CN105566661B - A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film - Google Patents
A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film Download PDFInfo
- Publication number
- CN105566661B CN105566661B CN201510970579.9A CN201510970579A CN105566661B CN 105566661 B CN105566661 B CN 105566661B CN 201510970579 A CN201510970579 A CN 201510970579A CN 105566661 B CN105566661 B CN 105566661B
- Authority
- CN
- China
- Prior art keywords
- gelatin
- modified gelatin
- film
- added
- terminated polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 121
- 229920000159 gelatin Polymers 0.000 title claims abstract description 121
- 239000008273 gelatin Substances 0.000 title claims abstract description 121
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 121
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 121
- -1 polysiloxane Polymers 0.000 title claims abstract description 64
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 52
- 239000001301 oxygen Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 8
- 108010025899 gelatin film Proteins 0.000 claims description 196
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- 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 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 39
- 230000008859 change Effects 0.000 abstract description 19
- 229910001868 water Inorganic materials 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 63
- 229910052710 silicon Inorganic materials 0.000 description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 36
- 239000010703 silicon Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 34
- 238000005191 phase separation Methods 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
- 238000010183 spectrum analysis Methods 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 13
- 239000010985 leather Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 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
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920001184 polypeptide Polymers 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 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
- 239000004472 Lysine Substances 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 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
- 239000003292 glue Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002156 mixing 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
- 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
- 230000009477 glass transition Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 230000010148 water-pollination Effects 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Method, which is adjusted, the present invention relates to a kind of pH prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film.Specific method is that surfactant sodium alkyl sulfate is dissolved in the water to be configured to aqueous solution, 1~2h is stirred under conditions of 40~60 DEG C, pH are 8~11, gelatin is added, stir 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 the middle layer after taking layering is mixed with water, HCl or NaOH is added and adjusts pH to 1~13, mixed solution is measured to be added drop-wise on gelatin-based bottom, 12~18h is stood, 40~50 DEG C of drying in oven is placed in, obtains Gradient Film.The features such as there is the Gradient Film concentration of component change of gradient is presented in longitudinal section, and film stretching intensity is high, hydrophobicity is good, soft.
Description
Technical field
The present invention relates to Gradient Film, in particular to a kind of pH adjusts method preparation monocycle oxygen terminated polysiloxane modified gelatin ladder
Spend film and preparation method.There is this Gradient Film concentration of component change of gradient is presented in longitudinal section, and film stretching intensity is high, hydrophobic
Property it is good, soft the features such as, be especially suitable for suitcase leather, clothing leather or car decoration leather finishing agent.
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 modified to provide a kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane
There is silicone components concentration ladder is presented in longitudinal section for gelatin Gradient Film modified gelatin Gradient Film and preparation method, invention preparation
The Gradient Film of the features such as degree variation, film stretching intensity is high, hydrophobicity is good, soft.
The technical scheme adopted by the invention is as follows:
A kind of pH adjusts method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film and preparation method, characterized in that
It 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 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) 2MHCl or 2MNaOH, regulation system pH to 1~13 are added in Xiang Baise turbid, it is mixed to measure 0.5~0.8ml
Drop is closed on gelatin-based bottom, 12~18h is stood, is placed in 40~50 DEG C of drying in oven, obtains Gradient Film.
The present invention adjusts method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film with following significant excellent using pH
Point: firstly, monocycle oxygen terminated polysiloxane is incompatible with gelatin, the two is formed in film forming procedure by intermolecular interaction
Micro phase separation structure promotes material to embody excellent, special performance.Secondly, ladder is presented in silicone components content in the longitudinal direction
Degree variation 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 oxygen
Alkane enrichment, siloxanes are one kind using duplicate Si-O key as main chain, and the polymer of organic group is directly connected on silicon atom；It is organic
This special construction of silicon and composition, having it, low-temperature flexibility is good, surface tension is low, good biocompatibility, resistance to combustion, weatherability
The features such as good, water-tolerant, thermostabilization be good and good permeability.Third, silicone components are orderly distributed in film, from low surface to
The variation range of the mass percentage of top surface element silicon be 0 ~ 20%, so that film is had the characteristics that softness, meet suitcase remove from office,
The high demand of clothing leather or car decoration leather.While developing superior performance, cheap hybrid protein finishing agent, preparation is new
Type gelatin membrane material, makes the waste of leather industry obtain high level conversion.
A kind of pH of the present invention, which adjusts method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, can be used as case
Bao Ge, 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 hydroxide of 0.65mL2 mol/L is added
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, even
Continue or be added portionwise monocycle oxygen terminated polysiloxane (Mw=500), the dosage of monocycle oxygen terminated polysiloxane is primary in gelatin molecule
0.8 times of amino mole, reaction starts, and the content of primary amine group reacted in 24 hours systems is no longer changed, and stops stirring
And heating, obtain monocycle oxygen terminated polysiloxane modified gelatin solution.Monocycle oxygen terminated polysiloxane modified gelatin solution is 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
In former polypeptide-CThe peak of HOH- group；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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 98 that the contact angle of modified gelatin film, which increases,o, illustrate to be modified bright
The hydrophobicity of glue film improves；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified gelatin film
There are 2 Tg, respectively 90 DEG C and 225 DEG C, illustrates that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Dispersion spectrum is analysis shows element silicon is enriched in upper surface.
Embodiment 2:
Described method and embodiment 1 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 82 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, appearance 2 Tg of modified gelatin film, respectively 210 DEG C and 225
DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon in film
Disorder distribution.
Embodiment 3:
Described method and embodiment 1 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 88 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, appearance 2 Tg of modified gelatin film, respectively 210 DEG C and 227
DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon in film
Disorder distribution.
Embodiment 4:
Described method and embodiment 1 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 86 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, 1 Tg of appearance of modified gelatin film, be 224 DEG C；Scanning electron is aobvious
Micro mirror-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 45 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, obtain modified gelatin film.Contact angle test shows raw material gelatin
The contact angle of film is 72o, it is 117 that the contact angle of modified gelatin film, which increases,o；The test of differential thermal calorimetric scan instrument shows raw material gelatin
The Tg of film is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microfacies by respectively 186 DEG C and 225 DEG C
Separated structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon is enriched in the upper surface of film.
Embodiment 6:
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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, obtain modified gelatin film.Contact angle test shows raw material gelatin
The contact angle of film is 72o, it is 118 that the contact angle of modified gelatin film, which increases,o；The test of differential thermal calorimetric scan instrument shows raw material gelatin
The Tg of film is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate that modified gelatin film has microfacies by respectively 192 DEG C and 223 DEG C
Separated structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon is enriched in the upper surface of film.
Embodiment 7:
Described method and embodiment 1 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, HCl is added and adjusts pH of mixed
To 6, measures 0.8ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 116 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, appearance 2 Tg of modified gelatin film, respectively 134 DEG C and 231
DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon on film
Surface enrichment.
Embodiment 8:
Described method and embodiment 1 are consistent, are not uniquely both that reaction temperature is changed to 40 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 91 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, appearance 2 Tg of modified gelatin film, respectively 196 DEG C and 227
DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon in film
Disorder distribution.
Embodiment 9:
Described method and embodiment 1 are consistent, are not uniquely both that reaction temperature is changed to 40 DEG C.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, it is 91 that the contact angle of modified gelatin film, which increases,o；Differential thermal calorimetric is swept
It retouches instrument test and shows that the Tg of raw material gelatin film is 223 DEG C, appearance 2 Tg of modified gelatin film, respectively 196 DEG C and 227
DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon in film
Disorder distribution.
Embodiment 10:
Described method and embodiment 1 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.04 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film 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, the appearance of modified gelatin film 1
Tg is 227 DEG C；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 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film 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, the appearance of modified gelatin film 1
Tg is 227 DEG C；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 dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.5 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film 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, the appearance of modified gelatin film 1
Tg is 225 DEG C；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 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 100o, illustrate 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, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 198 DEG C and 227 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is enriched in film upper surface.
Embodiment 14:
Described method and embodiment 1 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
1.5 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, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 91o, illustrate 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, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 201 DEG C and 227 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is enriched in film upper surface.
Embodiment 15:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 1, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 60o, illustrate modified gelatin
Film increased hydrophilicity；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 131 DEG C and 202 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is distributed in film middle layer.
Embodiment 16:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 2.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 2, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 65o, illustrate modified gelatin
Film increased hydrophilicity；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 131 DEG C and 209 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is distributed in film middle layer.
Embodiment 17:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 3.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 3, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 69o, illustrate modified gelatin
Film increased hydrophilicity；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 156 DEG C and 219 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is distributed in film middle layer.
Embodiment 18:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 4.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 4, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 60o, illustrate modified gelatin
Film increased hydrophilicity；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, the appearance 2 of modified gelatin film
A Tg, illustrates that modified gelatin film has micro phase separation structure by respectively 197 DEG C and 223 DEG C；Scanning electron microscope-energy dispersion
Spectrum analysis shows that element silicon is distributed in film middle layer.
Embodiment 19:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 5.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 5, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.It connects
Feeler test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 78o, modified gelatin film dredge
It is aqueous there is no significant change；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified gelatin film
There are 2 Tg, respectively 225 DEG C and 202 DEG C, illustrates that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Dispersion spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 20:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 8.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 8 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 78o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 225 DEG C and 202 DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Chromatic dispersion quantity spectrum analysis shows element silicon disorder distribution in film.
Embodiment 21:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 9.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 9 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 78o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 207 DEG C and 222 DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Chromatic dispersion quantity spectrum analysis shows element silicon disorder distribution in film.
Embodiment 22:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 10.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 103o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 127 DEG C and 212 DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Chromatic dispersion quantity spectrum analysis shows that change of gradient is presented in element silicon from film bottom surface to top surface.
Embodiment 23:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 11.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 11 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 68o, modified gelatin film
Hydrophily does 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, modified gelatin film
1 Tg of appearance, be 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 24:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 12.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 12 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 63o, modified gelatin film
Increased hydrophilicity；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 1
Tg is 217 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 25:
Described method and embodiment 1 are consistent, are not uniquely both that the pH of mixed liquor is adjusted to 13.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 13 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 63o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
1 Tg of appearance, be 223 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 26:
Described method and embodiment 22 are consistent, are not uniquely both to be changed to addition 1g gelatin (to account for solution gross mass
1%)。
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 78o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 225 DEG C and 202 DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Chromatic dispersion quantity spectrum analysis shows element silicon disorder distribution in film.
Embodiment 27:
Described method and embodiment 22 are consistent, are not uniquely both to be changed to addition 1g gelatin (to account for solution gross mass
3%)。
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 74o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 215 DEG C and 222 DEG C, illustrate that modified gelatin film has micro phase separation structure；Scanning electron microscope-energy
Chromatic dispersion quantity spectrum analysis shows element silicon disorder distribution in film.
Embodiment 28:
Described method and embodiment 22 are consistent, are not uniquely both to be changed to addition 7g gelatin (to account for solution gross mass
7%)。
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 73o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
1 Tg of appearance, be 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 29:
Described method and embodiment 22 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, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 74o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
1 Tg of appearance, be 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 30:
Described method and embodiment 22 are consistent, are not uniquely both to be changed to addition 0.1g surfactant (it is total to account for solution
The 0.1% of quality).
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 73o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
1 Tg of appearance, be 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 31:
Described method and embodiment 22 are consistent, are not uniquely both to be changed to addition 0.5g surfactant (it is total to account for solution
The 0.5% of quality).
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtains modified gelatin film.
Contact angle test shows that the contact angle of raw material gelatin film is 72o, the contact angle of modified gelatin film is 89o, modified gelatin film
Hydrophobicity does 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, modified gelatin film
2 Tg of appearance, respectively 191 DEG C 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon nothing in film
Sequence distribution.
Claims (5)
1. a kind of pH adjusts method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which is characterized in that including walking as follows
It is rapid:
(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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10, 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；
(3) white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.
2. a kind of pH adjusts method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which is characterized in that including walking as follows
It is rapid:
(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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10, 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；
(3) white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 45 DEG C of normal pressure drying in oven, obtain modified gelatin film.
3. a kind of pH adjusts method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which is characterized in that including walking as follows
It is rapid:
(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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10, 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；
(3) white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.8ml mixed solution and be added drop-wise on gelatin-based bottom, in 45 DEG C of normal pressure drying in oven, obtain modified gelatin film.
4. a kind of pH adjusts method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which is characterized in that including walking as follows
It is rapid:
(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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10, 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 1.0 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；
(3) white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 6, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.
5. a kind of pH adjusts method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which is characterized in that including walking as follows
It is rapid:
(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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10, 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 1.5 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；
(3) white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, HCl is added and adjusts pH of mixed
To 5, measures 0.5ml mixed solution and be added drop-wise on gelatin-based bottom, in 40 DEG C of normal pressure drying in oven, obtain modified gelatin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510970579.9A CN105566661B (en) | 2015-12-22 | 2015-12-22 | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510970579.9A CN105566661B (en) | 2015-12-22 | 2015-12-22 | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105566661A CN105566661A (en) | 2016-05-11 |
| CN105566661B true CN105566661B (en) | 2019-03-22 |
Family
ID=55877338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510970579.9A Active CN105566661B (en) | 2015-12-22 | 2015-12-22 | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105566661B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125759B (en) * | 2021-03-26 | 2023-06-23 | 齐鲁工业大学 | Modified gelatin for paper fireproof flame-retardant coating and preparation method and application thereof |
| CN115124721B (en) * | 2021-03-26 | 2023-09-19 | 齐鲁工业大学 | Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof |
Citations (3)
| 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 |
| CN103436168A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane and glycidol-containing strong-hydrophobicity gelatin leather finishing agent and preparation method |
-
2015
- 2015-12-22 CN CN201510970579.9A patent/CN105566661B/en active Active
Patent Citations (3)
| 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 |
| CN103436168A (en) * | 2013-08-22 | 2013-12-11 | 山东轻工业学院 | Polysiloxane and glycidol-containing strong-hydrophobicity gelatin leather finishing agent and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105566661A (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086779B (en) | Sliding block silicone oil of a kind of ultra-soft and preparation method thereof | |
| CN105837823B (en) | Organic silicon emulsion and preparation method thereof and fabric finishing agent | |
| CN105419350B (en) | Substrate adjusts method and prepares monocyclic oxygen terminated polysiloxane modified gelatin Gradient Film | |
| US8697829B2 (en) | Process for the manufacture of silicone ionomer | |
| CN114941244B (en) | Waterproof finishing method for nylon fabric, waterproof finishing liquid and waterproof component | |
| CN105566661B (en) | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN104262639B (en) | The preparation method of super-hydrophobic cross linking polysiloxane-polysilsesquioxane nanosphere hybrid material | |
| CN107522866A (en) | A kind of preparation method of solvent-free block silicone oil | |
| BRPI0908926B1 (en) | POLYNARBONATE-POLYGIORGANOSYLOXANE AND / OR POLYURETHANE-POLYURGANOSYLOXANE COMPOUNDS, METHOD FOR THEIR MANUFACTURING, ITS USES, AND FORMULATIONS AND COMPOSITIONS UNDERSTANDING THE SAME | |
| CN105399973B (en) | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN105694046A (en) | Preparation method of highly-branched block polyether-aminosiloxane finishing agent | |
| CN105567081B (en) | Mixing glycidol prepares modified gelatin Gradient Film with monocycle oxygen terminated polysiloxane | |
| CN107868253A (en) | A kind of cunning endures the preparation method for increasing deep silicone oil | |
| Cao et al. | Functional polysiloxanes: a novel synthesis method and hydrophilic applications | |
| CN104530330A (en) | Leather finishing agent and preparation method thereof | |
| CN105566662B (en) | It is centrifuged extraction method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| Zhang et al. | Structure of vinyl polysiloxane on properties of polyacrylates film and its pigment printing application | |
| CN105504291B (en) | A kind of linearity block amino-silicone oil softening agent and its preparation method and application | |
| CN105601934B (en) | Modified double-end amino dimethyl silicone polymer of ammonia hydrocarbyl side chain and preparation method thereof | |
| CN105566668B (en) | Solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN103103765B (en) | Self-emulsifying wet rubbing resistant leather top layer coating agent and preparation method thereof | |
| CN105542204B (en) | A kind of preparation method of monocycle oxygen terminated polysiloxane modified gelatin parents' film | |
| CN105384944B (en) | Solvent precipitation prepares monocycle oxygen terminated polysiloxane modified gelatin parents' film | |
| KR20090018819A (en) | Coloured organopolysiloxanes | |
| CN101070388A (en) | Design and preparation for controllable hydrophobic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee after: Qilu University of Technology (Shandong Academy of Sciences) Country or region after: China Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee before: Qilu University of Technology Country or region before: China |