CN115124720A - Modified gelatin for coating printing and dyeing adhesive and preparation method and application thereof - Google Patents
Modified gelatin for coating printing and dyeing adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN115124720A CN115124720A CN202110325823.1A CN202110325823A CN115124720A CN 115124720 A CN115124720 A CN 115124720A CN 202110325823 A CN202110325823 A CN 202110325823A CN 115124720 A CN115124720 A CN 115124720A
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- gelatin
- pdms
- coating
- modified
- dyeing
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Images
Classifications
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- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the field of gelatin application, and particularly relates to modified gelatin for a coating printing and dyeing adhesive, and a preparation method and application thereof, wherein the modified gelatin is obtained by modifying gelatin by using epoxy polysiloxane (PDMS-E) emulsion droplets, the average particle size of the epoxy polysiloxane emulsion droplets is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1: 0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12 mPa & s, the primary amino group conversion rate of the gelatin is 11-13% (mol percent), and the consumption of epoxy groups in PDMS-E is 22-24% (mol percent). The modified gelatin of the invention is used as a coating printing and dyeing adhesive to play a role in carrying between the fabric and the coating, and solves the problems of uneven coating and over-thick coating of the adhesive caused by over-high viscosity of the gelatin; and the heat resistance, flexibility and color fastness of the fabric are improved.
Description
Technical Field
The invention belongs to the field of gelatin application, and relates to modified gelatin for a coating printing and dyeing adhesive, and a preparation method and application thereof.
Background
The pigment dyeing has the advantages of wide fiber adaptation range, complete color spectrum, convenient color matching, small water consumption, energy conservation, consumption reduction and the like, thereby being widely praised in the dyeing and finishing industry. Unlike dyes, coatings do not have an affinity for fiber fabrics and require binders to fix the coatings to the fabric surface, and therefore binder preparation technology is one of the key technologies for developing pigment dyeing. The current binders for pigment printing are basically oil/water type emulsions of polymers, and under certain process conditions, the binders are treated on the surface of the fabric, and the binders can form a film to fix the paint on the fabric. Gelatin is an extremely important protein biomass material, is widely applied to various fields, particularly food, medicine and chemical engineering, and is also a raw material of a high-value adhesive.
Gelatin has long been used as an adhesive, and has the advantages of short glue layer solidification time, good adhesive force to wood and the like, high adhesive strength, simple glue mixing, no need of adding other additives and the like. However, the single gelatin adhesive has the defects of large viscosity, difficult glue brushing and leveling, poor stability, larger change of viscosity along with environment, low film forming fastness caused by extremely strong hydrophilicity of the gelatin and the like. Therefore, when gelatin is used as an adhesive, it needs to be modified. The molecular structure of gelatin mainly contains amino (-NH) 2 ) Carboxyl (-COOH), hydroxyl (-OH), mercapto (-SH), etc., the presence of which provides the possibility of gelatin modification.
Chinese patent document CN106833455A (201710079034.8) provides a preparation method of a modified gelatin-acrylic resin adhesive, which adopts potassium persulfate to initiate, polymerize and complete reaction at a temperature of 75-90 ℃ to obtain a yellow transparent adhesive with a solid content of 45% and a viscosity of 200-300 mPas. However, when the gelatin is applied to a pigment dyeing binder, the viscosity of the gelatin is preferably less than 100 mPas, and the gelatin structure is easily broken due to a high modification temperature, and thus the gelatin is easily denatured or gelled.
Chinese patent document CN106192473A (201610674824.6) discloses a polylysine-gelatin composite pigment dyeing adhesive, which belongs to the field of printing and dyeing, and is prepared by mixing polylysine and gelatin according to the weight ratio of 1: 150-170, wherein the preparation method comprises the steps of mixing a polylysine alcohol preparation and gelatin according to the weight ratio, and stirring for 20-30 hours under the irradiation of ultraviolet light; after the irradiation is finished, placing the mixture into a refrigerator for 24-36 hours, standing at a low temperature, taking out from the refrigerator, and immediately drying at a high temperature; the composite pigment dyeing adhesive and the paint are mixed according to the weight ratio of 1: 3-5 and applied to the textile, so that the dyeing depth of the paint can be obviously improved, the rubbing fastness and the washing fastness of the dyed fabric are improved, and the influence on the hand feeling of the fabric is small. However, the composite material of polylysine and gelatin in the patent is crosslinked by ultraviolet irradiation, the polylysine has strong hygroscopicity, and the modified gelatin has no hydrophobicity; and acidic polysaccharides, hydrochloride, phosphate, copper ions, etc. may be bonded thereto during use to lower the activity.
Disclosure of Invention
The invention provides a modified gelatin for a coating printing and dyeing adhesive, and a preparation method and application thereof, aiming at solving the problems of high viscosity, instability, difficult use and the like of the gelatin when the gelatin is used for the coating printing and dyeing adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified gelatin for the coating printing and dyeing adhesive is modified by epoxy polysiloxane (PDMS-E) emulsion droplets, wherein the average particle size of the epoxy polysiloxane emulsion droplets is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1: 0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12 mPa & s, the primary amino group conversion rate of the gelatin is 11-13% (mol percent), and the consumption of epoxy groups in PDMS-E is 22-24% (mol percent).
The modified gelatin has the secondary structure content as follows: beta-sheet is 30-31%; the random crimp is 26.2-27.5%; the alpha-helical structure is 21.4-23.5%; the beta-turn is 19.8-20.2%.
Preferably, the gelatin has a molecular weight (Mw) of 1.40X 10 5 g/mol, Mw/Mn 1.43, primary amino group content in gelatin 4.95X 10 -4 g mol -1 . The micro-morphology of the modified gelatin is a uniformly distributed shell-core structure.
The invention adopts the grafted PDMS-E emulsion to modify the gelatin, not only can the main performance of the parent body of the gelatin be kept, but also the modified polymer can obtain new performance from the grafted side chain. When the modified gelatin is used for treating the surface of the fabric, a film is formed to fix the coating on the fabric. The existence of the anionic surfactant enables the polymer to have strong adhesive capacity, and simultaneously endows the material with performances such as hydrophobicity, heat resistance, flexibility and the like. The unreacted primary amino group can form hydrogen bonds with other polar compounds added in the fabric, and the unreacted epoxy group can open a ring to generate hydroxyl, and further hydrogen bonds can be formed, so that the coating is more tightly combined with the fabric.
The invention also provides a preparation method of the modified gelatin, which comprises the following steps:
(1) synthesis of MonoSi-H terminated polysiloxane (PDMS-H): with hexamethylcyclotrisiloxane (D) 3 ) Is monomeric, n-butyllithium (C) 4 H 9 Li) as initiator, benzene as solvent, Tetrahydrofuran (THF) as promoter, dimethyl-monohydro-silane (C) 2 H 7 ClSi) as a blocking agent, and synthesizing PDMS-H by using a living anion polymerization technology;
the reaction equation is as follows:
n is 6 to 14;
(2) preparation of epoxy polysiloxane (PDMS-E): under the action of chloroplatinic acid serving as a catalyst, carrying out hydrosilylation reaction on Allyl Glycidyl Ether (AGE) and PDMS-H to obtain epoxy polysiloxane (PDMS-E);
the reaction equation is as follows:
(3) preparing monodisperse PDMS-E latex particles:
PDMS-E as the dispersed phase, under nitrogen pressure through the SPG membrane emulsifier membrane hole, adding into the containing Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid deionized water, forming PDMS-E oil-in-water emulsion;
(4) and (3) reacting the monodisperse PDMS-E emulsion particles with gelatin to modify the gelatin: and (3) adjusting the pH value of the gelatin solution to 10.0 +/-0.2, and dropwise adding the PDMS-E emulsion prepared in the step (3) into the gelatin solution and stirring to obtain the monodisperse PDMS-E latex particle modified gelatin.
Preferably, the specific method of step (1) is: firstly, C is firstly 4 H 9 Li is dissolved in benzene, D dissolved in benzene is added under the condition of reducing pressure and introducing argon 3 After a certain period of reaction, THF is added to continue the reaction for a certain period of time, and then C is injected 2 H 7 Stopping the reaction after ClSi; then, the product is filtered, distilled under reduced pressure and purified to obtain 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 2.3-2.5 times of that of benzene; the volume of THF is 4.8-5.2 times of benzene.
Further preferably, D is added 3 Carrying out post reaction for 28-32 min; and adding THF and continuing the reaction for 7.5-8.5 h.
Preferably, the specific method of step (2) is: introducing argon into the AGE, and adding chloroplatinic acid after 25-35 minutes; and heating to 78-82 ℃, dropwise adding PDMS-H, heating to 108-112 ℃ after dropwise adding, reacting for 5.5-6.5H, and purifying the product through 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 to 0.012.
More preferably, the molar ratio of PDMS-H to AGE is 1.5-1.7: 1.
Preferably, in the step (3), the ratio (w/w) of SDS/SDBS is 0.43-0.54, and the total concentration of the surfactant in the deionized water is 0.35-0.40 wt%.
Preferably, in step (3), the average pore diameter of the SPG membrane is 0.5. + -. 0.1. mu.m.
Preferably, in the step (3), the concentration of glacial acetic acid in 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 step (4) is:
dissolving gelatin in distilled water to prepare a gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 hours to ensure that the 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 at a speed of 19-21 mL/min -1 Adding the mixture into a gelatin solution at the speed of (1), stirring at 49-51 ℃, and reacting for 5-6 hours.
Further preferably, the concentration of the sodium hydroxide solution in the step (4) is 1.8-2.2 mol L -1 。
Further preferably, the mass percent of the gelatin in the gelatin solution in the step (4) is 4.95-5.05 wt%.
The invention also provides the application of the modified gelatin in coating printing and dyeing.
Preferably, the invention provides the application of the modified gelatin as a binder in coating printing and dyeing.
The modified printing and dyeing coating containing the modified gelatin comprises the modified gelatin and a coating, wherein the mass ratio of the modified gelatin to the coating is 1: 1.5-2.
Preferably, the coating is a conventional dyeing coating in the textile field, and comprises one or more of hydroxyethyl acrylate, sodium carboxymethyl cellulose, polymethyl vinyl ether and acrylonitrile.
The application method of the modified printing and dyeing paint comprises the step of mixing the printing and dyeing paint in an amount of 0.03-0.035 g/cm 2 Coating the coating amount of (2) on the textile; the base material of the textileIs a white blank pure cotton fabric.
The dyeing paint also comprises pigment, auxiliary agent and the like.
The pigment is a common pigment in the field of printing and dyeing.
The auxiliary agent comprises one or more of an antioxidant, a polymerization inhibitor and a defoaming agent.
The antioxidant, the polymerization inhibitor and the defoaming agent are conventional products in the field of textile printing and dyeing. Such as antioxidant 1010, chemical name: pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; antioxidant 168, chemical name: tris (2, 4-di-tert-butylphenyl) phosphite; the chemical name of the antioxidant 1076 is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, and the like.
The polymerization inhibitor includes polyhydric phenol polymerization inhibitor, quinone polymerization inhibitor, arylamine polymerization inhibitor and other common polymerization inhibitors, such as hydroquinone, p-tert-butylcatechol, p-toluidine, etc. The defoaming agent is an organic silicon defoaming agent, and the active ingredient is polysiloxane and silicone resin, such as an organic silicon defoaming agent DF-933 NS.
A textile fabric with good color fastness contains 0.03-0.035 g/cm 2 The above printing and dyeing paint; the glass transition temperatures Tg are 129 ℃ and 187.6 ℃. Preferably, the thermal decomposition temperature of the textile is 273.8 ℃.
Preferably, the base material of the textile is a white blank pure cotton fabric.
Preferably, the color fastness to rubbing is 4-5 as tested by the common standard GB/T3920, the fastness to wet ironing is 4 as tested by GB/T3921-2008 ' color fastness to soaping of textiles ' color fastness to washing ', and the fastness to perspiration is 4 as tested by the test method for the fastness to perspiration of textiles (GB/T3922 and 1995).
The invention has the following technical effects:
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 more than 60 ℃), the modification method can ensure that the gelatin has a complete structure and is not easy to denature or gel change.
2. The emulsion of the invention has good stability, emulsion particles can be uniformly dispersed along with the increase of reaction time, the particle size can not be continuously increased along with the reaction time, and the aggregation and emulsion breaking 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 be coated unevenly.
3. The latex particles of PDMS-E used as the modifying material are nontoxic and pollution-free, and do not harm human health;
4. the gelatin/PDMS-E latex particle polymer (modified gelatin) prepared by the invention has uniform and stable shape, and changes the defect that the gelatin is easy to deteriorate; the presence of anionic surfactants (SDS, SDBS) makes the polymer have strong adhesive capacity, and PDMS-E endows the material with properties of hydrophobicity, heat resistance, flexibility and the like.
5. According to the invention, the modified gelatin with the viscosity of 1.10-1.12 mPas is obtained by using the emulsion particles with the particle size of 500-750 nm, the viscosity is suitable, the modified gelatin can be used as a coating printing and dyeing adhesive to take a bearing effect between a fabric and a coating, and the problems of uneven coating and over-thick coating of the adhesive caused by over-high viscosity are solved. The modified gelatin used as the adhesive for coating printing and dyeing increases the heat resistance, flexibility and hydrophobicity of the fabric, and the coating and the fabric are more easily and tightly combined in the printing and dyeing process.
Drawings
FIG. 1 is an optical microscope picture and a particle size distribution chart of monodisperse latex particles in example 1;
FIG. 2 is an optical microscope picture and a particle size distribution chart of the monodisperse latex particles in example 2;
FIG. 3 is an optical microscope picture and a particle size distribution chart of the monodisperse latex particles of comparative example 4;
FIG. 4 is an optical microscope picture and a particle size distribution chart of the monodisperse latex particles of comparative example 5;
FIG. 5 is a microscopic topography of the modified gelatin of example 1;
FIG. 6 is a microscopic topography of the modified gelatin of comparative example 1;
FIG. 7 is a thermogravimetric analysis of a blank sample with example 1;
FIG. 8 is a DSC analysis chart of a blank sample and example 1.
Detailed Description
The invention will be further explained and explained with reference to the figures and examples.
Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS), Allyl Glycidyl Ether (AGE) and glacial acetic acid were all purchased from Alfa Aesar, Shanghai, China, and need to be recrystallized from ethanol before SDS and SDBS are used. Hexamethylcyclotrisiloxane (D) 3 ) 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 group corporation (beijing). The molecular formula of the chloroplatinic acid is H 14 Cl 6 O 6 Pt, molecular weight 517.9096, dark yellow transparent liquid, available from Jinan platinum sources chemical Co., Ltd. SPG porous glass membranes having a pore size of 0.5 μm were purchased from China pharmaceutical products, Inc. The pigskin type A gelatin is purchased from China pharmaceutical group company and is used after dialysis.
Molecular weight (M) of gelatin determined by gel permeation chromatography w ) About 1.40X 10 5 g mol -1 ，M w /M n Is 1.43. The content of primary amino groups in gelatin was measured by the Van-Slyke method at 50 ℃ and found to be 4.95X 10 -4 g mol -1 . The Van-Slyke method is a professional method for determining the content of amino groups in amino acids or protein molecules. The method is characterized in that nitrous acid reacts with primary amino groups in amino acid or protein to determine the content of the primary amino groups in the amino acid or protein. The error of the primary amino group content in the gelatin measured by the method is less than 1 percent.
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 the Mie scattering theory. First, the emulsion was carefully placed into a color matching tube. Then, the tube was put into a ZetaSizer 2000 laser particle instrument, and PDI or electrophoretic mobility was measured.
The method comprises the steps of measuring the viscosity of samples in reaction liquid at different times by using an acoustic viscometer, adjusting the temperature of a constant temperature tank to 50 ℃, vertically placing the acoustic viscometer in the constant temperature tank, adding 15mL of samples to be measured into the viscometer, sealing the rest two tubes except a capillary tube, pumping the liquid level to the upper scale mark of a glass ball at the upper end of the capillary tube by using an air pumping device, removing air pumping equipment at the same time, and recording the time required by the liquid level to flow down from the upper scale mark to the lower scale mark, thereby calculating the viscosity.
The Raman spectra of reaction samples in reaction liquid at different time are recorded by a Raman spectrometer, the Raman spectrum data is measured by an inVia type (Renisshaw, UK) laser confocal Raman spectrometer, the Raman spectrum data is firstly focused on the surface of a capillary tube by using an optical microscope mode, a stage is adjusted to focus on the surface of particles, and a 633nm laser light source is used for obtaining the Raman spectrum data.
Zeta potential of a reaction sample in a reaction solution at different times is measured by a Zetasizer Nano ZS90 type (Malvern, UK) laser particle size analyzer, the sample is sucked by a syringe and slowly injected into a cuvette with the Zeta potential, and the cuvette is placed in a sample tank of the instrument without air bubbles, so that a specific Zeta potential value can be measured. The test results were repeated 3 times.
The morphology of the PDMS-E latex particles was characterized by Transmission Electron Microscopy (TEM). First, TEM samples were prepared. The mixture of gelatin and emulsion was diluted about 20 fold at 50 ℃. The drop-like mixture was dropped onto a copper mesh. The excess liquid was taken up on filter paper and dried under nitrogen at room temperature. TEM images were measured with JEM-2100.
Epoxy group consumption was determined by Raman spectroscopy at 858cm -1 The peak represents an epoxy group.
The synthesis method of the epoxy polysiloxane (PDMS-E) used in the embodiment of the invention is as follows:
(1) synthesis of MonoSi-H terminated polysiloxane (PDMS-H):
10mL of benzene were added to the flask, followed by 24mL of C 4 H 9 After 3-5 times of vacuumizing and argon introducing operations, 45.99 g of D3 is dissolved in 40mL of benzene and is added into the flask dropwise. After 30min of reaction, 50mL of Tetrahydrofuran (THF) was added and the reaction was continued for 8 h. Subsequently, 11mL of C 2 H 7 ClSi is implanted and firedThe reaction was stopped in a flask. The obtained product PDMS-H is purified by filtration, reduced pressure distillation and other modes, 45.44g of product is obtained, and the yield is 56.11%. 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 in a flask, argon gas was introduced into the flask, and after 30 minutes, 40. mu.L of chloroplatinic acid (mass of chloroplatinic acid: 0.097g) was added. And (3) raising the reaction temperature to 80 ℃ under the condition of keeping introducing argon, starting adding PDMS-H with the mole ratio of 1.6:1 to AGE at the speed of 1-2 d/s, continuing raising the reaction temperature to 110 ℃ after the dropwise addition is finished, and continuing to react for 6 hours to finish the reaction. The product epoxy polysiloxane (PDMS-E) is obtained by purification by means of reduced pressure distillation and the like, and the yield is 84.32%.
Example 1
A modified gelatin for a papermaking reinforcing agent is prepared by the following steps:
(1) preparing monodisperse PDMS-E latex particles:
PDMS-E as a dispersed phase was passed through the pores of the SPG membrane (average pore diameter of the SPG membrane is 0.5 μm) under nitrogen pressure, added to deionized water containing SDS, SDBS and glacial acetic acid (concentration of glacial acetic acid is 2mol/L), and stirred at 1300rpm to form a PDMS-E oil-in-water emulsion (mass percentage of PDMS-E in oil-in-water emulsion is 1%). The SDS/SDBS ratio (w/w) was 0.54 and the total concentration of surfactant in deionized water was 0.4 wt%.
(2) And (3) reacting the monodisperse PDMS-E latex particles with gelatin to modify the gelatin:
stock solutions were prepared by dissolving gelatin in distilled water (5 wt%), and after 3h, the gelatin solution was heated to 50 ℃ to ensure complete dissolution of the gelatin. Subsequently, the pH of the gelatin solution was adjusted to 10.0. + -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E latex particles prepared above were added to the gelatin solution at a rate of 20mL/min and stirred at 50 ℃ for 5 hours. The mass ratio of PDMS-E to gelatin is 0.757: 1. the monodisperse PDMS-E latex particle modified gelatin with the viscosity of 1.10 mPas is obtained.
The average particle size of the epoxy polysiloxane obtained in example 1 is 678 +/-65 nm (shown in figure 1), and a TEM picture shows that the core-shell structure (shown in figure 6) appears in the structure of the modified gelatin, the shape of the core-shell structure is regularly and uniformly distributed, and the shell layer is convenient to be adsorbed on the textile material.
The conversion of primary amino groups in gelatin was 12.5% (mole percent) and the consumption of epoxy groups in PDMS-E was 23.24% (mole percent).
There is a certain difference between the particle size of the modified gelatin under optical microscope and that under TEM, because: the latex particles under the optical microscope are detected in the emulsion, the particle size of the latex particles is consistent with the actual particle size result, and the modified gelatin particles in the TEM image have certain collapse and atrophy after being subjected to treatment such as dropping coating on a copper net (carbon supporting film) and moisture drying during the test. The reason why the size of the modified gelatin in the TEM image is smaller than the particle size of the latex particles and the shape of some latex particles in the TEM image is not obviously spherical is also the reason, so the TEM image is only used for observing the microstructure and is not used for reflecting the particle size of the modified gelatin in the practical application state.
Example 2
A modified gelatin for a papermaking reinforcing agent is prepared by the following steps:
(1) preparing monodisperse PDMS-E latex particles:
PDMS-E as a dispersed phase was passed through the pores of the SPG membrane (average pore diameter of the SPG membrane is 0.5 μm) under nitrogen pressure, added to deionized water containing SDS, SDBS and glacial acetic acid (acetic acid concentration is 2mol/L), and stirred at a rotation speed of 1300rpm to form a PDMS-E oil-in-water emulsion (PDMS-E content in oil-in-water emulsion is 1% by mass). The SDS/SDBS ratio (w/w) was 0.43 and the total concentration of surfactant in deionized water was 0.4 wt%.
(2) And (3) reacting the monodisperse PDMS-E latex particles with gelatin to modify the gelatin:
stock solutions were prepared by dissolving gelatin in distilled water (5 wt%), and after 3h, the gelatin solution was heated to 50 ℃ to ensure complete dissolution of the gelatin. Subsequently, the pH of each prepared gelatin solution was adjusted to 10.0. + -. 0.2 using a 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 ℃ and the reaction was continued for 5 hours. The mass ratio of PDMS-E to gelatin in the PDMS-E emulsion is 0.757: 1. the monodisperse PDMS-E latex particle modified gelatin with the viscosity of 1.12mPas is obtained.
The monodisperse epoxy polysiloxane obtained in example 2 had an average particle size of 571. + -.70 nm, and a core-shell structure was also observed in the particle structure of the modified gelatin, the conversion of the primary amino group in the gelatin was 11.25% (mole percent), and the consumption of the epoxy group in PDMS-E was 22.12% (mole percent).
Comparative example 1
The preparation method of the modified gelatin comprises the following steps:
the other points are the same as example 1 except that the average pore diameter of the SPG membrane is 0.5 μm; SDBS (sodium dodecyl sulfate) is changed to be 0.25, the total concentration of the surfactant is changed to be 0.3 percent, and the monodisperse PDMS-E latex particle modified gelatin with the average particle size of 366 +/-70 nm is obtained. The TEM morphology of the modified gelatin was aggregated small particles (fig. 7), with a 7.5% (mole percent) conversion of primary amino groups in the gelatin.
Comparative example 2
The same as example 1 except that the average pore diameter of the SPG membrane was 0.7. mu.m; SDBS was changed to 0.67 in SDS and the total concentration of surfactant in deionized water was 0.5 wt%. Obtaining the monodisperse PDMS-E latex particle modified gelatin with the average particle size of 955 +/-70 nm. The viscosity of the modified gelatin was 1.057 mPas, the conversion of the primary amino group in the gelatin was 13.73% (mol%), and the consumption of the epoxy group in PDMS-E was 27.27% (mol%).
1. Particle size distribution of the monodisperse PDME-S latex particles obtained in examples 1-2 and comparative examples 1-2
The average particle size and the dispersion index (PDI) are used to describe the size of the prepared latex particles, and the results show that the PDI of the emulsion particles obtained in the embodiment of the invention is less than 0.1, which indicates that the emulsion particles are uniformly distributed in the solution. The Coefficient of Variation (CV) of the particle size was less than 21%, indicating that the distribution of the particle size was sufficiently narrow. The monodisperse PDME-S latex particles obtained by the invention are suitable for modifying gelatin to obtain the modified gelatin with stable performance.
2. Micro-topography of modified gelatins of examples and comparative examples
The reaction of gelatin with PDMS-E latex particles is influenced by a number of factors and the morphological changes are also very complex. The aggregation of the latex particle modified gelatin part with small particle size of less than 400nm can be visually observed through TEM images (attached figures 5 and 6). In contrast, monodisperse, regular core-shell structures are found in modified gelatin emulsions of medium particle size (500 to 750 nm). The larger size monodisperse latex particle modified gelatin helps to reduce viscosity. This is probably because when the gelatin carries out nucleophilic attack on the surface of the latex particles, ordered colloidal aggregates can be obtained; while for smaller droplets, collapse of the droplets, nucleophilic attack and complex formation occur simultaneously. So that the monodisperse latex particles with different particle sizes have different influences on the gelatin modification performance.
3. Secondary structure content of modified gelatin of examples and comparative examples
TABLE 1
The beta-sheet is a regular secondary structure, which is beneficial to the extension of polypeptide molecular chains, thereby promoting the exposure of primary amino groups, and the formation of the beta-sheet structure ensures that the primary amino groups of the gelatin are fully exposed on the surface of the emulsion particles. The gelatin is uniformly spread on the latex particles to promote the chemical grafting reaction between the latex particles and the gelatin, so that the viscosity of the emulsion can be reduced due to the increase of the beta-sheet structure. The secondary structures of the emulsion particle modified gelatin with different particle sizes are different, and the influence on the performance of the gelatin is different.
4. The modified gelatin is used as a bonding agent to be applied to the field of printing and dyeing
The following procedures and additives are conventional in the art or common commercial products unless otherwise specified. The performance test is carried out according to the common standards of GB/T3921-2008 soaping color fastness resistance of textile color fastness and rubbing color fastness test: GB/T3920, and a test method of the color fastness to perspiration of textiles (GB/T3922-.
The application method comprises the following steps:
the modified gelatins obtained in examples 1 and 2 and comparative examples 1 and 2 were applied to textiles as adhesives. In order to illustrate the influence of the coating of the modified gelatin on the performance of the textile material, the modified gelatin and the coating are uniformly coated on the surface of the textile, and the coating is selected to be coated on the whole or part of the surface of the textile according to requirements in actual use. The coating amount of the modified gelatin on the surface of the textile is 0.03-0.035 g/cm 2 。
Example 3
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1: 1.5. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in example 1.
The coating comprises the following components:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L, 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of a white blank pure cotton fabric, drying at 120 ℃, wherein the coating amount is 0.03g/cm 2 。
Example 4
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:2. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L and 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.03g/cm 2 。
Example 5
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1: 1.5. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in example 2.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L, 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.035g/cm 2 。
Comparative example 3
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose; .
Pigment: 8304 dark blue 0.4g/L and 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.03g/cm 2 。
Comparative example 4
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1: 2.5. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L and 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.03g/cm 2 。
Comparative example 5
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1: 1.5. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in comparative example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L and 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.03g/cm 2 。
Comparative example 6
A modified printing and dyeing coating and a using method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1: 1.5. The fabric is white blank pure cotton fabric. The modified gelatin was the gelatin obtained in comparative example 2.
The coating comprises the following components:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
pigment: 8304 dark blue 0.4g/L, 8601 green 0.3 g/L;
auxiliary agent: 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white-blank pure cotton fabric, wherein the coating amount is 0.03g/cm 2 。
Table 3 shows the effect of different modified gelatins as binders:
TABLE 3
| Sample (I) | Color fastness to washing | Fastness to wet ironing | Color resistance to perspirationFastness to light |
| Example 3 | 5 | 4 | 4 |
| Example 4 | 4-5 | 4 | 4 |
| Example 5 | 4 | 4 | 4 |
| Comparative example 3 | 3 | 3 | 2 |
| Comparative example 4 | 3 | 2 | 2 |
| Comparative example 5 | 2 | 2 | 2 |
| Comparative example 6 | 3 | 4 | 3 |
| Blank sample (gelatin only) | 1-2 | 1-2 | 1-2 |
The color fastness of the textile dyed by the modified gelatin adhesive is good, and compared with a blank sample, the color fastness to washing, the color fastness to wet ironing and the color fastness to perspiration are all obviously improved. When the modified gelatin and the printing and dyeing paint are in a certain mass ratio, the color fastness is good.
FIG. 7 is a thermogravimetric analysis of a blank sample (a) of a textile sample using gelatin alone as the coating and a sample (b) of a textile sample using the modified gelatin of example 1 as the coating; the fabric selected for the sample was a white blank pure cotton fabric.
The TG results show that the blank sample shows two weight losses at 46.5 ℃ and 264.5 ℃ while the coating modified material shows only one weight loss at 273.8 ℃, which indicates that the thermal stability of the material is improved after the emulsion coating modification.
FIG. 8 DSC analysis of blank sample (a) and sample (b). The results show that the Tg of the blank sample is 215.7 ℃ and that the Tg of the modified sample is two, 129 ℃ and 187.6 ℃, indicating that there is a microphase separation structure in the sample coated with the emulsion coating, and that the Tg after modification is significantly reduced, indicating that the relative mobility of the polymer molecular chains increases at low temperature, meaning that the flexibility of the modified material increases to some extent.
Claims (10)
1. The modified gelatin for the coating printing and dyeing adhesive is characterized in that the gelatin is modified by epoxy polysiloxane (PDMS-E) emulsion droplets, the average particle size of the epoxy polysiloxane emulsion droplets is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1: 0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12 mPa & s, the primary amino group conversion rate of the gelatin is 11-13% (mol percent), and the consumption of epoxy groups in PDMS-E is 22-24% (mol percent).
2. The modified gelatin of claim 1, wherein the modified gelatin has a secondary structure content of: beta-sheet is 30-31%; the random crimp is 26.2-27.5%; the alpha-helical structure is 21.4-23.5%; the beta-turn angle is 19.8-20.2%.
3. The process for producing a modified gelatin as claimed in claim 1 or 2, which comprises the steps of:
(1) synthesis of a Single Si-H terminated polysiloxane (PDMS-H): with hexamethylcyclotrisiloxane (D) 3 ) Is monomeric, n-butyllithium (C) 4 H 9 Li) as initiator, benzene as solvent, Tetrahydrofuran (THF) as promoter, dimethyl-monohydro-silane (C) 2 H 7 ClSi) as a blocking agent, and synthesizing PDMS-H by using a living anion polymerization technology;
the reaction equation is as follows:
n is 6 to 14;
(2) preparation of epoxy polysiloxane (PDMS-E): under the action of chloroplatinic acid serving as a catalyst, Allyl Glycidyl Ether (AGE) and PDMS-H undergo hydrosilylation reaction to obtain epoxy polysiloxane (PDMS-E);
the reaction equation is as follows:
(3) preparing monodisperse PDMS-E latex particles:
PDMS-E as the dispersed phase, under the pressure of nitrogen through the SPG membrane emulsifier membrane hole, adding into the containing Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid deionized water, forming PDMS-E oil-in-water emulsion;
(4) and (3) reacting the monodisperse PDMS-E emulsion particles with gelatin to modify the gelatin: and (4) adjusting the pH value of the gelatin solution to 10.0 +/-0.2, and dropwise adding the PDMS-E emulsion prepared in the step (3) into the gelatin solution and stirring to obtain the monodisperse PDMS-E latex particle modified gelatin.
4. The preparation method according to claim 3, wherein the specific method of step (1) is: firstly, C is added 4 H 9 Li is dissolved in benzene, D dissolved in benzene is added under the condition of reducing pressure and introducing argon 3 After a certain period of reaction, THF is added to continue the reaction for a certain period of time, and then C is injected 2 H 7 Stopping the reaction after ClSi; then, filtering, distilling under reduced pressure and purifying the product to obtain 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 2.3-2.5 times of that of benzene; the volume of the THF is 4.8-5.2 times of that of benzene;
further preferably, D is added 3 Post-reaction for 28-32 min; adding THF and continuing to react for 7.5-8.5 h;
preferably, the specific method of step (2) is: introducing argon into the AGE, and adding chloroplatinic acid after 25-35 minutes; heating to 78-82 ℃, dropwise adding PDMS-H, heating to 108-112 ℃ after dropwise adding, reacting for 5.5-6.5H, and purifying the product by reduced pressure distillation to obtain a product epoxy polysiloxane (PDMS-E);
further preferably, the mass ratio of AGE to chloroplatinic acid is 1: 0.011 to 0.012;
more preferably, the molar ratio of PDMS-H to AGE is 1.5 to 1.7: 1.
5. The method according to claim 3, wherein in the step (3), the ratio (w/w) of SDS/SDBS is 0.43 to 0.54, and the total concentration of the surfactant in the deionized water is 0.35 to 0.40 wt%;
preferably, in the step (3), the average pore diameter of the SPG membrane is 0.5 +/-0.1 μm;
preferably, in the step (3), the concentration of glacial acetic acid in 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%.
6. The preparation method according to claim 3, wherein the specific method of step (4) is:
dissolving gelatin in distilled water to prepare a gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 hours to ensure that the 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 at a speed of 19-21 mL/min -1 Adding the mixture into a gelatin solution at the speed of (1), stirring at 49-51 ℃, and reacting for 5-6 hours;
preferably, the concentration of the sodium hydroxide solution in the step (4) is 1.8-2.2 mol L -1 ；
Preferably, the mass percent of the gelatin in the gelatin solution in the step (4) is 4.95-5.05 wt%.
7. Use of the modified gelatin according to claim 1 or 2 or the modified gelatin prepared by the method according to any one of claims 3 to 6 as an adhesive in coating printing and dyeing.
8. A printing and dyeing coating containing the modified gelatin of claim 1 or 2 or the modified gelatin prepared by the method of any one of claims 3 to 6, which is characterized by comprising the modified gelatin and the coating, wherein the mass ratio of the modified gelatin to the coating is 1: 1.5-2;
preferably, the paint is conventional dyeing paint in the textile field, and comprises one or more of hydroxyethyl acrylate, sodium hydroxymethyl cellulose, polymethyl vinyl ether and acrylonitrile; the coating also comprises a pigment and an auxiliary agent.
9. The use method of the modified printing and dyeing paint as claimed in claim 8, characterized in that the printing and dyeing paint is used according to the proportion of 0.03-0.035 g/cm 2 Coating the coating amount of (2) on the textile;
preferably, the base material of the textile is a white blank pure cotton fabric.
10. The textile fabric with good color fastness is characterized by containing 0.03-0.035 g/cm 2 The printed coating of claim 8; the glass transition temperatures Tg are 129 ℃ and 187.6 ℃.
Preferably, the base material of the textile is a white blank pure cotton fabric.
Preferably, the color fastness to rubbing is 4-5 as tested by the common standard GB/T3920, the fastness to wet ironing is 4 as tested by GB/T3921-2008 ' color fastness to soaping of textiles ' color fastness to washing ', and the fastness to perspiration is 4 as tested by the test method for the fastness to perspiration of textiles (GB/T3922 and 1995).
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| CN202111061752.5A CN115124721B (en) | 2021-03-26 | 2021-03-26 | Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof |
| CN202110325823.1A CN115124720B (en) | 2021-03-26 | 2021-03-26 | Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof |
| PCT/CN2021/097453 WO2022198791A1 (en) | 2021-03-26 | 2021-05-31 | Modified gelatin for paint printing and dyeing adhesive, preparation method therefor, and application thereof |
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| CN115124721A (en) | 2022-09-30 |
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