CN111116819A - Synthesis method of novel printing and dyeing deepening agent - Google Patents
Synthesis method of novel printing and dyeing deepening agent Download PDFInfo
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- CN111116819A CN111116819A CN201911388826.9A CN201911388826A CN111116819A CN 111116819 A CN111116819 A CN 111116819A CN 201911388826 A CN201911388826 A CN 201911388826A CN 111116819 A CN111116819 A CN 111116819A
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- 238000004043 dyeing Methods 0.000 title claims abstract description 26
- 238000007639 printing Methods 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- -1 AEO-15 Chemical compound 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 24
- 239000000835 fiber Substances 0.000 description 23
- 239000000975 dye Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 11
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000012875 nonionic emulsifier Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A synthesis method of a novel printing and dyeing deepening agent specifically comprises the following steps: (1) the substrates CTAB, AEO-15 and water were placed in a round bottom flask and stirred well. (2) The pre-emulsion CTAB, AEO-15, MMA, BA and water were placed in a round bottom flask and stirred at high speed for 30 minutes. (3) Initiator Ammonium Persulfate (APS) and water are put in a beaker and stirred evenly for standby. (4) And (3) heating the substrate to 75 ℃, continuously stirring, and beginning to dropwise add the pre-emulsified material prepared in the step (2) and the initiator prepared in the step (3) by using a peristaltic pump. (5) After the addition was complete the reaction was incubated at 75 ℃ for one hour. (6) Cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion. The invention has the beneficial effects that: the process cost is low, the energy consumption is low, and the pollution is small; the deepening effect is obvious; the softness of the fabric can be obviously improved; the prepared emulsion has good stability.
Description
Technical Field
The invention belongs to the field of textile auxiliary agents, and particularly relates to a synthesis method of a novel printing and dyeing deepening agent.
Background
The deepening agent is used as a deep color processing finishing agent capable of reducing the optical refractive index of the fiber surface, is applied to the fabric through dipping or a conventional padding process, forms a uniform and complete film on the fiber surface, increases the diffuse reflection intensity of the fiber surface to light, reduces the refractive index, deepens the apparent color of the fiber, can obviously increase the apparent color depth of the fiber, and is suitable for various fiber fabrics. According to the deepening approach, the deepening agent can be roughly divided into 3 types: (1) roughening the surface of the fabric or yarn, wherein the roughening comprises a chemical erosion method, a physical etching method and a post-processing agent for endowing the fiber surface with fine concave-convex; (2) the dye uptake of the dye on the fabric is improved, the affinity of the fiber to the coating dye is improved by chemically modifying the surface of the fiber, the characteristics of the dye are changed by changing the solubility of the dye in a solution or slightly changing the structure of the dye and the like, and a proper auxiliary agent and dyeing process are selected to ensure that a coloring material can be better absorbed and fixed and the like; (3) the surface of the dyed cloth is coated with low-refractive-index resin, so that the surface reflectivity is reduced, and the color development, color depth and vividness of the fabric are improved. Depth enhancers can be divided into two categories depending on the method of use: a. a deepening agent used before or during the dyeing process, and b, a deepening agent used after the dyeing. The two types (1) and (2) are used as the deep dyeing agent before or during the dyeing process, and the other type (3) is used as the deep dyeing agent after the dyeing process.
In recent years, the continuous development of fabrics makes the problem of deep dyeing more prominent, which is mainly reflected in that the fabric has no deep color and no black color, and some black fabrics give a white and bright visual effect. In the dyeing process of certain fabrics, the deep color can be dyed by increasing the dye consumption, even the dye consumption is increased, the reduction of various dyeing fastness and the increase of the cost are brought, and meanwhile, a large amount of energy is consumed for treating the dyeing wastewater. The reason for poor fabric deep dyeing performance is mainly that the fabric fiber has a compact structure and a smooth surface, when light irradiates the surface of the dyed fabric with the compact structure, a large amount of incident light is reflected on the surface of the fabric, and only a part of the incident light is reflected into the fiber to be absorbed by the dye to become colored light, so that the fabric has poor deep dyeing performance, especially black. Some dye companies abroad put forward special disperse dyes for superfine fiber dyeing, select dyes with high affinity, good lifting performance and high molecular absorption coefficient or reasonably blend and dye by using some disperse dyes with additivity, improve the dye-uptake and improve the color rendering, but can not solve the problem fundamentally. Therefore, treating the surface of the fabric with the deepening agent to change the surface characteristics of the fabric and reducing the amount of reflected light as much as possible is an effective method for improving the deep color effect of the surface of the fabric, thereby achieving the deep color effect of the fabric.
The deepening agent is mainly composed of a polymer, and the core part of the polymer particle is a polymer with a refractive index of less than 1.50 and a glass transition temperature of 110-150 ℃. Methyl Methacrylate (MMA) is selected as a monomer, has the following structural formula, is a common acrylate, and has high glass transition temperature and TgMMA373.15K, refractive index 1.40; butyl Acrylate (BA) having the following structural formula, the BA having a very low glass transition temperature and a TgBA219.15K. The polymer having a high glass transition temperature is not completely melted in the heating step after adhering to the textile fibers, and forms fine irregularities on the fiber surfaces, thereby suppressing reflection light from the fiber surfaces, causing diffuse reflection, and enhancing the deep color effect of the fibers. The polymer with low glass transition temperature is adhered to the polyester fiber and is completely melted in the subsequent heating process, and a low-refractive-index coating film is formed on the surface of the fiber, so that the dark color effect of the fabric is caused. Since the core polymer maintaining a certain particle shape is supported on the fiber surface by the coating film formed of the polymer, the effect of darkening the polyester fiber can be maintained for a long period of time.
Methyl Methacrylate (MMA) structural formula is as follows:
butyl Acrylate (BA) has the following structural formula:
in the middle of the 80 s of the last century, the japanese same lines proposed a finishing method to darken the apparent color of dyed fabrics without changing the dye uptake. After the dyed fabric is finished by the low-refractive-index resin, a layer of uniform low-refractive-index resin film is formed on the surface of the dyed fabric, the fabric is completely coated, the refractive index of the dyed fabric is correspondingly reduced, and the total surface reflected light of the fabric is smaller than that before coating, so that the apparent color of the fabric is deepened. The low refractive index resins commonly used are: organic fluorine resins, silicone resins, polyamines and polyurethane resins. The organic silicon resin is a common low-refractive-index resin, the refractive index is about 1.4 generally, but the organic silicon resin has certain damage to a human body after being heated or degraded at high temperature, so that the organic silicon resin has certain limitation. The refractive index of the organic fluororesin is generally less than 1.4, the deepening effect is best, but the organic fluororesin is less applied to actual production due to serious environmental pollution, high cost and poor hand feeling after finishing. The polyamine and the polyurethane resin are compounded with a large amount of amino, so that the fabric has better hand feeling after being used, but the deepening effect is inevitably influenced. The common polymer emulsion is easy to cause color paste accumulation after finishing the fabric, and the fabric has hard hand feeling.
In view of the above problems, synthetic polymer latex particles have been developed in the prior art, and the use of the synthetic polymer latex particles enables a soft coating to be formed on the surface of fabric fibers when the fabric is subjected to heat treatment, so that the fabric is softer after finishing and the hand feeling after finishing the fabric is improved. With the progress of emulsion polymerization reaction, the surface area and volume of the original emulsion particles are larger and larger due to the polymerization of the subsequently dripped monomers on the surfaces, a certain amount of emulsifier needs to be added to maintain the stability of the original emulsion particles, but the addition amount is too large, new emulsion particles are easily generated, and the phenomenon of secondary nucleation occurs. If the emulsifier is added directly to the system at one time, the emulsifier added in bulk may cause the emulsifier concentration in a local area in the reaction system to be too high, resulting in the formation of new latex particles.
Disclosure of Invention
Based on the above background, the present application proposes finishing a fabric with an acrylic resin. The acrylic resin is a thermoplastic resin prepared by polymerizing acrylic acid, methacrylic acid and derivatives thereof (such as esters, nitriles and amides), can be a homopolymer or a copolymer, and a coating prepared from the acrylic resin is a macromolecular polymerized film after a solvent is volatilized.
In order to prepare stable emulsion with uniform particle size, the invention adopts a seed emulsion polymerization method and a starvation state feeding process, adopts a method of preparing an emulsifier into a water solution with a certain concentration and then gradually dripping the water solution into a system by a peristaltic pump to replenish the emulsifier, the emulsifier in the system can be replenished in time along with the reaction, the stability of the system is maintained, meanwhile, the content of the emulsifier in the reaction system at any time is not too high, the phenomenon of 'secondary nucleation' is effectively prevented, the stability of the polymerization system is improved, and the aim of controlling the morphology and the particle size distribution of polymer latex particles is achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthesis method of a novel printing and dyeing deepening agent specifically comprises the following steps:
(1) the substrates Cetyl Trimethyl Ammonium Bromide (CTAB), fatty alcohol polyoxyethylene (15) ether (AEO-15) and water were placed in a round bottom flask and stirred well.
(2) The pre-emulsion CTAB, AEO-15, MMA, BA and water were placed in a round bottom flask and stirred at high speed for 30 minutes.
(3) Initiator Ammonium Persulfate (APS) and water are put in a beaker and stirred evenly for standby.
(4) And (3) heating the substrate to 75 ℃, continuously stirring, and beginning to dropwise add the pre-emulsified material prepared in the step (2) and the initiator prepared in the step (3) by using a peristaltic pump.
(5) After the addition was complete the reaction was incubated at 75 ℃ for one hour.
(6) Cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion.
The polymerization of methyl methacrylate and n-butyl acrylate is as follows:
further, the mass ratio of the substrates used in the step (1) is as follows: CTAB: AEO-15: water-0.26: 0.33: 164.
further, the mass ratio of the pre-emulsified materials used in the step (2) is as follows: CTAB: AEO-15: MMA: BA: water 1.83: 1.1: 78.75: 7.8 g: 33.
further, the mass ratio of the initiator APS and the water used in the step (3) is as follows: APS: water-0.45: 131.
further, in the step (4), the stirring speed is kept at 200 r/min.
Further, the time for dripping the pre-emulsion material and the initiator in the step (4) is 50 min.
The coverage area of the single molecules of the nonionic emulsifier is larger, more monomer molecules enter, the particle size of the generated polymer is larger, meanwhile, the nonionic emulsifier has good chemical stability to dielectrics and is not influenced by the pH value, and the nonionic emulsifier used in the patent is fatty alcohol polyoxyethylene (15) ether (AEO-15). The chemical fiber shows electronegativity in water, so the emulsion is preferably cationic, the chemical fiber and the emulsion are easy to contact and adsorb, and the finishing effect is good. The nonionic emulsifier is not ionized in water, so that the compatibility is good, the nonionic emulsifier can be used together with the cationic emulsifier in a bath, a synergistic effect can be generated after the nonionic emulsifier is mixed, the emulsifying property can be obviously improved, and a better emulsifying effect can be obtained. The nonionic emulsifier has excellent emulsifying and solubilizing performances, while the cationic emulsifier enables the surface of the liquid drop to be charged to form an electric double layer, so that the probability of coalescence of the liquid drop due to approach and collision is reduced.
The stirring speed during emulsion polymerization has great influence on the reaction, when the stirring speed is too low, the strength is too low, the monomer is not well dispersed, the local concentration is too high, and the delamination phenomenon is generated when the stirring speed is serious, the local over-concentrated monomers are easy to generate bulk polymerization on the wall of a reactor or a dropping part, so that the generation of gel is caused, meanwhile, the heat transfer is poor, the local high-temperature area exists in the emulsion, and the emulsion is easy to generate gel stably. However, when the stirring speed is too high, the stirring gives great kinetic energy to the latex particles, the dropwise added reaction liquid reacts on the liquid level, the latex particles collide with each other and are easy to coalesce to generate a large amount of white foam, and then the added reaction liquid coagulates on the foam to generate a large amount of white solid or even gel, so that the reaction is seriously hindered, and the emulsion is unstable, therefore, the stirring speed is within a certain proper range. Aiming at the phenomenon, the invention selects about 200r/min when preparing the polymer, disperses the monomer into monomer liquid drops, promotes heat transfer and mass transfer, ensures that a reaction system is uniformly mixed, keeps constant temperature and prevents local overheating.
Since the reaction is an emulsion polymerization reaction, the reaction temperature not only affects the speed of the polymerization reaction, but also affects the stability of the emulsion polymerization and the size of the formed latex particles. The higher the reaction temperature is, the rate of generating free radicals is increased, the number of polymer latex particles is increased, the mass fraction of monomers in the latex particles is reduced, and the rate of diffusing the free radicals and the monomers into the latex particles is increased. The combined result of the elevated temperature is an increase in polymerization rate and a decrease in molecular mass, but the elevated temperature can cause a number of side reactions, such as coagulation and emulsion breaking of the emulsion, the production of branched and gelled polymers, and the influence on polymer microstructure and molecular mass distribution, which is detrimental to emulsion stability. The initiation speed is slow when the reaction temperature is lower, the particle size of the emulsion is large, the distribution is wide, and the like. Therefore, the invention is researched and selected through repeated tests that the optimal temperature for preparing the polymer is 75 ℃, so that the emulsion has stability and rapidness during polymerization, and the average diameter of emulsion particles is larger and the particle size is uniform.
The invention has the beneficial effects that:
1) the invention has low process cost, low energy consumption and little pollution.
2) The synthetic polymeric emulsion K/S of the invention is 40.6%, and the deepening effect is obvious.
3) The polymerized emulsion synthesized by the process can obviously improve the softness of the fabric.
4) The invention develops the appropriate reaction temperature, reaction time, dropping speed and stirring speed, and the emulsion particles with large and uniform particle size are prepared by using the emulsion particles and the cationic and nonionic emulsifiers in a synergistic manner, so that the stability of the emulsion is enhanced.
Detailed Description
For the convenience of understanding, the present invention will be described in further detail below by way of examples.
Example 1:
a synthesis method of a novel printing and dyeing deepening agent specifically comprises the following steps:
(1) the substrate 0.13g CTAB, 0.16g AEO-15 and 82g water were placed in a 100mL round bottom flask and stirred well.
(2) The preemulsifier, 0.91g CTAB, 0.55g AEO-15, 39.37g MMA, 3.9g BA and 16.5g water were placed in a 100mL round bottom flask and stirred at high speed for 30 minutes.
(3) Initiator 0.22g APS and 65.5g water were placed in a 100mL beaker and stirred well until needed.
(4) Heating the substrate to 75 ℃, stirring and maintaining at 200r/min, beginning to dropwise add the pre-emulsified material by a peristaltic pump, and finishing dripping for 50 min. And (3) beginning to drip the initiator by using a peristaltic pump while dripping the pre-emulsified material, and finishing dripping within 50 min.
(5) After the addition was complete the reaction was incubated at 75 ℃ for one hour.
(6) Cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion.
Example 2:
a synthesis method of a novel printing and dyeing deepening agent specifically comprises the following steps:
(1) the substrate 0.26g CTAB, 0.33g AEO-15 and 164g water were placed in a 250mL round bottom flask and stirred well.
(2) The pre-emulsion, 1.83g CTAB, 1.1g AEO-15, 78.75g MMA, 7.8g BA and 33g water were placed in a 250mL round bottom flask and stirred at high speed for 30 minutes.
(3) Initiator 0.45g APS and 131g water were placed in a 150mL beaker and stirred well until needed.
(4) Heating the substrate to 75 ℃, stirring and maintaining at 200r/min, beginning to dropwise add the pre-emulsified material by a peristaltic pump, and finishing dripping for 50 min. And (3) beginning to drip the initiator by using a peristaltic pump while dripping the pre-emulsified material, and finishing dripping within 50 min.
(5) After the addition was complete the reaction was incubated at 75 ℃ for one hour.
(6) Cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion.
Example 3:
a synthesis method of a novel printing and dyeing deepening agent specifically comprises the following steps:
(1) the substrate 1.3g CTAB, 1.65g AEO-15 and 820g water were placed in a 1000mL round bottom flask and stirred well.
(2) The pre-emulsion, 9.15g CTAB, 5.5g AEO-15, 393.75g MMA, 39g BA and 165g water were placed in a 750mL round bottom flask and stirred at high speed for 30 minutes.
(3) Initiator 2.25g APS and 665g water were placed in a 1000mL beaker and stirred well until needed.
(4) Heating the substrate to 75 ℃, stirring and maintaining at 200r/min, beginning to dropwise add the pre-emulsified material by a peristaltic pump, and finishing dripping for 50 min. And (3) beginning to drip the initiator by using a peristaltic pump while dripping the pre-emulsified material, and finishing dripping within 50 min.
(5) After the addition was complete the reaction was incubated at 75 ℃ for one hour.
(6) Cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion.
And the color difference grade is 5-1 grade, the color difference grade number is large, the color difference is small, the color difference grade number is small, and the color difference is large. The reflectance R of the stained specimen was measured at the maximum absorption wavelength according to the Kubelka-Munk equation K/S ═ 1-R2and/(2R), calculating the K/S value. The larger the K/S value, the darker the color, and the smaller the K/S value, the lighter the color. The emulsion K/S of the invention is 40.6 percent, and the deepening effect is obvious.
According to the method, methyl methacrylate and n-butyl acrylate are used as monomers, and the copolymer deepening agent is obtained through emulsion polymerization. The emulsion prepared by adopting the polymerization process is softer than the cloth sample finished by the common emulsion, the depth of the black fabric product can be increased by 40% after the black fabric product is deepened, the strength, softness, resilience and the like of the fabric are improved, and compared with the conventional deepening agent, the fabric has great advantages in the aspects of reducing pollution, reducing cost and the like.
The above embodiments are only illustrative or explanatory of the technical solution of the present invention and should not be construed as limiting the technical solution of the present invention, and it is apparent that various modifications and variations can be made to the present invention by those skilled in the art within the scope of the claims of the present invention and the equivalent technology thereof, provided they do not depart from the spirit and scope of the present invention.
Claims (6)
1. A synthetic method of a novel printing and dyeing deepening agent is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) putting substrates CTAB, AEO-15 and water into a round-bottom flask, and uniformly stirring;
(2) placing the pre-emulsified materials CTAB, AEO-15, MMA, BA and water in a round-bottom flask, and stirring at a high speed for 30 minutes;
(3) putting initiator Ammonium Persulfate (APS) and water in a beaker, and uniformly stirring for later use;
(4) heating a substrate to 75 ℃, continuously stirring, and dropwise adding the pre-emulsified material prepared in the step (2) and the initiator prepared in the step (3) by using a peristaltic pump;
(5) after the dropwise addition, the reaction is kept at 75 ℃ for one hour;
(6) cooling the reaction to 45 ℃, and filtering out of the pot to obtain the polymerization emulsion.
2. The method for synthesizing a novel printing and dyeing deepening agent according to claim 1, wherein the method comprises the following steps: the mass ratio of the substrates used in the step (1) is as follows: CTAB: AEO-15: water-0.26: 0.33: 164.
3. the method for synthesizing a novel printing and dyeing deepening agent according to claim 1, wherein the method comprises the following steps: the mass ratio of the pre-emulsified materials used in the step (2) is as follows: CTAB: AEO-15: MMA: BA: water 1.83: 1.1: 78.75: 7.8 g: 33.
4. the method for synthesizing a novel printing and dyeing deepening agent according to claim 1, wherein the method comprises the following steps: the mass ratio of the initiator Ammonium Persulfate (APS) to the water used in the step (3) is as follows: APS: water-0.45: 131.
5. the method for synthesizing a novel printing and dyeing deepening agent according to claim 1, wherein the method comprises the following steps: in the step (4), the stirring speed is kept at 200 r/min.
6. The method for synthesizing a novel printing and dyeing deepening agent according to claim 1, wherein the method comprises the following steps: and (4) dropwise adding the pre-emulsion material and the initiator for 50 min.
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Citations (3)
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|---|---|---|---|---|
| US4373043A (en) * | 1981-02-13 | 1983-02-08 | Kao Soap Co., Ltd. | Color deepening agent |
| CN105113247A (en) * | 2015-08-26 | 2015-12-02 | 浙江理工大学 | Coating liquid with latex particle reflection deducting capability as well as preparation method and application of coating liquid |
| KR20160011037A (en) * | 2014-07-21 | 2016-01-29 | 영우씨엠에스 주식회사 | Acrylic Color Deepening Agent, and Method for Manufacturing the Same |
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| US4373043A (en) * | 1981-02-13 | 1983-02-08 | Kao Soap Co., Ltd. | Color deepening agent |
| KR20160011037A (en) * | 2014-07-21 | 2016-01-29 | 영우씨엠에스 주식회사 | Acrylic Color Deepening Agent, and Method for Manufacturing the Same |
| CN105113247A (en) * | 2015-08-26 | 2015-12-02 | 浙江理工大学 | Coating liquid with latex particle reflection deducting capability as well as preparation method and application of coating liquid |
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| 郎添: "有机硅丙烯酸酯聚合物复合乳液的制备及其织物增深性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑（月刊）》 * |
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