CN115960300A - Acrylic emulsion for leather treatment and preparation method thereof - Google Patents
Acrylic emulsion for leather treatment and preparation method thereof Download PDFInfo
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- CN115960300A CN115960300A CN202211727991.4A CN202211727991A CN115960300A CN 115960300 A CN115960300 A CN 115960300A CN 202211727991 A CN202211727991 A CN 202211727991A CN 115960300 A CN115960300 A CN 115960300A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 135
- 239000010985 leather Substances 0.000 title claims abstract description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000000149 penetrating effect Effects 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 23
- 230000035699 permeability Effects 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 238000004049 embossing Methods 0.000 description 8
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- -1 4, sodium fatty alcohol Chemical class 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002357 osmotic agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses an acrylic emulsion for leather treatment and a preparation method thereof, and relates to the field of emulsion preparation. The acrylic emulsion for leather treatment comprises the following raw materials in parts by weight: 100 parts of deionized water, 27.5-29 parts of butyl acrylate, 1.5-1.8 parts of methyl methacrylate, 3-4 parts of methacrylic acid, 0.15-0.25 part of n-dodecyl mercaptan, 0.3-0.5 part of emulsifier, 0.1-0.2 part of initiator, 2-3 parts of ammonia water and 2-3 parts of penetrant. The acrylic emulsion for leather treatment provided by the invention has small particle size and excellent permeability and softness.
Description
Technical Field
The invention relates to the field of emulsion preparation, and particularly relates to an acrylic emulsion for leather treatment and a preparation method thereof.
Background
Leather emulsions are commonly used to fill leather and bind loose leather fibers together to improve pattern set. The existing emulsion for leather generally has the problem of insufficient permeability, so that the leather still has rough surface, poor hand feeling and insufficient fullness after being treated by the emulsion.
In addition, because the permeability of the emulsion for leather is insufficient, the emulsion cannot penetrate into the leather, deep loose fibers cannot be adhered, the tensile toughness and the bending resistance of the loose leather fibers are poor, and the leather is easy to have creases when being bent, and the creases are difficult to recover or cannot be recovered. In addition, the conventional emulsion for leather has problems of poor blocking property and softness.
It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an acrylic emulsion for leather treatment and a preparation method thereof, and aims to solve the technical problems of insufficient permeability and poor softness of the emulsion for leather treatment in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acrylic emulsion for leather treatment comprises the following raw materials in parts by weight: 100 portions of deionized water, 27.5 to 29 portions of butyl acrylate, 1.5 to 1.8 portions of methyl methacrylate, 3 to 4 portions of methacrylic acid, 0.15 to 0.25 portion of n-dodecyl mercaptan, 0.3 to 0.5 portion of emulsifier, 0.1 to 0.2 portion of initiator, 2 to 3 portions of ammonia water and 2 to 3 portions of penetrant.
The acrylic emulsion for leather treatment is characterized in that the emulsifier comprises at least one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
The acrylic emulsion for leather treatment, wherein the penetrating agent comprises dioctyl sodium sulfosuccinate.
The acrylic emulsion for leather treatment is characterized in that the initiator comprises ammonium persulfate.
The acrylic emulsion for leather treatment is prepared from raw materials and a bactericide.
A preparation method of the acrylic emulsion for leather treatment is used for preparing the acrylic emulsion for leather treatment, and comprises the following steps:
s1, preparing a base material liquid: adding 60-65 parts of deionized water and 0.15-0.28 part of emulsifier into a polymerization kettle, uniformly stirring, and raising the temperature of the polymerization kettle to 85 ℃;
s2, preparing a pre-emulsion: mixing 14.5-17 parts of deionized water, methacrylic acid, butyl acrylate, methyl methacrylate, n-dodecyl mercaptan and the rest of emulsifier, and uniformly stirring to prepare a pre-emulsion for later use;
s3, preparing an initiator solution A: dissolving 0.05-0.12 part of initiator into 4.5-6.0 parts of deionized water to prepare initiator solution A for later use;
s4, preparing an initiator solution B: dissolving 0.02-0.08 part of initiator into 0.6-1.0 part of deionized water to prepare initiator solution B for later use;
s5, adding 5% of the total amount of the pre-emulsion and an initiator solution B into the polymerization kettle, and reacting for 20 minutes to prepare a seed emulsion;
s6, simultaneously dripping an initiator solution A and the residual pre-emulsion into the polymerization kettle, and preserving heat for 45 minutes after dripping is finished;
s7, after heat preservation is finished, adding ammonia water, neutralizing and stirring, adding a penetrating agent and the rest deionized water when the temperature is reduced to be below 50 ℃, uniformly stirring, filtering and discharging to obtain the acrylic emulsion for leather treatment. In the preparation method of the acrylic emulsion, in the step S6, the initiator solution a and the remaining pre-emulsion are added dropwise at a constant speed.
The preparation method of the acrylic emulsion comprises the step of dropwise adding the residual pre-emulsion in the step S6 for 1 hour.
In the S6, the initiator solution a is controlled to be added 10 minutes later than the pre-emulsion.
The preparation method of the acrylic emulsion comprises the step of controlling the heat preservation temperature in S6 to be 85-87 ℃.
Has the beneficial effects that:
the invention provides an acrylic emulsion for leather treatment, which is mainly composed of butyl acrylate and is supplemented with a small amount of methacrylic acid and methyl methacrylate, wherein the methacrylic acid can increase the emulsifying effect of an emulsifier, so that the emulsion has smaller particle size and has more excellent permeability, blocking property and flexibility.
The invention also provides a preparation method of the acrylic emulsion, which is used for preparing the acrylic emulsion for leather treatment, the preparation method adopts the polymerization under the condition of lower temperature, the stability is good, the safety is high, and the emulsion particles with ultra-small particle size can be prepared.
Detailed Description
The invention provides an acrylic emulsion for leather treatment and a preparation method thereof, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail by the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an acrylic emulsion for leather treatment, which comprises the following preparation raw materials in parts by weight: 100 portions of deionized water, 27.5 to 29 portions of butyl acrylate, 1.5 to 1.8 portions of methyl methacrylate, 3 to 4 portions of methacrylic acid, 0.15 to 0.25 portion of n-dodecyl mercaptan, 0.3 to 0.5 portion of emulsifier, 0.1 to 0.2 portion of initiator, 2 to 3 portions of ammonia water and 2 to 3 portions of penetrant.
The acrylic emulsion of the invention takes butyl acrylate as a main component, is supplemented with a small amount of methacrylic acid and methyl methacrylate, and reduces the molecular weight through n-dodecyl mercaptan, so that the Tg of the polymer is low, the polymer has good flexibility and strong adhesion.
In addition, the methyl methacrylate can improve the polymerization effect in the formula, plays a role of a bridge, enables the reaction to be more stable and the conversion rate to be higher, and can change the refractive index of the polymer, so that the refractive index of the final finished product is closer to that of water, and the finished product is clearer and more transparent in appearance.
Methacrylic acid tends to aggregate on the surface of emulsion particles during reaction, so that the emulsifier adsorbed on the surface of polymerized microemulsion particles is reduced, the emulsifier participating in the emulsification monomer is increased, the micelle amount is increased, and the particle size of emulsion particles can be smaller.
The ammonia water is used for neutralizing carboxylic acid groups in a system, when methacrylic acid is polymerized, the carboxylic acid groups are not neutralized by the ammonia water, the refractive index is different, and the ammonia water can present different colors and transparencies before and after neutralization: before the emulsion is neutralized, the color of the emulsion is milky white with blue; after neutralization of the emulsion, it was clear and transparent.
Preferably, the emulsifier comprises at least one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate. Wherein, the acrylic emulsion prepared by only adopting the sodium dodecyl sulfate has the smallest particle size, the particle size range is 20-40 nm, and the permeability is the best.
In the present invention, the content of the emulsifier is not so excessive that the emulsifier remains on the surface of the leather, and the emulsifier remaining on the surface of the leather causes uneven patterns and coloring in the subsequent embossing process of the leather.
Preferably, the osmotic agent includes dioctyl sodium sulfosuccinate. And the penetrant is further added, so that the penetrating power of the emulsion is stronger.
Preferably, the initiator comprises ammonium persulfate.
Preferably, the raw materials for preparing the acrylic emulsion for leather treatment further comprise a bactericide, and the using amount of the bactericide is 0.4-0.6 part.
A preparation method of the acrylic emulsion for leather treatment is used for preparing the acrylic emulsion for leather treatment, and comprises the following steps:
s1, preparing a base material liquid: adding 60-65 parts of deionized water and 0.15-0.28 part of emulsifier into a polymerization kettle, uniformly stirring, and raising the temperature of the polymerization kettle to 85 ℃;
s2, preparing a pre-emulsion: mixing 14.5-17 parts of deionized water, methacrylic acid, butyl acrylate, methyl methacrylate, n-dodecyl mercaptan and the rest of emulsifier, and uniformly stirring to prepare a pre-emulsion for later use;
s3, preparing an initiator solution A: dissolving 0.05-0.12 part of initiator into 4.5-6.0 parts of deionized water to prepare initiator solution A for later use;
s4, preparing an initiator solution B: dissolving 0.02-0.08 part of initiator into 0.6-1.0 part of deionized water to prepare initiator solution B for later use;
s5, adding 5% of the total amount of the pre-emulsion and an initiator solution B into the polymerization kettle, and reacting for 20 minutes to prepare a seed emulsion;
s6, simultaneously dripping an initiator solution A and the residual pre-emulsion into the polymerization kettle, and preserving heat for 45 minutes after dripping is finished;
s7, after heat preservation is finished, adding ammonia water, neutralizing and stirring, adding a penetrating agent and the rest deionized water when the temperature is reduced to be below 50 ℃, uniformly stirring, filtering and discharging to obtain the acrylic emulsion for leather treatment. Preferably, in S6, the initiator solution a and the remaining pre-emulsion are added dropwise at a constant speed.
Preferably, in S6, the remaining pre-emulsion is added dropwise for 1 hour.
Preferably, in S6, the initiator solution a is controlled to be added dropwise 10 minutes later than the pre-emulsion.
Preferably, in the step S6, the heat preservation temperature is controlled to be 85-87 ℃. Specifically, the ammonia water is added at 85-87 ℃, the thermal motion of a molecular chain is stronger when the temperature is high, the neutralization reaction of carboxylic acid and the ammonia water is more sufficient, if the temperature is reduced to below 50 ℃, latex particles are basically shaped, part of carboxylic acid groups are wrapped in the latex particles, and in addition, the carboxylic acid on the outer layer of the latex particles forms steric hindrance after being neutralized, so that the carboxylic acid in the latex particles is more difficult to be neutralized, the structure of the emulsion cannot be expected, and the appearance of the emulsion can present a clear bluish phase.
In S7, when the temperature is reduced to below 50 ℃, a bactericide can be added. The biocide is used to increase the shelf life of the emulsion for a longer life.
The present invention will be further described below by way of specific examples and comparative examples.
Example 1
An acrylic emulsion for leather treatment comprises the following raw materials in parts by weight: 100 parts of deionized water, 29 parts of butyl acrylate, 1.5 parts of methyl methacrylate, 3 parts of methacrylic acid, 0.15 part of n-dodecyl mercaptan, 0.3 part of emulsifier, 0.15 part of initiator, 2 parts of ammonia water, 0.6 part of bactericide and 2.5 parts of penetrant;
the initiator is ammonium persulfate;
the emulsifier is sodium dodecyl sulfate;
the preparation method of the acrylic emulsion for leather treatment comprises the following steps:
s1, preparing a base material liquid: adding 60.5 parts of deionized water and 0.173 part of emulsifier into a polymerization kettle, uniformly stirring, and raising the temperature of the polymerization kettle to 85 ℃;
s2, preparing a pre-emulsion: mixing 14.8 parts of deionized water, methacrylic acid, butyl acrylate, methyl methacrylate, n-dodecyl mercaptan and the rest of emulsifier, and uniformly stirring to prepare a pre-emulsion for later use;
s3, preparing an initiator solution A: dissolving 0.1 part of initiator in 4.6 parts of deionized water to prepare an initiator solution A for later use;
s4, preparing an initiator solution B: dissolving 0.05 part of initiator into 0.62 part of deionized water to prepare initiator solution B for later use;
s5, adding 5% of the total amount of the pre-emulsion and an initiator solution B into the polymerization kettle, and reacting for 20 minutes to prepare a seed emulsion;
s6, simultaneously dripping an initiator solution A and the rest pre-emulsion into the polymerization kettle, keeping the constant speed during dripping, controlling the dripping time of the pre-emulsion to be 1 hour, finishing dripping the initiator solution A10 minutes later than the pre-emulsion, and keeping the temperature for 45 minutes after finishing dripping, wherein the heat preservation temperature is controlled to be 85-87 ℃;
s7, after heat preservation is finished, adding ammonia water, neutralizing and stirring, adding a penetrating agent and the rest deionized water when the temperature is reduced to be below 50 ℃, uniformly stirring, filtering and discharging to obtain the acrylic emulsion for leather treatment.
Example 2
An acrylic emulsion for leather treatment comprises the following raw materials in parts by weight: 100 parts of deionized water, 27.5 parts of butyl acrylate, 1.8 parts of methyl methacrylate, 4 parts of methacrylic acid, 0.25 part of n-dodecyl mercaptan, 0.5 part of emulsifier, 0.2 part of initiator, 3 parts of ammonia water, 0.6 part of bactericide and 3 parts of penetrant;
the initiator is ammonium persulfate;
the emulsifier is sodium dodecyl sulfate;
the preparation method of the acrylic emulsion for leather treatment comprises the following steps:
s1, preparing a base material liquid: adding 65 parts of deionized water and 0.28 part of emulsifier into a polymerization kettle, uniformly stirring, and raising the temperature of the polymerization kettle to 85 ℃;
s2, preparing a pre-emulsion: mixing 17 parts of deionized water, methacrylic acid, butyl acrylate, methyl methacrylate, n-dodecyl mercaptan and the rest of emulsifier, and uniformly stirring to prepare a pre-emulsion for later use;
s3, preparing an initiator solution A: dissolving 0.12 part of initiator into 6.0 parts of deionized water to prepare an initiator solution A for later use;
s4, preparing an initiator solution B: dissolving 0.08 part of initiator into 1.0 part of deionized water to prepare initiator solution B for later use;
s5, adding 5% of the total amount of the pre-emulsion and an initiator solution B into the polymerization kettle, and reacting for 20 minutes to prepare a seed emulsion;
s6, simultaneously dripping an initiator solution A and the rest pre-emulsion into the polymerization kettle, keeping the constant speed during dripping, controlling the dripping time of the pre-emulsion to be 1 hour, finishing dripping the initiator solution A10 minutes later than the pre-emulsion, and keeping the temperature for 45 minutes after finishing dripping, wherein the heat preservation temperature is controlled to be 85-87 ℃;
s7, after heat preservation is finished, adding ammonia water, neutralizing and stirring, adding a penetrating agent and the rest deionized water when the temperature is reduced to be below 50 ℃, uniformly stirring, filtering and discharging to obtain the acrylic emulsion for leather treatment.
Example 3
An acrylic emulsion for leather treatment, which is different from example 2 in that sodium dodecylbenzenesulfonate is used instead of sodium dodecylsulfate in the preparation raw material.
Example 4
An acrylic emulsion for leather treatment, which is different from example 2 in that sodium lauryl sulfate was replaced with sodium fatty alcohol-polyoxyethylene ether sulfate as a raw material for preparation.
Comparative example 1
An acrylic emulsion for leather treatment, which is different from example 2 in that 1 part of methacrylic acid was used as a raw material for the preparation thereof.
Comparative example 2
An acrylic emulsion for leather treatment, which is different from example 2 in that acrylic acid is used instead of methacrylic acid.
Comparative example 3
An acrylic emulsion for leather treatment, which is different from example 2 in that ammonia water is added after the temperature is lowered to below 50 ℃ in S7.
Comparative example 4
An acrylic emulsion for leather treatment, which is different from example 2 in that t-dodecyl mercaptan is used instead of n-dodecyl alcohol.
Comparative example 5
Acrylic emulsion product for leather treatment (model: langsheng FGR)
The acrylic emulsions of examples 1 to 4 and comparative examples 1 to 5 were tested for various properties by the following methods:
appearance: the transparency and color of the emulsion were visually observed, and 110g of the emulsion was filled in a disposable transparent plastic cup, and the emulsion was observed in front view and in plan view, respectively. Transparency scoring: randomly selecting 10 persons, scoring according to the transparency of the emulsion, wherein the scoring range is 0-5 points, the transparency of 0 point is very small, the transparency of 5 points is very large, and finally, the average value of the scores of 10 persons is taken as a result.
Odor: randomly selecting 10 people, scoring according to the odor of the emulsion, wherein the scoring range is 0-5 points, 0 point is small odor, 5 points is large odor, and finally, the average value of the scores of 10 people is taken as a result.
Emulsion film hardness and hand: pouring 3.8g of emulsion into a petri dish with the diameter of 100mm, drying for 48 hours in a constant temperature chamber, then drying for 24 hours in an oven at 50 ℃, forming a film by the dried emulsion, and judging the hardness, the meat feel and the fullness by touching with hands.
Permeability: dropping emulsion beads on the buffalo hide by using a disposable plastic dropper, and recording the time of the emulsion beads penetrating into the leather by taking seconds as a unit.
The fracture resistance performance is as follows: reference is made to QB/T2714-2005, "determination of the resistance to folding in physical and mechanical tests of leather".
And (3) embossing effect: and (3) after the buffalo skin is subjected to emulsion treatment, embossing treatment is carried out on the surface, and the embossing effect is observed.
The corresponding test results are as follows:
from the above results, it can be seen that the emulsion particles of examples 1 and 2 have the smallest particle size range, clear and transparent appearance, moderate hardness of the emulsion film, and fast permeation speed, and the times of fracture resistance of the scalped cowhide of examples 1 and 2 under normal and low temperature conditions are far superior to that of the prior art (comparative example 5), and the embossed three-dimensional effect is strong.
In example 3, sodium dodecylbenzenesulfonate was used as an emulsifier, and the prepared emulsion had a particle size ranging from 60 to 120nm, which was inferior in permeability to examples 1 and 2. Accordingly, the treated scalded cowhide also did not have the same number of folds as examples 1 and 2.
In example 4, sodium fatty alcohol polyoxyethylene ether sulfate is used as an emulsifier, the particle size range of the prepared emulsion is 40-60 nm, and the permeability is poorer than that of example 1 and example 2. Accordingly, the treated scalded cowhide also did not have the same number of folds as examples 1 and 2.
The amount of the methacrylic acid used in comparative example 1 is only 1 part, which is less than that used in examples 1 and 2, the obtained emulsion has a larger particle size range, the permeability is obviously inferior to that of examples 1 and 2, the folding times of the treated scaly cowhide are also obviously reduced, and the result shows that the proper amount of the methacrylic acid can effectively improve the permeability of the emulsion.
In the comparative example 2, acrylic acid is used for replacing methacrylic acid, so that the prepared emulsion has larger particle size and higher viscosity, and the permeability of the emulsion is poor; the large particle size of the emulsion particles means that the molecular weight is also larger, so that the film forming property is increased, the film is easily formed on the surface layer of the leather, and the filling adhesion effect is not realized, therefore, the folding times of the treated scalded cowhide are inferior to those of examples 1 and 2, and even lower than that of comparative example 1.
In comparative example 3, in the preparation of acrylic emulsion, in S7, ammonia water is added after the system temperature is reduced to below 50 ℃, the particle size of the prepared acrylic emulsion is 100-140 nm, the permeability is obviously reduced, and the folding times and the embossing effect of the treated scalded cowhide are not as good as those of examples 1 and 2 in terms of application effect.
In comparative example 4, in which t-dodecyl mercaptan was used instead of n-dodecyl alcohol, the acrylic emulsion obtained was inferior in permeability, smells strong, and the number of folds and embossing effects of the treated buffy coat were inferior to those of examples 1 and 2.
Comparative example 5 is an acrylic emulsion for leather of the prior art, which has a hard emulsion film, insufficient softness, poor permeability, and a large odor, and the number of folding times and embossing effects of the treated scaly cowhide were significantly inferior to those of examples 1 and 2.
In conclusion, the acrylic emulsion for leather provided by the invention has excellent permeability and adhesion, can effectively maintain the softness of leather and improve the fracture resistance when being applied to the leather, and can also enable the embossing three-dimensional effect to be better.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (10)
1. The acrylic emulsion for leather treatment is characterized by comprising the following preparation raw materials in parts by weight: 100 portions of deionized water, 27.5 to 29 portions of butyl acrylate, 1.5 to 1.8 portions of methyl methacrylate, 3 to 4 portions of methacrylic acid, 0.15 to 0.25 portion of n-dodecyl mercaptan, 0.3 to 0.5 portion of emulsifier, 0.1 to 0.2 portion of initiator, 2 to 3 portions of ammonia water and 2 to 3 portions of penetrant.
2. The leather-treating acrylic emulsion of claim 1 wherein the emulsifier comprises sodium lauryl sulfate.
3. The leather treatment acrylic emulsion of claim 1 wherein the penetrating agent comprises dioctyl sodium sulfosuccinate.
4. The leather-treating acrylic emulsion of claim 1, wherein the initiator comprises ammonium persulfate.
5. The acrylic emulsion for leather treatment according to claim 1, wherein the raw material for the preparation further comprises a bactericide.
6. A method for preparing the acrylic emulsion for leather treatment according to any one of claims 1 to 5, comprising the steps of:
s1, preparing a base material liquid: adding 60-65 parts of deionized water and 0.15-0.28 part of emulsifier into a polymerization kettle, uniformly stirring, and raising the temperature of the polymerization kettle to 85 ℃;
s2, preparing a pre-emulsion: mixing 14.5-17 parts of deionized water, methacrylic acid, butyl acrylate, methyl methacrylate, n-dodecyl mercaptan and the rest of emulsifier, and uniformly stirring to prepare a pre-emulsion for later use;
s3, preparing an initiator solution A: dissolving 0.05-0.12 part of initiator into 4.5-6.0 parts of deionized water to prepare initiator solution A for later use;
s4, preparing an initiator solution B: dissolving 0.02-0.08 part of initiator into 0.6-1.0 part of deionized water to prepare initiator solution B for later use;
s5, adding 5 percent of the total amount of the pre-emulsion and an initiator solution B into the polymerization kettle, and reacting for 20 minutes to prepare a seed emulsion;
s6, simultaneously dripping an initiator solution A and the residual pre-emulsion into the polymerization kettle, and preserving heat for 45 minutes after dripping is finished;
s7, after heat preservation is finished, adding ammonia water, neutralizing and stirring, adding a penetrating agent and the rest deionized water when the temperature is reduced to be below 50 ℃, uniformly stirring, filtering and discharging to obtain the acrylic emulsion for leather treatment.
7. The method according to claim 6, wherein in S6, the initiator solution A and the remaining pre-emulsion are added dropwise at a constant rate.
8. The method of claim 6, wherein the step of adding the pre-emulsion remaining in S6 is performed for 1 hour.
9. The method of claim 8, wherein in S6, the initiator solution a is controlled to be added 10 minutes later than the pre-emulsion.
10. The method for producing an acrylic emulsion according to claim 8, wherein the holding temperature in S6 is controlled to 85 to 87 ℃.
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| CN116536460A (en) * | 2023-05-10 | 2023-08-04 | 四川大学 | Method for preparing transparent leather based on refractive index phase matching principle |
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