CN105399973B - Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film - Google Patents
Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film Download PDFInfo
- Publication number
- CN105399973B CN105399973B CN201510970528.6A CN201510970528A CN105399973B CN 105399973 B CN105399973 B CN 105399973B CN 201510970528 A CN201510970528 A CN 201510970528A CN 105399973 B CN105399973 B CN 105399973B
- Authority
- CN
- China
- Prior art keywords
- gelatin
- modified gelatin
- terminated polysiloxane
- monocycle oxygen
- film
- 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
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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to freeze-dryings 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 the middle layer after taking layering is mixed with water, ethyl alcohol is added, after mixing, 0.5~0.8ml mixing drop is measured on gelatin-based bottom, stands 12~18h, it is dry using freeze-drying with liquid nitrogen frozen, obtain 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 freeze-drying 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 freeze-drying preparation monocycle oxygen terminated polysiloxane modification
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:
Freeze-drying 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 2000 is single epoxy-capped poly-
The dosage of siloxanes is 0.5 ~ 1.0 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 is added into white turbid, is uniformly mixed, the volume ratio of ethyl alcohol and reaction solution is (3~5): 1, it measures
0.5~0.8ml mixing drop stands 12~18h on gelatin-based bottom, dry using freeze-drying with liquid nitrogen frozen, obtains
Gradient Film.
The present invention has following significant using freeze-drying 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.
Freeze-drying 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, in 40 DEG C
Normal pressure drying in oven obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified bright
It is 102 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 100 DEG C and 225 DEG C
Micro phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows ladder is presented in element silicon from film bottom surface to top surface
Degree variation.
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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, in 45 DEG C
Normal pressure drying in oven obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified bright
It is 85 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 218 DEG C
Micro phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, in 50 DEG C
Normal pressure drying in oven obtains modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified bright
It is 85 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 165 DEG C and 203 DEG C
Micro phase separation 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 freeze-drying.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 95 that the contact angle of gelatin film, which increases, afterwardso, illustrate that the hydrophobicity of modified gelatin film improves；The test of differential thermal calorimetric scan instrument shows
The Tg of raw material gelatin film is 223 DEG C, and 2 Tg of appearance of modified gelatin film, illustrate modified gelatin by respectively 135 DEG C and 233 DEG C
Film has micro phase separation structure；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon is in from film bottom surface to top surface
Existing change of gradient.
Embodiment 5:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.8ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 96 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 134 DEG C and 231 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows change of gradient is presented in element silicon from film bottom surface to top surface.
Embodiment 6:
Described method and embodiment 4 are consistent, are not uniquely both that mixed liquor and ethyl alcohol volume ratio are changed to 4:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 4:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 90 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 157 DEG C and 222 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 7:
Described method and embodiment 4 are consistent, are not uniquely both that mixed liquor and ethyl alcohol volume ratio are changed to 5:1.
White product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 5:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 92 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 140 DEG C and 230 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 8:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 85 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 176 DEG C and 220 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 9:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 82 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 186 DEG C and 219 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 10:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 89 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 163 DEG C and 229 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 11:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 72o, modified
It is 82 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 169 DEG C and 221 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 12:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 89 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 193 DEG C and 223 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 13:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 73 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 197 DEG C and 220 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 14:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 75 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 189 DEG C and 215 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 15:
Described method and embodiment 4 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 79 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 189 DEG C and 214 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 16:
Described method and embodiment 4 are consistent, are not uniquely both that the dosage of monocycle oxygen terminated polysiloxane is changed to gelatin
0.6 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 83 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 187 DEG C and 224 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 17:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 91 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 177 DEG C and 213 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 18:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 85 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 165 DEG C and 212 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 19:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 74 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 187 DEG C and 227 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 20:
Described method and embodiment 4 are consistent, are not uniquely both to be changed to that 3g 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 83 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 169 DEG C and 217 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 21:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 85 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 176 DEG C and 214 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 22:
Described method and embodiment 4 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, add then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.Contact angle test shows that the contact angle of raw material gelatin film is 75o, modified
It is 78 that the contact angle of gelatin film, which increases, afterwardso；The test of differential thermal calorimetric scan instrument shows that the Tg of raw material gelatin film is 223 DEG C, modified
2 Tg of appearance of gelatin film, illustrate that modified gelatin film has micro phase separation structure by respectively 185 DEG C and 224 DEG C；Scanning electron is aobvious
Micro mirror-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 23:
Described method and embodiment 4 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, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, freezed with liquid nitrogen, be then freeze-dried, obtain 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
1 Tg of appearance of film is 225 DEG C；Scanning electron microscope-energy dispersive spectrum is analysis shows element silicon disorder distribution in film.
Embodiment 24:
Described method and embodiment 4 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, NaOH is added and adjusts mixed liquor
PH to 10 measures 0.5ml mixed solution and is added drop-wise on gelatin-based bottom, freezed with liquid nitrogen, be then freeze-dried, obtain 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
2 Tg of appearance of film, respectively 191 DEG C 225 DEG C；Scanning electron microscope-energy dispersive spectrum analysis shows element silicon in upper table
Face enrichment.
Claims (6)
1. freeze-drying 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 0.65mL2 mol/L 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；
(3) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
2. freeze-drying 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 0.65mL2 mol/L 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；
(3) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 4:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
3. freeze-drying 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 60 DEG C, and after surfactant is completely dissolved, the hydroxide of 0.65mL2 mol/L 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；
(3) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
4. freeze-drying 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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 9.0, 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；
(3) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
5. freeze-drying 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 0.65mL2 mol/L is added
Sodium, adjusting reaction pH is 10.0, and 7g 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) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
6. freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film, which comprises the steps of:
(1) the addition 0.5g 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 10.0, 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；
(3) middle layer white product and deionized water are uniformly mixed according to the ratio that mass ratio is 1:1, then according to mixed liquor with
The ratio that ethyl alcohol volume ratio is 3:1 is uniformly mixed, and is measured 0.5ml mixed solution and is added drop-wise in polytetrafluoroethylene (PTFE) substrate, uses liquid nitrogen
It freezes, is then freeze-dried, obtain modified gelatin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510970528.6A CN105399973B (en) | 2015-12-22 | 2015-12-22 | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510970528.6A CN105399973B (en) | 2015-12-22 | 2015-12-22 | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105399973A CN105399973A (en) | 2016-03-16 |
| CN105399973B true CN105399973B (en) | 2019-02-15 |
Family
ID=55465760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510970528.6A Active CN105399973B (en) | 2015-12-22 | 2015-12-22 | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105399973B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125758B (en) * | 2021-03-26 | 2023-04-11 | 齐鲁工业大学 | Modified gelatin for paper fire-resistant 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 (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 |
-
2015
- 2015-12-22 CN CN201510970528.6A patent/CN105399973B/en active Active
Patent 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105399973A (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086779B (en) | Sliding block silicone oil of a kind of ultra-soft and preparation method thereof | |
| CN105419350B (en) | Substrate adjusts method and prepares monocyclic oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN105399973B (en) | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN105567081B (en) | Mixing glycidol prepares modified gelatin Gradient Film with monocycle oxygen terminated polysiloxane | |
| CN114941244B (en) | Waterproof finishing method for nylon fabric, waterproof finishing liquid and waterproof component | |
| 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 | |
| CN105566661B (en) | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN106118314A (en) | Modified urethane acrylate water-borne wood latex and preparation method thereof | |
| CN107868253A (en) | A kind of cunning endures the preparation method for increasing deep silicone oil | |
| CN105694046A (en) | Preparation method of highly-branched block polyether-aminosiloxane finishing agent | |
| US20130172510A1 (en) | Process for the manufacture of silicone ionomer | |
| Cao et al. | Functional polysiloxanes: a novel synthesis method and hydrophilic applications | |
| CN103436167A (en) | Polysiloxane, glycidol and quaternary ammonium salt-containing multifunctional gelatin leather finishing agent and preparation method | |
| CN105566662B (en) | It is centrifuged extraction method and prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| CN104530330A (en) | Leather finishing agent and preparation method thereof | |
| CN103436169B (en) | A kind of germ resistance gelatin hide finishes and preparation method containing polysiloxane and quaternary ammonium salt | |
| CN105601934B (en) | Modified double-end amino dimethyl silicone polymer of ammonia hydrocarbyl side chain and preparation method thereof | |
| Zhang et al. | Structure of vinyl polysiloxane on properties of polyacrylates film and its pigment printing application | |
| US6239211B1 (en) | Emulsions containing silicone polymers | |
| CN105566668B (en) | Solvent subscription prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film | |
| US20130317243A1 (en) | Polysiloxane-N, N-Dihydrocarbylene Sugar-Modified Multiblock Copolymer And Method For Producing The Same | |
| CN105504291B (en) | A kind of linearity block amino-silicone oil softening agent and its preparation method and application | |
| CN103103765B (en) | Self-emulsifying wet rubbing resistant leather top layer coating agent and preparation method thereof | |
| CN108530635A (en) | A kind of manufacturing method of the hydrophilic block silicone oil of quaternary ammonium salt sealing end |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211125 Address after: 250303 2-3-2a039, second floor, building 3, zone 2, Hexin 2025, Jinan innovation Valley, Changqing District, Jinan City, Shandong Province Patentee after: Shandong Shanke Meigu Technology Development Co.,Ltd. Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee before: Qilu University of Technology |