatin polymkeric substance (B) and Racemic glycidol grafted gelatin polymkeric substance (C) composition, wherein A accounts for 20～40% of gross weight, and B accounts for 10～50% of gross weight, and C accounts for 30～50% of gross weight; The viscosity of this mixing solutions is less than 1200 centipoises (60 ℃), 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 the polysiloxane that contains claimed in claim 1, 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 ℃, obtain gelatin film, its second-order transition temperature is 20～238 ℃, and the swelling ratio in deionized water is 20～160X, Young's modulus 2～65MPa, contact angle is 85～122
o.
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, comprise the steps:
(1) gelatin is dissolved in to water, prepares 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 be take mass ratio as (1 ~ 6): (2～6): (1～5) ratio mixes after mixing, and obtains described polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt of containing.
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, comprise the steps:
(1) gelatin is dissolved in to water, prepares 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 be take mass ratio as (1 ~ 6): (2～6): (1～5) ratio mixes after mixing, and obtains described polysiloxane, the multifunctional type gelatin leather finish agent solution of Racemic glycidol and quaternary ammonium salt of containing;
(6) take the above-mentioned polysiloxane that contains of 15-20g, 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 mould, under the temperature rise rate of 2～10 ℃, be warming up to 40～80 ℃ of oven dry in the normal pressure baking oven, obtain the gelatin film that contains epoxy quaternary ammonium salt, Racemic glycidol and polysiloxane.
5. method as described as claim 3 or 4, is characterized in that, the described aqueous gelatin solution for preparing of step (1) is, gelatin is dissolved in the water and is mixed with the aqueous solution, regulates its temperature at 40-70 ℃, and regulation system pH is 6-12; In step (1), the mass concentration of gelatin solution is 2～16%.
6. method as described as claim 3 or 4, it is characterized in that, the described epoxy quaternary ammonium salt grafted gelatin polymkeric substance for preparing of step (2) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, add the epoxy quaternary ammonium salt in reaction flask, the 0.2-8 that the consumption of epoxy quaternary ammonium salt is primary amine groups molar weight in gelatin molecule is doubly, in 40-70 ℃ of reaction 6-12h, obtain the solution 1 of polymer A.
7. method as described as claim 3 or 4, it is characterized in that, the described Racemic glycidol grafted gelatin polymkeric substance for preparing of step (3) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, add Racemic glycidol in reaction flask, the 0.1-10 that the consumption of Racemic glycidol is primary amine groups molar weight in gelatin molecule is doubly, in 40-70 ℃ of reaction 6-12h, obtain the solution 2 of polymkeric substance C;
The described epoxy polysiloxane grafted gelatin polymkeric substance for preparing of step (4) is, the solution stirring that step (1) is obtained, after the pH of system value stabilization, to add tensio-active agent in reaction flask and containing the epoxy polysiloxane of Si-O-Si repeating unit 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 ℃ of reaction 12～24h, obtains polymer B solution 3.
8. method as claimed in claim 7, is characterized in that, preferred, and the described tensio-active agent that in batches adds of step (3) adds for dividing 1～4 batch, and the weight of every batch is identical, every minor tick 30 minutes; The described tensio-active agent of step (3) is alkyl-sulphate, alkylbenzene sulfonate and EPE polyol EPE compatibility, and proportion compatibility is (6 ~ 8): (1 ~ 3): 1, and weight ratio.
9. method as claimed in claim 4, it is characterized in that, the mixed solvent that the described solvent of step (6) is a kind of in ethanol, tetrahydrofuran (THF), acetone, methyl alcohol or three kinds, four kinds, the mixed solvent proportioning is ethanol: tetrahydrofuran (THF): acetone: methyl alcohol=(1 ~ 10): (0～10): (0～10): (0～10), volume ratio.
10. method as described as claim 3 or 4, is characterized in that, the described solution 1 of step (5), the proportioning of solution 2 and solution 3 is 1:(2～6): any one proportioning in (1～5), weight ratio.
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