Solvent-free hydrophilic block silicone oil and preparation method thereof

Abstract

The invention discloses solvent-free hydrophilic block silicone oil and a preparation method thereof, and the method comprises the following steps: carrying out equilibrium reaction on chloropropyl alkyl alkoxy silane and hydroxyl-terminated polydimethylsiloxane in an acid catalyst to prepare linear silicone oil of which the two end structures are chloropropyl alkyl alkoxy; the linear silicone oil is neutralized and filtered and then reacts with tertiary amine, and the quaternary ammonium salt-terminated hydrophilic block silicone oil is prepared. According to the method, no solvent participates in the whole synthesis process of the block silicone oil, a monomer polymerization process is adopted, and compared with a traditional method, operation is easy, raw materials are easy to obtain, cost is low, and the process saves energy, reduces consumption, is environmentally friendly and is suitable for industrial production of a monomer factory. The block silicone oil prepared by the invention has excellent hydrophilicity, and can endow fabrics with excellent fluffy, soft and smooth handfeel and hydrophilic performance when being used as a finishing agent for fabrics such as cotton, polyester, polyester cotton and the like.

Description

Technical Field

[0001] The invention relates to the field of textile dyeing and finishing auxiliaries, and in particular to a solvent-free hydrophilic block silicone oil and a preparation method thereof. Background Art

[0002] The textile industry is a traditional pillar industry of the national economy and an important livelihood industry. In recent years, organopolysiloxane has developed rapidly in the field of textile printing and dyeing, and has been widely used in various processes such as weaving, dyeing, finishing, and sewing in the textile industry. Fabrics finished with traditional amino-modified silicone oil are smooth, elastic, soft, comfortable to the touch, and have good washability. However, when used for chemical fiber and blended fabrics, the fabrics are prone to yellowing, are stuffy to wear, have poor moisture absorption, and greatly reduce comfort. With the improvement of material living standards, it has become a basic requirement that textiles finished with softeners should have good hydrophilicity. Therefore, the development of silicone softeners with good hand feel and hydrophilicity has become an urgent need in the market. Block silicone oil can embed functional groups on the basis of traditional amino silicone oil. The hydrophobic siloxane segment and the hydrophilic polyoxyethylene segment are in a straight line. The macromolecular segments are regular and have excellent orientation with the fibers. The amino groups on the block copolymer silicone oil interact with the hydroxyl and carboxyl groups on the fiber surface, so that the siloxane main chain can be attached to the fiber surface in a direction, giving the textiles excellent softness, smoothness, fluffy and hydrophilic properties. To a certain extent, it overcomes the problems of poor hydrophilicity and easy oil bleaching and demulsification of traditional amino silicone oil.

[0003] The preparation of conventional block silicone oil is mainly a solvent method. First, octamethylcyclotetrasiloxane (D4) is used as a monomer, tetramethyldihydrodisiloxane (hydrogen-containing end-capping agent) is used as a capping agent, and concentrated sulfuric acid is used as a catalyst to prepare terminal hydrogen silicone oil; then, terminal hydrogen silicone oil and terminal allyl terminal epoxy polyether are used as reaction monomers, diethylene glycol monobutyl ether is used as a solvent, and a hydrosilylation reaction is carried out under the catalysis of chloroplatinic acid to obtain terminal epoxy silicone oil; terminal epoxy silicone oil reacts with amino polyether to obtain ternary block silicone oil. The invention patent with publication number CN102643436A discloses a super soft hydrophilic block silicone oil intermediate compound and preparation method, which adopts block polymerization of terminal epoxy polyether and α, ω-aminosiloxane intermediate to obtain an intermediate compound of polysiloxane polyether block copolymer, and the structure of polyorganosiloxane polyether block copolymer is converted into polysiloxane polyether block copolymer by cationic modification, which increases its application effect and stability on fabrics. The invention patent with publication number CN104072783A discloses a method for preparing an ultra-smooth hydrophilic quaternary ammonium salt-modified silicone copolymer, wherein a cationic modified polyetheramine intermediate is synthesized by using an aliphatic polyether diamine and an alkylating agent under the action of an acidic catalyst; the cationic modified polyetheramine intermediate is subjected to addition polymerization of amino and epoxy groups with terminal epoxy polyether silicone oil in the presence of an organic solvent, and then glacial acetic acid is added to synthesize a ternary block silicone oil, thereby giving the fabric an excellent soft, delicate and ice-smooth silky effect.

[0004] In recent years, more and more people have started to study the synthesis of cationic block silicone oils, but basically a large amount of solvents need to be added during the synthesis process. At present, environmental protection requirements are becoming more and more stringent, and the EU's restrictions on solvents are constantly updated and strengthened. The use of solvents is not only related to workshop production, transportation safety and printing and dyeing factory use, but also has a certain impact on the color and color fastness of dyed fabrics. Therefore, it is necessary to prepare a solvent-free block silicone oil. Summary of the invention

[0005] The purpose of the present invention is to provide a solvent-free hydrophilic block silicone oil and a preparation method thereof. The whole process of the block silicone oil synthesis is solvent-free, the operation is simple, the raw materials are easily available, the cost is low, the process is energy-saving and consumption-reducing, and the environment is environmentally friendly, and the block silicone oil is suitable for industrial production.

[0006] The solvent-free hydrophilic block silicone oil has the following structural formula: The technical solution of the present invention is as follows:

[0007] In the formula: R1 is one or more of CH3, CH2CH3, CH2CH2OH, CH2CH2N(CH3)2; R2 is one of CH3, CH2CH3, CH2CH2OH, CH2CH2N(CH3)2, CH2CH2CH2N(CH3)2, CH2CH2CH2CH2CH2CH2N(CH3)2, methyl ether, ethyl ether; R3 is one or more of CH3, CH2CH3, CH3O, CH2CH3O; x is a natural number from 1 to 100.

[0008] The technical solution adopted by the present invention to solve the technical problem is a solvent-free hydrophilic block silicone oil and a preparation method thereof, characterized in that the preparation process comprises the following steps: (1) firstly subjecting the hydroxyl-terminated polydimethylsiloxane to a dehydration pretreatment; The hydroxyl-terminated polydimethylsiloxane is one or more of organic silicone linear body, hydroxyl silicone oil and 107 glue; The dehydration pretreatment has a dehydration temperature of 10-120°C, a dehydration time of 10-120min, and a dehydration pressure of ≤-0.08MPa; The water content of the hydroxyl-terminated polydimethylsiloxane after dehydration treatment is between 0.1-200 ppm; preferably, the water content is between 0.1-100 ppm; (2) placing the hydroxyl-terminated polydimethylsiloxane, chloropropyl alkyl alkoxy silane and acid catalyst after dehydration in a reaction bottle, raising the temperature after adding the materials and keeping the temperature for several hours, removing the excess chloropropyl alkyl alkoxy silane, and then neutralizing and filtering the product to obtain an intermediate product A; The chloropropyl alkyl alkoxysilane is one or more of chloropropyl methyl dimethoxy silane, chloropropyl dimethyl methoxy silane, chloropropyl trimethoxy silane, chloropropyl methyl diethoxy silane, chloropropyl dimethyl ethoxy silane and chloropropyl triethoxy silane; The acid catalyst is one or more of acid clay, trifluoromethanesulfonic acid, acid resin, and p-toluenesulfonic acid; the dehydrated hydroxyl-terminated polydimethylsiloxane accounts for 10-98% of the total feed weight, and preferably, the feed weight accounts for 30-90%; The chloropropyl alkyl alkoxy silane accounts for 2-90% of the total feed weight, and preferably, the feed weight accounts for 5-60%; The acid catalyst dosage is 10-1000ppm, preferably 50-500ppm; the reaction temperature is 5-120°C, preferably 40-100°C; the insulation time is 0.5-8h, preferably 0.5-5h, preferably, the temperature for removing chloropropyl alkyl alkoxy silane is 50-200°C, and the pressure is ≤-0.08MPa; (3) Add tertiary amine to the intermediate product A and keep it warm for a certain period of time to obtain the target block silicone oil. The entire preparation process is carried out under nitrogen protection.

[0009] The tertiary amine is one or more of trimethylamine, triethylamine, methyldiethylamine, N,N-dimethylethylamine, triethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, bis(dimethylaminoethyl)ether, and tertiary amine type polyether; The amount of tertiary amine added accounts for 1-50% of the total feed mass, preferably, the feed amount accounts for 2-35%; the reaction temperature is 30-180°C, preferably, the temperature is 40-100°C; the insulation time is 0.5-8h, preferably, the insulation time is 0.5-5h.

[0010] The solvent-free hydrophilic block silicone oil and the preparation method thereof provided by the present invention have the following advantages: (1) The entire process of block silicone oil synthesis does not involve solvent, which is a green and environmentally friendly process; (2) Compared with the traditional block silicone oil preparation process, the operation is simple, the raw materials are easily available, and the cost is low; (3) The product structure design is highly controllable and can be adjusted according to the performance requirements of the user; (4) The product has excellent hydrophilic properties and an outstanding application feel, which can give the fabric an excellent fluffy, soft, smooth feel and hydrophilic properties. DETAILED DESCRIPTION

[0011] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the protection scope of the present invention.

[0012] Example 1 800g of organosilicon linear body was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 90°C, and the vacuum degree was adjusted to -0.07MPa. After heat preservation and dehydration for 30min, the water content was 28ppm. 385g of dehydrated organosilicon linear body and 175g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, and 100ppm of catalyst acid clay was added. The temperature was raised to 100°C and reacted for 4h, then filtered, and then the temperature was raised to 150°C and the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, and 138g of triethanolamine was added thereto. After heat preservation for 3h, the temperature was lowered and the material was discharged to obtain block silicone oil.

[0013] Example 2 800g of organosilicon linear body was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 90°C, the vacuum degree was -0.07MPa, and after heat preservation and dehydration for 30min, the water content was 25ppm. 385g of dehydrated organosilicon linear body and 168g of chloropropylmethyldiethoxysilane were placed in a four-necked flask, 100ppm of catalyst acid clay was added, the temperature was raised to 100°C and reacted for 4h, then filtered, and then the temperature was raised to 50°C and the pressure was 0.05MPa to remove chloropropylmethyldiethoxysilane, 140g of triethanolamine was added thereto, and the temperature was lowered and discharged after heat preservation for 3h to obtain block silicone oil.

[0014] Example 3 800g of organosilicon linear body was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 60°C, the vacuum degree was -0.06MPa, and after heat preservation and dehydration for 60min, the water content was 32ppm. 380g of dehydrated organosilicon linear body and 165g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, 100ppm of catalyst acid clay was added, the temperature was raised to 100°C and reacted for 4h, then filtered, and then the temperature was raised to 150°C and the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, 138g of triethanolamine was added thereto, and the temperature was lowered and discharged after heat preservation for 3h to obtain block silicone oil.

[0015] Example 4 800g of hydroxy silicone oil was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 85°C for insulation, the vacuum degree was -0.07MPa, and after dehydration for 30min, the water content was 35ppm. 220g of dehydrated hydroxy silicone oil and 245g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, 100ppm of catalyst acid clay was added, the temperature was raised to 100°C for reaction for 4h, and then filtered, and then the temperature was raised to 150°C, the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, 198g of triethanolamine was added thereto, and the temperature was lowered and discharged after insulation for 3h to obtain block silicone oil.

[0016] Example 5 800g of organosilicon linear body was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 90°C, the vacuum degree was -0.06MPa, and after heat preservation and dehydration for 30min, the water content was 28ppm. 385g of dehydrated organosilicon linear body and 166g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, 100ppm of catalyst trifluoromethylsulfonic acid was added, the temperature was raised to 100°C and reacted for 4h, and then neutralized with sodium bicarbonate. After neutralization, it was filtered, and then the temperature was raised to 150°C and the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, and 110g of methyldiethanolamine was added thereto. After heat preservation for 3h, the temperature was lowered and the material was discharged to obtain block silicone oil.

[0017] Example 6 800g of 107 glue with a viscosity of 300cPs was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 90°C, the vacuum degree was -0.07MPa, and after heat preservation and dehydration for 30min, the water content was 27ppm. 650g of dehydrated 107 glue and 45g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, 200ppm of catalyst acid clay was added, the temperature was raised to 100°C, the reaction was carried out for 4h, and then filtered, and then the temperature was raised to 150°C, the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, 35g of triethanolamine was added, and the temperature was lowered and discharged after 3h of heat preservation to obtain block silicone oil.

[0018] Comparative Example 1 Take 385g of organic silicon linear body that has not been dehydrated pretreatment and 175g of chloropropylmethyldimethoxysilane and put them in a four-necked flask, add 100ppm catalyst acidic clay, heat to 100℃ and react for 4h, then filter, then heat to 150℃ and pressure 0.05MPa to remove chloropropylmethyldimethoxysilane, add 138g of triethanolamine, keep warm for 3h and then cool and discharge to obtain block silicone oil.

[0019] Comparative Example 2 800g of organosilicon linear body was placed in a 1000mL three-necked flask after washing and drying, and the temperature was raised to 90°C, and the vacuum degree was adjusted to -0.07MPa. After heat preservation and dehydration for 30min, the water content was 28ppm. 385g of dehydrated organosilicon linear body and 175g of chloropropylmethyldimethoxysilane were placed in a four-necked flask, and 100ppm of catalyst acid clay was added. The temperature was raised to 100°C and reacted for 4h, then filtered, and then the temperature was raised to 150°C and the pressure was 0.05MPa to remove chloropropylmethyldimethoxysilane, and 138g of diethanolamine was added thereto. After heat preservation for 3h, the temperature was lowered and the material was discharged to obtain block silicone oil.

[0020] Comparative Example 3 Take 786.57g of dimethylsiloxane mixed ring (DMC), 13.43g of tetramethyldihydrodisiloxane, and 0.96g of trifluoromethanesulfonic acid and place them in a 2000mL three-necked flask equipped with a condensation reflux device, heat to 35℃ and react for 5h. After the reaction is completed, add 1.92g of sodium carbonate to neutralize for 3h. After neutralization, filter under reduced pressure to obtain terminal hydrogen silicone oil. Then add 105g of allyl-terminated epoxy polyether with a molecular weight of 500, 226.25g of isopropanol, and then add chloroplatinic acid catalyst to the flask, heat to 85℃ and react for 4h to obtain terminal epoxy polyether silicone oil. Then add 135.75g of polyetheramine ED900 and 467.58g of isopropanol to the flask, and react at 83℃ for 10h to obtain hydrophilic block silicone oil.

[0021] Block silicone oil application test The block silicone oil prepared above was diluted with water at a dilution ratio of 1:3, and then prepared into a 10 g / L finishing solution. The cotton fabric was treated by a dipping and rolling method, and baked at 150°C for 90 seconds. After the fabric sample was cooled, the feel was evaluated.

[0022] (1) Hand feel level: The hand feel of fabrics is mainly evaluated from the perspective of softness and smoothness. Ten people are invited to blindly touch and score the fabrics, with the hand feel being divided into levels 1 to 5, with level 5 being the best and level 1 being the worst. The average of the scores of the ten people is then calculated.

[0023] (2) Bending rigidity: Tested using the YG821 fabric style tester. The smaller the bending rigidity, the better the softness.

[0024] (3) Dynamic friction coefficient: Tested using the YG821 fabric style tester. The smaller the dynamic friction coefficient, the better the fabric's slipperiness.

[0025] (4) Fluffiness: Tested using the YG821 fabric style meter. The greater the fluffiness, the better the fabric.

[0026] (5) Whiteness: measured using DRK-103B whiteness colorimeter. The greater the whiteness, the less yellowing the fabric will undergo.

[0027] (6) Hydrophilicity: Spread the fabric horizontally, absorb water with a 1 mL dropper, and then drop a drop of water from about 10 cm away from the fabric surface. Measure the time it takes for the water drop to diffuse and completely penetrate the fabric surface. The shorter the time, the better the hydrophilicity.

[0028] (7) VOC emission: The test is conducted using the industry standard SN / T 3778-2014 "Small-scale emission chamber method for volatile organic compound emissions from textiles". The greater the VOC emission, the less environmentally friendly it is.

[0029] The test results of relevant performance indicators of the embodiment products are shown in Table 1: Table 1 Evaluation of application performance of block silicone oils obtained in Examples 1 to 6 and Comparative Examples 1 to 3 sample Feel Rating Bending rigidity CN / Cm Dynamic friction coefficient <![CDATA[Fluffiness cm 3 / g]]> Whiteness Hydrophilicity <![CDATA[VOC emission μg / m 3 > Example 1 4 65.43 6.35 7.626 100.51 3.55 123 Example 2 4 60.20 5.72 7.995 100.14 2.68 131 Example 3 5 67.75 4.98 8.516 99.86 3.89 124 Example 4 4 68.52 6.53 7.473 100.74 2.91 128 Example 5 4 67.82 6.46 8.125 101.63 3.26 132 Example 6 5 62.51 5.24 8.204 99.74 3.57 126 Comparative Example 1 3 70.46 7.17 6.853 98.23 4.39 134 Comparative Example 2 3 68.94 6.81 7.251 99．52 5.25 127 Comparative Example 3 4 67.38 6.67 7.541 100.05 3.41 352 Blank fabric swatch 2 90.31 9.87 3.671 101.85 5.63 23 As can be seen from Table 1 above, the block silicone oils prepared in various embodiments of the present invention are applied to fabrics with good effects, and the application performance of the synthesized products is greatly affected by the type of amino group. By comparing Example 1 with Comparative Example 1, it can be seen that the raw materials subjected to dehydration treatment have a greater impact on product performance. Dehydration causes the reaction to proceed in a beneficial direction, and the functional structural groups are better distributed, so the treated fabric feels better. By comparing Example 1 with Comparative Example 2, it can be seen that the tertiary amine has a large reaction activity, and its reactant has a cation, and the hydrophilicity is more prominent. By comparing Example 1 with Comparative Example 3, it can be seen that the present invention adopts a solvent-free bulk polymerization to generate a hydrophilic block silicone oil, and the fabric sample treated therewith has a low VOC release, which is more environmentally friendly.

[0030] Compared with the current related technology (solvent synthesis method), the solvent-free hydrophilic block silicone oil prepared by the present invention has simple process operation, easy-to-obtain raw materials and low cost; and the whole process is solvent-free and environmentally friendly; the product has excellent hydrophilic properties and outstanding application feel, and can be used in the field of textile printing and dyeing finishing auxiliaries.

[0031] The technical solution of the present invention is explained through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above specific embodiments to be implemented. Any improvements made by technicians in the relevant field based on the present invention, or equivalent replacement of the materials selected by the present invention, etc., fall within the scope of protection of the patent.

Claims

1. A method for preparing a solvent-free hydrophilic block silicone oil, characterized in that: The preparation method comprises the following steps: (1) firstly subjecting the hydroxyl-terminated polydimethylsiloxane to a dehydration pretreatment; (2) placing the hydroxyl-terminated polydimethylsiloxane, chloropropyl alkyl alkoxy silane, and acid catalyst after dehydration in a reaction bottle, raising the temperature after adding the materials and keeping the temperature, removing the excess chloropropyl alkyl alkoxy silane, and then neutralizing and filtering the product to obtain an intermediate product A; (3) Add tertiary amine to the intermediate product A and keep it warm for a certain period of time to obtain the target block silicone oil.

2. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, characterized in that: The general chemical structure of the block silicone oil is as follows: ； Wherein: R1 is one or more of CH3, CH2CH3, CH2CH2OH, CH2CH2N(CH3)2; R2 is one or more of CH3, CH2CH3, CH2CH2OH, CH2CH2N(CH3)2, CH2CH2CH2N(CH3)2, CH2CH2CH2CH2CH2CH2N(CH3)2, methyl ether, and ethyl ether; R3 is one or more of CH3, CH2CH3, CH3O, CH2CH3O; x is a natural number from 1 to 100.

3. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, characterized in that: The hydroxyl-terminated polydimethylsiloxane in step (1) is one or more of organic silicone linear body, hydroxyl silicone oil and 107 glue.

4. The solvent-free hydrophilic block silicone oil and the preparation method thereof according to claim 1, characterized in that: The dehydration pretreatment in step (1) has a dehydration temperature of 10-120° C., a dehydration time of 10-120 min, and a dehydration pressure of ≤-0.08 MPa.

5. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, characterized in that: The chloropropyl alkyl alkoxysilane described in step (2) is one or more of chloropropyl methyl dimethoxy silane, chloropropyl dimethyl methoxy silane, chloropropyl trimethoxy silane, chloropropyl methyl diethoxy silane, chloropropyl dimethyl ethoxy silane, and chloropropyl triethoxy silane; and the acid catalyst is one or more of acidic clay, trifluoromethyl sulfonic acid, acidic resin, and p-toluenesulfonic acid.

6. The method for preparing the solvent-free hydrophilic block silicone oil according to claim 5, characterized in that: After dehydration, the hydroxyl-terminated polydimethylsiloxane accounts for 10-98% of the total feed mass, the chloropropyl alkyl alkoxy silane accounts for 2-90% of the total feed mass, the amount of the acid catalyst is 10-1000ppm, the reaction temperature is 5-120°C, and the insulation time is 0.5-8h.

7. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, wherein the tertiary amine in step (3) is one or more of trimethylamine, triethylamine, methyldiethylamine, N,N-dimethylethylamine, triethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, bis(dimethylaminoethyl) ether, and tertiary amine type polyether.

8. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, characterized in that: The reaction temperature of step (3) is 30-180°C, the insulation time is 0.5-8h, and the amount of tertiary amine added accounts for 1-50% of the total feed mass.

9. The method for preparing a solvent-free hydrophilic block silicone oil according to claim 1, characterized in that: The preparation process of the method is carried out under nitrogen protection.

Images