CN114182525A - A kind of hydrophobic modification method of polyacrylate - Google Patents
A kind of hydrophobic modification method of polyacrylate Download PDFInfo
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- CN114182525A CN114182525A CN202111624738.1A CN202111624738A CN114182525A CN 114182525 A CN114182525 A CN 114182525A CN 202111624738 A CN202111624738 A CN 202111624738A CN 114182525 A CN114182525 A CN 114182525A
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- silicon dioxide
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- polyacrylate
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 64
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 139
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 61
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000010008 shearing Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000742 Cotton Polymers 0.000 claims abstract description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920006222 acrylic ester polymer Polymers 0.000 claims abstract description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 244000282866 Euchlaena mexicana Species 0.000 claims abstract description 3
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 229910007156 Si(OH)4 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
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- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a hydrophobic modification method of polyacrylate, which comprises the following steps of: adding ethanol and TEOS into a three-neck flask, stirring, heating to 27-30 ℃, uniformly mixing, adding ammonia water, and reacting in a constant-temperature constant-pressure magnetic stirrer after deionized water is added; preparation of acrylate polymer: mixing sodium dodecyl sulfate, AE0-9, small-particle-size silicon dioxide and water, emulsifying and shearing, adding methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate, emulsifying and shearing, heating to 70-75 ℃ under the protection of nitrogen, dropwise adding initiator ammonium persulfate, and continuously reacting for 2-3 hours at 70-75 ℃; and (3) soaking the cotton fabric in the acrylic ester polymer emulsion, taking out and baking.
Description
Technical Field
The invention belongs to the technical field of hydrophobic modification, and particularly relates to a hydrophobic modification method of polyacrylate.
Background
Nowadays, society is continuously developed, various high and new materials are continuously emerged, and nano SiO2The nano silicon dioxide has many hydroxyl groups and is easy to dissolve in water, and the structure of the nano silicon dioxide is a three-dimensional net structure so that the nano silicon dioxide has good supporting force, and the nano silicon dioxide is uniformly dispersed by using an ultrasonic oscillator when in use. However, the dispersion of the nano-silica may be improved by surface modification of the nano-silicaAnd reduces the hydrophilicity of the nano silicon dioxide.
The application range of the nano silicon dioxide is very wide, the application mode is also very simple, the adding amount is generally controlled to be 0.5 to 2 percent when the nano silicon dioxide is used, and certain special product systems can be added by more than 10 percent. The nano silicon dioxide has the advantages of fully dispersing into a system for the product performance. When in use, the nano silicon dioxide is dispersed in various solvents such as water, acetone, alcohols and the like in advance according to different systems, and an auxiliary agent can be supplemented for pretreatment of an oily system. The antibacterial paint is mainly used for manufacturing (1) an electronic packaging material (2), a resin composite material (3), a plastic (4), a coating (5), a rubber (6), a pigment (7), a ceramic (8), a sealant, a binder (9), a glass fiber reinforced plastic product (10), a drug carrier (11) and a cosmetic (12) antibacterial material.
According to the research of the invention, the influence of the addition amount and the particle size of the silicon dioxide on the hydrophobicity of the acrylate polymer is large, and the silicon dioxide can perform hydrophobic modification on the acrylate polymer.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention provides a hydrophobic modification method of polyacrylate.
In order to solve the technical problems, the invention provides the following technical scheme: a method for hydrophobically modifying a polyacrylate, comprising,
preparing small-particle-size silicon dioxide: adding ethanol and TEOS into a three-neck flask, stirring, heating to 27-30 ℃, uniformly mixing, adding ammonia water, and reacting in a constant-temperature constant-pressure magnetic stirrer at 27-30 ℃ for 16-20 h after deionized water is added;
preparation of acrylate polymer: mixing sodium dodecyl sulfate, AEO-9, small-particle-size silicon dioxide and water, emulsifying and shearing, adding methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate, emulsifying and shearing, heating to 70-75 ℃ under the protection of nitrogen, dropwise adding initiator ammonium persulfate, and continuously reacting for 2-3 hours at 70-75 ℃;
and (3) soaking the cotton fabric in the acrylic ester polymer emulsion, taking out and baking.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the preparation method comprises the step of preparing small-particle-size silicon dioxide, wherein the particle size of the silicon dioxide is 50-60 nm.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the concentration of the TEOS is 8-10%.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the concentration of the ammonia water is 0.5-5%; the concentration of the deionized water is 0.5-10%.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the mass percentage of the small-particle-size silicon dioxide in the acrylate polymer is 0.1-0.5%.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the mass ratio of the sodium dodecyl sulfate, the AEO-9 and the small-particle-size silicon dioxide is 2: 4: 1.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the mass ratio of the methyl methacrylate to the butyl acrylate to the hydroxyethyl methacrylate is 1: 1.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the cotton fabric is soaked in the acrylic ester polymer emulsion for 30-40 min at room temperature.
As a preferable embodiment of the method for hydrophobically modifying polyacrylate according to the present invention: the baking is to bake at 100 ℃ for 10min, then to heat to 160 ℃ for 10min, and then to take out.
The invention has the beneficial effects that: the hydrophobicity of the acrylate polymer tends to be better and better along with the increase of the content of the silicon dioxide, the contact angle gradually increases in the process of adding the 60nm silicon dioxide, and the contact angle begins to become smaller until the contact angle is added to 0.1g, because the excessive silicon dioxide is added to cause the silicon dioxide to be attached to the surface of the fabric, the contact angle is reduced, and the hydrophobicity is also reduced; further, when 480nm silica was added, the contact angle tended to increase until the contact angle began to decrease when the silica was added to 0.075g, that is, the contact angle decreased when the silica was excessively added, and the hydrophobicity also decreased.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a particle size spectrum of a polyacrylate emulsion.
FIG. 2 is a Zeta potential diagram of a polyacrylate emulsion.
FIG. 3 is an infrared test chart of the polymer.
FIG. 4 is a diagram of SiO with a small particle size2SEM spectrum of (d).
FIG. 5 shows SiO with a large particle size2SEM spectrum of (d).
Fig. 6 is the contact angle of a polyacrylate polymer without added silica.
FIG. 7 is the contact angle of an acrylate polymer with 0.025g of 60nm silica added.
FIG. 8 is the contact angle of an acrylate polymer with 0.05g of 60nm silica added.
FIG. 9 is the contact angle of an acrylate polymer with 0.075g of 60nm silica added.
FIG. 10 is the contact angle of an acrylate polymer with 0.1g 60nm silica added.
FIG. 11 is the contact angle of an acrylate polymer with 0.025g 480nm silica added.
FIG. 12 is the contact angle of an acrylate polymer with 0.05g 480nm silica added.
FIG. 13 is the contact angle of an acrylate polymer with 0.075g 480nm silica added.
FIG. 14 is the contact angle of an acrylate polymer with 0.1g 480nm silica added.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
the main synthetic reaction steps and routes are as follows:
(A) and (3) hydrolysis reaction: si (OC)2H5)4+4H2O→Si(OH)4+4C2H5OH
(B) Condensation reaction: si (OH)4→nSiO2+2nH2O。
Preparation scheme of small-particle-size silicon dioxide: 100ml of ethanol and 8.33g of TEOS were put into a three-necked flask, stirred for 10 minutes, and then heated to 27 ℃ to be uniformly mixed. 1.5g of ammonia water and 2.6g of deionized water are added in one portion and then reacted for 18 hours in a constant temperature and pressure magnetic stirrer at 27 ℃.
Preparation scheme of large-particle-size silicon dioxide: 50ml of ethanol is added into a three-neck flask, 5ml of ammonia water and 25ml of deionized water are added, then a glass rod is used for stirring for 10 minutes, then the temperature is raised to 27 ℃, after the mixture is fully mixed, TEOS25ml is slowly dripped by using a constant pressure dropping funnel, and after the dripping is finished, the mixture reacts at the temperature of 27 ℃ for 18 hours and is taken out.
And (3) carrying out post-treatment on the product: and carrying out suction filtration on the product to obtain white solid nano silicon dioxide, washing twice by using ethanol, carrying out suction filtration again, drying and then packaging by using a plastic tube.
TABLE 1 Ammonia to Nano SiO2Influence factor of particle size
TABLE 2 distilled water dosage vs. nano SiO2Influence of particle size
Emulsion polymerization: adding SDS (sodium dodecyl sulfate), AEO-9 and 157 ml deionized water into a 250 ml beaker, emulsifying and shearing for 3 minutes by an emulsifying machine, adding (methyl methacrylate) MMA, (butyl acrylate) BA and (hydroxyethyl methacrylate) HEMA after the emulsification and the shearing are finished, emulsifying and shearing again, transferring into a 250 ml three-neck flask after 15 minutes, heating to 75 ℃ under the protection of nitrogen, dropwise adding initiator ammonium persulfate (dissolved in 20 ml of deionized water), wherein the dropwise adding time is 1 hour, and continuously reacting for 3 hours at 75 ℃ after the dropwise adding is finished. And (5) cooling, and finishing the reaction.
The effect of silica addition on the hydrophobicity of polyacrylate polymers:
TABLE 3 Effect of Small particle size silica addition on hydrophobicity of acrylate polymers
| Acrylate polymer emulsion PA | 50nm silica |
| 40g | 0g |
| 40g | 0.025g |
| 40g | 0.05g |
| 40g | 0.075g |
| 40g | 0.1g |
Particle size and ZETA potential test analysis:
the sol solution was diluted with water and the potential was obtained on the instrument.
There are many zeta potential measuring methods, and the current measuring methods mainly include electrophoresis, electroosmosis, streaming potential and ultrasonic method, of which electrophoresis is the most common method. The zeta potential meaning is related to its value and its stability. The relationship is shown in the following table:
TABLE 4 relationship between potential and System stability
| Zeta potential/mv | Colloidal stabilizationProperty of (2) |
| 0-±5 | Rapid coagulation or coagulation |
| ±10-±30 | Begin to become unstable |
| ±30-±40 | Stability in general |
| ±40-±6 | Better stability |
| ＞±60 | Excellent stability |
Infrared spectrum analysis:
the infrared spectrum can obtain functional groups according to wave crests and wave troughs, the spectrum is a molecular spectrum, and the tabletting method comprises the following steps: respectively taking tiny pieces of raw cloth and finished cotton fabric, cutting into pieces, placing the pieces into an infrared drying oven for drying, then drying the pieces in the drying oven, then grinding dried potassium chloride, mixing the pieces according to the proportion of 1: 200, tabletting, setting a certain scanning range of an instrument, testing the infrared absorption spectra of the raw cloth and the finished cotton fabric after blank debugging.
A. Principle of infrared spectrometer
When light passing through an object passes through a monochromator, the light waves will be dispersed as such, the composite light will be dispersed into monochromatic light, and the alignment will vary according to the wavelength. The spectrogram of the sample is obtained after receiving the measurement. And finally, converting the interference signal into a common signal, and waiting for the detector to receive the signal. When the signal arrives, the detector will check and scan the monochromatic light, so that the teaching quality and efficiency are sensitively improved.
B. Preparation of the samples
The infrared spectrum sample can be prepared by pressing, pasting, film forming, attenuated total reflection, diffuse reflection preparation and other methods. The tabletting method is the simplest of several methods, and the test method used is to press KBr into a thin film which is placed on the sample holder of the tester and analyzed by infrared light.
Fabric contact angle test analysis:
the contact angle refers to the angle between the liquid attached to the fabric and the solid-liquid boundary. If the angle is as small as 90 degrees, the hydrophilicity is good; if the angle is larger than 90 degrees, the solid surface is hydrophobic, liquid is not easy to invade the fabric part, move on the surface easily, and is not easy to wet, and the good vegetable and water performance is shown.
The contact angle tester can also test the contact angles of various liquid boiled beads on various fiber fabrics, and the application range is wider. There are many kinds of contact angle measuring methods, including direct method, quantitative method and angle measuring method. The mass method is the most common method, and has the advantages of simple operation, short time consumption and cost saving.
The experiment is carried out by a high-dosage method. The high gauge method can be calculated by the following formula:
Θ＝2atctan(h/x)
particle size and Zeta potential of polyacrylate emulsion:
as shown in FIG. 1, the particle size of the present polyacrylate emulsion is about 85.58nm, and the particle size of the emulsion particles is relatively small, which indicates that the silica particles are relatively well dispersed and the state is stable. FIG. 2 is a Zeta potential diagram of a polyacrylate emulsion. Zeta potential is commonly referred to as shear surface potential, also known as electromotive force (Zeta potential), and is an important indicator of colloidal dispersion stability. The smaller the molecule or dispersed particle, the higher the absolute value of the Zeta potential (positive or negative), the more stable the overall system, corresponding to dissolution or dispersion resistance to aggregation. On the contrary, it is known that the lower the Zeta potential (positive or negative), the more likely it is to be coagulated or aggregated, that is, the attractive force exceeds the repulsive force, and the dispersibility is destroyed to coagulate or aggregate. As shown in FIG. 2, the Zeta potential of the present polymer emulsion is-49.7, the absolute value thereof is 49.7, which is close to 50, and the value is still relatively high, which indicates that the whole system of the polyacrylate polymer emulsion is stable.
Infrared analysis of the polymer emulsion: FIG. 3 is an infrared test chart of a polymer in which atoms constituting a chemical bond or a functional group in an organic molecule are in a constant vibration state, and the vibration frequency of the atoms is the same as that of infrared light. Since infrared absorption peaks of various functional groups appear in a specific wavelength range, these characteristic absorption peaks have strong characteristics and are not easily affected by surrounding portions, and therefore, what functional groups exist in an organic molecule can be judged according to the positions and shapes of the absorption peaks in the spectrum. As shown in fig. 3, from which we can infer that 2955.23cm is shown-1The nearby absorption peaks represent the C-H and stretching vibration peaks and bending vibration of the emulsion, respectively, 1731.19cm-1The nearby absorption peaks represent the C-O and stretching vibration peaks and bending vibration of the emulsion, respectively, 1640cm-1The carbon-carbon double bond gradually disappears, which indicates that all the monomers participate in the reaction.
FIG. 4 is a diagram of SiO with a small particle size2SEM spectrum of (d). The particle size of the silica obtained by the experiment is basically about 60nm and 480nm through the detection of a scanning electron microscope, and the particle size is shown in figure 4. FIG. 5 shows SiO with a large particle size2SEM spectrum of (d).
Contact angle of 60nm silicon dioxide whole and polyacrylate mixed finishing fabric: 4 experiments were performed at 60nm and a control was added, with no silica added, at 0.025g, 0.05g, 0.075g, 0.1 g. The contact angles obtained by the test are shown in FIGS. 6-10. Fig. 6 is the contact angle of a polyacrylate polymer without added silica. FIG. 7 is the contact angle of an acrylate polymer with 0.025g of 60nm silica added. FIG. 8 is the contact angle of an acrylate polymer with 0.05g of 60nm silica added. FIG. 9 is the contact angle of an acrylate polymer with 0.075g of 60nm silica added. FIG. 10 is the contact angle of an acrylate polymer with 0.1g 60nm silica added.
Contact angle of 480nm silicon dioxide whole and polyacrylate mixed finishing fabric: the contact angles of the modified msilica monolith and polyacrylate hybrid-finished fabric for 480nm are shown in FIGS. 11-14. FIG. 11 is the contact angle of an acrylate polymer with 0.025g 480nm silica added. FIG. 12 is the contact angle of an acrylate polymer with 0.05g 480nm silica added. FIG. 13 is the contact angle of an acrylate polymer with 0.075g 480nm silica added. FIG. 14 is the contact angle of an acrylate polymer with 0.1g 480nm silica added.
TABLE 560 nm silica addition Effect on acrylate Polymer hydrophobicity
| Acrylate polymer emulsion PA | 60nm silica | Contact angle CA |
| 40g | 0g | 121.16° |
| 40g | 0.025g | 125.24° |
| 40g | 0.05g | 131.5° |
| 40g | 0.075g | 139.82° |
| 40g | 0.1g | 130.22° |
From the above data, it is known that the hydrophobicity of the acrylate polymer tends to be better as the content of silica increases, and the contact angle gradually increases during the addition of 60nm silica, and becomes smaller until the addition of 0.1g, because the excess silica is added to adhere to the surface of the fabric, and the contact angle is rather decreased, and the hydrophobicity is also decreased; further, when 480nm silica was added, the contact angle tended to increase until the contact angle began to decrease when the silica was added to 0.075g, that is, the contact angle decreased when the silica was excessively added, and the hydrophobicity also decreased.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A method for hydrophobically modifying polyacrylate, which is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing small-particle-size silicon dioxide: adding ethanol and TEOS into a three-neck flask, stirring, heating to 27-30 ℃, uniformly mixing, adding ammonia water, and reacting in a constant-temperature constant-pressure magnetic stirrer at 27-30 ℃ for 16-20 h after deionized water is added;
preparation of acrylate polymer: mixing sodium dodecyl sulfate, AEO-9, small-particle-size silicon dioxide and water, emulsifying and shearing, adding methyl methacrylate, butyl acrylate and hydroxyethyl methacrylate, emulsifying and shearing, heating to 70-75 ℃ under the protection of nitrogen, dropwise adding initiator ammonium persulfate, and continuously reacting for 2-3 hours at 70-75 ℃;
and (3) soaking the cotton fabric in the acrylic ester polymer emulsion, taking out and baking.
2. The method for the hydrophobic modification of polyacrylates according to claim 1, characterized in that: the preparation method comprises the step of preparing small-particle-size silicon dioxide, wherein the particle size of the silicon dioxide is 50-60 nm.
3. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the concentration of the TEOS is 8-10%.
4. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the concentration of the ammonia water is 0.5-5%; the concentration of the deionized water is 0.5-10%.
5. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the mass percentage of the small-particle-size silicon dioxide in the acrylate polymer is 0.1-0.5%.
6. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the mass ratio of the sodium dodecyl sulfate, the AEO-9 and the small-particle-size silicon dioxide is 2: 4: 1.
7. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the mass ratio of the methyl methacrylate to the butyl acrylate to the hydroxyethyl methacrylate is 1: 1.
8. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the cotton fabric is soaked in the acrylic ester polymer emulsion for 30-40 min at room temperature.
9. The method for the hydrophobic modification of polyacrylates according to claim 1 or 2, characterized in that: the baking is to bake at 100 ℃ for 10min, then to heat to 160 ℃ for 10min, and then to take out.
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| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN102605621A (en) * | 2012-03-08 | 2012-07-25 | 陕西科技大学 | Method for preparing fabric waterproof and moisture-permeable coating agent by nano-SiO2 modified polyacrylate |
| CN102911308A (en) * | 2012-11-19 | 2013-02-06 | 陕西科技大学 | A preparation method of fluorine-containing polyacrylate/double-size nano-SiO2 composite emulsion |
| CN107778405A (en) * | 2017-11-28 | 2018-03-09 | 陕西启源科技发展有限责任公司 | The preparation method of nano silicon/Polyacrylate Composites |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN102605621A (en) * | 2012-03-08 | 2012-07-25 | 陕西科技大学 | Method for preparing fabric waterproof and moisture-permeable coating agent by nano-SiO2 modified polyacrylate |
| CN102911308A (en) * | 2012-11-19 | 2013-02-06 | 陕西科技大学 | A preparation method of fluorine-containing polyacrylate/double-size nano-SiO2 composite emulsion |
| CN107778405A (en) * | 2017-11-28 | 2018-03-09 | 陕西启源科技发展有限责任公司 | The preparation method of nano silicon/Polyacrylate Composites |
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