CN114702680B - Ultrahigh-stability block silicone oil and preparation method thereof - Google Patents
Ultrahigh-stability block silicone oil and preparation method thereof Download PDFInfo
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- D—TEXTILES; PAPER
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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 relates to the field of textile finishing auxiliaries, and provides block silicone oil with ultrahigh stability, aiming at the problem of poor emulsion stability of silicone oil, wherein the structural formula is as follows:
Description
Technical Field
The invention relates to the field of textile finishing auxiliaries, in particular to block silicone oil with ultrahigh stability and a preparation method thereof.
Background
Common amino silicone oil has been gradually replaced by various types of block polyether modified amino silicone oil due to the disadvantage of poor emulsion stability. For example, runing fine chemical industries ltd discloses synthesis and performance research of amino polyether modified silicone oil (daily chemical science, no. 1, page 28-30 of 2017, synthesis and performance research of amino polyether modified silicone oil), which synthesizes amino polyether by taking N-beta- (aminoethyl) -gamma-guanamine propyl methyl dimethoxy silane and epoxy polyether (alcohol terminated) as raw materials; the amino polyether and octamethylcyclotetrasiloxane are used as raw materials to synthesize the amino polyether modified cassia oil, and the prepared amino polyether modified silicone oil has good water absorption due to the introduction of the hydrophilic polyether chain segment, but the stability of the amino polyether modified silicone oil needs to be further improved. Accordingly, an ideal solution is needed.
Disclosure of Invention
The invention provides block silicone oil with ultrahigh stability, aiming at overcoming the problem of poor emulsion stability of silicone oil, and the emulsion stability is improved by regulating and controlling the proportion of a silicon-oxygen-based chain segment and a polyether chain segment.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultrahigh-stability block silicone oil has the following structural formula:
Compared with amino silicone oil, the triblock silicone oil has the characteristics of self-emulsification in water, shear resistance, acid and alkali resistance, hydrophilicity and the like, but the triblock silicone oil is only a characteristic and is not a common property. The size of the molecular weight of the siloxy chain segment, the polymerization degree of the polyether chain segment, the percentage of amino groups and other factors can influence the performance of the finally prepared block silicone oil, so that the performance regulation and control of the block silicone oil are much more complicated than that of amino silicone oil. Among them, the silicone segment plays a decisive role in the softening effect and also influences the self-emulsifying dispersibility of silicone oil in water. The long silica linkages, while providing good softening and smoothing results, are too long to allow dispersion in water by the addition of an emulsifier. The polyether linkage mainly influences the state of the silicone oil in water and the hydrophilic-hydrophobic properties of the silicone oil, and also influences the softening effect of the silicone oil. Considering the water dispersivity, heat resistance and fabric softening effect of the block silicone oil comprehensively, n is set to 150-200. The product has good flexibility by adopting a large number of EO, can compensate for the softening effect of the short and reduced silica chain link, and increases the ratio value between EO and PO to (20-30) to (2-6). The amino can adjust the hydrophilic-hydrophobic performance and the water dissolving and dispersing performance of the silicone oil, the state of the silicone oil in water and the hand feeling finishing style are directly influenced by different amino amounts, the amino ratio cannot be too much in consideration of the heat resistance of the silicone oil, and the m value is preferably 10-20.
Preferably, the block silicone oil is modified, and the method comprises the following steps:
1) Dissolving malic acid and aminoacetic acid in water, adding methyl methacrylate, reacting for 4-6h at 80-90 ℃, putting the product into an acetonitrile solvent after crystal separation, adding methyl iodide, heating and refluxing for reaction for 2-4h, and carrying out crystal separation to obtain a malic acid derivative, wherein the molar ratio of the malic acid, the aminoacetic acid, the methyl methacrylate to the methyl iodide is 1 (1-3) to (0.1-0.3) to (1-1.2);
2) Mixing the malic acid derivative prepared in the step 1) with cyclodextrin and sodium hypophosphite, and reacting at 100-110 ℃ for 3-5h to obtain a precipitate, and purifying the precipitate to obtain grafted cyclodextrin;
3) Dissolving the grafted cyclodextrin prepared in the step 2), the block silicone oil and 4-dimethylaminopyridine in dichloromethane, stirring for 10-12h at room temperature, filtering, and freeze-drying to obtain the modified block silicone oil.
When the block silicone oil is used, the block silicone oil and an emulsifier are required to be prepared into emulsion in water, and when the dosage of the emulsifier is small, the block silicone oil can generate self-polymerization or incomplete reaction, so that the oil floating phenomenon of the emulsion is caused, and the stability of the emulsion is insufficient. The cyclodextrin is of a vertex-free conical cavity structure, the outer hydrophilic inner layer is hydrophobic, the cyclodextrin is grafted on the block silicone oil, a hydrophobic silicone long chain can enter the hydrophobic cavity of the cyclodextrin, the cyclodextrin has a hydrophilic outer part, the solubility of the block silicone oil can be effectively increased, the demulsification phenomenon is reduced, and the dispersion stability of the block silicone oil in water is improved. When the silicone oil is used for finishing the fabric, the cyclodextrin releases the silicon-oxygen chain through slow release, and the finishing effect of the silicone oil cannot be influenced. In the prior art, cyclodextrin is used for modifying a polymer, but cyclodextrin is polymerized into a main chain, the inventor finds that a silicone oil chain segment obtained by the polymerization reaction of cyclodextrin has higher rigidity and obviously reduces the smoothness after being used on a fabric, and experiments find that the effect of stabilizing an emulsion can be achieved by grafting cyclodextrin on the side surface of the silicone oil chain segment, so that the polymerization condition is reduced, and the influence of cyclodextrin on the main chain is reduced.
The grafting of macromolecular cyclodextrin onto the side of the block silicone oil also has an effect on the hand feel and smoothness of the finished fabric, and for this reason, malic acid derivatives are grafted onto the cyclodextrin. The malic acid has a lubricating effect, and the malic acid contains 2 carboxyl groups, so that a reaction group is provided for the subsequent connection with cyclodextrin and block silicone oil, and an additional bridging reaction step is saved. According to the invention, the active functional group of malic acid is utilized to modify the quaternary ammonium salt of malic acid, so that the smoothness of the finished fabric is further improved. Hydroxyl of malic acid reacts with carboxyl of aminoacetic acid to enable galacturonic acid to have amino, quaternary ammonium salt is obtained through reaction of the amino and methyl iodide, the quaternary ammonium salt has smooth and soft effects on finished fabrics, static friction coefficient between fibers is greatly reduced, fabric handfeel is smooth, and the problem of fabric smoothness reduction caused by cyclodextrin grafting is solved.
As a further preference, the molar ratio of grafted cyclodextrin to block silicone oil in step 3) is (3-5): 1. The grafting of cyclodextrin can improve the stability of emulsion, but the molecular structure of cyclodextrin is larger, and the hand feeling of the finished fabric is hard due to excessive grafting on the side chain of the block silicone oil, so the grafting proportion of cyclodextrin needs to be controlled.
As a further preference, the cyclodextrin, the malic acid derivative and the sodium hypophosphite in the step 2) are mixed in a molar ratio of 1 (4-6) to (1-1.5). When the amount of the malic acid derivative is too small, the effect of improving smoothness is not obtained, and when the amount is too large, the malic acid derivative is easily agglomerated and affects the heat resistance of the block silicone oil.
The invention also provides a preparation method of the block silicone oil with ultrahigh stability, which comprises the following steps:
(1) Adding the epoxy double-end socket into diamine under the protection of inert gas, stirring for 6-10h, and reacting for 6-10h at 60-80 ℃ to obtain an amino double-end socket;
structural formula of amino double-end socket
(2) Uniformly mixing the amino double-end socket and the organic siloxane ring body, adding an alkaline catalyst, and reacting for 12-18h at 80-110 ℃; reacting for 1-2h at 140-150 ℃ to obtain alpha, omega-diamino silicone oil;
(3) Adding epoxy-terminated polyether and the alpha, omega-diamino silicone oil into a solvent, uniformly mixing, reacting for 15-20 h at 60-80 ℃, and adjusting the pH value to be neutral to prepare the diamino block polyether amino silicone oil, namely the product block silicone oil.
Compared with the method of directly preparing epoxy silicone oil by using the epoxy double-end socket and then preparing the amino-terminated silicone oil by reacting with diamine, the method has the advantages that the retention rate of the reaction groups at two ends is high, and the high reaction activity of block polymerization with polyether groups is ensured.
Preferably, the basic catalyst in step (2) is (CH) 3 ) 4 NOH alkali glue or (n-C) 4 H 9 ) 4 The dosage of the POH alkali glue and the alkaline catalyst (the effective content of the catalyst) is 0.05-0.1 percent of the total mass of reactants.
Preferably, the solvent in the step (3) is one or a combination of more of isopropanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and diethylene glycol monomethyl ether; the dosage of the solvent is 5 to 65 percent of the total mass of the reaction system.
Therefore, the beneficial effects of the invention are as follows: (1) The block silicone oil has high stability by regulating and controlling the molecular weight of the siloxy chain segment, the polymerization degree of the polyether chain segment and the percentage value of amino; (2) Cyclodextrin is grafted on the block silicone oil, so that the demulsification phenomenon is reduced, and the dispersion stability of the block silicone oil in water is improved; (3) In the preparation method of the block silicone oil, the amino double-end socket reacts with the organic siloxane ring body, the retention rate of the reaction groups at two ends is high, and the high reaction activity of block polymerization with polyether groups is ensured.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
General examples
An ultrahigh-stability block silicone oil has the following structural formula:
(1) Synthesis of amino double-end socket: adding epoxy double-end sockets into diamine while stirring under the protection of inert gas, after dropwise adding within 2h, stirring at room temperature for 6-10h, heating to 60-80 ℃ for reacting for 6-10h, and carrying out reduced pressure distillation to extract redundant diamine to obtain amino double-end sockets, wherein the structural formula is as follows;
structural formula of amino double-end socket
(2) Synthesis of alpha, omega-bisamino silicone oil: uniformly mixing the amino double-end socket and the organic siloxane ring body, and adding an alkaline Catalyst (CH) accounting for 0.05-0.1 percent of the total mass of reactants 3 ) 4 NOH alkali glue or (n-C) 4 H 9 ) 4 POH alkali glue is firstly reacted for 12 to 18 hours at a temperature of between 80 and 110 ℃, then reacted for 1 to 2 hours at a temperature of between 140 and 150 ℃ to decompose a catalyst, and then the low-boiling-point substances are removed by reduced pressure distillation to prepare alpha, omega-diamino silicone oil;
(3) Block polymerization of α, ω -diamino silicone oil and epoxy terminated polyether: adding epoxy-terminated polyether and the alpha, omega-diamino silicone oil into an organic solvent which accounts for 5-65% of the total mass of a reaction system, uniformly mixing, wherein the organic solvent is one or a combination of more of isopropanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, reacting for 15-20 h at the temperature of 60-80 ℃, and neutralizing with acetic acid or lauric acid until the pH is =6-7 to prepare the diamino type block polyether amino silicone oil, namely the product block silicone oil.
Structural formula of epoxy terminated polyether
Example 1
An ultrahigh-stability block silicone oil has the following structural formula:
(1) Adding epoxy double-end enclosure into 50g of 1, 3-propane diamine under the protection of inert gas while stirring, finishing dripping within 2h, stirring at room temperature for 8h, heating to 70 ℃ for reacting for 8h, and carrying out reduced pressure distillation to extract redundant diamine to obtain amino double-end enclosure;
(2) Uniformly mixing the amino double-end socket and the organic siloxane ring body, and adding (CH) accounting for 0.1 percent of the total mass of reactants 3 ) 4 NOH alkali glue reacts for 15h at 100 ℃, then reacts for 2h at 145 ℃ to decompose the catalyst, and is subjected to reduced pressure distillation to remove low-boiling-point substances, so that alpha, omega-diamino silicone oil is prepared;
(3) And uniformly mixing the alpha, omega-diamino silicon, epoxy terminated polyether and isopropanol, reacting for 16h at 70 ℃, and neutralizing with acetic acid until the pH is =7 to obtain the diamino block polyether amino silicone oil, namely the product block silicone oil.
Comparative example 1
The difference from example 1 is that n is 120, a is 30, b is 2.
Example 2 (grafted Cyclodextrin)
An ultra-high stability block silicone oil, wherein part of hydroxyl groups are replaced by cyclodextrin on the basis of the structural formula of example 1. The preparation method comprises the following steps: dissolving 10g of beta-cyclodextrin in 50mL of NaOH aqueous solution with the concentration of 0.02mol/L, dropwise adding 5mL of acetonitrile solution containing 1.5g of p-toluenesulfonyl chloride, stirring for 3 hours, carrying out suction filtration, adjusting the pH of filtrate to 10, separating out a precipitate, precipitating and purifying to obtain p-toluenesulfonic acid grafted cyclodextrin; the p-toluenesulfonic acid grafted cyclodextrin, the block silicone oil prepared in example 1 and a catalyst 4-dimethylaminopyridine are mixed and dissolved in dichloromethane according to a molar ratio of 4. (since malic acid was not used initially, bridging between the block silicone oil and the cyclodextrin was required by p-toluenesulfonic acid, which showed some reduction in intermediate steps after malic acid use.)
Comparative example 2 (too little cyclodextrin grafting)
The difference from example 2 is that the mass ratio of p-toluenesulfonic acid grafted cyclodextrin to block silicone oil is 2:1.
Comparative example 3 (too much cyclodextrin graft)
The difference from example 2 is that the mass ratio of p-toluenesulfonic acid grafted cyclodextrin to block silicone oil is 7:1.
Example 3 (grafting of Cyclodextrin onto the graft)
An ultrahigh-stability block silicone oil, wherein part of hydroxyl groups are replaced by grafted cyclodextrin on the basis of the structural formula of example 1. The preparation method comprises the following steps:
1) Dissolving malic acid and glycine in water, adding methyl methacrylate, reacting for 5h at 80 ℃, removing most of solvent by rotary evaporation, adding acetone for crystallization, filtering out crystals, adding the crystals into an acetonitrile solvent, adding methyl iodide, heating and refluxing for reaction for 3h, removing the solvent by rotary evaporation, washing, filtering, cooling, crystallizing and drying the product to obtain a malic acid derivative, wherein the molar ratio of the malic acid to the glycine to the methyl methacrylate to the methyl iodide is 1.2;
2) Mixing cyclodextrin, malic acid derivative prepared by 1) and sodium hypophosphite according to a molar ratio of 1;
3) Dissolving the grafted cyclodextrin prepared in the step 2), the block silicone oil and 4-dimethylaminopyridine in a molar ratio of 4.
Comparative example 4 (too little quaternary ammonium salt)
The difference from the example 3 is that the molar ratio of the cyclodextrin and the malic acid derivative is 1:2.
COMPARATIVE EXAMPLE 5 (excess Quaternary ammonium salt)
The difference from the example 3 is that the molar ratio of the cyclodextrin to the malic acid derivative is 1.
Comparative example 6 (grafting malic acid only)
An ultrahigh-stability block silicone oil, wherein part of hydroxyl groups are replaced by grafted cyclodextrin on the basis of the structural formula of example 1. The preparation method comprises the following steps:
1) Mixing cyclodextrin, malic acid and sodium hypophosphite according to a molar ratio of 1;
2) Dissolving the grafted cyclodextrin prepared in the step 1), the block silicone oil and 4-dimethylaminopyridine in a molar ratio of 4.
Comparative example 7 (grafting quaternary ammonium salt only)
An ultrahigh-stability block silicone oil, wherein part of hydroxyl groups are replaced by grafted cyclodextrin on the basis of the structural formula of example 1. The preparation method comprises the following steps:
1) Mixing the p-toluenesulfonic acid grafted cyclodextrin obtained in example 2, dodecyl dimethyl benzyl ammonium bromide and sodium hypophosphite according to a molar ratio of 1;
2) Dissolving the grafted cyclodextrin prepared in the step 2), the block silicone oil and 4-dimethylaminopyridine in a molar ratio of 4.
Performance test
Preparing a finishing agent: the block silicone oil prepared in each example and comparative example and a small amount of non-ionic emulsifier are stirred uniformly, then water containing glacial acetic acid is slowly added while stirring, and the mixture is diluted into 10wt.% emulsion, and finally the pH is adjusted to about 6 by using the glacial acetic acid.
1. And (3) stability testing: the shear resistance, salt resistance, acid and alkali resistance, high temperature resistance, alkali and high temperature resistance and long-term stability were tested and the results are shown in the following table.
As can be seen from the above table, the silicone oil prepared by the embodiments of the present invention has good shear resistance, salt resistance, acid and alkali resistance and stability. In the embodiment 2, the cyclodextrin is grafted, so that the high temperature resistance and the lasting stability are improved, because the hydrophobic and hydrophilic structures in the cyclodextrin improve the compatibility and are not easy to delaminate, and the silicon-oxygen bond can be retracted into the cyclodextrin cavity, so that the high temperature resistance of the silicone oil can be improved; in contrast, comparative example 2 has a small amount of cyclodextrin, and has limited improvement in high temperature resistance and long-term stability. Comparative example 3 the cyclodextrin was used in a larger amount and the improvement effect was not much higher than that of example 2. Example 3 the grafted cyclodextrin with malic acid derivatives improves the alkali resistance and high temperature, the malic acid derivatives, especially the quaternary ammonium salt therein, can broaden the tolerance of the silicone oil to pH, and the connection between the quaternary ammonium salt and the cyclodextrin is firm and can withstand high temperature; in contrast, comparative examples 4 and 5 have a reduced high temperature resistance due to a smaller or larger number of quaternary ammonium salt groups. The difference between the comparative example 6 and the example 3 is that malic acid is not modified by quaternary ammonium salt, and the alkali resistance and high temperature resistance are not as good as those of the example 3.
2. Fabric application testing
The application process of the finishing agent comprises the following steps:
treating the fabric: the polyester-cotton twill cloth is made of polyester cotton,
the treatment process comprises the following steps: the dosage of the compound is 30g/L,
one-dipping and one-rolling (rolling residual ratio: 70%) → drying and shaping (150 ℃ X60S) → cooling and moisture regaining → performance evaluation;
the hand feeling is evaluated by a multi-person hand touch evaluation method according to comprehensive factors such as bulkiness, softness, resilience, smoothness and the like after the fabric is treated, the evaluation is divided into 1-5 grades, and the hand feeling is better when the numerical value is larger; because the hand feeling is subjective feeling, and the grade is divided into thicker grades, the difference in a smaller range is difficult to be reflected. The smoothness was tested by the reference (Hu Yong, guo Xiaoting, ren Xiaocui. Importance of smoothing agent for textile sizing and test methods in research [ C ]// national size and sizing technology 2005 council), and the smoothness was tested by form-sewing with a cordless electric sewing machine (46-50 stitches are rolled in 10 cm), the number of broken yarns in 10cm of cloth surface was better in smoothing performance, the smaller the coefficient of friction between yarns was, the smaller the number of broken ends was.
As can be seen from the above table, the silicone oil prepared by the embodiments of the present invention has good effect when applied to fabric. In comparative example 1, the siloxane chain length was too short as in example 1, and even if the value of a: b was increased, the smoothness of the product was not comparable to that of the long siloxane chain. In the example 2 and the comparative examples 2 and 3, cyclodextrin is grafted on the side chain of the block silicone oil, so that the smoothness of the fabric after the block silicone oil is finished is influenced; particularly, the side chains of the block silicone oil of the comparative example 3 are grafted too much, which causes the hand feeling of the finished fabric to be hard, and the stability data of the comparative example 3 show that the grafting ratio of the cyclodextrin needs to be controlled. Example 3 the cyclodextrin with malic acid derivatives is grafted, so that the static friction coefficient between fibers is greatly reduced, the fabric feels smooth, and the problem of fabric smoothness reduction caused by cyclodextrin grafting is solved; comparative example 4 quaternary ammonium salt has a short segment and has a limited effect of improving smoothness. Comparative example 5 has too many quaternary ammonium salt groups, and the stability data of comparative example 5 show that the grafting proportion of the quaternary ammonium salt is controlled within a reasonable range to realize excellent high temperature resistance and smoothness. Comparative example 6 and example 3 are different in that malic acid is not modified with quaternary ammonium salt, comparative example 7 and example 3 are different in that only quaternary ammonium salt is grafted and malic acid does not participate in the reaction, and both comparative examples 6 and 7 are inferior in smoothing effect to example 3, indicating that the effect of malic acid derivatives is superior to that of malic acid or quaternary ammonium salt alone.
In conclusion, the cyclodextrin with the malic acid derivative is grafted in the example 3, and meanwhile, the alkali resistance, high temperature resistance, fabric smoothness and smoothness are improved, and the comprehensive performance is optimal.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the modified block silicone oil is characterized by comprising the following steps:
1) Dissolving malic acid and aminoacetic acid in water, adding methyl methacrylate, reacting at 80-90 ℃ for 4-6h, putting the product into an acetonitrile solvent after crystallization and separation, adding methyl iodide, heating and refluxing for reaction for 2-4h, and performing crystallization and separation to obtain a malic acid derivative, wherein the molar ratio of the malic acid to the aminoacetic acid to the methyl methacrylate to the methyl iodide is 1 (1-3) to 0.1-0.3 to 1-1.2;
2) Mixing the malic acid derivative prepared in the step 1) with cyclodextrin and sodium hypophosphite, and reacting at 100-110 ℃ for 3-5h to obtain a precipitate, and purifying the precipitate to obtain grafted cyclodextrin;
3) Dissolving the grafted cyclodextrin prepared in the step 2), the block silicone oil and 4-dimethylamino pyridine in dichloromethane, stirring at room temperature for 10-12h, filtering, and freeze-drying to obtain modified block silicone oil; the structural formula of the block silicone oil is as follows:
2. The method for preparing modified block silicone oil according to claim 1, wherein in step 2) the cyclodextrin, the malic acid derivative and sodium hypophosphite are mixed in a molar ratio of 1 (4-6) to 1 (1-1.5).
3. The method for preparing modified block silicone oil according to claim 1, wherein the molar ratio of grafted cyclodextrin to block silicone oil in step 3) is (3-5): 1.
4. The method for preparing modified block silicone oil according to claim 1, wherein the block silicone oil is obtained by the following steps:
(1) Adding the epoxy double-end socket into diamine under the protection of inert gas, stirring for 6-10h, and reacting for 6-10h at 60-80 ℃ to obtain an amino double-end socket;
(2) Uniformly mixing the amino double-end socket and the organosiloxane ring body, adding an alkaline catalyst, and reacting at 80-110 ℃ for 12-18 h; then reacting at 140-150 ℃ for 1-2h to prepare the alpha, omega-diamino silicone oil;
(3) Adding epoxy-terminated polyether and the alpha, omega-diamino silicone oil into a solvent, uniformly mixing, reacting at 60-80 ℃ for 15-20 h, and adjusting the pH value to be neutral to prepare the block silicone oil.
5. The method for preparing modified block silicone oil according to claim 4, wherein the basic catalyst in step (2) is (CH) 3 ) 4 NOH alkali glue or (n-C) 4 H 9 ) 4 The dosage of the POH alkali glue is 0.05-0.1% of the total mass of reactants.
6. The method for preparing modified block silicone oil according to claim 4, wherein the solvent in step (3) is one or more of isopropanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, and the amount of the solvent is 5-65% of the total mass of the reaction system.
7. A modified block silicone oil, characterized by being prepared by the method of any one of claims 1 to 6.
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| CN104650363B (en) * | 2015-02-05 | 2017-04-12 | 南通斯恩特纺织科技有限公司 | Preparation method of hyperbranched ternary polymerization organic silicon |
| CN106397776A (en) * | 2016-08-30 | 2017-02-15 | 浙江科峰有机硅有限公司 | Double amino type block polyether amino silicone oil and preparation method thereof |
| CN106279710A (en) * | 2016-08-30 | 2017-01-04 | 浙江科峰有机硅有限公司 | Sliding block polyether amino silicone oil of a kind of ultra-soft and preparation method thereof |
| US11746193B2 (en) * | 2018-11-20 | 2023-09-05 | Wacker Chemie Ag | Block-modified polysiloxanes and compositions formed thereof |
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