CN111137881A - Siloxane modified graphene oxide, spandex spinning oil agent and preparation method thereof - Google Patents
Siloxane modified graphene oxide, spandex spinning oil agent and preparation method thereof Download PDFInfo
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- CN111137881A CN111137881A CN201911390199.2A CN201911390199A CN111137881A CN 111137881 A CN111137881 A CN 111137881A CN 201911390199 A CN201911390199 A CN 201911390199A CN 111137881 A CN111137881 A CN 111137881A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
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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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
The invention relates to siloxane modified graphene oxide, a spandex spinning oil agent and a preparation method thereof, belonging to the technical field of textile, wherein the preparation method of the siloxane modified graphene oxide provided by the invention comprises the following steps: mixing and dispersing graphene oxide and fatty alcohol-polyoxyethylene ether to obtain a first dispersion liquid; dropwise adding amino modified siloxane into the first dispersion, and reacting at 40-60 ℃ for 1-2h to obtain a second dispersion; shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid; wherein the mass ratio of the graphene oxide to the fatty alcohol-polyoxyethylene ether to the amino-modified siloxane is 2-5: 100: 0.4-5. The spandex spinning oil prepared from the siloxane-modified graphene oxide can be quickly spread on the surface of spandex and uniformly coated on the surface of the spandex, so that the spandex is endowed with good astringency and smoothness and excellent unwinding property.
Description
Technical Field
The invention belongs to the technical field of spinning, and particularly relates to siloxane modified graphene oxide, a spandex spinning oil agent and a preparation method thereof.
Background
Polyurethane elastic fiber, also called spandex, has high elongation, high elastic recovery rate and excellent dyeing property, and is widely applied to the field of textile and clothing. However, since spandex is a polyurethane fiber composed of urethane block copolymers and polar groups such as urethane and allophanate exist in the molecular structure, spandex filaments are easily bonded due to the action of hydrogen bonds.
In order to ensure that spandex has good formability and bundling property in the spinning forming process, simultaneously endow spandex with good smoothness and antistatic property, and enable spandex to be easily unwound in subsequent use without edge collapse, oiling the spandex in the spinning forming process is needed. In addition, the presence of the finish affects subsequent dyeing, and therefore the finish needs to be easily and thoroughly cleaned after weaving is completed.
At present, spandex oil agents have insufficient performance and stability, so that a spandex spinning oil agent with excellent performance and stability is urgently needed in the field.
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a siloxane-modified graphene oxide, a spandex spin finish, and a method for preparing the same, which overcome the above problems or at least partially solve the above problems.
The embodiment of the invention provides a preparation method of siloxane modified graphene oxide, which comprises the following steps:
mixing and dispersing graphene oxide and fatty alcohol-polyoxyethylene ether to obtain a first dispersion liquid;
dripping amino modified siloxane into the first dispersion liquid, and reacting for 1-2h at 40-60 ℃ to obtain a second dispersion liquid
Shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the fatty alcohol-polyoxyethylene ether to the amino-modified siloxane is 2-5: 100: 0.4-5.
Optionally, the diameter of a sheet layer of the graphene oxide is less than 50 μm, and the number of layers is 1-20.
Optionally, the amino-modified siloxane comprises at least one of: amino-terminated polydimethylsiloxane, side-chain amino polydimethylsiloxane and polyether amino co-modified polydimethylsiloxane; the amino-modified siloxane has an ammonia value of 0.5 to 1 mmol/g.
Optionally, the second dispersion liquid is subjected to high-speed shear dispersion to obtain a siloxane modified graphene oxide dispersion liquid, which comprises
Dropwise adding amino modified siloxane into the first dispersion, and reacting at 40-60 ℃ for 1-2h to obtain a second dispersion;
and shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid.
Based on the same inventive concept, the embodiment of the invention also provides siloxane modified graphene oxide prepared by the preparation method of the siloxane modified graphene oxide.
Based on the same inventive concept, the embodiment of the present invention further provides a spandex spinning oil, wherein the functional component of the spandex spinning oil is the siloxane-modified graphene oxide according to claim 5, and the spandex spinning oil comprises the following components by mass:
30-80% of dimethyl silicone oil, 0.01-0.5% of siloxane modified graphene oxide, 20-60% of mineral oil, 1-3% of antistatic agent, 3-20% of modified silicone oil and 2-10% of surfactant.
Based on the same inventive concept, embodiments of the present invention also provide a method for preparing a spandex spin finish according to claim 6, comprising:
mixing dimethyl silicone oil and siloxane modified graphene oxide, and shearing and dispersing to obtain a colorless and transparent component A;
mixing and reacting mineral oil and an antistatic agent to obtain a first reactant;
mixing and reacting a surfactant with the first reactant to obtain a second reaction product;
mixing and reacting modified silicone oil and the second reactant to obtain a component B;
and mixing and reacting the component A, the component B and dimethyl silicone oil to obtain the spandex spinning oil agent.
Optionally, the mass fraction ratio of the siloxane modified graphene oxide, the mineral oil, the antistatic agent, the surfactant, the modified silicone oil and the dimethyl silicone oil is 0.01-0.5: 20-60: 1-3: 2-10: 3-20: 30-80.
Optionally, the modified silicone oil and the siloxane-modified graphene oxide dispersion liquid are mixed and subjected to shear dispersion to obtain a colorless and transparent component a, which includes:
mixing dimethyl silicone oil and siloxane modified graphene oxide dispersion liquid, and shearing and dispersing at the rotating speed of 10000-;
mixing and reacting a mineral oil and an antistatic agent to obtain a first reactant comprising:
mixing mineral oil and antistatic agent, and reacting at 20-60 deg.C and 20-90r/min under stirring for 0.5-2h to obtain first reactant
Said mixing and reacting a surfactant and said first reactant to obtain a second reaction product comprising:
mixing a surfactant with the first reactant, and reacting for 0.5-2h at the temperature of 20-40 ℃ and the rotating speed of 20-90r/min under stirring to obtain a second reaction product;
the modified silicone oil and the second reactant are mixed and reacted to obtain component B, which comprises:
mixing the modified silicone oil with the second reactant, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain a component B.
Optionally, the step of mixing and reacting the component a, the component B and dimethyl silicone oil to obtain a spandex spinning oil agent comprises:
and mixing the component A, the component B and dimethyl silicone oil, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain the spandex spinning oil agent.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the siloxane modified graphene oxide provided by the embodiment of the invention can be applied to a spandex oil agent instead of the existing stearate, the specific surface area of the siloxane modified graphene oxide increases the contact area between the oil agent and the spandex filament, so that the oil agent is rapidly spread on the surface of the spandex filament and uniformly coated on the surface of the spandex filament, and thus the spandex filament is endowed with good astringent performance and excellent unwinding performance, wherein the unwinding surface layer of the spandex filament can reach 1.23 at most, and the bottom layer of the spandex filament can reach 1.45 at most.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
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Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
fig. 1 is a flow chart of a preparation method of siloxane-modified graphene oxide in an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
It should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Meanwhile, the terms "first", "second", etc. in the present invention do not denote any order or order, and these words may be interpreted as names.
In order to solve the technical problems, the technical scheme in the embodiment of the invention has the following general idea:
referring to fig. 1, an embodiment of the present invention provides a method for preparing siloxane-modified graphene oxide, where the method includes:
s1, mixing and dispersing graphene oxide and fatty alcohol-polyoxyethylene ether to obtain a first dispersion liquid;
s2, dropwise adding amino modified siloxane into the first dispersion, and reacting at 40-60 ℃ for 1-2h to obtain a second dispersion
S3, shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the fatty alcohol-polyoxyethylene ether to the amino-modified siloxane is 2-5: 100: 0.4-5.
According to the invention, the self-made amino modified siloxane modified graphene oxide is used as an anti-adhesion component to replace stearate and silicon dioxide isolation components in the existing spandex oil agent, and the selected graphene oxide is nano-scale, so that the contact area of the oil agent and spandex filaments is increased in the oiling process due to the large specific surface area of the graphene oxide, the oil agent can be spread on the surfaces of the spandex filaments, and meanwhile, a layer of protective isolation film is formed on the surfaces of the spandex filaments, so that the oil agent is prevented from permeating into the spandex filaments, and the filament breakage and adhesion probability of the spandex filaments in the unwinding process is reduced. Meanwhile, the graphene oxide modified by the amino modified siloxane has a similar molecular chain segment-Si-O-Si-with the silicone oil, so under the action of high-speed mechanical shearing, the graphene oxide modified by the amino modified siloxane can be uniformly dispersed in the silicone oil and always keeps a stable state.
The mass ratio of the graphene oxide to the fatty alcohol-polyoxyethylene ether to the amino modified siloxane is 2-5: 100: 0.4-5. If the mass ratio is too large, the graphene oxide is not easy to disperse uniformly; if the mass ratio is too small, the effective component of the siloxane-modified graphene oxide dispersion liquid is low, and the anti-sticking effect is not desirable.
The chemical structural formula of the graphene oxide is shown as follows:
in this embodiment, the fatty alcohol-polyoxyethylene ether functions to disperse the graphene oxide therein, and the fatty alcohol-polyoxyethylene ether includes, but is not limited to, at least one of the following: MOA-3, MOA-4 and MOA-5.
In some optional embodiments, the graphene oxide has a lamella diameter of < 50 μm and a number of layers of 1-20.
The sheet diameter and the number of sheets of the graphene oxide directly affect the specific surface area of the graphene oxide. When the specific surface area of the graphene oxide is within the range, a layer of isolating film can be formed on the surface of the spandex filament to prevent adhesion between the spandex filaments and optimize unwinding property. The diameter of the lamella and the number of layers are larger than the above values, the specific surface area of the graphene oxide is reduced, a uniform isolation layer cannot be formed on the surface of the spandex filament, and partial adhesion among the spandex filaments can be caused to generate filament breakage, so that the quality and the unwinding performance of the spandex filament are influenced.
In some alternative embodiments, the amino-modified siloxane includes at least one of: amino-terminated polydimethylsiloxane, side-chain amino polydimethylsiloxane and polyether amino co-modified polydimethylsiloxane; the amino-modified siloxane has an ammonia value of 0.5 to 1 mmol/g.
The amino-terminated polydimethylsiloxane has good compatibility with the dimethyl silicone oil, and can stably exist in an oil agent system in the preparation process of the spandex oil agent.
The side chain amino polydimethylsiloxane and the dimethyl silicone oil have good compatibility, and can stably exist in an oil agent system in the preparation process of the spandex oil agent.
The polyether amino co-modified polydimethylsiloxane has good compatibility with a surfactant and can stably exist in a spandex oil agent system.
In some alternative embodiments, the second dispersion is dispersed in high shear to obtain a siloxane-modified graphene oxide dispersion comprising
Dropwise adding amino modified siloxane into the first dispersion, and reacting at 40-60 ℃ for 1-2h to obtain a second dispersion;
and shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid.
Based on the same inventive concept, the embodiment of the invention also provides siloxane modified graphene oxide prepared by the preparation method of the siloxane modified graphene oxide.
Compared with the prior art, the siloxane modified graphene oxide can replace stearate and silicon dioxide isolation components, and endow the spandex yarn with good astringent and smooth properties. The prepared spandex oil agent improves the stability of the spandex oil agent and avoids the blockage of oil agent pipelines and the damage to weaving equipment on the basis of endowing spandex yarns with excellent smoothness, antistatic property, unwinding property and the like.
Based on the same inventive concept, the embodiment of the present invention further provides a spandex spinning oil, wherein the functional component of the spandex spinning oil is the siloxane-modified graphene oxide according to claim 5, and the spandex spinning oil comprises the following components by mass:
30-80% of dimethyl silicone oil, 0.01-0.5% of siloxane modified graphene oxide, 20-60% of mineral oil, 1-3% of antistatic agent, 3-20% of modified silicone oil and 2-10% of surfactant.
Mineral oil and silicone oil are used as main components of spandex oil agent, and the mutual matching can adjust the astringent and slippery balance of the oil agent. The mineral oil can endow the oil agent with certain smoothness, and is low in price.
And the compatibility with most of surfactants and antistatic agents is better than that of silicone oil, but the oil film strength is lower, the adhesion between spandex filaments is easy to cause, and the bottom unwinding property is poor. Compared with mineral oil, the silicone oil or modified silicone oil has more excellent smoothness, high oil film strength, small surface tension and more uniform oiling, but the silicone oil has extremely strong hydrophobicity and poor compatibility with an antistatic agent, and a certain amount of mineral oil and a surfactant must be added to stabilize the oil agent.
The siloxane modified graphene oxide is used as an anti-sticking component in the spandex oil agent, has good compatibility with silicone oil, and can be stably dispersed in the spandex oil agent.
In order to impart antistatic property and washability to the spandex finish, one or more antistatic agents and surfactants must be added to the finish. The selected surfactant and the antistatic agent need to have good compatibility and good compatibility with mineral oil, so that the antistatic agent can be stably dispersed in the oil agent without coagulation. Meanwhile, the selected surfactant can enable the oil agent to form stable emulsion in water, so that the oil agent is easy to wash off in subsequent processing.
The mass fractions of the components in the spandex finish directly influence the performance of the spandex finish, and in the limited range of the components, on one hand, the spandex finish has good stability and low cost and is easy to clean in the subsequent process, and on the other hand, the spandex yarn can be endowed with excellent smoothness, antistatic property, bundling property and excellent unwinding property of the bottom after being placed for a long time.
In this embodiment, the mineral oil includes, but is not limited to, one of the following: c10-C40Alkane, C10-C40Olefin of (C)10-C40Cyclic hydrocarbons of (a);
antistatic agents include, but are not limited to, one of the following: sodium polyoxyethylene ether sulfonate, isomeric tridecanol ether phosphate, fatty alcohol-polyoxyethylene ether phosphate and fatty alcohol-polyoxyethylene ether potassium phosphate;
the modified silicone oil includes, but is not limited to, one of the following: hydroxyl-terminated polyether modified silicone oil and hydroxyl-terminated amino-modified silicone oil;
surfactants include, but are not limited to, one of the following: anionic surfactants, cationic surfactants, nonionic surfactants.
Based on the same inventive concept, embodiments of the present invention also provide a method for preparing a spandex spin finish according to claim 6, comprising:
mixing and stirring the dimethyl silicone oil and the siloxane modified graphene oxide to obtain a colorless and transparent component A;
mixing and reacting mineral oil and an antistatic agent to obtain a first reactant;
mixing and reacting a surfactant with the first reactant to obtain a second reaction product;
mixing and reacting modified silicone oil and the second reactant to obtain a component B;
and mixing and reacting the component A, the component B and dimethyl silicone oil to obtain the spandex spinning oil agent.
In order to uniformly disperse siloxane modified graphene oxide in spandex oil, the siloxane modified graphene oxide has a similar structure to modified silicone oil and is good in compatibility, so that the siloxane modified graphene oxide is firstly dispersed in the modified silicone oil. The antistatic agent and the surfactant have good compatibility with the mineral oil, so that the antistatic agent and the surfactant are uniformly dispersed in the mineral oil, and the silicone oil has good compatibility with the mineral oil, so that the stable spandex oil agent can be obtained by mixing the antistatic agent and the surfactant together finally.
In some optional embodiments, the siloxane-modified graphene oxide, the mineral oil, the antistatic agent, the surfactant, the modified silicone oil, and the dimethicone have a mass fraction ratio of 0.01-0.5: 20-60: 1-3: 2-10: 3-20: 30-80.
The mass fraction of each component in the spandex oil agent directly influences the performance of the spandex oil agent, the mass fraction of siloxane modified graphene oxide is low, the spunbond effect is not obvious, and spandex filaments are easy to adhere to each other; the mass fraction is higher, and the astringency and the smoothness of the spandex oil agent are higher, so that the friction force among spandex filaments is large, and the quality of the spandex filaments is influenced. The mass fraction of the antistatic agent and the surfactant is low, and the spandex oil agent has poor antistatic property and stability and is not easy to clean; the mass fraction is higher, the polyurethane oil is not easy to be uniformly dispersed in the polyurethane oil and the cost is high. The mass fraction of the silicone oil and the modified silicone oil is low, the mass fraction of the mineral oil is high, the oil film strength is low, the oiling is uneven, and the unwinding property at the bottom of the spandex filament is poor; the mass fraction of the silicone oil and the modified silicone oil is higher, the mass fraction of the mineral oil is lower, the cost is high, the dispersibility of the surfactant and the antistatic agent is poor, and the stability of the oil agent is poor.
In some alternative embodiments, the mixing and shear dispersing the dimethicone and the siloxane-modified graphene oxide to obtain the colorless transparent component a comprises:
mixing dimethyl silicone oil and siloxane modified graphene oxide dispersion liquid, and shearing and dispersing at the rotating speed of 10000-;
mixing and reacting a mineral oil and an antistatic agent to obtain a first reactant comprising:
mixing mineral oil and antistatic agent, and reacting at 20-60 deg.C and 20-90r/min under stirring for 0.5-2h to obtain first reactant
Said mixing and reacting a surfactant and said first reactant to obtain a second reaction product comprising:
mixing a surfactant with the first reactant, and reacting for 0.5-2h at the temperature of 20-40 ℃ and the rotating speed of 20-90r/min under stirring to obtain a second reaction product;
the modified silicone oil and the second reactant are mixed and reacted to obtain component B, which comprises:
mixing the modified silicone oil with the second reactant, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain a component B.
In some alternative embodiments, said mixing and reacting said component a, said component B, and dimethicone to obtain a spandex spin finish, comprises:
and mixing the component A, the component B and dimethyl silicone oil, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain the spandex spinning oil agent.
The siloxane-modified graphene oxide, the spandex spinning oil and the preparation methods thereof provided by the embodiments of the present invention will be described in detail below with reference to the embodiments and experimental data.
Example 1
The preparation method of siloxane-modified graphene oxide provided in this embodiment and the siloxane-modified graphene oxide prepared according to the preparation method include:
s11, mixing and dispersing graphene oxide and MOA-3 to obtain a first dispersion liquid;
s12, dropwise adding amino modified siloxane into the first dispersion, and reacting for 1h at 60 ℃ to obtain a second dispersion;
s13, shearing and dispersing the second dispersion liquid at a high speed of 10000r/min for 30min to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the MOA-3 to the amino modified siloxane is 5: 100: 3.
Wherein the diameter of a sheet layer of the graphene oxide is 20 μm, and the number of layers of the graphene oxide is 5.
Wherein the amino-modified siloxane is: amino terminated polydimethylsiloxanes.
Example 2
The preparation method of siloxane-modified graphene oxide provided in this embodiment and the siloxane-modified graphene oxide prepared according to the preparation method include:
s11, mixing and dispersing graphene oxide and MOA-4 to obtain a first dispersion liquid;
s12, dropwise adding amino modified siloxane into the first dispersion, and reacting for 1h at 60 ℃ to obtain a second dispersion;
s13, shearing and dispersing the second dispersion liquid at a high speed of 10000r/min for 30min to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the MOA-4 to the amino modified siloxane is 5: 100: 3.
Wherein the diameter of a sheet layer of the graphene oxide is 20 μm, and the number of layers of the graphene oxide is 5.
Wherein the amino-modified siloxane is: side chain amino polydimethyl siloxane.
Example 3
The preparation method of siloxane-modified graphene oxide provided in this embodiment and the siloxane-modified graphene oxide prepared according to the preparation method include:
s11, mixing and dispersing graphene oxide and MOA-5 to obtain a first dispersion liquid;
s12, dropwise adding amino modified siloxane into the first dispersion, and reacting for 1h at 60 ℃ to obtain a second dispersion;
s13, shearing and dispersing the second dispersion liquid at a high speed of 10000r/min for 30min to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the MOA-5 to the amino modified siloxane is 5: 100: 3.
Wherein the diameter of a sheet layer of the graphene oxide is 20 μm, and the number of layers of the graphene oxide is 5.
Wherein the amino-modified siloxane is: polyether amino co-modified polydimethylsiloxane.
Example 4
The siloxane-modified graphene oxide in this example was prepared according to the method of example 1.
S101, shearing and dispersing 15 parts of dimethyl silicone oil and 4 parts of siloxane modified graphene oxide dispersion liquid for 1 hour at the rotating speed of 10000r/min to obtain a colorless and transparent component A for later use.
S102, adding 40 parts of mineral oil and 2 parts of sodium polyoxyethylene ether sulfonate into a beaker, stirring for 1.5 hours at the temperature of 60 ℃ at the rotating speed of 90r/min, then adding 4 parts of fatty alcohol-polyoxyethylene ether, stirring for 1 hour at the temperature of 40 ℃ at the rotating speed of 60r/min, finally adding 15 parts of double-end hydroxyl polyether modified silicone oil, and stirring for 2 hours at the temperature of 40 ℃ at the rotating speed of 60r/min to obtain the colorless and transparent component B.
S103, adding the component A and the component B into 20 parts of dimethyl silicone oil, and stirring at the temperature of 30 ℃ at the rotating speed of 40r/min for 2 hours to obtain the final spandex oil agent.
Example 5
The siloxane-modified graphene oxide in this example was prepared according to the method of example 1.
S101, shearing and dispersing 15 parts of dimethyl silicone oil and 4 parts of siloxane modified graphene oxide dispersion liquid for 1 hour at the rotating speed of 10000r/min to obtain a colorless and transparent component A for later use.
S102, adding 40 parts of mineral oil and 2 parts of isomeric tridecanol polyoxyethylene ether phosphate into a beaker, stirring for 1.5 hours at the temperature of 60 ℃ at the rotating speed of 90r/min, then adding 2 parts of isomeric tridecanol polyoxyethylene ether and 2 parts of fatty alcohol polyoxyethylene ether, stirring for 1 hour at the temperature of 40 ℃ at the rotating speed of 60r/min, finally adding 15 parts of double-end hydroxyl amino modified silicone oil, and stirring for 2 hours at the temperature of 40 ℃ at the rotating speed of 60r/min to obtain a colorless and transparent component B.
S103, adding the component A and the component B into 20 parts of dimethyl silicone oil, and stirring at the temperature of 30 ℃ at the rotating speed of 40r/min for 2 hours to obtain the final spandex oil agent.
Comparative example 1
Adding 40 parts of mineral oil and 2 parts of sodium polyoxyethylene ether sulfonate into a beaker, stirring for 1.5 hours at the temperature of 60 ℃ at the rotating speed of 90r/min, then adding 4 parts of fatty alcohol-polyoxyethylene ether, stirring for 1 hour at the temperature of 40 ℃ at the rotating speed of 60r/min, then adding 15 parts of double-end hydroxyl polyether modified silicone oil, stirring for 1 hour at the temperature of 40 ℃ at the rotating speed of 60r/min, finally adding 35 parts of dimethyl silicone oil, and stirring for 2 hours at the temperature of 30 ℃ at the rotating speed of 40r/min to obtain the spandex oil agent.
Experimental example 1
The stability of the spandex oil agents obtained in examples 4 to 5 of the present invention and comparative example 1 was evaluated by a static observation method, and the specific operation method was as follows: placing 100mL of spandex oil agent in a 100mL measuring cylinder, sealing and standing for 60 days, observing whether the surface layer of the oil agent is layered or not and whether the bottom of the oil agent is precipitated or not, and showing the test results in table 1. As can be seen from Table 1, the spandex oil agents prepared in examples 4 to 5 and comparative example 1 had excellent stability.
TABLE 1
The spandex oil agents of examples 4 to 5 and comparative example 1 of the invention were applied to 40D spandex yarn prepared by dry spinning, and the oiling rate was controlled at 5 ± 0.5% by a roller method, and wound up at 600m/min to form a cheese. The fresh yarn surface, inner layer unwinding and unwinding tension results are shown in table 2; the results of the aged yarn surface, inner layer unwinding property and unwinding tension after aging at 60 ℃ for 24 hours are shown in table 3, wherein the unwinding property is tested by recording the output speed of the spandex filament when the spandex filament is adhered to the surface of a yarn package at a prescribed input speed by using an electronic constant tension conveying system, the unwinding property of the spandex filament is represented by the output speed/input speed, and the smaller the ratio, the better the unwinding property of the spandex filament is represented.
TABLE 2
TABLE 3
As can be seen from table 2, the oils prepared in examples 4 to 5 and comparative example 1 had excellent anti-blocking effect, and example 4 and example 5, in which the amino-modified siloxane-modified nano-scaled graphene oxide was added, had better unwinding property than comparative example 1, so it can be inferred that the amino-modified siloxane-modified nano-scaled graphene oxide can be used as an anti-blocking agent for spandex oils instead of a stearate.
As can be seen from the data in tables 2 and 3, the aged spandex still maintains lower unwinding property and unwinding tension value, so that it can be further proved that the spandex finish prepared by the present invention has good anti-blocking effect and unwinding property, and compared with imported finishes, the unwinding property of the spandex finish treated by the spandex finish prepared in example 5 is comparable to that of the spandex finish treated by the present invention.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of siloxane modified graphene oxide is characterized by comprising the following steps:
mixing and dispersing graphene oxide and fatty alcohol-polyoxyethylene ether to obtain a first dispersion liquid;
dripping amino modified siloxane into the first dispersion liquid, and reacting for 1-2h at 40-60 ℃ to obtain a second dispersion liquid
Shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid;
wherein the mass ratio of the graphene oxide to the fatty alcohol-polyoxyethylene ether to the amino-modified siloxane is 2-5: 100: 0.4-5.
2. The method for preparing siloxane modified graphene oxide according to claim 1, wherein the graphene oxide has a lamella diameter of less than 50 μm and a number of layers of 1 to 20.
3. The method according to claim 1, wherein the amino-modified siloxane comprises at least one of the following: amino-terminated polydimethylsiloxane, side-chain amino polydimethylsiloxane and polyether amino co-modified polydimethylsiloxane; the amino-modified siloxane has an ammonia value of 0.5 to 1 mmol/g.
4. The method for preparing siloxane-modified graphene oxide according to claim 1, wherein the second dispersion liquid is subjected to high-speed shear dispersion to obtain a siloxane-modified graphene oxide dispersion liquid, and the method comprises the following steps:
dropwise adding amino modified siloxane into the first dispersion liquid, and reacting at 40-60 deg.C for 1-2h to obtain second dispersion liquid
And shearing and dispersing the second dispersion liquid at a high speed to obtain siloxane modified graphene oxide dispersion liquid.
5. Siloxane-modified graphene oxide, which is produced by the production method according to any one of claims 1 to 4.
6. A spandex spinning finish, characterized in that the functional component of the spandex spinning finish is the siloxane-modified graphene oxide of claim 5, and the siloxane-modified graphene oxide comprises the following components in parts by mass:
30-80% of dimethyl silicone oil, 0.01-0.5% of siloxane modified graphene oxide, 20-60% of mineral oil, 1-3% of antistatic agent, 3-20% of modified silicone oil and 2-10% of surfactant.
7. A method for producing the spandex spin finish according to claim 6, comprising:
mixing dimethyl silicone oil and siloxane modified graphene oxide dispersion liquid, and shearing and dispersing to obtain a colorless and transparent component A;
mixing and reacting mineral oil and an antistatic agent to obtain a first reactant;
mixing and reacting a surfactant with the first reactant to obtain a second reaction product;
mixing and reacting modified silicone oil and the second reactant to obtain a component B;
and mixing and reacting the component A, the component B and dimethyl silicone oil to obtain the spandex spinning oil agent.
8. The method of claim 7, wherein the ratio of the siloxane-modified graphene oxide to the mineral oil to the antistatic agent to the surfactant to the modified silicone oil to the dimethicone is 0.01-0.5: 20-60: 1-3: 2-10: 3-20: 30-80 by mass.
9. The preparation method of the spandex spin finish according to claim 7, wherein the modified silicone oil and the siloxane-modified graphene oxide dispersion are mixed and shear-dispersed to obtain a colorless and transparent component A, comprising:
mixing dimethyl silicone oil and siloxane modified graphene oxide dispersion liquid, and shearing and dispersing at the rotating speed of 10000-;
mixing and reacting a mineral oil and an antistatic agent to obtain a first reactant comprising:
mixing mineral oil and an antistatic agent, and reacting for 0.5-2h at the temperature of 20-60 ℃ and the rotating speed of 20-90r/min under stirring to obtain a first reactant;
said mixing and reacting a surfactant and said first reactant to obtain a second reaction product comprising:
mixing a surfactant with the first reactant, and reacting for 0.5-2h at the temperature of 20-40 ℃ and the rotating speed of 20-90r/min under stirring to obtain a second reaction product;
the modified silicone oil and the second reactant are mixed and reacted to obtain component B, which comprises:
mixing the modified silicone oil with the second reactant, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain a component B.
10. The method for preparing a spandex spin finish according to claim 7, wherein the component A, the component B and dimethyl silicone oil are mixed and reacted to obtain a spandex spin finish, comprising:
and mixing the component A, the component B and dimethyl silicone oil, and reacting for 1-2h at the temperature of 30-40 ℃ and the rotating speed of 40-60r/min under stirring to obtain the spandex spinning oil agent.
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