CN112646062A - Preparation method and application of temperature response type fabric finishing agent - Google Patents
Preparation method and application of temperature response type fabric finishing agent Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- D06N2209/00—Properties of the materials
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Abstract
The invention discloses a preparation method of a temperature response type fabric finishing agent and a unidirectional moisture-conducting finishing technology thereof, wherein the finishing agent has a structure shown in a formula I or a formula II. Firstly, synthesizing omega-vinyl terminated temperature-sensitive copolymer with clear structure and controllable molecular weight by adopting a catalytic chain transfer polymerization method; then, obtaining the temperature response type fabric finishing agent with a single end containing reactive functional groups through silicon-hydrogen addition reaction or sulfydryl-double bond click chemical reaction; and finally, coating the synthesized finishing agent on one surface of cotton, hemp and blended fabrics thereof and polyester fabrics (subjected to alkali reduction treatment) through a sol-gel reaction, controlling the permeation of the finishing agent, and performing pre-drying and baking to obtain the durable and stable temperature response type unidirectional moisture-conducting fabric. The temperature-sensitive fabric finishing agent is designed, synthesized and optimized, the coating finishing process is simple, the time consumption is short, and the large-scale practical application of the textile industry can be met.
Description
Technical Field
The invention relates to the field of functional finishing of textiles, in particular to a preparation method and application of a temperature response type fabric finishing agent.
Background
Although technologists have made decades of innovation in fabrics with high-tech thermal properties to keep marathon athletes cool or hikers warm, research and development of fabrics that can change their own thermal insulation properties in response to environmental changes is still an urgent problem to be solved in the field of intelligent textiles.
The traditional moisture absorption and sweat releasing fabric mostly adopts the construction of special wettability and the regulation of a fiber or fabric structure as a strategy for assisting moisture conduction. At present, a great deal of research is carried out on a preparation method of Janus type fabrics for driving liquid to conduct moisture in one direction based on pressure gradient (wettability gradient or structure gradient) generated by asymmetric properties of two sides of the fabrics at home and abroad, for example: wang et al prepared a bionic porous Murray one-way wet-conducting fiber membrane [ ACS Nano,2019,13(2): 1060-. Lao et al designed a "skin-mimicking" directional-delivery liquid fabric. The fabric forms a spatial channel with unidirectional liquid transmission on a super-hydrophobic substrate, like sweat glands, the fabric can not only discharge sweat well, but also repel external liquid pollutants [ Science additives, 2020,6: eaaz0013 ]. CN201811581266.4 Chinese patent application discloses a method for preparing a single-side super-hydrophobic single-side super-hydrophilic Janus type fabric, which adopts a single-side plasma induced grafting method to prepare the single-side super-hydrophobic single-side super-hydrophilic Janus type fabric. CN201911100294.4 patent application discloses a preparation method and application of a double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material, which utilizes an ultraviolet irradiation initiation method to respectively construct a hydrophilic-oil modified solution and a hydrophobic-oleophobic surface on two sides of a substrate to prepare the double-sided oleophobic super-hydrophobic-super-hydrophilic Janus type material. However, the Janus materials prepared by the methods do not have environmental (temperature) responsiveness and are not suitable for the application field of intelligent textiles.
Recently, "temperature adaptive humidity regulating fabric and preparation method thereof" disclosed in CN201911382323.0 chinese patent application, respectively grafts two temperature sensitive monomers with LCST and UCST to the front and back sides of cotton fabric by single-sided spraying-in-situ cross-linking method to construct intelligent fabric with double-sided cooperative temperature responsiveness, realizing reversible one-way humidity conducting and thermal convection regulation when temperature changes [ advanced Functional materials, 2019,1907851 ]. However, the method has complicated steps and long time consumption, is not suitable for actual production requirements, and the prepared Janus fabric does not have wearability.
Although a lot of reports exist on the preparation method of the moisture-absorbing and sweat-releasing unidirectional moisture-conducting Janus textile, most of the reports still stay in a small test stage, the Janus textile based on a single mode from inside to outside wetting gradient at the present stage lacks the moisture and heat management cooperativity and environmental adaptability, and the preparation process and the wearing performance cannot meet the large-scale practical application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a temperature response type fabric finishing agent, a preparation method and application thereof, and a preparation method and a finishing technology thereof, which are used for the fabric temperature response type directional moisture-conducting durable finishing agent, and overcome the defects of poor heat preservation and moisture absorption and air permeability of the existing textile, endow the textile with excellent moisture absorption and heat preservation performance, and maintain the heat and humidity comfort of a human body at any time.
A preparation method of a fabric finishing agent with temperature response comprises the following steps:
(1) dissolving a temperature-sensitive monomer shown in a formula (A) structure, a synergistic monomer shown in a formula (B) structure, a catalyst and an initiator in a solvent, introducing protective gas, and fully reacting in a one-pot polymerization manner to obtain the temperature-sensitive copolymer with the structure shown in the formula (C) and omega-vinyl at one end.
(A)：
(B)：
(C)：
Wherein R in the formula (A)1is-CH3or-H; r2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3Or CN (CH)2)3N+(CH3)2(CH2)3SO- 3；
R in the formula (B)1is-CH3or-H; r3Is RfCH2O or RfCHO, wherein RfIs CF3、C3F3、CF3CF(CF3)CFHCF(CF3)、C6F13CH2Or (CH)2)2Si(CH3)2[(CH3)2SiO]xCH2CH2CH2CH3WhereinXIs 3 to 100;
r in the formula (C)2And R in the formula (A)2Have the same meaning; r in the formula (C)3And R in the formula (B)3Have the same meaning.
(2) Adding a temperature-sensitive copolymer with a structure shown in the formula (C) and a omega-vinyl group at one end obtained in the step (1) into a synergistic monomer with a structure shown in the formula (D) to obtain a temperature-response type fabric finishing agent through hydrosilylation reaction or sulfydryl-double bond click chemical reaction, wherein the temperature-response type fabric finishing agent is shown in the formula I or the formula II:
formula I:
formula II:
in the formulae I and II, R2And R3The same as in formula (C), wherein n is 1-200 and m is 0-100.
In the step (3), the temperature response type fabric finishing agent obtained in the step (2) is preferably applied to finishing of the fabric, the pH value of the temperature response type fabric finishing agent is adjusted to be alkalescent, and the temperature response type fabric finishing agent is sprayed to one side of the fabric for finishing. And then, pre-drying, baking and drying the fabric, and performing sol-gel reaction to obtain the durable and stable temperature response type unidirectional moisture-conducting fabric.
The preparation method of the fabric finishing agent with temperature response of the invention adopts the following raw materials in parts by weight:
the catalyst is independently calculated according to the parts per million (ppm) of the total weight of the temperature-sensitive monomer and the synergistic monomer, namely the catalyst is 1-100 ppm of the total weight of the temperature-sensitive monomer and the synergistic monomer.
In the step (1), designing and synthesizing a temperature-sensitive fabric finishing agent: dissolving the temperature-sensitive monomer (A), the synergistic monomer (B), the catalyst and the initiator in a solvent, introducing nitrogen for a period of time under the magnetic stirring state to remove oxygen, heating to a preset temperature, and fully reacting in a one-pot polymerization manner to obtain a series of temperature-sensitive copolymers (C) with controllable molecular structures and omega-vinyl contained at one end.
In the step (1), the temperature-sensitive monomer (A) is a UCST temperature-sensitive monomer comprising: and (c) any one of acrylic acid sulfonic acid betaines and acrylamide sulfonic acid betaines such as N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium betaine (SPE), N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt (DMAPS), and [3- (methylvinylamide) propyl ] dimethyl- (3-sulfonic acid) ammonium (DMMPPS).
In the step (1), the selection of the solvent comprises: one of trifluoroethanol, methanol, ethanol, 1, 4-dioxane and water in any proportion;
the catalyst is bis (boron trifluoride) bis (dimethyl) cobaltous oxime (CoBF).
In the step (1), the selection of the synergistic monomer comprises the following steps: one or more of methacryloxypolydimethylsiloxane (PDMS-MA), trifluoroethyl methacrylate (G01), hexafluorobutyl methacrylate (G02), dodecafluoroheptyl methacrylate (G04), and tridecafluoroctyl methacrylate (G06B).
In the step (1), the protective gas is nitrogen, and the introduction of the protective gas is nitrogen introduction for 30-40 min. The full reaction condition by adopting a one-pot polymerization mode is as follows: and (3) adding an initiator, and reacting for 3-24 hours at the reaction temperature of 30-120 ℃.
In the step (1), the initiator comprises: one or more of azodiisobutyramidine hydrochloride, 4' -azobis (cyanovaleric acid), sulfur peroxide, potassium persulfate, ammonium persulfate, azodiisobutyronitrile and other initiators.
In the step (2), the synergistic monomer is selected from trimethoxyhydrosilane and triethoxyhydrosilane; 1-8 parts by weight of one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and other mercaptosilane coupling agents.
In the step (3), the alkali-reducing amount processing parameters of the polyester fabric are as follows: the bath ratio is 1: 30; the concentration of NaOH is 20-50 g/L; the accelerator comprises: any one (0.5-2 g/L) of accelerators 1221, 1231, 1631 and 1627; the temperature is 95-108 ℃; the treatment time is 40-60 min;
the spraying process in the step (3) comprises the following steps: the spraying time is 10-30 s, the spraying distance is 5-20 cm, and the spraying frequency is 2-5 times. The baking process parameters are as follows: the pre-drying temperature is 75-95 ℃, and the pre-drying time is 3-5 min; the baking process parameters are as follows: the baking temperature is 140-160 ℃, and the baking time is 2-4 min; the drying temperature is about 95-105 ℃, and the drying time is 10-40 min.
The fabric selects cotton, hemp and blended fabrics thereof and polyester fabrics as base materials, and the temperature response type finishing agent obtained by reaction is sprayed on the fabric by a spraying process and by controlling spraying process parameters, so that a series of functional fabrics with good temperature-sensitive moisture-conducting durable effects are obtained, the microclimate near the skin of a human body can be flexibly adjusted, the body is kept warm and moist, and the problem of personal comfort to environment induction is solved.
Compared with the prior art, the invention has the following beneficial effects:
firstly, bis (boron trifluoride) bis (dimethyl) cobaltous oxime (CoBF) is used as a catalyst, CoBF is an efficient chain transfer reagent, a polymer with functionalized terminal double bonds can be obtained under mild reaction conditions, and the polymer is further reacted to prepare a graft or block copolymer.
Designs and synthesizes a temperature-sensitive copolymer with omega-vinyl end by catalyzing chain transfer one-pot copolymerization, and obtains the temperature-responsive fabric finishing agent with single end containing reactive functional group by silicon-hydrogen addition reaction or sulfydryl-double bond click chemical reaction
And the adopted catalytic chain transfer one-pot copolymerization method has mild reaction conditions and simple and convenient operation, and the obtained temperature-sensitive copolymer has clear structure, no sulfur, controllable molecular weight and narrower distribution.
The temperature response type fabric finishing agent prepared by catalytic chain transfer one-pot copolymerization can be used for preparing various temperature sensitive textiles, has good temperature and humidity regulation, soaking and water storage resistance and one-way moisture conductivity, and has wide application prospect in the field of intelligent textiles.
The invention is further illustrated below with reference to specific embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It should be understood that the preferred embodiments of the present invention are not intended to limit the present invention, and it should be noted that several changes and modifications can be made by those skilled in the art, and those suitable changes and modifications also fall within the protection scope of the present invention.
Drawings
FIG. 1 is a graph showing the relationship between the equilibrium swelling ratio and the temperature of temperature-sensitive fabric finishing agents synthesized by temperature-sensitive monomers in different mass percentages in examples 1-5 after finishing pure cotton fabrics (in the figure, a square is a pure cotton fabric which is not finished by the temperature-sensitive fabric finishing agent, a circle is a temperature-sensitive monomer 5 parts by weight, a regular triangle is a temperature-sensitive monomer 10 parts by weight, an inverted triangle is a temperature-sensitive monomer 20 parts by weight, a five-pointed star is a temperature-sensitive monomer 30 parts by weight, a diamond is a temperature-sensitive monomer 40 parts by weight);
fig. 2 is a nuclear magnetic resonance spectrum of the temperature-sensitive copolymer having a structure of formula (C) and a single end containing an ω -vinyl group (δ is 6.16ppm, δ is 5.75ppm, which is a chemical shift of a vinyl proton peak), and the nuclear magnetic resonance spectrum of the temperature-sensitive copolymer is consistent with the structural formula, which indicates that the temperature-sensitive copolymer having a single end containing an ω -vinyl group is successfully synthesized;
FIG. 3 is an infrared spectrum of a temperature responsive (UCST) textile finish;
FIG. 4 is a general formula of a (UCST) temperature responsive fabric conditioner and a schematic representation of fabric finishing;
FIG. 5 is a graph showing the surface topography change of a pure cotton fabric before and after spray finishing of a (UCST) temperature responsive fabric finishing agent (a: an unfinished pure cotton fabric; b, c: a finished pure cotton fabric), wherein a layer of polymer film is attached to the surface of the cotton fabric finished by the (UCST) temperature responsive fabric finishing agent.
Detailed Description
The following examples of the invention:
(1) and (3) testing the conversion rate: the nuclear magnetic resonance hydrogen spectrogram of the polymer is measured by a Bruker, Avance AV 400MHz type superconducting Fourier digital nuclear magnetic resonance spectrometer at normal temperature. Deuterium substituted D is selected2O, deuterated DMSO is used as a solvent.
(2) And (3) testing molecular weight: the molecular weight and distribution of the product were determined by means of a Water, Waters-breeze gel permeation chromatograph. THF was used as the mobile phase, polystyrene was used as a standard, the flow rate was 1mL/min, and the test temperature was 30 ℃.
(3) The Equilibrium Swelling Ratio (ESR) of the fabric was ═ mass of the fabric after swelling equilibrium-mass of fabric in dry state)/mass of fabric in dry state ] × 100%.
(4) The tested textiles were the pure cotton fabrics, cotton-linen blended fabrics, polyester fabrics as samples (cotton-linen blended fabrics: cotton-55%, linen-45%).
Examples 1 to 5
(1) Fabric with temperature sensitivityDesigning and synthesizing a finishing agent: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 5, 10, 20, 30 and 40 parts by weight of synergistic monomer (B and R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of a temperature-sensitive copolymer with a controllable molecular structure and omega-vinyl contained at one end is obtained by dissolving 30ppm of a CoBF single-exclusive total monomer catalyst and 1 part by weight of AIBN initiator in trifluoroethanol solvent serving as the rest parts by weight, uniformly stirring by magnetic force, introducing nitrogen for 0.5-1 h to remove oxygen, heating to 60 ℃ and reacting for 12h by adopting a catalytic chain transfer one-pot copolymerization mode.
(2) Adding 3 parts by weight of synergistic monomer 3-mercaptopropyltrimethoxysilane into the temperature-sensitive copolymer obtained in the step (1) to react for 12 hours at 60 ℃, and obtaining the (UCST) temperature-responsive fabric finishing agent through a hydrosilylation reaction or a mercapto-double bond click chemical reaction.
(3) Preparing the temperature response type fabric finishing agent obtained in the step (2) into a coating material, effectively spraying the coating material on one surface of a pure cotton fabric at a constant speed by using a spray gun, controlling the spraying time to be 10s and the spraying distance to be 10cm, spraying for three times in total, then pre-drying the fabric at 80 ℃ for 3min, baking the fabric at 140 ℃ for 2min, and then drying the fabric in a 105 ℃ drying oven for 30min to obtain the fabric with the temperature response type directional moisture-guiding and durable property.
Table 1 specific formulations of examples 1-5
As shown in fig. 1, the pure cotton fabric which is not finished is used as a blank group, the temperature-sensitive monomers (a) are 5, 10, 20, 30 and 40 parts by weight of the pure cotton fabric which is finished by the temperature-sensitive fabric finishing agent which is synthesized is used as an experimental group, and the Equilibrium Swelling Ratio (ESR) of six components along with the change of temperature is calculated by a weighing method; the temperature-sensitive monomer (A) is 5 parts by weight of the synthesized temperature-sensitive fabric finishing agent, the equilibrium swelling rate of the finished pure cotton fabric at 30 ℃ (lower than TT) reaches 120%, the equilibrium swelling rate at 50 ℃ (higher than TT) is 104%, the equilibrium swelling rate at 30 ℃ (lower than TT) of the synthesized temperature-sensitive fabric finishing agent is respectively 121%, 126%, 133% and 131% when the temperature-sensitive monomer (A) is increased to 10%, 20%, 30% and 40 parts by weight, the equilibrium swelling rate at 50 ℃ (higher than TT) of the finished pure cotton fabric is obviously reduced respectively 103%, 106%, 110% and 109%, and 30 parts by weight of the temperature-sensitive monomer (A) reaches a critical value because a large number of hydroxyl groups on the pure cotton fibers react with the reactive groups in the synthesized temperature-responsive fabric finishing agent to reach a saturated value, and the fibers are difficult to provide redundant reactive groups for further reaction. In general, the fabric finished by the temperature-sensitive fabric finishing agent has obvious hydrophilic and hydrophobic changes at the transition temperature, and the hydrophilicity of the fabric finished by the synthesized temperature-sensitive fabric finishing agent is improved along with the increase of the weight part of the temperature-sensitive monomer.
FIG. 2 shows the reaction of temperature-sensitive monomers (A, R) according to example 41is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 parts by weight of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of CoBF catalyst 30ppm and AIBN initiator 1 part by weight are polymerized in one-pot RAFT to obtain the temperature-sensitive copolymer with omega-vinyl at one end, and each chemical shift corresponds to the copolymer one by one. Indicating that the omega-vinyl temperature-sensitive copolymer is successfully synthesized. FIG. 3 shows temperature-sensitive monomers (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 parts by weight of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of CoBF catalyst, 30ppm of total monomer, AIBN initiator, 1 part by weight, 3 parts by weight of 3-mercaptopropyltrimethoxysilane as a synergistic monomer, in a one-pot RAFT polymerization (U C)ST) infrared spectrum of temperature-responsive fabric finish. 1726cm therein-1The peak of the synergistic monomer (B) at 1649cm is the absorption peak of C ═ O in stretching vibration-1Is the stretching vibration absorption peak of C ═ O in the temperature-sensitive monomer (A), 1481cm-1is-N (CH)3)2-CH in the structure3Asymmetric bending vibration absorption peak of key, 1186cm-1is-SO- 3Middle S ═ O stretching vibration absorption peak, 1042cm-1Is the symmetric stretching vibration peak of Si-O-C, and combines with figure 2 and figure 3 to show that (UCST) temperature response type fabric finishing agent is successfully synthesized.
Examples 6 to 10
(1) Designing and synthesizing a fabric finishing agent with temperature sensitivity: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 portions of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight, 1 part by weight of AIBN initiator, 2, 6, 10, 20 and 30ppm of CoBF catalyst exclusive of total monomers are dissolved in the rest parts by weight of trifluoroethanol solvent, wherein the parts by weight of CoBF catalyst can be ignored. Uniformly stirring the mixture by using a magnetic stirrer, introducing nitrogen for 0.5-1 h to remove oxygen, heating to 60 ℃, and reacting for 12h by adopting a catalytic chain transfer one-pot copolymerization mode to obtain a series of temperature-sensitive copolymers with controllable molecular structures and omega-vinyl contained at one end. Dried under high vacuum at ambient temperature for 48h, the solvent was removed and the assay was performed by gel permeation chromatography, GPC, with TFH as the eluting phase at a flow rate of 1mL/min, all samples were diluted to 3mg/mL in THF and filtered through a 0.22 μm filter membrane and then loaded into 2mL sample vials.
Comparative example 1
(1) Designing and synthesizing a fabric finishing agent with temperature sensitivity: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 portions of synergistic monomer (B, R)1For the purpose ofCH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight, 1 part by weight of initiator AIBN, 50ppm of catalyst CoBF in total monomer, dissolved in the remaining part by weight of solvent trifluoroethanol, wherein the parts by weight of catalyst CoBF are negligible. Uniformly stirring the mixture by using a magnetic stirrer, introducing nitrogen for 0.5-1 h to remove oxygen, heating to 60 ℃, and reacting for 12h by adopting a catalytic chain transfer one-pot copolymerization mode to obtain a series of temperature-sensitive copolymers with controllable molecular structures and omega-vinyl contained at one end. Dried under high vacuum at ambient temperature for 48h, the solvent was removed and the assay was performed by gel permeation chromatography, GPC, with TFH as the eluting phase at a flow rate of 1mL/min, all samples were diluted to 3mg/mL in THF and filtered through a 0.22 μm filter membrane and then loaded into 2mL sample vials.
TABLE 2 influence of different concentrations of catalyst on the molecular weight of temperature-sensitive copolymers
As can be seen from the data in Table 2, the vinyl-terminated temperature-sensitive copolymers with different molecular weights can be obtained by changing the amount of the catalyst, and the molecular weight of the temperature-sensitive copolymer can be effectively controlled with the increase of the concentration of the catalyst bis (boron trifluoride) bis (dimethyl) cobaltosim (CoBF), so that the temperature-sensitive copolymer which is free of sulfur, controllable in molecular weight and narrow in distribution and has a reactive group at the end can be obtained, because the CoBF has a higher chain transfer constant. The polymer molecular weight is 3575g moL L when the catalyst dosage is 30ppm-1And the distribution is the narrowest, and the temperature-sensitive copolymer can be further used as a macromolecular RAFT reagent to provide a large number of effective reactive groups to carry out hydrosilylation reaction or sulfydryl-double bond click chemical reaction with a subsequently added synergistic monomer.
Examples 11 to 15
(1) Designing and synthesizing a fabric finishing agent with temperature sensitivity: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 portions of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of a temperature-sensitive copolymer with a controllable molecular structure and a single end containing omega-vinyl, 30ppm of a single total monomer of a catalyst CoBF, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight and 2 parts by weight of an initiator AIBN, which are dissolved in the rest parts by weight of solvent trifluoroethanol, uniformly stirring by magnetic force, introducing nitrogen for 0.5 h-1 h to remove oxygen, heating to 60 ℃ and reacting for 12h by adopting a catalytic chain transfer one-pot copolymerization mode to obtain a series of temperature-sensitive copolymers with controllable molecular structures and single end containing omega-vinyl.
(2) Adding 3 parts by weight of synergistic monomer 3-mercaptopropyltrimethoxysilane into the temperature-sensitive copolymer obtained in the step (1) to react for 12 hours at 60 ℃, and obtaining the (UCST) temperature-responsive fabric finishing agent through a hydrosilylation reaction or a mercapto-double bond click chemical reaction. Drying at room temperature under high vacuum for 48 hr, removing solvent, and finally using1HNMR with deutero-D2O or deuterated DMSO was used as a solvent to calculate the conversion of the synergistic monomer in the polymer.
Comparative example 2
(1) Designing and synthesizing a fabric finishing agent with temperature sensitivity: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 portions of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of CoBF, 30ppm of catalyst which is exclusive to total monomers, 3 parts by weight of AIBN, the mixture is dissolved in trifluoroethanol which is solvent in the rest parts by weight, nitrogen is introduced for 0.5 to 1 hour after the mixture is stirred evenly by magnetic force to remove oxygen, the mixture is heated to 60 ℃ and reacts for 12 hours by adopting a catalytic chain transfer one-pot copolymerization mode, and a series of temperature-sensitive copolymers with controllable molecular structures and omega-vinyl contained at single ends are obtained.
(2) Adding 3 parts by weight of synergistic monomer 3-mercaptopropyltrimethoxysilane into the temperature-sensitive copolymer obtained in the step (1) to react for 12 hours at 60 ℃, and obtaining the (UCST) temperature-responsive fabric finishing agent through a hydrosilylation reaction or a mercapto-double bond click chemical reaction.
TABLE 2 Effect of different mass percentages of initiator on the conversion of synergistic monomers
From the data in Table 2, the conversion of the synergistic monomers in the polymer is shown1The HNMR results show that the conversion rate is in positive correlation with the initiator concentration, the conversion rate reaches 92% when the initiator (ACVA) is 2 parts by weight, and the monomer conversion rate is not obviously changed when the initiator is more than 2 parts by weight as shown in the comparative example 2, because the polymerization rate is increased by the initiator, and redundant monomer free radicals are difficult to form in the reaction process to react with the initiator.
Examples 16 to 18
(1) Designing and synthesizing a fabric finishing agent with temperature sensitivity: temperature sensitive monomer (A, R)1is-CH3，R2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3) 30 parts by weight of synergistic monomer (B, R)1is-CH3，R3Is RfCHO, wherein RfIs C6F13CH2) 6 parts by weight of a catalyst CoBF, 30ppm of single exclusive total monomer and 2 parts by weight of an initiator AIBN are dissolved in the rest part by weight of solvent trifluoroethanol, nitrogen is introduced for 0.5 to 1 hour after the mixture is magnetically stirred uniformly to remove oxygen, and the mixture is heated to 60 ℃ to react for 12 hours by adopting a catalytic chain transfer one-pot copolymerization mode to obtain a series of temperature-sensitive copolymers with controllable molecular structures and omega-vinyl contained at single ends.
(2) Adding 3 parts by weight of synergistic monomer 3-mercaptopropyltrimethoxysilane into the temperature-sensitive copolymer obtained in the step (1) to react for 12 hours at 60 ℃, and obtaining the (UCST) temperature-responsive fabric finishing agent through a hydrosilylation reaction or a mercapto-double bond click chemical reaction. Drying at room temperature under high vacuum for 48 hr, removing solvent, and finally using1HNMR with deutero-D2Calculation of synergistic monomers in polymers with O or deuterated DMSO as solventConversion of the body.
(3) Preparing the temperature response type fabric finishing agent obtained in the step (2) into a coating material, respectively and effectively spraying the coating material on one surfaces of pure cotton fabrics, cotton and linen fabrics and cotton and linen fabrics at a constant speed by using a spray gun, controlling the spraying time to be 10s and the spraying distance to be 10cm, spraying for three times in total, then pre-drying the fabrics at 80 ℃ for 3min, baking at 140 ℃ for 2min, and then drying in a 105 ℃ drying oven for 30min to obtain the temperature response type directional moisture-conducting durable fabrics.
TABLE 3 Effect of temperature-responsive Fabric finishes on different Fabric Wash fastnesses
| Number of washing/graft ratio (%) | 10 | 20 | 50 |
| Pure cotton fabric | 27.6 | 23.3 | 21.5 |
| Cotton and linen fabric | 21.9 | 15.4 | 11.6 |
| Terylene fabric | 18.9 | 13.9 | 12.7 |
As shown in the table 3, the results of the wash fastness tests of the temperature response type fabric finishing agent on different fabrics show that the grafting rate of the samples after washing and drying is reduced along with the increase of the washing times; the grafting rate of the cotton and linen fabric is obviously reduced, and the pure cotton fabric has good washing fastness. This is because pure cotton fibers contain a large number of hydroxyl groups that are better able to cross-link with the silicone in the temperature responsive fabric finish being synthesized. According to example 16, fig. 5 is a surface topography of a cotton fabric finished with a (UCST) temperature responsive textile finish, and the surface of the finished fiber is uniformly covered with a polymer film, indicating that the textile finish with a temperature responsive type successfully reacts with the fabric.
Claims (10)
1. A preparation method of a fabric finishing agent with temperature response is characterized by comprising the following steps:
(1) dissolving a temperature-sensitive monomer shown in a formula (A) structure, a synergistic monomer shown in a formula (B) structure, a catalyst and an initiator in a solvent, introducing protective gas, and fully reacting in a one-pot polymerization manner to obtain the temperature-sensitive copolymer with the structure shown in the formula (C) and omega-vinyl at one end.
(A)：
(B)：
(C)：
Wherein R in the formula (A)1is-CH3or-H; r2Is CO (CH)2)3N+(CH3)2(CH2)3SO- 3Or CN (CH)2)3N+(CH3)2(CH2)3SO- 3；
R in the formula (B)1is-CH3or-H; r3Is RfCH2O or RfCHO, wherein RfIs CF3、C3F3、CF3CF(CF3)CFHCF(CF3)、C6F13CH2Or (CH)2)2Si(CH3)2[(CH3)2SiO]xCH2CH2CH2CH3WhereinXIs 3 to 100;
r in the formula (C)2And R in the formula (A)2Have the same meaning; r in the formula (C)3And R in the formula (B)3Have the same meaning;
(2) adding a temperature-sensitive copolymer with a structure shown in the formula (C) and a omega-vinyl group at one end obtained in the step (1) into a synergistic monomer with a structure shown in the formula (D) to obtain a temperature-response type fabric finishing agent through hydrosilylation reaction or sulfydryl-double bond click chemical reaction, wherein the temperature-response type fabric finishing agent is shown in the formula I or the formula II:
formula I:
formula II:
in the formulae I and II, R2And R3Has the same meaning as in formula (C).
2. The preparation method of the fabric finishing agent with the temperature response function according to claim 1, characterized by adopting the following raw materials in parts by weight:
the catalyst is 1-100 ppm of the total weight of the temperature-sensitive monomer and the synergistic monomer.
3. The method for preparing a fabric finishing agent with temperature response according to claim 1, wherein in the step (1), the temperature-sensitive monomer is any one of N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium betaine (SPE), N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt (DMAPS), and [3- (methylvinylamide) propyl ] dimethyl- (3-sulfonic acid) ammonium;
the synergistic monomer is one or more of methacryloxy polydimethyl siloxane, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoro heptyl methacrylate and tridecyl octyl methacrylate.
4. The method for preparing a fabric finishing agent with temperature response according to claim 1, wherein in the step (1), the catalyst is bis (boron trifluoride) bis (dimethyl) cobaltous oxime.
5. The method for preparing the fabric finishing agent with the temperature response property according to the claim 1, wherein in the step (1), the solvent is at least one of trifluoroethanol, methanol, ethanol and 1, 4-dioxane which is mixed with water in any proportion;
the protective gas is nitrogen, and the introduction of the protective gas is nitrogen introduction for 30-40 min.
6. The method for preparing the fabric finishing agent with the temperature response property according to claim 1, wherein in the step (1), the conditions for fully reacting in a one-pot polymerization mode are as follows: the reaction is carried out for 3-24 h, and the reaction temperature is 30-120 ℃.
7. The method for preparing the fabric finishing agent with the temperature response property according to claim 1, wherein in the step (1), the initiator is one or more of azobisisobutyramidine hydrochloride, 4' -azobis (cyanovaleric acid), sulfur peroxide, potassium persulfate, ammonium persulfate and azobisisobutyronitrile.
8. The method for preparing a fabric finishing agent with temperature response according to claim 1, wherein in the step (2), the synergistic monomer is trimethoxyhydrosilane, triethoxyhydrosilane; 3-mercaptopropyltrimethoxysilane and/or 3-mercaptopropyltriethoxysilane.
9. Use of the temperature-responsive fabric finishing agent prepared by the preparation method according to any one of claims 1 to 8 in finishing fabrics.
10. The application according to claim 9, comprising in particular: the temperature response type fabric finishing agent is sprayed to one side of the fabric for finishing, and then the fabric is pre-dried, baked and dried, and the durable and stable temperature response type unidirectional moisture-conducting fabric is prepared through a sol-gel reaction.
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