CN111925528A - Preparation method of amide modified polysiloxane - Google Patents

Preparation method of amide modified polysiloxane Download PDF

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CN111925528A
CN111925528A CN202010883289.1A CN202010883289A CN111925528A CN 111925528 A CN111925528 A CN 111925528A CN 202010883289 A CN202010883289 A CN 202010883289A CN 111925528 A CN111925528 A CN 111925528A
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modified polysiloxane
isocyanate
amide
diisocyanate
heating
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CN111925528B (en
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孙恒华
林伟
李科
徐治平
梁国斌
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Changzhou Henglun Textile Co ltd
Jiangsu University of Technology
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Changzhou Henglun Textile Co ltd
Jiangsu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

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Abstract

The invention discloses a preparation method of amide modified polysiloxane, belonging to the technical field of silane finishing agents. The method comprises the steps of taking bi-terminal aminopropyl polysiloxane and isocyanate as raw materials, taking dibutyltin dilaurate (DBTDL) as a catalyst, reacting to obtain an isocyanate-terminated modified polysiloxane prepolymer, taking succinimide as a terminating agent, and reacting to obtain the isocyanate-terminated modified polysiloxane. The organic silicon finishing agent with the block structure is synthesized, the mutual restriction and balance among various functional groups of the side chain type multifunctional silicone oil are overcome, and the integration of hydrophilic and flexible performances is perfectly realized. By exploring a catalyst, an organic solvent, a blocking agent and reaction conditions, the blocking rate can reach about 90 percent at most; meanwhile, the fabric treated by the organosilane finishing agent prepared by synthesizing the amide modified polysiloxane in the invention has the advantages of increased crease recovery angle, reduced bending length, enhanced elasticity and improved flexibility.

Description

Preparation method of amide modified polysiloxane
Technical Field
The invention relates to a preparation method of amide modified polysiloxane, belonging to the technical field of silane finishing agents.
Background
The organic silicon finishing agent is a softening agent with the most outstanding effect of finishing fabrics, has wide application and extremely excellent performance in the textile field, can effectively endow fabrics with various performances of softness, smoothness, moisture absorption, static resistance, bacteria resistance and the like, and the polysiloxane has excellent lubricity and film forming property.
Silicone finishes are applied for crease-resistant finishing of fabrics and must have groups that react with reactive groups on the fabric. The molecular chain of a general reactive organosilicon crosslinking agent contains active groups such as amino, epoxy, hydroxyl, vinyl and the like, and the reactive groups are often adopted to modify at two ends or in the molecular chain. The modified silicone oil has different finishing effects by adopting different reactive groups, and common modification methods comprise amino modification, carboxyl modification, fatty alcohol modification, epoxy modification and the like, but various functional groups of the side chain type multifunctional silicone oil are easy to restrict mutually.
Disclosure of Invention
[ problem ] to
Silicone finishes are used for crease-resistant finishing of fabrics and must have groups that react with reactive groups on the fabric. The modified silicone oil has different finishing effects by adopting different reactive groups, and common modification methods comprise amino modification, carboxyl modification, fatty alcohol modification, epoxy modification and the like, but the interaction between various functional groups of the side chain type multifunctional silicone oil is easy to occur.
[ solution ]
In view of the above problems, the present invention provides a method for preparing amide-modified polysiloxane, wherein an isocyanate group-terminated modified polysiloxane prepolymer is obtained by reacting a bisaminopropyl polysiloxane SA and an isocyanate as raw materials with dibutyltin dilaurate (DBTDL) as a catalyst, and an isocyanate group-terminated modified polysiloxane is obtained by reacting an isocyanate group-terminated modified polysiloxane prepolymer as a raw material with succinimide as a capping agent. The organic silicon finishing agent with the block structure is synthesized, so that the mutual restriction and balance among various functional groups of the side chain type multifunctional silicone oil are overcome, and the integration of hydrophilic and flexible properties is realized.
The invention provides a method for preparing amide modified polysiloxane, which specifically comprises the following steps:
(1) adding a solvent and isocyanate into a reactor, heating to 50-60 ℃ under the protection of nitrogen after the solvent and the isocyanate are fully dissolved, then dropwise adding bi-terminal aminopropyl polysiloxane (SA), heating to 70-80 ℃ after the dropwise addition is finished, adding a catalyst, and reacting for 2-4 hours to obtain an amide modified polysiloxane prepolymer;
(2) and (2) adding an end-capping agent into the amide modified polysiloxane prepolymer prepared in the step (1), heating to 70-100 ℃ for end-capping reaction for 3-6h, and obtaining the amide modified polysiloxane after the reaction is finished.
In one embodiment, the isocyanate in step (1) is any one of cyclohexane-1, 3-diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, diphenylmethane 4, 4-diisocyanate, 1, 4-tetramethylene diisocyanate, cyclohexane-1, 4-diisocyanate, and dicyclohexylmethane diisocyanate.
In one embodiment, in step (1) the isocyanate is cyclohexane-1, 3-diisocyanate.
In one embodiment, the formula of the bisaminopropyl polysiloxane (SA) in step (1) is as follows:
Figure BDA0002654807230000021
wherein n is 1-20.
In one embodiment, the method for preparing the bisaminopropyl polysiloxane (SA) in step (1) is: under the protection of nitrogen, adding octamethylcyclotetrasiloxane and 1, 3-bis (aminopropyl) tetramethyldisiloxane into a reaction vessel provided with a stirrer, a thermometer and a condensation reflux device, wherein the mass ratio of octamethylcyclotetrasiloxane to 1, 3-bis (aminopropyl) tetramethyldisiloxane is 20:1, starting stirring, heating to 75 ℃, adding tetramethylammonium hydroxide silicon alkoxide which accounts for 0.1 percent of the total mass of reactants and serves as a catalyst, heating to 100 ℃, reacting for 10 hours, heating to 140 ℃ after the reaction is completed, and removing low-boiling-point substances by decompression to obtain the double-end aminopropyl polysiloxane (SA).
In one embodiment, the molar ratio of isocyanate to bisaminopropylpolysiloxane SA in step (1) is (1.5:1) to (2.5: 1).
In one embodiment, the solvent in step (1) is an aprotic organic solvent, specifically any one of acetone, dioxane, methyl ethyl ketone, N-methylpyrrolidone, and tetrahydrofuran.
In one embodiment, the solvent in step (1) is acetone.
In one embodiment, the catalyst in step (1) is any one of dibutyl tin dilaurate, triethylene diamine, stannous octoate, lead octoate, zinc naphthenate or tetraisobutyl titanate.
In one embodiment, the catalyst in step (1) is dibutyl tin dilaurate.
In one embodiment, the blocking agent in step (2) is any one of succinimide, caprolactam, acetanilide, or cyclobutylimide.
In one embodiment, the capping agent in step (2) is succinimide.
In one embodiment, the molar ratio of isocyanate to blocking agent in step (2) is (2.5:1) - (3: 1).
In one embodiment, the temperature of the end-capping reaction in step (2) is from 70 to 100 ℃.
In one embodiment, the capping reaction in step (2) is carried out for a reaction time of 4 to 6 hours.
In one embodiment, the reaction scheme for preparing the amide-modified polysiloxane prepolymer in step (1) is shown as (a) in FIG. 1; the reaction formula for preparing the isocyanate modified polysiloxane in the step (2) is shown as (b) in the attached figure 1.
The invention provides amide modified polysiloxane prepared by the method.
The invention provides a clothes finishing agent which contains the amide modified polysiloxane.
In one embodiment of the present invention, the method for formulating the clothing finish comprises: the amide modified polysiloxane and the penetrant fatty alcohol-polyoxyethylene ether JFC are mixed according to the mass ratio of (15-20) to 1, and the mixture is subjected to ultrasonic emulsification to obtain the clothing finishing agent.
[ advantageous effects ]:
(1) at present, textile enterprises use reactive organic silicon as a finishing agent, the finishing agent can improve the crease resistance of knitted fabrics, meanwhile, the organic silicon can solve the problem of strength reduction caused by stress concentration generated by crosslinking of finished fabrics, and reduce the strength damage of the finished fabrics, but the durable press performance of the fabrics finished by the organic silicon is poor. In order to increase the pressure-resistant performance of the fabric, the invention adopts isocyanate modified polysiloxane with high reaction activity on the basis of the existing epoxy modified polysiloxane, and introduces active end group isocyanate (-NCO) to react with groups containing active hydrogen on the fabric while keeping the polysiloxane, thereby achieving the crease resistance, increasing the pressure-resistant performance of the fabric, and simultaneously keeping the original hydrophilicity and softness of the fabric.
(2) The prepared amide modified polysiloxane has high end capping rate, and the end capping rate can reach about 90% at most by exploring a catalyst, an organic solvent, an end capping agent and reaction conditions; meanwhile, when the amide modified polysiloxane synthesized by the method is used for preparing the organic silane finishing agent, the wrinkle recovery angle of the treated fabric is increased, the bending length is reduced, the elasticity is enhanced, the softness is good, and the softness is improved.
Drawings
FIG. 1 shows a reaction scheme for synthesizing an amide-modified polysiloxane.
FIG. 2 is an infrared spectrum of the amide-modified polysiloxane synthesized in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
1. The method for calculating the blocking rate comprises the following steps:
firstly, the content of free isocyanate groups in a product is measured by adopting a di-n-butylamine method, and the blocking rate is calculated by measuring the mass percentage of free-NCO groups before and after the blocking reaction. The blocking ratio was calculated as follows:
Figure BDA0002654807230000031
in the formula, W1Is the mass fraction of free-NCO groups before end capping;
W2is the mass fraction of free-NCO groups after blocking.
The method for measuring the content of the isocyanic acid radical comprises the following steps: the content of-NCO before and after reaction is determined by a chemical titration method, and the test principle is as follows:
RNCO+(C4H9)2NH→RNHCON(C4H9)2
(C4H9)2NH+HCl→(C4H9)2NH·HCl
the specific test method comprises the following steps: weighing the product into a beaker, adding 20mL of anhydrous toluene for dissolving, accurately transferring 25mL of di-n-butylamine-toluene solution, mixing and shaking up. Standing at room temperature for 20-30 min, adding 40-50 mL of isopropanol, adding a few drops of bromocresol green indicator, titrating with 0.5459mol/L standard hydrochloric acid, and taking a blank test when the solution is changed from blue to yellow. The calculation formula is as follows:
Figure BDA0002654807230000041
in the formula, V0The volume of hydrochloric acid standard solution (mL) consumed for the blank;
V1the volume of hydrochloric acid standard solution (mL) consumed for the sample;
c is the concentration (mol/L) of the hydrochloric acid standard solution;
and m is the sample mass (g).
2. Fold recovery angle: tested according to GB/T3819-1997. And (3) sampling the front surface, the warp direction and the weft direction of the sample, testing by using a full-automatic fabric wrinkle elasticity instrument according to a vertical method, calculating the average value of the recovery angles of the warp and weft direction creases, and taking the sum of the average values of the recovery angles of the warp and weft direction creases.
3. Fabric strength: the tensile breaking strength of the fabric was tested according to GB/T3923.1-2013. And (3) measuring the breaking strength of the real silk fabric subjected to crease-resistant finishing by using a breaking strength instrument, and calculating the breaking strength retention rate of the fabric.
Retention rate of breaking strength ═ Rb/Ra)×100％
RaBreaking strength before finishing the fabric;
Rbto obtain breaking strength after finishing the fabric.
4. Bending length: the bending length of the fabric is measured by adopting a fabric stiffness tester according to a fabric bending length measuring method.
[ example 1 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of double-ended aminopropyl polysiloxane SA (n is 10), heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) and (2) reducing the temperature of the amide modified polysiloxane prepolymer prepared in the step (1) to room temperature, adding 0.1mol of succinimide, and continuously heating to 80 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by the method for calculating the blocking ratio as described above, and the calculation results are shown in Table 1.
The product prepared in this example was subjected to infrared testing, and fig. 2 is an infrared spectrum of the product, as can be seen from fig. 2: the wave number is 1000-1100 cm-1The strong broad peak of stretching vibration at Si-O bond is 1260cm in wave number-1Is of Si-CH3of-CH3The symmetric deformation vibration peak of (1) is at 1680cm-1Characteristic absorption peak of C ═ O at wave number of 2900cm-1Is represented by-CH3Has antisymmetric stretching vibration peak and symmetric stretching vibration peak, and has wave number of 700cm-1A bending vibration absorption peak at a C-H bond of 800-860cm-1The strong peak is the stretching vibration peak of Si-C and is 3500-3600 cm-1The stretching vibration peak of N-H appears.
The solvents of the reactions were compared and the corresponding experiments were carried out:
[ example 2 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of dioxane, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 1.
[ example 3 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of methyl ethyl ketone into the flask, stirring and dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 1.
[ example 4 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of N-methylpyrrolidone, stirring and dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyltin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 1.
[ example 5 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of tetrahydrofuran, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 1.
TABLE 1
Examples End capping ratio (%)
Example 1 88.62
Example 2 88.12
Example 3 85.13
Example 4 75.85
Example 5 77.22
The catalysts of the reaction were compared and the corresponding experiments were carried out:
[ example 6 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of dioxane, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 2.
[ example 7 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of methyl ethyl ketone into the flask, stirring and dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 2.
[ example 8 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of N-methylpyrrolidone, stirring and dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyltin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 2.
[ example 9 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of tetrahydrofuran, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 2.
[ example 10 ]
(1) Adding 0.25mol of cyclohexane-1, 3-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of tetrahydrofuran, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) the blocking ratio was calculated in the same manner as in the step (2) in example 1 with reference to the above-mentioned method for calculating the blocking ratio, and the calculation results are shown in Table 2.
TABLE 2
Examples End capping ratio (%)
Example 1 88.62
Example 6 82.14
Example 7 84.33
Example 8 81.35
Example 9 86.12
Example 10 86.34
The reacted blocking agents were compared and the corresponding experiments were performed:
[ example 11 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the amide modified polysiloxane prepolymer prepared in the step (1), adding 0.1mol of caprolactam, and continuously heating to 80 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 3.
[ example 12 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the amide modified polysiloxane prepolymer prepared in the step (1), adding 0.1mol of acetanilide, and continuously heating to 80 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 3.
[ example 13 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of cyclobutylimide, and continuously heating to 80 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 3.
TABLE 3
Examples End capping ratio (%)
Example 1 88.62
Example 11 85.22
Example 12 79.43
Example 13 85.25
Compared with the influence of the end capping temperature of the reaction system on the end capping effect, the experimental result is as follows:
[ example 14 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 70 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 4.
[ example 15 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 90 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 4.
[ example 16 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 100 ℃ to react for 4 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 4.
TABLE 4
Examples End capping ratio (%)
Example 1 88.62
Example 14 83.34
Example 15 81.65
Example 16 75.29
Comparing the influence of the end capping time of the reaction system on the end capping effect, the experimental results are as follows:
[ example 17 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 80 ℃ to react for 3 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 5.
[ example 18 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 80 ℃ to react for 5 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 5.
[ example 19 ]
(1) Same as in step (1) in example (1);
(2) and (2) reducing the temperature of the isocyanate group-terminated polysiloxane prepolymer prepared in the step (1), adding 0.1mol of succinimide, and continuously heating to 80 ℃ to react for 6 hours to obtain a final product. The mixture was cooled to room temperature, and water was added thereto under vigorous stirring to disperse the mixture to obtain an amide-modified polysiloxane as a pale yellow transparent viscous liquid. The blocking ratio was calculated by referring to the above method for calculating the blocking ratio, and the calculation results are shown in Table 5.
TABLE 5
Examples End capping ratio (%)
Example 1 88.62
Example 17 69.34
Example 18 88.60
Example 19 88.23
After the optimal blocking condition is determined, the reaction of different isocyanates is researched, and different isocyanates are selected to prepare the modified polysiloxane, which specifically comprises the following steps:
[ example 20 ]
(1) Adding 0.25mol of toluene diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 21 ]
(1) Adding 0.25mol of 1, 6-hexamethylene diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 22 ]
(1) Adding 0.25mol of diphenylmethane 4, 4-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyltin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 23 ]
(1) Adding 0.25mol of 1, 4-tetramethylene diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 24 ]
(1) Adding 0.25mol of cyclohexane-1, 4-diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone into the flask, stirring and dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyl tin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 25 ]
(1) Adding 0.25mol of dicyclohexylmethane diisocyanate into a four-neck flask with a thermometer, a condenser and magnetic stirring, adding 15mL of acetone, stirring for dissolving, stirring under the protection of nitrogen, heating to 50 ℃, slowly dropwise adding 0.125mol of SA, heating to 70 ℃ after the addition is finished, adding 3 drops of dibutyltin dilaurate as a catalyst, and reacting for 3 hours to obtain an isocyanate-terminated polysiloxane prepolymer;
(2) same as in step (2) in example 1.
[ example 26 ]
The amide modified polysiloxane prepared in the embodiment 1, 20-25 and fatty alcohol-polyoxyethylene ether JFC are compounded to prepare the corresponding finishing agent. The process flow comprises the following steps: the prepared isocyanate group blocked polysiloxane and a penetrating agent (JFC) are mixed according to the mass ratio of 20:1 to prepare a finishing agent with a certain concentration. Citric acid and glyoxal are mixed with JFC according to the mass ratio of 20:1 to prepare a finishing agent with a certain concentration. And (3) soaking and rolling the plain woven fabric twice, pre-drying for 3min at 80 ℃, then baking the fabric at 120 ℃ for 3min, and standing for later test. The amount of the finishing agent is 50g/L, crease-resistant finishing is carried out on the fabric, the influence on the crease recovery angle, the breaking strength retention rate and the bending length performance of the finished fabric is researched, and the test method is as above. The test results are shown in Table 6.
TABLE 6
Figure BDA0002654807230000111
Figure BDA0002654807230000121
As can be seen from Table 2, the synthesized amide modified polysiloxane finishing agent contains amide and ester carbonyl active groups, and can generate an acetal reaction with hydroxyl in cotton fibers to increase the degree of network crosslinking among the fibers, the breaking strength is reduced slightly after the finishing agent is added, the bending length reflects the softness of the fabric, and the smaller the bending length of the fabric is, the better the softness is. The finished fabric has the advantages of increased crease recovery angle, reduced bending length, enhanced elasticity, good softness and improved softness, and is obviously superior to epoxy modified polysiloxane, citric acid and glyoxal finishing agents.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for preparing an amide-modified polysiloxane, characterized in that the method specifically comprises the steps of:
(1) adding a solvent and isocyanate into a reactor, heating to 50-60 ℃ under the protection of nitrogen after the solvent and the isocyanate are fully dissolved, then dropwise adding aminopropyl polysiloxane into the mixture, heating to 70-80 ℃ after the dropwise addition is finished, adding a catalyst, and reacting for 2-4 hours to obtain an amide modified polysiloxane prepolymer;
(2) and (2) adding an end-capping agent into the amide modified polysiloxane prepolymer prepared in the step (1), heating to 70-100 ℃ for end-capping reaction for 3-6h, and obtaining the amide modified polysiloxane after the reaction is finished.
2. The method according to claim 1, wherein the isocyanate in step (1) is any one of cyclohexane-1, 3-diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, diphenylmethane 4, 4-diisocyanate, 1, 4-tetramethylene diisocyanate, cyclohexane-1, 4-diisocyanate, and dicyclohexylmethane diisocyanate.
3. The method according to claim 1, wherein the formula of the bisaminopropyl polysiloxane in step (1) is as follows:
Figure FDA0002654807220000011
wherein n is 1-20.
4. The process according to claim 1, wherein the molar ratio of the isocyanate to the bisaminopropylpolysiloxane in step (1) is (1.5:1) to (2.5: 1).
5. The method according to claim 1, wherein the solvent in step (1) is an aprotic organic solvent, specifically any one of acetone, dioxane, methyl ethyl ketone, N-methylpyrrolidone, and tetrahydrofuran.
6. The method of claim 1, wherein the catalyst in step (1) is any one of dibutyl tin dilaurate, triethylene diamine, stannous octoate, lead octoate, zinc naphthenate, or tetraisobutyl titanate.
7. The method of claim 1, wherein the blocking agent in step (2) is any one of succinimide, caprolactam, acetanilide, or cyclobutylimide.
8. The method of claim 1, wherein the temperature of the end-capping reaction in step (2) is 70-100 ℃ and the reaction time of the end-capping reaction is 4-6 h.
9. An amide-modified polysiloxane prepared by the method according to any one of claims 1 to 8.
10. A clothing finish, characterized in that the clothing finish contains the amide-modified polysiloxane according to claim 9.
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Publication number Priority date Publication date Assignee Title
EP0487487A2 (en) * 1990-10-16 1992-05-27 Lenzing Aktiengesellschaft Process for the preparation of polysiloxane imides
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Publication number Priority date Publication date Assignee Title
EP0487487A2 (en) * 1990-10-16 1992-05-27 Lenzing Aktiengesellschaft Process for the preparation of polysiloxane imides
CN108929425A (en) * 2018-07-19 2018-12-04 芜湖维软新材料有限公司 A kind of silicone oil preparation method applied to textile

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