CN115125759B - Modified gelatin for paper fireproof flame-retardant coating and preparation method and application thereof - Google Patents
Modified gelatin for paper fireproof flame-retardant coating and preparation method and application thereof Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention belongs to the field of application of gelatin, and in particular relates to modified gelatin for a paper fireproof flame-retardant coating, a preparation method and application thereof, wherein the modified gelatin is prepared by modifying gelatin by using epoxy polysiloxane (PDMS-E) emulsion drops, the average particle size of the epoxy polysiloxane emulsion drops is 850-1050 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.76; the viscosity of the modified gelatin is 1.05-1.09 mPas, the conversion rate of primary amino groups in the gelatin is 12-14 mol percent, and the consumption of epoxy groups in PDMS-E is 25-28 mol percent. The modified gelatin serving as the fireproof flame-retardant coating layer is coated on the surface of paper to form a uniformly distributed coating, and the epoxy polysiloxane modified gelatin can endow the coating with fireproof, flame-retardant and hydrophobic properties when being coated on the paper, and does not change the material of the paper.
Description
The application is a divisional application of application No. 202110327374.4 (application date 2021-03-26, the invention name is modified gelatin for paper fireproof flame-retardant coating, and preparation method and application thereof)
Technical Field
The invention belongs to the field of gelatin application, and relates to modified gelatin for a paper fireproof flame-retardant coating, and a preparation method and application thereof.
Background
Paper and paper products are generally made from plant fibers, wherein the plant fibers are mainly condensates of the anhydroglucose and are extremely combustible substances, the ignition point of the paper is about 130-230 ℃, and the oxygen index is 15-20%. It is often the ignition material of a fire, and the economic loss per year due to the combustion of paper-based materials is quite large, and the flame retardance of the paper-based materials has become a necessary performance index for some application fields.
The production methods of flame retardant paper can be generally classified into 2 types: (1) Flame-retardant paper is produced by utilizing the flame retardance of special fibers, and the flame-retardant paper is not added with natural cellulose fibers; (2) And (3) adding a flame retardant in the production process of the common natural fiber paper to produce the flame-retardant paper. The special flame-retardant fibers in the first production method mainly comprise carbon fibers, glass fibers, ceramic fibers, aramid fibers, asbestos fibers and the like, and the fibers are inorganic or chemical fibers with flame retardance. The second method for producing the flame-retardant paper is to take common natural fibers as raw materials, and utilize the traditional papermaking process to fill flame retardant for papermaking. The flame retardant elements may be classified into halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, and the like, depending on the type of flame retardant element contained; the flame retardant can be classified into an additive flame retardant and a reactive flame retardant according to the method of use, wherein the additive flame retardant can be classified into an inorganic flame retardant and an organic flame retardant.
However, general organic flame retardants release toxic and corrosive gases when burned, or have disadvantages such as poor thermal stability and high volatility. The organic silicon flame retardant is commonly silicone oil, polysiloxane, silicone resin and the like, and has the advantages of good compatibility with polymers, strong binding force, difficult migration and the like. The organic silicon can form a composite carbon layer during combustion, and the carbon layer has good heat insulation and flame retardance effects and can prevent combustible gas from escaping.
Epoxy polysiloxane (PDMS-E) is a polymer material with flame retardant property, and has good flame retardance and high temperature resistance. However, the nature of epoxy polysiloxanes is oily polymers and cannot be applied directly to flame retardant coatings for paper.
Disclosure of Invention
In order to solve the problem that epoxy polysiloxane cannot be directly applied to a flame-retardant coating of paper, the invention provides modified gelatin for the flame-retardant coating of paper, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a modified gelatin for a fire-resistant and flame-retardant coating of paper, which is characterized in that the gelatin is modified by using epoxy polysiloxane (PDMS-E) emulsion liquid drops, wherein the average particle size of the epoxy polysiloxane emulsion liquid drops is 850-1050 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.76; the viscosity of the modified gelatin is 1.05-1.09 mPas, the conversion rate of primary amino groups in the gelatin is 12-14% (mol percent), and the consumption of epoxy groups in PDMS-E is 25-28% (mol percent).
The modified gelatin molecule secondary structure and the specific content are as follows: 21.0 to 22.0 percent of alpha-helical structure; 31-32% of beta-sheet; beta-rotation angle is 20.5-23%; 24.5 to 26.0 percent of random coil. The microstructure is a uniformly dispersed multilayer structure.
Further preferably, the modified gelatin molecule secondary structure and specific content are: 21.46 to 21.72 percent of alpha-helical structure; beta-sheet 31.18-31.87%; beta-rotation angle is 20.52-22.67%; 24.75 to 25.89 percent of random coil.
Preferably, the molecular weight (Mw) of the gelatin is about 1.40X105 g/mol and the Mw/Mn is 1.43. The primary amino group content in gelatin was 4.95X10 -4 g mol -1 。
The invention adopts grafted PDMS-E emulsion drop modified gelatin, which not only can keep main properties of main chain of gelatin matrix, but also can obtain new properties from grafted side chain. Epoxy polysiloxane is a material with high temperature resistance and flame retardant property, and can be endowed with flame retardant and fire resistant properties by chemical grafting with gelatin.
The preparation method of the modified gelatin comprises the following steps:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H): with hexamethylcyclotrisiloxane (D) 3 ) Is monomer, n-butyllithium (C) 4 H 9 Li) as initiator, benzene as solvent, tetrahydrofuran (THF) as accelerator, dimethyl-hydrosilyl-chlorane (C) 2 H 7 ClSi) as a capping agent, and synthesizing PDMS-H using living anionic polymerization techniques;
the reaction equation:
making n in the process be 6-14;
(2) Preparation of epoxy polysiloxane (PDMS-E): under the action of a catalyst chloroplatinic acid, performing hydrosilylation reaction on Allyl Glycidyl Ether (AGE) and PDMS-H to obtain epoxy polysiloxane (PDMS-E);
the reaction equation is:
(3) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E is taken as a disperse phase, passes through the membrane pores of an SPG membrane emulsifier under the pressure of nitrogen, and is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid to form PDMS-E oil-in-water emulsion;
(4) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin: and (3) regulating the pH value of the gelatin solution to 10.0+/-0.2, dropwise adding the PDMS-E emulsion prepared in the step (3) into the gelatin solution, and stirring to obtain the monodisperse PDMS-E emulsion particle modified gelatin.
Preferably, the specific method of the step (1) is as follows: first C is carried out 4 H 9 Li is dissolved in benzene, D dissolved in benzene is added under the condition of decompressing and introducing argon 3 After a period of reaction, THF is added for a period of time, and then C is injected 2 H 7 Stopping the reaction after ClSi; the product was then filtered, distilled under reduced pressure and purified to give PDMS-H.
Further preferably, D 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is 1.9-2.1:3.9-4.1:1.
Further preferably, C 4 H 9 The volume of Li is 2.3 to 2.5 times that of benzene; the volume of THF is 4.8-5.2 times that of benzene.
Advancing oneStep (D) is preferably added 3 Post-reaction for 28-32 min; after THF is added, the reaction is continued for 7.5 to 8.5 hours.
Preferably, the specific method of the step (2) is as follows: argon is introduced into the AGE, and chloroplatinic acid is added after 25 to 35 minutes; heating to 78-82 ℃, dropwise adding PDMS-H, heating to 108-112 ℃ after the dropwise adding, reacting for 5.5-6.5H, and purifying the product by reduced pressure distillation to obtain the product epoxy polysiloxane (PDMS-E).
Further preferably, the mass ratio of AGE to chloroplatinic acid is 1: 0.011-0.012.
It is further preferred that the molar ratio of PDMS-H to AGE is 1.5 to 1.7:1.
Preferably, in step (3), the SDS/SDBS ratio (w/w) is 0.55-0.67, and the total concentration of the surfactant in the deionized water is 0.45-0.50 wt%.
Preferably, in step (3), the SPG membrane has an average pore size of 0.7.+ -. 0.1. Mu.m.
Preferably, in the step (3), the concentration of glacial acetic acid in the deionized water is 2-3 mol/L.
Preferably, in the step (3), the mass fraction of PDMS-E in the oil-in-water emulsion is 0.95-1.05%.
Preferably, the specific method of the step (4) is as follows:
dissolving gelatin in distilled water to prepare gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the PDMS-E emulsion prepared in the step (3) is mixed with the water according to the proportion of 19-21 mL.min -1 Is added to the gelatin solution and stirred at 49-51 c for 5-6 hours.
It is further preferred that the concentration of the sodium hydroxide solution in the step (4) is 1.8 to 2.2mol L -1 。
It is further preferred that the mass percentage of gelatin in the gelatin solution in step (4) is 4.95 to 5.05wt%.
The invention also provides application of the modified gelatin in a fireproof flame-retardant coating of paper.
Fire-resistant paper, modified by the aboveThe modified gelatin is used as a flame-retardant and fire-resistant coating, and the spraying amount of the modified gelatin on the surface of the paper base material is 0.16-0.20 mL/cm 2 。
Preferably, the thickness of the paper base is 0.1-1.6 mm, and the basis weight is 19-80 g/m 2 。
Further preferably, the paper base index is: the thickness is 1-1.6 mm, and the ration is 19-80 g/m 2 The tensile strength is 12-20 MPa, the elongation at break is 7-10%, and the water content is 5-8%.
Preferably, the paper base is writing paper, copying paper and xerographic paper.
Preferably, the flame retardant properties are measured according to GB/T14656-2009 national standard: the average continuous burning time is 2-5 s; the average burning time is 20-45 s; the average carbonization length is 80-105 mm.
The preparation method of the fire-resistant paper comprises the steps of preparing the paper pulp into the molded paper, uniformly coating the modified gelatin flame retardant on the paper, and drying at 20-25 ℃ for 12-24 h.
The invention has the following technical effects:
the invention uses monodisperse PDMS-E emulsion particles to modify gelatin, the particle size of the emulsion particles is 850-1050 nm, and the viscosity is 1.05-1.19 mPas. Has the following advantages:
1. the modification temperature of the modified gelatin is 50 ℃, the condition is mild, and compared with the prior art (the reaction temperature of other methods is above 60 ℃), the modification method can ensure the structural integrity of the gelatin, and the denaturation or gel change is not easy to occur;
2. the emulsion disclosed by the invention has good stability, emulsion particles can be uniformly dispersed along with the increase of the reaction time, the particle size can not be continuously increased along with the reaction time, and aggregation and demulsification phenomena generated by long-time placement can be avoided. The emulsion with good stability can maintain uniform dispersion and uniform structure, and the modified gelatin has uniform properties when in use and can not generate uneven coating phenomenon.
3. The modified material used in the invention uses the PDMS-E latex particles which are nontoxic and pollution-free, and can not cause harm to human health;
4. the gelatin/PDMS-E latex polymer (modified gelatin) prepared by the invention has uniform and stable morphology, and the defect that gelatin is easy to deteriorate is overcome; the existence of anionic surfactants (SDS, SDBS) makes the polymer have strong adhesion capability, and simultaneously PDMS-E endows the material with high temperature resistance, flame retardance, flexibility and other properties.
5. Paper used in daily life is very easy to burn when meeting a flame or a high-heat environment, and especially important files or art works are very afraid of burning. The gelatin is coated on the surface of the paper to form a uniformly distributed coating, and the epoxy polysiloxane modified gelatin can endow the coating with fire-resistant, flame-retardant and hydrophobic properties when used for coating the paper, and the material of the paper is not changed. When the modified gelatin is used as the fire-resistant flame-retardant coating layer to be coated on the surface of the paper, the paper is not easy to ignite, the burnout speed of the paper is prolonged, and the rescue files and the fire extinguishing time can be increased.
Drawings
FIG. 1 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of example 1;
FIG. 2 is an optical microscope image and a particle size distribution diagram of monodisperse emulsion particles of comparative example 1;
FIG. 3 is a graph of the microtopography of the modified gelatin of example 1;
FIG. 4 is a graph of the micro-morphology of the modified gelatin of comparative example 1.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and examples.
Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), allyl Glycidyl Ether (AGE) and glacial acetic acid are all available from Alfa Aesar (Alfa Aesar) Inc. of Shanghai China and SDS and SDBS require recrystallization from ethanol prior to use. Hexamethylcyclotrisiloxane (D3), n-butyllithium (C) 4 H 9 Li) and chlorodimethylsilane (C) 2 H 7 ClSi) was purchased from Sigma Aldrich. Benzene and Tetrahydrofuran (THF) were purchased from chinese pharmaceutical groups company (beijing). Chloroplatinic acid formula H 14 Cl 6 O 6 Pt, molecular weight 517.9096, dark yellow transparent liquid, available from atanan platinum source chemical limited. SPG porous glass membranes with pore size of 0.5 μm were purchased fromChinese pharmaceutical group Co. Pigskin A gelatin is purchased from China medical group company, and is used after dialysis.
Molecular weight of gelatin (M) as determined by gel permeation chromatography w ) About 1.40×10 5 g mol -1 ，M w /M n 1.43. The primary amino group content of gelatin was measured by Van-Slike method at 50℃and found to be 4.95X10 -4 g mol -1 . Van-Slike method is a specialized method for determining the amino content of amino acids or protein molecules. The method is to determine the primary amino content in amino acid or protein by reacting nitrous acid with the primary amino in amino acid or protein. The error in primary amino content in gelatin measured using this method is less than 1%.
The physical size of the emulsion droplets and the Polymer Dispersion Index (PDI) were measured with a laser particle size analyzer (Zetasizer 2000, malvern instruments, uk). The instrument converts the diffraction spectrum into a particle size distribution curve based on Mie scattering theory. First, the emulsion was carefully placed into a color matching tube. The tube was then placed in a ZetaSizer 2000 laser particle meter to measure PDI or electrophoretic mobility.
The viscosity of the sample in the reaction liquid at different time is measured by using a black-bone viscometer, the constant temperature tank is adjusted to 50 ℃, the black-bone viscometer is vertically placed in the constant temperature tank, 15mL of the sample to be measured is taken and added into the viscometer, the two pipes except the capillary are sealed, the liquid level is pumped to the upper scale mark of the glass ball at the upper end of the capillary by using an air pumping device, meanwhile, the air pumping device is removed, and the time required for the liquid level to flow down from the upper scale mark to the lower scale mark is recorded, so that the viscosity is calculated.
Raman spectra of reaction samples in the reaction solutions at different times were recorded with a raman spectrometer, raman spectral data were measured using an inVia type (Renishaw, uk) laser confocal raman spectrometer, first focused on the capillary surface using an optical microscope mode, stage focused on the particle surface was adjusted, and raman spectral data were obtained using a 633nm laser source. The consumption of epoxy groups is detected by Raman spectroscopy, 858cm -1 The peak represents an epoxy group.
The Zeta potential of the reaction sample in the reaction liquid at different times is measured by a Zetasizer Nano ZS type (Malvern, UK) laser particle sizer, the sample is sucked by a syringe and slowly injected into a cuvette with the Zeta potential, and a specific Zeta potential value can be measured by putting the cuvette into a sample tank of the instrument without bubbles. The experimental results were repeated 3 times.
The morphology of PDMS-E latex particles was characterized by Transmission Electron Microscopy (TEM). First, a TEM sample was prepared. The mixture of gelatin and emulsion was diluted about 20-fold at 50 ℃. The drop-like mixture was dropped onto the copper mesh. The excess liquid was absorbed by filter paper and dried with nitrogen at room temperature. TEM images were measured with JEM-2100.
The synthetic method of the epoxy polysiloxane (PDMS-E) used in the embodiment of the invention is as follows:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H):
first 10mL of benzene was added to the flask, followed by 24mL of C 4 H 9 Li, 45.99 g of D after 3-5 times of vacuumizing and argon introducing operations 3 Dissolved in 40mL benzene and added dropwise to the flask. After 30min of reaction, 50mL of Tetrahydrofuran (THF) was added and the reaction was continued for 8h. Subsequently, 11mL of C 2 H 7 ClSi was injected into the flask to terminate the reaction. The obtained product PDMS-H is purified by filtration, reduced pressure distillation and the like, and 45.44g of the product is obtained, and the yield is 56.11%. D (D) 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is about 2:4:1.
(2) Preparation of epoxy polysiloxane (PDMS-E): 8.51g of AGE was charged into the flask, and after 30 minutes, 40. Mu.L of chloroplatinic acid (mass of chloroplatinic acid: 0.097 g) was added thereto. And under the condition of keeping argon gas, the reaction temperature is increased to 80 ℃, PDMS-H with the molar ratio of 1.6:1 with AGE is added at the speed of 1-2 d/s, after the dropwise addition is finished, the reaction temperature is continuously increased to 110 ℃, the reaction is continued for 6 hours, and then the reaction is finished. The product epoxy polysiloxane (PDMS-E) is obtained through purification by means of reduced pressure distillation and the like, and the yield is 84.32%.
Example 1
A modified gelatin for a fire-resistant flame-retardant coating of paper, the preparation method comprises the following steps:
(1) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E was used as the dispersed phase, and was passed through SPG membrane pores (average pore diameter of SPG membrane 0.7 μm) under nitrogen pressure, added to deionized water (glacial acetic acid concentration 2 mol/L) containing SDS, SDBS and glacial acetic acid, and stirred at a rotation speed of 1300rpm to form PDMS-E oil-in-water emulsion (PDMS-E mass percentage in oil-in-water emulsion 1%). The SDS/SDBS ratio (w/w) was 0.67 and the total concentration of surfactant in deionized water was 0.5wt%.
(2) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin: the stock solution was prepared by dissolving gelatin in distilled water (5 wt%) and after 3 hours the gelatin solution was heated to 50 ℃ to ensure complete dissolution of gelatin. Subsequently, the pH of each prepared gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E emulsion prepared above was added to the gelatin solution at a rate of 20ml/min and stirred at 50℃for 5 hours.
The mass ratio of PDMS-E and gelatin in PDMS-E emulsion is 1:0.757. monodisperse PDMS-E latex particle modified gelatins with a viscosity of 1.057mPas were obtained. The particle size of the epoxy polysiloxane emulsion droplets obtained in example 1 was 955.+ -. 70nm; the morphology is a uniformly distributed multilayer structure (shown in fig. 3), the conversion rate of primary amino groups in gelatin is 13.73% (mole percent), and the consumption of epoxy groups in PDMS-E is 27.27% (mole percent).
Example 2
A modified gelatin for a fire-resistant flame-retardant coating of paper, the preparation method comprises the following steps:
(1) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E was used as the dispersed phase, and was passed through SPG membrane pores (average pore diameter of SPG membrane 0.7 μm) under nitrogen pressure, added to deionized water (acetic acid concentration 2 mol/L) containing SDS, SDBS and glacial acetic acid, and stirred at a rotation speed of 1300rpm to form PDMS-E oil-in-water emulsion (mass percentage of PDMS-E in oil-in-water emulsion 1%). The SDS/SDBS ratio (w/w) was 0.55 and the total concentration of surfactant in deionized water was 0.45wt%.
(2) Monodisperse PDMS-E emulsion particle and gelatin reaction pairGelatin is modified: the stock solution was prepared by dissolving gelatin in distilled water (5 wt%) and after 3 hours the gelatin solution was heated to 50 ℃ to ensure complete dissolution of gelatin. Subsequently, the pH of each prepared gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E emulsion prepared above was stirred at 20ml min -1 Is added to the gelatin solution and stirred at 50 c for 5 hours.
The mass ratio of PDMS-E and gelatin in PDMS-E emulsion is 1:0.757. monodisperse PDMS-E latex particle modified gelatins with a viscosity of 1.09mPas were obtained. The epoxy polysiloxane emulsion droplets obtained in example 2 had a particle size of 864.+ -.60 nm and a morphology of a uniformly distributed multilayer structure, the conversion of primary amino groups in gelatin was 12.84% (mole%) and the epoxy group consumption in PDMS-E was 25.62% (mole%).
Comparative example 1
A modified gelatin and its preparation method are provided:
otherwise, the same as in example 1 was conducted except that the SPG film had an average pore diameter of 0.5. Mu.m; change SDS: SDBS is 0.25, the total concentration of the surfactant is 0.3wt%, monodisperse emulsion particles with the particle size of 366+/-70 nm are obtained, and then gelatin is modified. The emulsion stability is reduced, and the heat resistance, the hydrophobicity and the flexibility are correspondingly reduced.
TEM pictures of the modified gelatin showed morphology of aggregated small particles (FIG. 4), with a primary amino conversion of 7.5% (mole percent) in the gelatin.
Comparative example 2
A modified gelatin, the preparation method:
other than the same as in example 1, the average pore diameter of the SPG membrane was 0.7. Mu.m, SDS was changed: SDBS is 0.67, the total concentration of the surfactant is 0.55wt%, monodisperse emulsion particles with the particle size of 1100+/-55 nm are obtained, and then gelatin is modified. The viscosity was 1.02 mPa.s and the conversion of primary amino groups in the gelatin was 13.95 mol%.
1. The particle sizes of the obtained monodisperse PDME-S emulsion particles with different particle sizes
The size of the latex particles produced was described by mean particle size and dispersion index (PDI), which indicated that the PDI of the emulsion particles was less than 0.1, indicating that the emulsion particles were uniformly distributed in the solution. Particle size variation Coefficient (CV) of less than 21% also indicates a sufficiently narrow particle size distribution. The monodisperse PDME-S latex particles are suitable for modifying gelatin to obtain the modified gelatin with stable performance.
2. Electron microscopy of modified gelatins of different examples and comparative examples
The reaction of gelatin with PDMS-E latex particles is affected by a number of factors, the morphology of which is also very complex. In comparative example 1, the aggregation of latex particles of small particle size scale (less than 400 nm) was observed visually using a TEM image. This phenomenon also occurs on other particle size scales, but as the particle size decreases, agglomeration increases. In example 1, core-shell structures appear in large scale (greater than 850 nm) emulsions. Over time, gelatin molecules gradually adsorb onto latex particles and chemically bind. It stretches on the surface to form a shell layer, and the PDMS section is curled into a core. The hydrophobic portion of the gelatin penetrates the oil phase and the hydrophilic portion is thoroughly mixed within the shell. Meanwhile, a multi-layer structure was found in the large particle size emulsion. The outermost layer is a polypeptide layer, the inner layer is a PDMS segment layer, then the polypeptide layer and the PDMS layer are alternately arranged, and the multilayer structure is formed as a result of stable grafting reaction of gelatin and PDMS-E.
The particle size of the modified gelatin under the optical microscope and the particle size of the modified gelatin under the TEM are somewhat different because: the latex particles under the optical microscope are detected in the latex, the particle size is consistent with the actual particle size result, and the modified gelatin particles in the TEM image can collapse and shrink to a certain extent after being dripped on a copper mesh (carbon support film) and moisture-dried during the test. The size of the modified gelatin in the TEM image is smaller than the particle size of the latex particles, and the reason why some of the latex particles in the TEM image are not significantly spherical is that the TEM image is merely for observing the microstructure, and is not for reflecting the size of the modified gelatin particle size in the actual application state.
3. Secondary structure content of modified gelatins of different examples and comparative examples
TABLE 1
Beta-sheet is a regular secondary structure, which is favorable for the extension of polypeptide molecular chains, so that the exposure of primary amino groups is promoted, and the formation of the beta-sheet structure enables the primary amino groups of gelatin to be fully exposed on the surface of latex particles. Gelatin spreads uniformly in latex particles to promote chemical grafting reaction of the latex particles and gelatin, so that the viscosity of the emulsion is reduced due to the beta-sheet structure. The particle size, the secondary structure, the grafting rate and other reasons affect the performance of the modified gelatin together, so that different modified gelatins have different characteristics and application prospects.
4. Modified gelatin emulsion as fire-resistant and flame-retardant coating for paper
A fire-resistant paper is prepared from modified gelatin through coating fire-resistant flame-retarding layer on paper, and preparing flame-retarding coating agent. To test the effect of the modified gelatin of the present invention on paper properties for use in paper flame retardant coatings, three different papers were selected as test subjects. Respectively, xerographic papers (national standard ZBY32004-86, quantitative 70.0 g/m) 2 Writing paper (national standard GB12654-90, quantitative 50.0 g/m) 2 Tensile strength 12.09MPa, elongation at break 7.4%), copy paper (: GB1911-91 with a basis weight of 19.0g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength 19.38MPa; elongation at break 7.3%). Three kinds of paper were prepared as substrates to 70X 210mm in the same size. Then the prepared emulsion is dripped on paper by a dropper, and the dripping amount is about 0.18mL/cm according to the single-sided surface area of the paper 2 A distance of about 5cm was maintained between the substrate and the dropper. And uniformly dripping or spraying by using a spray gun on the surface, standing to uniformly coat, and preserving for 12 hours at the room temperature of 25 ℃ to obtain a test paper sample. The blank sample was an uncoated paper substrate.
Horizontal flame test: the samples were subjected to a horizontal flame test using methane flame (around 500 ℃) and the total burn time of the samples was evaluated. Flame retardant property detected according to GB/T14656-2009 national standard. The national standard for flame retardant paper specifies: the average continuous burning time is less than or equal to 5s; the average burning time is less than or equal to 60s; the average carbonization length is less than or equal to 115mm.
TABLE 2
From the test results, it was found that the paper without the modified gelatin was completely burned and almost no residue was left. After coating the modified gelatin, a burning residue was found, which means that the flame spread rate on the treated samples was slowed down. The result shows that the modified gelatin coating has certain fireproof performance.
Comparison test:
when the coating amount of the modified gelatin is 0.10mL/cm 2 The horizontal flame test results are shown in Table 3.
TABLE 3 Table 3
When the coating amount of the modified gelatin is 0.30mL/cm 2 The horizontal flame test results are shown in Table 4.
TABLE 4 Table 4
It can be seen that when the coating amount of the modified gelatin is too small, the flame retardant effect is poor; when the coating amount is too large, the flame retardant effect is not obviously increased, and the coating amount is too large, so that the coating is too thick, the softness of the paper pattern can be influenced, and the smoothness of writing can be influenced when the paper pattern is used for writing paper. Therefore, the modified gelatin of the present invention has an optimal coating amount of 0.16 to 0.2mL/cm 2 。
Claims (10)
1. A fire-resistant paper is characterized in that modified gelatin is used as a fire-retardant fire-resistant coating, and the spraying amount of the modified gelatin on the surface of a paper base material is 0.16-0.20 mL/cm 2 ；
The modified gelatin is as follows: the method comprises the steps of modifying gelatin by using monodisperse epoxy polysiloxane emulsion droplets, wherein the average particle size of the monodisperse epoxy polysiloxane emulsion droplets is 850-1050 nm, and the mass ratio of the gelatin to the epoxy polysiloxane is 1:0.75 to 0.76; the viscosity of the modified gelatin is 1.05-1.09 mPas, the conversion rate of primary amino groups in the gelatin is 12-14 mol percent, and the consumption of epoxy groups in the epoxy polysiloxane is 25-28 mol percent;
preparation of monodisperse epoxy polysiloxane emulsion droplets:
epoxy polysiloxane as disperse phase is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid under nitrogen pressure through the membrane pores of an SPG membrane emulsifier to form epoxy polysiloxane oil-in-water emulsion; the ratio (w/w) of SDS/SDBS is 0.55-0.67, and the total concentration of the surfactant in the deionized water is 0.45-0.50 wt%; the average pore diameter of the SPG film is 0.7+ -0.1 μm;
the method for modifying gelatin by monodisperse epoxy polysiloxane emulsion droplets comprises the following steps:
dissolving gelatin in distilled water to prepare gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the prepared PDMS-E emulsion is treated with the method of 19 to 21 mL.min -1 Is added to the gelatin solution and stirred at 49-51 c for 5-6 hours.
2. A fire resistant paper as claimed in claim 1, wherein,
the flame retardant property detected according to GB/T14656-2009 national standard is: the average continuous burning time is 2-5 s; the average burning time is 20-45 s; the average carbonization length is 80-105 mm.
3. The fire resistant paper according to claim 1, wherein the paper base is indexed as: the thickness is 1-1.6 mm, and the ration is 19-80 g/m 2 The tensile strength is 12-20 MPa, and the elongation at break is 7-10%.
4. A fire resistant paper according to claim 3, wherein the paper base has a thickness of 0.1 to 1.6mm and a basis weight of 19 to 80g/m 2 。
5. The fire resistant paper according to claim 1, wherein the modified gelatin molecule secondary structure and specific content are: 21.0 to 22.0 percent of alpha-helical structure; 31-32% of beta-sheet; beta-rotation angle is 20.5-23%; 24.5 to 26.0 percent of random coil.
6. The fire resistant paper according to claim 1, wherein the glacial acetic acid concentration in deionized water is 2-3 mol/L.
7. The fire resistant paper according to claim 1, wherein the mass fraction of epoxy polysiloxane in the oil-in-water emulsion is 0.95-1.05%.
8. Refractory paper according to claim 1, wherein the sodium hydroxide solution has a concentration of 1.8 to 2.2mol L -1 。
9. The fire resistant paper according to claim 1, wherein the mass percentage of gelatin in the gelatin solution is 4.95-5.05 wt%.
10. The method for preparing fire-resistant paper according to any one of claims 1 to 9, characterized in that after the pulp is made into a molded paper, the modified gelatin flame retardant is uniformly coated on the paper and dried at 20 to 25 ℃ for 12 to 24 hours.
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