CN115787301A - Polyurethane modified organic silicon softener and preparation method and application thereof - Google Patents
Polyurethane modified organic silicon softener and preparation method and application thereof Download PDFInfo
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- CN115787301A CN115787301A CN202211446589.9A CN202211446589A CN115787301A CN 115787301 A CN115787301 A CN 115787301A CN 202211446589 A CN202211446589 A CN 202211446589A CN 115787301 A CN115787301 A CN 115787301A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 89
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- 239000004671 silicon softener Substances 0.000 title claims description 6
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- 238000001514 detection method Methods 0.000 claims description 5
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane modified organic silicon softening agent, a preparation method and application thereof, belonging to the field of finishing after textile printing and dyeing, wherein the preparation method comprises the following steps: carrying out polymerization reaction on isophorone diisocyanate and N-methyldiethanolamine in a first organic solvent, and then adding a sealing agent to seal the residual active isocyanate to obtain a polyurethane prepolymer; under the action of an acid catalyst, carrying out polymerization reaction on the prepared polyurethane prepolymer and epoxy-terminated silicone oil in a second organic solvent to obtain a polyurethane silicone oil component; reacting the epoxy-terminated silicone oil with polyether amine in a second organic solvent to obtain a block silicone oil component; and compounding the prepared polyurethane silicone oil component and the block silicone oil component according to a preset proportion, and then adding an emulsifier for emulsification to finally prepare the polyurethane modified organosilicon softener. The polyurethane modified organosilicon softener prepared by the method provided by the invention can further increase the molecular weight of the polymer and more tightly combine the softener with the fabric.
Description
Technical Field
The invention belongs to the field of finishing after textile printing and dyeing, and particularly relates to a polyurethane modified organic silicon softening agent as well as a preparation method and application thereof.
Background
The organosilicon softener is one of the most popular softeners in the field of finishing after textile printing and dyeing, can enable fabrics to have silk-like or cotton-like hand feeling after finishing, and always focuses attention on technical personnel in the printing and dyeing industry on how to further improve the performance of the organosilicon softener.
Through the intensive research of researchers on organic silicon polymers in recent years, the preparation technology of the ternary block silicone oil is already highly mature. The ternary block silicone oil softener has polyether chain segment and amino group introduced simultaneously into organosilicon structure. The polyether chain segment endows the silicone oil emulsion with excellent stability, is suitable for various processing procedures, is attached to the surface of a fabric after finishing, and endows the fabric with good hydrophilicity; the amino group has weak cationic property after acidification, and can form directional adsorption on the surface of the fabric, thereby endowing the fabric with good hand feeling. There are also some disadvantages, however, such as poor wash durability resulting from the combination of the softener and the fabric relying solely on electrostatic adsorption; the organic silicon is softer and has poorer mechanical property, so that the rebound resilience and the smoothness of the fabric are poor and the like. The polyurethane has many special properties, such as good mechanical properties, strong flexibility, good weather resistance, strong cohesive force and the like. More and more researchers have begun to introduce polyurethanes into silicones to synthesize polyurethane-silicone block copolymers of various properties.
The technical scheme is that firstly, polyurethane resin capable of reacting with epoxy silicone oil is prepared, then the polyurethane resin is continuously subjected to ring-opening polymerization with the epoxy silicone oil, the prepared high-elasticity resin modified silicone oil is arranged on a fabric, the resilience and the smoothness of the fabric are improved, but a molecular chain only contains quaternary ammonium groups and carbamate groups, does not contain other active groups, can only produce directional adsorption on the fabric through electrostatic adsorption of quaternary ammonium salts and hydrogen bond action formed by carbamate, and cannot combine the softener with the fabric more tightly. CN110527052A discloses a quaternary ammonium salt-containing polyurethane modified organosilicon copolymer, which comprises the following specific technical scheme: firstly, epoxy silicone oil reacts with tertiary amine compound to prepare silicone oil with a quaternized structure, then diisocyanate is added to continuously react with the silicone oil, finally, the residual isocyanate is sealed by polyether and the like to obtain a copolymer, and the copolymer is finished on the fabric to ensure that the fabric has good hydrophilicity and hand feeling, but does not contain a group capable of continuously reacting with an active group on the fabric, so that the requirement of the market on the post finishing of the cotton fabric can not be met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane modified organic silicon softening agent, a preparation method and application thereof, and aims to solve the problems that the existing softening agent is not tightly combined with fabric and does not contain a group which continuously reacts with an active group on the fabric.
In order to achieve the purpose, the invention provides a preparation method of a polyurethane modified organic silicon softening agent, which comprises the following steps:
s1, carrying out a polymerization reaction on isophorone diisocyanate and N-methyldiethanolamine in a first organic solvent, and then adding a sealing agent to seal the residual active isocyanate to obtain a polyurethane prepolymer;
s2, under the action of an acidic catalyst, carrying out polymerization reaction on the polyurethane prepolymer prepared in the step S1 and epoxy-terminated silicone oil in a second organic solvent to obtain a polyurethane silicone oil component;
s3, reacting the epoxy-terminated silicone oil with polyether amine in a second organic solvent to obtain a block silicone oil component;
and S4, compounding the polyurethane silicone oil component prepared in the step S2 and the block silicone oil component prepared in the step S3 according to a preset proportion, and then adding an emulsifier for emulsification to finally prepare the polyurethane modified organic silicon softener.
As a further preference, step S1 comprises the following substeps:
s11, adding isophorone diisocyanate and N-methyldiethanolamine into a first organic solvent according to a molar ratio of 3:2 or 2:1, wherein the N-methyldiethanolamine is added in a dropwise manner for 15-180 min, and the mass of the first organic solvent is 10-80% of the total mass of the isophorone diisocyanate and the N-methyldiethanolamine;
s12, stirring for 2-8 hours at 30-70 ℃ to perform polymerization reaction;
s13, after the polymerization reaction is finished, keeping the reaction temperature at 40-80 ℃, adding a blocking agent to block the residual active isocyanate, wherein the molar ratio of the blocking agent to the residual active isocyanate is 1.05;
and S14, continuously reacting for 2-6 hours, after infrared detection shows that no isocyanate peak exists, distilling under reduced pressure to remove the first organic solvent, and adding a second organic solvent for dilution to obtain the polyurethane prepolymer.
As a further preference, step S2 comprises the following substeps:
s21, adding a second organic solvent into the polyurethane prepolymer and the epoxy-terminated silicone oil according to the proportion of the molar ratio of the epoxy value to the amine value of 1:1-1:2, and simultaneously adding an acid catalyst with the mole number of the amine value of 100-200% into the polyurethane prepolymer;
and S22, stirring and reacting for 4-24 hours at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the polyurethane silicone oil component.
As a further preference, step S3 comprises the following sub-steps:
s31, putting the epoxy-terminated silicone oil and the polyether amine into a second organic solvent according to the molar ratio of the epoxy value to the amine value of 1:1-1:2;
and S32, stirring and reacting for 6-24 hours at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the block silicone oil component.
As a further preference, in step S1, the blocking agent is one or more of butanone oxime, phenol, sodium bisulfite, caprolactam, acetylacetone and diethyl malonate; in the step S2, the acidic catalyst is one or more of formic acid, acetic acid, diluted hydrochloric acid, lauric acid and citric acid; in the step S3, the polyetheramine is one or more of polyetheramine ED600, polyetheramine ED900, polyetheramine ED2003, and polyetheramine T403.
More preferably, in step S4, the polyurethane silicone oil component and the block silicone oil component are compounded according to a mass ratio of 2:1 to 1:1.
It is further preferred that the first organic solvent is one or more of acetone, methyl ethyl ketone and tetrahydrofuran, and the second organic solvent is one or more of diethylene glycol butyl ether, ethylene glycol butyl ether, dipropylene glycol, propylene glycol acetate and isopropyl alcohol.
More preferably, the emulsifier is obtained by compounding isomeric tridecanol polyoxyethylene ethers with different EO addition numbers, and the HLB value of the emulsifier is 4-18.
According to another aspect of the present invention, there is provided a polyurethane-modified silicone softener prepared by the above method.
According to another aspect of the present invention, there is provided an application of the polyurethane modified silicone softener in cotton fabric, specifically: the polyurethane modified organic solvent is applied to cotton fabrics, a one-dip one-roll process is adopted, then the cotton fabrics are pre-baked for 30 to 90 seconds at the temperature of between 90 and 110 ℃, and finally the cotton fabrics are baked for 30 to 120 seconds at the temperature of between 160 and 170 ℃.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. the polyurethane modified organosilicon softener provided by the invention consists of a polyurethane silicone oil component and a block silicone oil component, and the polyurethane modified organosilicon softener is synthesized by using a block copolymerization technology, so that the problems of poor compatibility, phase separation and the like of polyurethane and organosilicon do not exist, wherein the molecular structure of the polyurethane silicone oil component is regular and controllable, the molecular structure can be freely controlled by the molar ratio of a polyurethane prepolymer and an end epoxy silicone oil, a molecular chain of the polyurethane modified organosilicon softener not only contains a carbamate group and a quaternary ammonium salt group, but also contains a blocked active isocyanate group at the side edge of the molecular chain; the block silicone oil component mainly comprises amino, polyether and siloxane chain segments, a molecular chain contains a large amount of active amino, and linear or reticular block silicone oil can be prepared according to the polyether amine structure; when the polyurethane modified organic silicon softener is padded and finished on cotton fabric, quaternary ammonium salt groups in polyurethane silicone oil components provide cationic property and hydrophilic property, carbamate groups provide the characteristic of polyurethane, the polyurethane modified organic silicon softener is microphase separated from organic silicon chain segments, active isocyanate groups sealed on side chains can generate in-situ crosslinking reaction with active hydrogen-containing groups such as amino groups in block silicone oil components and hydroxyl groups on the cotton fabric after being baked and unsealed at high temperature, the molecular weight of a polymer is further increased, and the softener is combined with the fabric more tightly;
2. meanwhile, the molar ratio of isophorone diisocyanate to N-methyldiethanolamine is optimized, so that the reaction of the prepared polyurethane prepolymer and epoxy silicone oil can be controlled, the structure is regular, and gel is prevented from being generated in the subsequent polymerization process;
3. in addition, the invention also optimizes the molar ratio of the polyurethane prepolymer to the epoxy-terminated silicone oil, can avoid the occurrence of free polyurethane prepolymer in the polyurethane silicone oil component, and simultaneously avoids the phenomenon that the polyurethane silicone oil component is blocked by an epoxy group, which is not beneficial to the compounding stability with the block silicone oil component in the next step;
4. the polyurethane modified organosilicon softener prepared by the invention is applied to cotton fabrics, can endow the fabrics with the functions of softness, good hydrophilicity, washing resistance, good rebound resilience and the like, and has application performance superior to that of original fabrics and commercial softeners.
Drawings
FIG. 1 is a flow chart of the preparation of the polyurethane modified silicone softener provided by the preferred embodiment of the invention;
FIG. 2 is an IR spectrum of a polyurethane prepolymer prepared in example 1 of the present invention;
FIG. 3 is an infrared spectrum of the polyurethane silicone oil component prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the invention provides a preparation method of a polyurethane modified organosilicon softener, which comprises the following steps:
s1, carrying out a polymerization reaction on isophorone diisocyanate and N-methyldiethanolamine in a first organic solvent, and then adding a sealing agent to seal the residual active isocyanate to obtain a polyurethane prepolymer capable of reacting with epoxy;
s2, under the action of an acidic catalyst, carrying out polymerization reaction on the polyurethane prepolymer prepared in the step S1 and epoxy-terminated silicone oil in a second organic solvent to obtain a polyurethane silicone oil component;
s3, reacting the epoxy-terminated silicone oil with polyether amine in a second organic solvent to obtain a block silicone oil component;
and S4, compounding the polyurethane silicone oil component prepared in the step S2 and the block silicone oil component prepared in the step S3 according to a preset proportion, and then adding an emulsifier for emulsification to finally prepare the polyurethane modified organic silicon softening agent.
The synthetic route of the polyurethane modified organosilicon softener provided by the invention is as follows:
(1) Synthesizing a polyurethane prepolymer:
feeding isophorone diisocyanate and N-methyldiethanolamine in a ratio of 3:2 or 2:1 in a first organic solvent for polymerization, adding a sealing agent to seal the rest active isocyanate, performing infrared detection to remove an isocyanate characteristic peak, performing reduced pressure distillation to remove the first organic solvent, and adding a proper amount of a second organic solvent to dilute to obtain a polyurethane prepolymer;
(2) Synthesizing a polyurethane silicone oil component:
acidifying the polyurethane prepolymer by an acid catalyst, then carrying out polymerization reaction with epoxy-terminated silicone oil in a second organic solvent, and after the reaction is finished, carrying out reduced pressure distillation to remove the second organic solvent to obtain a polyurethane silicone oil component;
(3) Synthesizing a block silicone oil component:
performing polymerization reaction on the epoxy-terminated silicone oil and polyether amine in a second organic solvent according to the molar ratio of 1:1-1:2, and removing the second organic solvent by reduced pressure distillation after the reaction is finished to obtain a block silicone oil component, namely the block silicone oil;
(4) The polyurethane silicone oil component and the block silicone oil component are compounded according to the mass ratio of 2:1-1:1, and then an emulsifier is added for emulsification to obtain the polyurethane modified organic silicon softening agent.
Further, step S1 comprises the following substeps:
s11, adding isophorone diisocyanate and N-methyldiethanolamine into a first organic solvent according to a molar ratio of 3:2 or 2:1 to ensure that a polyurethane prepolymer contains 2 or 1 tertiary amine group capable of reacting with epoxy, so that the reaction of the polyurethane prepolymer and epoxy silicone oil is controllable, the structure is regular, and gel is prevented from being generated in a subsequent polymerization process;
s12, stirring for 2-8 hours at 30-70 ℃ to perform polymerization reaction;
s13, after the polymerization reaction is finished, keeping the reaction temperature at 40-80 ℃, adding a blocking agent to block the residual active isocyanate, wherein the molar ratio of the blocking agent to the residual active isocyanate is 1.05;
and S14, continuing to react for 2-6 hours, and after infrared detection shows that no isocyanate peak exists, distilling under reduced pressure to remove the first organic solvent, and adding a proper amount of second organic solvent for dilution to obtain the polyurethane prepolymer.
Further, step S2 comprises the following substeps:
s21, adding a second organic solvent into the polyurethane prepolymer and the end epoxy silicone oil according to the molar ratio of the epoxy value to the amine value of 1:1-1:2, so as to prevent a free polyurethane prepolymer which does not react with the end epoxy silicone oil from appearing in the polyurethane silicone oil component, and simultaneously prevent the polyurethane silicone oil component from being blocked by the epoxy group, because the epoxy group can slowly react with the amine group at room temperature, the subsequent compounding stability with the block silicone oil component is not facilitated, and simultaneously adding an acidic catalyst with the amine value of 100-200% in the polyurethane prepolymer, wherein the acidic catalyst is one or more of formic acid, acetic acid, diluted hydrochloric acid, lauric acid and citric acid, the end epoxy silicone oil structure can be free of polyether chain segments and contains polyether chain segments, and the end epoxy silicone oil does not contain polyether chain segments and has the chemical structural formula:
wherein n is a natural number of 30 to 200,
the epoxy-terminated silicone oil contains a polyether chain segment and has the chemical structural formula:
wherein n is a natural number of 30-200, p is a natural number of 3-25, and q is a natural number of 0-10;
s22, stirring and reacting for 4-24 h at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the polyurethane silicone oil component.
Further, step S3 includes the following substeps:
s31, adding epoxy-terminated silicone oil and polyether amine into a second organic solvent according to the molar ratio of the epoxy value to the amine value of 1:1-1:2, wherein the polyether amine is one or more of polyether amine ED600, polyether amine ED900, polyether amine ED2003 and polyether amine T403;
s32, stirring and reacting for 6-24 h at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the block silicone oil component.
Further, the first organic solvent is one or more of acetone, butanone and tetrahydrofuran; the second organic solvent is one or more of diethylene glycol butyl ether, ethylene glycol butyl ether, dipropylene glycol, propylene glycol acetate and isopropanol.
According to another aspect of the present invention, there is provided a polyurethane-modified silicone softener prepared by the above method, comprising a polyurethane silicone oil component and a block silicone oil component, both of which are synthesized using a block copolymerization technique, and thus there is no problem of poor compatibility of polyurethane and silicone, phase separation, etc. The segmented silicone oil component mainly comprises amino, a polyether chain segment and a siloxane chain segment, wherein the cationic amino in the molecular chain is directionally adsorbed on the surface of the fabric to provide soft hand feeling for the fabric, and can be continuously reacted with the active isocyanate deblocked in the polyurethane silicone oil component to form a polyurea group which belongs to a hard segment, so that the polyurea group is formed by reaction with the amino, and the polyurea group not only provides smoothness for the fabric on the surface of the fabric, but also can be subjected to hydrogen bond crosslinking with groups such as carbamate and the like. The polyurethane silicone oil mainly comprises a polyurethane chain segment and an organosilicon chain segment, wherein a carbamate group in the polyurethane chain segment belongs to a hard segment, can form a hydrogen bond with hydroxyl and the like, can also endow the cotton fabric with flexibility by covering the cotton fabric with the polyurethane silicone oil, after the isocyanate blocked on a side chain is baked at high temperature and unsealed, can perform a chemical reaction with the hydroxyl on the surface of the cotton fabric, the amino and the hydroxyl in a block silicone oil molecular chain, the hydroxyl at the tail end of an emulsifier molecule and other groups containing active hydrogen, and continuously perform in-situ polymerization on the surface of the cotton fabric to form a high polymer on the surface of a fiber, and the four components of the block silicone oil, the polyurethane silicone oil, the emulsifier and the cotton fiber are tightly combined through chemical bonds, so that the application performance of the cotton fabric is further improved.
According to another aspect of the present invention, there is provided an application of the polyurethane modified silicone softener in cotton fabric, specifically: the polyurethane modified organic solvent is applied to cotton fabrics, a one-dipping one-rolling process is adopted, then the cotton fabrics are pre-baked for 30 to 90 seconds at the temperature of between 90 and 110 ℃, and finally the cotton fabrics are baked for 30 to 120 seconds at the temperature of between 160 and 170 ℃.
The present invention will be further specifically described below with reference to specific examples.
Example 1
Step 1: prepolymer for synthesizing polyurethane
Weighing 100g of isophorone diisocyanate and 55g of acetone, adding the isophorone diisocyanate and the acetone into a four-neck flask, heating to 40-45 ℃, dropwise adding 35.74g of N-methyldiethanolamine after finishing dropwise adding within 30min, keeping the temperature for reaction for 4h, heating to 55-60 ℃, continuing to react for 2h, dropwise adding 27.50g of butanone oxime, finishing dropwise adding within 60min, continuing to keep the temperature for reaction for 3h at 60 ℃, carrying out infrared detection to remove an isocyanate characteristic peak, removing the acetone by reduced pressure distillation, continuing to add 107g of dipropylene glycol butyl ether for dilution, cooling to room temperature, discharging to obtain a light yellow transparent polyurethane prepolymer with the solid content of 59-63%;
the infrared spectrum of the polyurethane prepolymer is shown in FIG. 1, and it can be seen from FIG. 1 that 3327cm -1 And 1510cm -1 The absorption peak is the stretching vibration peak and deformation vibration peak of N-H in carbamate, 1713cm -1 Is the stretching vibration peak of carbonyl in carbamate, 2260cm -1 The characteristic peak of isocyanate does not appear nearby, which indicates that the end capping of the sealing agent is finished, and the characteristic peak indicates that the structure and the design of the polyurethane prepolymer are consistent;
and 2, step: preparation of polyurethane Silicone oil
Weighing 30g of prepared polyurethane prepolymer, adding the weighed polyurethane prepolymer into a four-neck flask, adding 100g of epoxy-terminated silicone oil (without polyether chain segment) with the molecular weight of 8000, adding 2.50g of glacial acetic acid, adding 100g of isopropanol, heating to 83-86 ℃, carrying out heat preservation reaction for 12h, removing a solvent through reduced pressure distillation after the reaction is finished, and adding 20g of dipropylene glycol butyl ether to obtain light yellow transparent viscous polyurethane silicone oil with the solid content of 78-83%;
the infrared spectrum of the polyurethane silicone oil is shown in figure 2, and can be seen from figure 2, 3324cm -1 And 1545cm -1 Absorption peaks are a stretching vibration peak and a deformation vibration peak of N-H in carbamate; 2961cm -1 Is the stretching vibration peak of methyl; 1700cm -1 Is the stretching vibration peak of carbonyl in carbamate; 1257cm -1 Is Si-CH 3 The bending vibration peak of (1); 1020cm -1 And 1082cm -1 Characteristic peaks of Si-O-Si and C-O-C; 789cm -1 Is the bending vibration peak of Si-C; 2260cm -1 An isocyanate characteristic peak does not appear nearby, and the characteristic peaks show that the structure and the design of the polyurethane silicone oil are consistent;
and step 3: preparation of Block Silicone oil
Weighing 100g of epoxy-terminated silicone oil (without polyether chain segment) with molecular weight of 8000, adding 100g of isopropanol, heating to 80-85 ℃, carrying out heat preservation reaction for 8h, carrying out reduced pressure distillation to remove an organic solvent, adding 26g of diethylene glycol butyl ether to adjust viscosity, and obtaining light yellow transparent three-dimensional network block silicone oil with solid content of 78-83%;
and 4, step 4: preparation of polyurethane modified organosilicon softener
Uniformly mixing the polyurethane silicone oil composition and the block silicone oil component according to a mass ratio of 2:1 to obtain 250g of crude oil of the polyurethane modified silicone softener, adding 30g of isomeric tridecanol polyoxyethylene ether 1303 (EO addition number is 3), 30g of isomeric tridecanol polyoxyethylene ether 1312 (EO addition number is 12) and 3.50g of glacial acetic acid, stirring at a high speed, and adding 550g of deionized water step by step to obtain the polyurethane modified silicone softener emulsion.
Example 2
Step 1: prepolymer for synthesizing polyurethane
Weighing 100g of isophorone diisocyanate, adding 65g of acetone into a four-necked flask, heating to 55-60 ℃, dropwise adding 26.80g of N-methyldiethanolamine, finishing dropwise adding within 150min, carrying out heat preservation reaction for 2h, dropwise adding 42g of butanone oxime, finishing dropwise adding within 2h, heating to 65 ℃, carrying out heat preservation reaction for 1.5h, detecting no isocyanate characteristic peak by infrared, continuously adding 84g of isopropanol for dilution after removing the acetone by reduced pressure distillation, cooling to room temperature, and discharging to obtain a light yellow transparent polyurethane prepolymer, wherein the solid content of the polyurethane prepolymer is 66-72%;
and 2, step: preparation of polyurethane Silicone oil
Weighing 57.50g of the prepared polyurethane prepolymer, adding 100g of epoxy-terminated silicone oil (without polyether chain segment) with the molecular weight of 4000, adding 3.40g of glacial acetic acid, adding 60g of isopropanol, heating to 80-83 ℃, and carrying out heat preservation reaction for 6 hours. After the reaction is finished, removing the solvent by reduced pressure distillation, and adding 36g of dipropylene glycol butyl ether to obtain light yellow transparent polyurethane silicone oil with the solid content of 79-83%;
and step 3: preparation of Block Silicone oil
Weighing 100g of epoxy terminated silicone oil (containing polyether chain segments) with the molecular weight of 10000, adding 5.40g of polyetheramine T403, adding 80g of isopropanol, heating to 80-82 ℃, carrying out heat preservation reaction for 12 hours, carrying out reduced pressure distillation to remove an organic solvent, adding 28g of dipropylene glycol butyl ether to adjust the viscosity, and obtaining light yellow transparent three-dimensional reticular block silicone oil with the solid content of 79-83%;
and 4, step 4: preparation of polyurethane modified organosilicon softener
Uniformly mixing the polyurethane silicone oil composition and the block silicone oil component according to a mass ratio of 3:2 to obtain 260g of crude polyurethane modified silicone softener, adding 40g of isomeric tridecanol polyoxyethylene ether 1306 (EO addition number is 6), 20g of isomeric tridecanol polyoxyethylene ether 1309 (EO addition number is 9) and 4.50g of glacial acetic acid, stirring at a high speed, and adding 550g of deionized water step by step to obtain polyurethane modified silicone softener emulsion;
example 3
In step 2 of example 1, 30g of polyurethane prepolymer is changed into 27g of polyurethane prepolymer, 100g of epoxy-terminated silicone oil (without polyether chain segment) with molecular weight of 8000 is changed into 133g of epoxy-terminated silicone oil (containing polyether chain segment) with molecular weight of 10000, 2.50g of glacial acetic acid is changed into 2.00g, the using amount of isopropanol is changed into 118g, the mixture is heated to 83-86 ℃ for heat preservation reaction for 12h and is changed into 85 ℃ for heat preservation reaction for 8h, 20g of dipropylene glycol butyl ether is changed into 27g of diethylene glycol butyl ether, and the rest is the same as example 1, so that light yellow transparent viscous polyurethane silicone oil with the solid content of 78-83% is obtained.
Example 4
In the step 3 of the embodiment 1, 7.80g of the polyether amine T403 is changed into 32.40g of polyether amine ED2003, 100g of isopropanol is changed into 170g, the temperature is increased to 80-85 ℃ and is increased to 81 ℃, the heat preservation reaction is changed into 16h of heat preservation reaction, the organic solvent is removed by reduced pressure distillation, 27g of diethylene glycol butyl ether is added, 34g of dipropylene glycol is added instead of adjustment, and the rest is the same as the embodiment 1, so that the light yellow transparent block silicone oil with the solid content of 78-82% is obtained.
Example 5
In step 1 of example 2, acetone 65g was changed to butanone 90g, heating to 55-60 ℃ was changed to 55 ℃, the dropwise addition time of N-methyldiethanolamine was changed to 180min for 150min, butanone oxime 42g was added dropwise to phenol 44.50g, the dropwise addition was changed to 1.5h, heating to 65 ℃ for heat preservation reaction for 1.5h, heating to 70 ℃ for heat preservation reaction for 4h, and after butanone was removed by distillation under reduced pressure, isopropanol 81g was continuously added to dissolve the prepolymer, and finally a polyurethane prepolymer with a solid content of 68% was obtained, as in example 2.
Example 6
In the step 1 of the embodiment 2, the acetone 65g is changed into tetrahydrofuran 57g, the temperature is increased to 55-60 ℃ to 60 ℃, the dripping time of N-methyldiethanolamine is changed to 90min, the temperature is increased to 72 ℃ after the dripping is finished, caprolactam 54g is added in batches instead of butanone oxime 42g, the caprolactam is added in 1.5h after the dripping is finished, the polyurethane prepolymer with the solid content of 71 percent is finally obtained after the temperature is increased to 65 ℃ for heat preservation reaction for 1.5h and the temperature is maintained for continuous reaction for 3.5h after the temperature is maintained for 72 ℃, and isopropanol 74g is continuously added for dilution after the tetrahydrofuran is removed by reduced pressure distillation, and the rest is the same as the step 2 of the embodiment 2.
The samples obtained in examples 1 and 2 and two commercially available softeners were applied to a cotton knitted fabric at a dose of 20g/L and a percentage of rolling loss of 85%, and the evaluation results are shown in tables 1 and 2.
The application process comprises the following steps: liquid preparation → one dipping and one rolling → pre-baking (105 ℃ X70 s) → baking (165 ℃ X90 s) → conditioning → evaluation.
And (3) testing the application performance:
1) Grading the hand feeling: and (4) evaluating by using a hand touch method, adopting a 1-5-point evaluation method, wherein the worst and the best of 1 point is 5 points, simultaneously evaluating 5 persons, and taking an average value. The evaluation includes the contents: softness and smoothness.
2) The hydrophilicity was evaluated by the water dropping method: dripping water drops at a height of 2cm from the fabric by using a dropper, starting timing, observing that the water drops completely wet the fabric surface, and ending timing when no mirror reflection exists.
3) Tensile elastic recovery test: and testing by using a universal material testing machine according to the textile woven fabric tensile elasticity test method FZ/T-01034-2008. The fabric was uneven after washing, so only the resilience before washing was tested.
4) Fabric washing procedure: and (3) washing the fabric according to the AATCC 135-2018t standard, washing for 10 times, and drying in a roller.
5) And (3) testing the silicon content: the cloth cover silicon content is obtained by EDS test.
TABLE 1 evaluation of the Performance of different softeners before washing
TABLE 2 evaluation of the performance of different softeners after washing 10 times with water
As can be seen from tables 1 and 2, the cotton knitted fabric treated by the polyurethane modified organosilicon softener provided by the invention has better application performance before and 10 times of washing than the original fabric and the commercial softener.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (10)
1. A preparation method of a polyurethane modified organosilicon softener is characterized by comprising the following steps:
s1, carrying out a polymerization reaction on isophorone diisocyanate and N-methyldiethanolamine in a first organic solvent, and then adding a sealing agent to seal the residual active isocyanate to obtain a polyurethane prepolymer;
s2, under the action of an acidic catalyst, carrying out polymerization reaction on the polyurethane prepolymer prepared in the step S1 and epoxy-terminated silicone oil in a second organic solvent to obtain a polyurethane silicone oil component;
s3, reacting the epoxy-terminated silicone oil with polyether amine in a second organic solvent to obtain a block silicone oil component;
and S4, compounding the polyurethane silicone oil component prepared in the step S2 and the block silicone oil component prepared in the step S3 according to a preset proportion, and then adding an emulsifier for emulsification to finally prepare the polyurethane modified organic silicon softener.
2. The method of preparing a polyurethane modified silicone softener according to claim 1, wherein step S1 comprises the substeps of:
s11, adding isophorone diisocyanate and N-methyldiethanolamine into a first organic solvent according to a molar ratio of 3:2 or 2:1, wherein the N-methyldiethanolamine is added in a dropwise manner for 15-180 min, and the mass of the first organic solvent is 10-80% of the total mass of the isophorone diisocyanate and the N-methyldiethanolamine;
s12, stirring for 2-8 hours at 30-70 ℃ to perform polymerization reaction;
s13, after the polymerization reaction is finished, keeping the reaction temperature at 40-80 ℃, and adding a blocking agent to block the residual active isocyanate, wherein the molar ratio of the blocking agent to the residual active isocyanate is (1.05);
and S14, continuously reacting for 2-6 hours, after infrared detection shows that no isocyanate peak exists, distilling under reduced pressure to remove the first organic solvent, and adding a second organic solvent for dilution to obtain the polyurethane prepolymer.
3. The method for preparing the polyurethane modified silicone softener according to claim 1, wherein the step S2 comprises the substeps of:
s21, adding a second organic solvent into the polyurethane prepolymer and the epoxy-terminated silicone oil according to the proportion of the molar ratio of the epoxy value to the amine value of 1:1-1:2, and simultaneously adding an acid catalyst with the mole number of the amine value of 100-200% into the polyurethane prepolymer;
and S22, stirring and reacting for 4-24 hours at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the polyurethane silicone oil component.
4. The method of preparing a polyurethane modified silicone softener according to claim 1, wherein step S3 comprises the substeps of:
s31, putting the epoxy-terminated silicone oil and the polyether amine into a second organic solvent according to the molar ratio of the epoxy value to the amine value of 1:1-1:2;
and S32, stirring and reacting for 6-24 hours at the temperature of 60-120 ℃, and then vacuumizing to remove the second organic solvent to obtain the block silicone oil component.
5. The method of claim 1, wherein in step S1, the blocking agent is one or more of butanone oxime, phenol, sodium bisulfite, caprolactam, acetylacetone, and diethyl malonate; in the step S2, the acidic catalyst is one or more of formic acid, acetic acid, diluted hydrochloric acid, lauric acid and citric acid; in the step S3, the polyetheramine is one or more of polyetheramine ED600, polyetheramine ED900, polyetheramine ED2003, and polyetheramine T403.
6. The method for preparing the polyurethane modified silicone softener according to claim 1, wherein in step S4, the polyurethane silicone oil component and the block silicone oil component are compounded according to a mass ratio of 2:1 to 1:1.
7. The method of claim 1, wherein the first organic solvent is one or more of acetone, methyl ethyl ketone and tetrahydrofuran, and the second organic solvent is one or more of diethylene glycol butyl ether, ethylene glycol butyl ether, dipropylene glycol, propylene glycol acetate and isopropyl alcohol.
8. The method of preparing the polyurethane modified silicone softener according to any one of claims 1 to 7, wherein the emulsifier is a combination of isomeric tridecanol polyoxyethylene ethers with different EO addition numbers, and has an HLB value of 4 to 18.
9. A polyurethane modified silicone softener prepared by the method of any one of claims 1 to 8.
10. The application of the polyurethane modified organosilicon softener in cotton fabrics as claimed in claim 9, wherein the specific application method is as follows: the polyurethane modified organic solvent is applied to cotton fabrics, a one-dip one-roll process is adopted, then the cotton fabrics are pre-baked for 30 to 90 seconds at the temperature of between 90 and 110 ℃, and finally the cotton fabrics are baked for 30 to 120 seconds at the temperature of between 160 and 170 ℃.
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