CN105566668B - Solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film - Google Patents
Solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film Download PDFInfo
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- CN105566668B CN105566668B CN201510970629.3A CN201510970629A CN105566668B CN 105566668 B CN105566668 B CN 105566668B CN 201510970629 A CN201510970629 A CN 201510970629A CN 105566668 B CN105566668 B CN 105566668B
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 102
- 229920000159 gelatin Polymers 0.000 title claims abstract description 102
- 239000008273 gelatin Substances 0.000 title claims abstract description 102
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 102
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 102
- -1 polysiloxane Polymers 0.000 title claims abstract description 50
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002904 solvent Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 108010025899 gelatin film Proteins 0.000 claims description 189
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 235000019441 ethanol Nutrition 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 65
- 229910052710 silicon Inorganic materials 0.000 description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 38
- 239000010703 silicon Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 35
- 238000001228 spectrum Methods 0.000 description 28
- 238000004458 analytical method Methods 0.000 description 26
- 238000005191 phase separation Methods 0.000 description 19
- 230000008859 change Effects 0.000 description 15
- 239000003292 glue Substances 0.000 description 14
- 239000010985 leather Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 229920001184 polypeptide Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 102000004196 processed proteins & peptides Human genes 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000004475 Arginine Substances 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to solvent subscriptions to prepare monocycle oxygen terminated polysiloxane modified gelatin Gradient Film.Surfactant sodium alkyl sulfate is dissolved in the water and is configured to aqueous solution, 1~2h is stirred under conditions of 40~60 DEG C, pH are 8~11, gelatin is added, and stirs 4~8h, the monocycle oxygen terminated polysiloxane that molecular weight is 500 is added, obtains monocycle oxygen terminated polysiloxane modified gelatin solution.By monocycle oxygen terminated polysiloxane modified gelatin solution low-temperature centrifugation, after middle layer after taking layering is mixed with water, a certain proportion of organic solvent is added, after mixing, mixed solution is measured to be added drop-wise in different base, 12~18h is stood, 40~60 DEG C of drying in oven is placed in, obtains Gradient Film.The Gradient Film has the characteristics that tensile strength is high, hydrophobicity is good, film is soft.
Description
Technical field
The present invention relates to Gradient Film, in particular to solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin gradient
Film.There is this Gradient Film concentration of component change of gradient is presented in longitudinal section, and film stretching intensity is high, hydrophobicity is good, soft etc.
Feature, the finishing agent be especially suitable for suitcase leather, clothing leather or car decoration leather.
Background technique
Gelatin is obtained from the by-product or waste of cheap process hides, pharmacy and food, is a kind of renewable
Resource has biological degradability, and there are no pollution to the environment.Gelatin has become the important raw material for preparing protein film, such as other
Natural macromolecular material is the same, after this kind of protein material film forming, there are plastic senses it is strong, water-resistance and rotproofness are poor the problems such as.Silicon
Siloxane modified gelatin can improve the water-resistance and flexibility [201310012009.X] of gelatin film to a certain extent, but silicon
Disorder distribution of the oxygen alkane component in film directly affects membrane structure, film properties and film application.Gradient Film can make silicone components
Consecutive variations are presented along film longitudinal direction, to make the property of membrane material and function that change of gradient also be presented.The present invention will utilize
Interaction between each macromolecular prepares novel gelatin Gradient Film by Macromolecular self-assembly process.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned deficiency, it is bright to provide the preparation monocycle oxygen terminated polysiloxane modification of solvent subscription
There is silicone components concentration change of gradient, film stretching intensity height, hydrophobicity is presented in longitudinal section for glue Gradient Film, invention preparation
The Gradient Film of the features such as good, soft.
The technical scheme adopted by the invention is as follows:
Solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, characterized in that comprises the following steps that
(1) surfactant sodium alkyl sulfate is dissolved in the water and is configured to aqueous solution, adjust its temperature at 40~60 DEG C,
Adjusting mass percentage concentration is 0.1~0.5%, and wherein the long alkyl chains of sodium alkyl sulfate are 12,14 or 16；
(2) gelatin is added into surfactant solution, the dosage of gelatin is the 1~10% of solution quality, regulation system pH
It is 8~11, stirs 4~8h；
(3) continue to stir, the monocycle oxygen terminated polysiloxane that point 1~8 batch of addition molecular weight is 500 is single epoxy-capped poly-
The dosage of siloxanes is 0.04 ~ 1.5 times of primary amino group mole in gelatin molecule, in 40~60 DEG C of 12~30h of reaction, is obtained white
Color emulsion, wherein the mass concentration of white " milky " liquid is 1 ~ 30%；
(4) by milky white solution low-temperature centrifugation, middle layer product is taken, deionized water mixing is added, the dosage of deionized water is
1 ~ 10 times of middle layer product quality, obtains white turbid；
(5) ethyl alcohol, acetone, normal propyl alcohol are added into white turbid, is uniformly mixed, the volume ratio of solvent and white turbid liquid
For (1~10): 1,0.5~0.8 ml mixed solution drop is measured on gelatin-based bottom, is stood 12~18h, is placed in 40~60 DEG C of bakings
Drying, obtains Gradient Film in case.
The present invention has following significant using solvent subscription preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film
Advantage: firstly, monocycle oxygen terminated polysiloxane is incompatible with gelatin, the two passes through intermolecular interaction shape in film forming procedure
At micro phase separation structure, material is promoted to embody excellent, special performance.Secondly, silicone components content is presented in the longitudinal direction
Change of gradient makes the two sides of film that heterogeneity be presented, and is on one side gelatin enrichment, can combine closely with hide；Another side is silicon
The enrichment of oxygen alkane, siloxanes are one kind using duplicate Si-O key as main chain, and the polymer of organic group is directly connected on silicon atom；Have
This special construction of machine silicon and composition, make it have low-temperature flexibility is good, surface tension is low, good biocompatibility, it is resistance to combustion, it is weather-proof
The features such as good, water-tolerant of property, thermostabilization be good and good permeability.Third, silicone components are orderly distributed in film, from low surface
Variation range to the mass percentage of top surface element silicon is 0 ~ 20%, so that film is had the characteristics that softness, meets suitcase
The high demand of leather, clothing leather or car decoration leather.While developing superior performance, cheap hybrid protein finishing agent, system
Standby novel gelatin membrane material, makes the waste of leather industry obtain high level conversion.
Solvent subscription preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film of the present invention can be used as luggage
Leather, dress ornament leather, car decoration leather, decoration leather, sport are covered with paint, lacquer, colour wash, etc. with leather.
Detailed description of the invention
Fig. 1 is the infrared spectrum of gelatin；
Fig. 2 is the infrared spectrum of Gradient Film of the present invention；
Fig. 3 is the nuclear magnetic spectrogram of gelatin and the nuclear magnetic spectrogram of Gradient Film of the present invention；
Fig. 4 is that the continuous lines of Gradient Film section energy dispersive spectrum of the present invention scan spectrogram.
Specific embodiment:
Carry out the present invention is described in detail below by specific embodiment:
Primary amino group content measures [ using the method for patent CN102393466A ] with primary amino radical tester in gelatin molecule；
Monocycle oxygen terminated polysiloxane is synthesized with anionic polymerization；
Polymer architecture is with nuclear-magnetism, infrared, x-ray photoelectron spectroscopy characterization；
Contact angle is measured with contact angle instrument；
Glass transition temperature (Tg) is with the measurement of differential thermal calorimetric scan instrument；
Element silicon distribution is with scanning electron microscope-energy dispersive spectrum combined instrument analysis measurement.
Embodiment 1:
0.3g surfactant is added in three mouthfuls of reaction flasks equipped with thermometer socket, sample tap and condenser socket,
95 grams of deionized waters, are heated with stirring to 50 DEG C, and after surfactant is completely dissolved, the hydrogen-oxygen of 0.65 mL, 2 mol/L is added
Change sodium, adjust reaction pH be 10.0, be added 5g gelatin (account for solution gross mass 5%), continue stirring be completely dissolved to gelatin after,
Continuously or monocycle oxygen terminated polysiloxane (Mw=500) is added portionwise, the dosage of monocycle oxygen terminated polysiloxane is in gelatin molecule
0.8 times of primary amino group mole, reaction starts, and the content of primary amine group reacted in 24 hours systems is no longer changed, and stops stirring
Heating is mixed and stirred, monocycle oxygen terminated polysiloxane modified gelatin solution is obtained.By monocycle oxygen terminated polysiloxane modified gelatin solution
Low-temperature centrifugation, middle layer whiteness are monocycle oxygen terminated polysiloxane modified gelatin polymer.
There are 3 collagen polypeptides in the infrared spectrogram (Fig. 2) of monocycle oxygen terminated polysiloxane modified gelatin polymer
The new bands of a spectrum not having in infrared spectrogram, their ownership are as follows: (1) 802cm-1The peak that place occurs is Si-CH3Middle C-H's shakes
Pendular oscillation absorption peak, this is one of characteristic peak of polysiloxanes；(2)1261cm-1The peak that place occurs is Si-CH3Middle C-H's is symmetrical
Bending vibration absorption peak, this is also one of characteristic peak of polysiloxanes；(3)2963cm-1The peak that place occurs is the flexible of C-H
Vibration absorption peak passes through 3 Si-CH occurred in spectrogram3Characteristic absorption peak, the ring in the epoxy-capped polysiloxanes of instruction sheet
Primary amino group on oxygen groups and collagen polypeptide is reacted.
Monocycle oxygen terminated polysiloxane modified gelatin polymer13C NMR shows epoxy polysiloxane modified gelatin product
Lysine on middle gelatin molecule, γ-C signal disappears on arginine molecule, new peak occurs at 61 and 63ppm, is epoxy-modified glue
The peak of-CHOH- group in former polypeptide；γ-C signal disappears on lysine, arginine molecule, the signal peak shape of organosilicon Si-C
At the primary amino group in epoxy group and collagen polypeptide in the epoxy-capped polysiloxanes of instruction sheet is reacted.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 1:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 99 that feeler, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 90 DEG C and 210 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows change of gradient is presented in element silicon from film bottom surface to top surface.
Embodiment 2:
Described method and embodiment 1 are consistent, are not uniquely both that normal pressure oven temperature is changed to 45 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 1:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 45 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 95 that feeler, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 130 DEG C and 218 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon is enriched in the upper surface of film.
Embodiment 3:
Described method and embodiment 1 are consistent, are not uniquely both that normal pressure oven temperature is changed to 50 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 1:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 50 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 90 that feeler, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 156 DEG C and 228 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 4:
Described method and embodiment 1 are consistent, are not uniquely both that normal pressure oven temperature is changed to 60 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 1:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 60 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 85 that feeler, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 176 DEG C and 223 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 5:
Described method and embodiment 1 are consistent, are not uniquely both that normal pressure oven temperature is changed to freeze-drying.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 1:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 89 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 166 DEG C and 225 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 6:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 2:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 2:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 87 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 163 DEG C and 213 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 7:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 3:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 98 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 128 DEG C and 223 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows gradient is presented in element silicon from film bottom surface to top surface
Variation.
Embodiment 8:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 4:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 4:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 90 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 143 DEG C and 217 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 9:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 5:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 5:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 93 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 163 DEG C and 211 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 10:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 6:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 6:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 91 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 169 DEG C and 210 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 11:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 7:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 7:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 89 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 181 DEG C and 212 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 12:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 8:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 8:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 90 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 171 DEG C and 219 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 13:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 9:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 9:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 86 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 171 DEG C and 221 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 14:
Described method and embodiment 1 are consistent, are not uniquely both that the ratio of ethyl alcohol and mixed liquor is changed to 10:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 10:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen,
It is dry with refrigerator again, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified bright
It is 81 that the contact angle of glue film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material
The Tg of gelatin film is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has by respectively 173 DEG C and 219 DEG C
Micro phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 15:
Described method and embodiment 6 are consistent, are not uniquely both that ethyl alcohol is changed to acetone.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and third
The ratio that ketone volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then
It is dry with refrigerator, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin
It is 91 that the contact angle of film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows that raw material is bright
The Tg of glue film is 223 DEG C, and respectively 190 DEG C and 220 DEG C, it is micro- to illustrate that modified gelatin film has by 2 Tg of appearance of modified gelatin film
Phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 16:
Described method and embodiment 6 are consistent, are not uniquely both that ethyl alcohol is changed to normal propyl alcohol.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and just
The ratio that propyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen,
It is dry with refrigerator again, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified bright
It is 81 that the contact angle of glue film, which increases,o, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows raw material
The Tg of gelatin film is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has by respectively 179 DEG C and 231 DEG C
Micro phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 17:
Described method and embodiment 6 are consistent, are not uniquely both that the molten measurement volume of mixing is changed to 0.8ml.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.8ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 98 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 149 DEG C and 231 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is enriched in film upper surface.
Embodiment 18:
Described method and embodiment 6 are consistent, are not uniquely both that reaction temperature is changed to 50 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 50 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 90 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 166 DEG C and 211 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows element silicon disorder distribution in film.
Embodiment 19:
Described method and embodiment 6 are consistent, are not uniquely both that reaction temperature is changed to 60 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 60 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 87 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 169 DEG C and 221 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows element silicon disorder distribution in film.
Embodiment 20:
Described method and embodiment 6 are consistent, are not uniquely both that reaction pH is changed to 8.0.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 79 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 171 DEG C and 209 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows element silicon disorder distribution in film.
Embodiment 21:
Described method and embodiment 6 are consistent, are not uniquely both that reaction pH is changed to 9.0.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 82 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 177 DEG C and 215 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows element silicon disorder distribution in film.
Embodiment 22:
Described method and embodiment 6 are consistent, are not uniquely both that reaction pH is changed to 11.0.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
It is 85 that feeler, which increases,o；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance of modified gelatin film
2 Tg, illustrate that modified gelatin film has micro phase separation structure by respectively 179 DEG C and 227 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows element silicon disorder distribution in film.
Embodiment 23:
Described method and embodiment 6 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.1 times of primary amino group mole in molecule.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 73o, material hydrophobic do not have significant change；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223
DEG C, 1 Tg of appearance of modified gelatin film is 227 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon exists
Disorder distribution in film.
Embodiment 24:
Described method and embodiment 6 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.2 times of primary amino group mole in molecule.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 73o, material hydrophobic do not have significant change；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223
DEG C, 1 Tg of appearance of modified gelatin film is 227 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon exists
Disorder distribution in film.
Embodiment 25:
Description method and embodiment 6 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin point
0.5 times of primary amino group mole in son.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 83o, material hydrophobic do not have significant change；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223
DEG C, 1 Tg of appearance of modified gelatin film is 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon exists
Disorder distribution in film.
Embodiment 26:
Described method and embodiment 6 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
1.0 times of primary amino group mole in molecule.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 100o, illustrate that modified gelatin film hydrophobicity increases；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is
223 DEG C, 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated knot by respectively 198 DEG C and 227 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon is enriched in film upper surface.
Embodiment 27:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to that 1g gelatin (account for solution gross mass 1%) is added.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 78o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 225 DEG C and 202 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 28:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to that 1g gelatin (account for solution gross mass 3%) is added.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 74o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microphase-separated by respectively 215 DEG C and 222 DEG C
Structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 29:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to that 7g gelatin (account for solution gross mass 7%) is added.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 73o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, 1 Tg of appearance of modified gelatin film, is 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows silicon
Element disorder distribution in film.
Embodiment 30:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to addition 10g gelatin (to account for solution gross mass
10%)。
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 74o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, 1 Tg of appearance of modified gelatin film, is 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows silicon
Element disorder distribution in film.
Embodiment 31:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to addition 0.1g surfactant (to account for the total matter of solution
The 0.1% of amount).
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 73o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, 1 Tg of appearance of modified gelatin film, is 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows silicon
Element disorder distribution in film.
Embodiment 32:
Described method and embodiment 6 are consistent, are not uniquely both to be changed to addition 0.5g surfactant (to account for the total matter of solution
The 0.5% of amount).
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor and second
The ratio that alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure baking ovens
Interior drying obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified gelatin film connects
Feeler is 89o, modified gelatin film hydrophobicity do not have significant change；The test of differential thermal calorimetric scan instrument shows raw material gelatin film
Tg is 223 DEG C, 2 Tg of appearance of modified gelatin film, respectively 191 DEG C 225 DEG C；Scanning electron microscope-energy dispersive spectrum
Analysis shows element silicon disorder distribution in film.
Claims (2)
1. solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which comprises the steps of:
(1) the addition 0.3g surfactant in three mouthfuls of reaction flasks equipped with thermometer socket, sample tap and condenser socket, 95
Gram deionized water, is heated with stirring to 50 DEG C, and after surfactant is completely dissolved, the hydroxide of 2 mol/L of 0.65mL is added
Sodium, adjusting reaction pH is 10.0, and 5g gelatin is added；
(2) continue after stirring is completely dissolved to gelatin, it is continuous or monocycle oxygen terminated polysiloxane is added portionwise, it is single epoxy-capped poly-
The dosage of siloxanes is 0.8 times of primary amino group mole in gelatin molecule, and reaction starts, and reacts the primary amine groups in 24 hours systems
Content is no longer changed, and is stopped stirring and heating, is obtained monocycle oxygen terminated polysiloxane modified gelatin solution；Monocycle oxygen is sealed
Polysiloxane-modified gelatin solution low-temperature centrifugation is held, middle layer whiteness is the polymerization of monocycle oxygen terminated polysiloxane modified gelatin
Object；
It (3) is 1:1's according to mass ratio by whiteness monocycle oxygen terminated polysiloxane modified gelatin polymer and deionized water
Ratio is uniformly mixed, and is then uniformly mixed according to the ratio that mixed liquor and ethyl alcohol volume ratio are 1:1, is measured 0.5ml mixed solution
It is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
2. solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which comprises the steps of:
(1) the addition 0.3g surfactant in three mouthfuls of reaction flasks equipped with thermometer socket, sample tap and condenser socket, 95
Gram deionized water, is heated with stirring to 50 DEG C, and after surfactant is completely dissolved, the hydroxide of 2 mol/L of 0.65mL is added
Sodium, adjusting reaction pH is 10.0, and 5g gelatin is added；
(2) continue after stirring is completely dissolved to gelatin, it is continuous or monocycle oxygen terminated polysiloxane is added portionwise, it is single epoxy-capped poly-
The dosage of siloxanes is 0.8 times of primary amino group mole in gelatin molecule, and reaction starts, and reacts the primary amine groups in 24 hours systems
Content is no longer changed, and is stopped stirring and heating, is obtained monocycle oxygen terminated polysiloxane modified gelatin solution；Monocycle oxygen is sealed
Polysiloxane-modified gelatin solution low-temperature centrifugation is held, middle layer whiteness is the polymerization of monocycle oxygen terminated polysiloxane modified gelatin
Object；
It (3) is 1:1's according to mass ratio by whiteness monocycle oxygen terminated polysiloxane modified gelatin polymer and deionized water
Ratio is uniformly mixed, and is then uniformly mixed according to the ratio that mixed liquor and ethyl alcohol volume ratio are 3:1, is measured 0.5ml mixed solution
It is added drop-wise on gelatin-based bottom, is first freezed with liquid nitrogen, then is dry with refrigerator, obtain modified gelatin film.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712767A (en) * | 2009-11-17 | 2010-05-26 | 武汉理工大学 | Preparation method of organic silicon acrylic ester self-organizing gradient emulsion film |
| CN103087631A (en) * | 2013-01-14 | 2013-05-08 | 山东轻工业学院 | Polysiloxane-modified gelatin leather finishing agent and preparation method thereof |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712767A (en) * | 2009-11-17 | 2010-05-26 | 武汉理工大学 | Preparation method of organic silicon acrylic ester self-organizing gradient emulsion film |
| CN103087631A (en) * | 2013-01-14 | 2013-05-08 | 山东轻工业学院 | Polysiloxane-modified gelatin leather finishing agent and preparation method thereof |
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