Organosilicon polymer, preparation method thereof, organosilicon polymer microemulsion and application thereof

Abstract

The invention provides an organosilicon polymer and a preparation method thereof, a molecular chain segment of the organosilicon polymer contains amino, polyether group and cationic group at the same time, so that the organosilicon polymer can have multiple functions at the same time; after the pure cotton fabric is treated by the microemulsion, the fabric is plump, smooth and soft in hand feeling, has good water absorption and has a very high bacteriostasis rate on escherichia coli and staphylococcus aureus.

Description

Technical Field

[0001] The present invention relates to the technical field of organosilicon polymers, in particular to an organosilicon polymer and a preparation method thereof, an organosilicon polymer microemulsion and applications thereof. Background Art

[0002] Since its introduction, amino-modified silicone softeners have been widely used in the finishing of cotton, silk, wool, polyester and other textiles for their excellent smoothness, softness and film-forming properties. Silicone softeners are mainly polysiloxane compounds. Since the bond angle of the Si-O-Si chain constituting its main chain is large, the distance between atoms is long, and the intermolecular effect is weak, the air permeability and moisture permeability of the finished fabric are good; the spiral structure and methyl groups of silicone polymers extend outward, giving them extremely low surface tension and good water repellency, but at the same time, they also make the finished fabric hydrophobic, making it feel stuffy and difficult to wash when worn; many amino-modified silicone emulsions have poor stability, and often experience "emulsification and oil floating" during storage, transportation and application. At the same time, the product has a roller sticking phenomenon during padding and use. In order to make cotton, linen and silk retain their original hydrophilic style after finishing, to make chemical fiber fabrics have good hand feel and hydrophilicity after finishing, and to overcome their shortcomings such as static electricity, dust absorption, pilling and stuffiness when worn, domestic and foreign scientific and technological workers have researched and developed various hydrophilic amino silicone oils.

[0003] Hydrophilic amino silicone oil is generally composed of two parts. One is the hydrophilic part, which is generally required to be resistant to washing, have a lasting hydrophilic effect, can make water diffuse rapidly on the surface of the fabric, and has stable chemical properties. The other is the fixative part, which is generally required to form a soft film. Hydrophilicity generally refers to the ability of fiber fabrics to absorb moisture. Under hot and humid conditions, in order to improve the comfort of fabrics, it is necessary to relatively reduce the relative humidity between the fabric and the skin, which requires the fiber material to absorb a large amount of water vapor and absorb quickly. Especially in the case of heavy sweating, the fiber is required to have higher moisture absorption and water absorption, and can quickly release sweat to the outside world so that the human body does not feel stuffy. In order to improve the hydrophilicity of the fiber, it is only through the treatment of hydrophilic amino silicone emulsion, while giving the fabric a good feel.

[0004] Related research at home and abroad is centered on modifying the side chain of amino silicone oil: epoxy amination method, active polyether ring opening method, and organic anhydride introduction method. Through these methods, a large number of mature products have been launched. However, the products obtained by these methods have a contradiction between hand feel and hydrophilicity. How to solve this technical problem is the direction that technicians in this field are committed to researching. Summary of the invention

[0005] An object of the present invention is to provide an organosilicon polymer to solve the problems mentioned in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solution: an organosilicon polymer, the structural formula of which is as follows:

[0007]

[0008] Among them: A, B, C, D are all positive integers; and A>B≥C≥D,

[0009] A=0~2000;

[0010] B = 0-60;

[0011] C = 0-50;

[0012] D = 0-40;

[0013] R is selected from: -OH, -CH3 or -OCH3;

[0014] R1 is selected from: -C3H6NHC2H4NH2 or -C3H6NHC3H6N(CH3)2 or

[0015]

[0016] R2 is selected from:

[0017]

[0018] R3 is selected from:

[0019]

[0020] Wherein m and n are positive integers, m=3~29, n=1~31.

[0021] Preferably, in the structural formula of the organosilicon polymer, A=80-1000; B=5-50; C=2-40; D=1-40.

[0022] A second object of the present invention is to provide a method for synthesizing the above-mentioned organosilicon polymer, comprising the following steps:

[0023] Step 1, preparation of aminopolyether silane:

[0024] 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane and single-terminated amino polyether are stirred and heated under the action of a solvent, the reaction temperature is controlled at 80-85°C, the reaction is kept warm for 2h-3h, and low molecular weight substances are removed by vacuum to obtain amino polyether silane. The reaction formula is as follows:

[0025]

[0026] Step 2, preparation of polyether / amino silicone oil:

[0027] The hydroxyl-terminated linear silicone oil, the amino polyether silane obtained in step 1 and the amino coupling agent are used as reaction raw materials, the temperature is raised to 85-90° C. with stirring, a catalyst is added, and the reaction is stirred for 30 minutes, the reaction temperature is controlled at 105-110° C., the reaction is kept warm for 4-6 hours, low molecular weight substances are removed by vacuuming, and solid insolubles are filtered out with a filter after cooling to obtain an intermediate product polyether / amino silicone oil, wherein the solid insolubles are the catalyst;

[0028] Step 3, preparation of silicone polymer:

[0029] In the reactor, the intermediate product polyether / amino silicone oil and 2,3-epoxypropyltrimethylammonium chloride obtained in the above reaction are added in proportion, and then an organic solvent is added. The mixture is stirred and heated to 80-90°C for reflux reaction. After the reaction is kept warm for 3h-5h, low molecular weight substances are removed by vacuum to obtain the desired silicone polymer.

[0030] As a specific implementation, the hydroxyl-terminated linear silicone oil in step 2 has a non-volatile matter content of ≥99.5%, a water content of ≤0.1%, a viscosity of 20 to 120 mPa.S, and an amount thereof accounting for 60% to 85% of the total weight of the reaction system in step 2.

[0031] As a specific implementation, the amino polyether siloxane has a structural formula containing R3, and the amount of the amino polyether siloxane used accounts for 2% to 15% of the total weight of the reaction system in step 2; the amino coupling agent has a structural formula containing R1, and the amount of the amino coupling agent used accounts for 1% to 10% of the total weight of the reaction system in step 2.

[0032] As a specific implementation, the catalyst in step 2 is lithium hydroxide, and its usage accounts for 50 to 500 ppm of the total weight of the reaction system in step 2.

[0033] As a specific implementation method, in step 3, the amount of polyether / amino silicone oil accounts for 50% to 85% of the total weight of the reaction system in step 3; the amount of organic solvent accounts for 20% to 40% of the total weight of the reaction system in step 3; the amount of 2,3-epoxypropyltrimethylammonium chloride accounts for 5% to 40% of the total weight of the reaction system in step 3.

[0034] As a specific implementation, the solvent used in step 1 and the organic solvent used in step 3 are selected from one or a mixture of isopropanol, ethanol, ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.

[0035] The third object of the present invention is to provide a silicone polymer microemulsion prepared by the following steps:

[0036] After adding deionized water and neutralizing acid into the reactor and stirring evenly, the above-mentioned organosilicon polymer or the organosilicon polymer prepared according to the above-mentioned synthesis method of the organosilicon polymer is slowly added under stirring, and after stirring for 20-40 minutes, the desired organosilicon polymer microemulsion is obtained.

[0037] The main quality indicators of the above microemulsions are:

[0038] Appearance: blue transparent liquid;

[0039] Solid content: (1.0~60)%;

[0040] Ionic type: cationic;

[0041] PH value: 6.0~8.0;

[0042] Stability: No stratification or oil floating after centrifugal separation at 3000r / min for 30min.

[0043] As a specific implementation manner, the neutralizing acid is selected from formic acid, glacial acetic acid or aminosulfonic acid, and its usage is 0.1% to 4.0% of the total weight of the reaction system.

[0044] The fourth object of the present invention is to provide the use of the above-mentioned organosilicon polymer microemulsion in textile printing and dyeing smoothing finishing agents and daily chemical care agents.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows: the organosilicon polymer of the present invention contains amino groups, polyether groups and cationic groups in its molecular chain segments at the same time, so that it is possible for the organosilicon polymer to have multiple functional effects at the same time; after the microemulsion is used to treat pure cotton fabric, the fabric feels plump, smooth and soft, has good water absorption, and has a high antibacterial rate against Escherichia coli and Staphylococcus aureus. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the infrared spectrum of the organosilicon polymer in Example 1 of the present invention. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0048] The present invention provides an organosilicon polymer, the structural formula of which is as follows:

[0049]

[0050] Among them: A, B, C, D are all positive integers; and A>B≥C≥D,

[0051] A=0~2000;

[0052] B = 0-60;

[0053] C = 0-50;

[0054] D = 0-40;

[0055] R is selected from: -OH, -CH3 or -OCH3;

[0056] R1 is selected from: -C3H6NHC2H4NH2 or -C3H6NHC3H6N(CH3)2 or

[0057]

[0058] R2 is selected from:

[0059]

[0060] R3 is selected from:

[0061]

[0062] Wherein m and n are positive integers, m=3~29, n=1~31.

[0063] Unless otherwise specified, the viscosity referred to in the following examples refers to the viscosity at 25°C.

[0064] The test method for the non-volatile matter content in the following examples refers to the standard "HGT 4266-2011 Determination of solid content of textile dyeing and finishing auxiliaries".

[0065] In the following embodiments, unless otherwise specified,

[0066] 3-(2,3-Epoxypropyloxy)propylmethyldiethoxysilane was purchased from Shinetsu Chemical Industry Co., Ltd. with the brand name KBE-402;

[0067] The single-terminated amino polyether (M = 1000 g / mol) was purchased from Huntsman Company, USA, with the brand name M-1000;

[0068] Hydroxyl-terminated linear silicone oil was purchased from Dow Chemical Company, USA, with the brand name HMX-0156;

[0069] Aminoethylaminopropylmethyldimethoxysilane was purchased from Zhangjiagang Guotai Huarong Chemical Co., Ltd. with the brand name SCA-602;

[0070] 2,3-Epoxypropyltrimethylammonium chloride was purchased from Shandong Guohua Chemical Co., Ltd.;

[0071] Isopropanol: reagent grade.

[0072] Example 1

[0073] This example provides an organosilicon polymer, and the preparation method thereof comprises the following steps:

[0074] Step 1, preparation of aminopolyether silane:

[0075] In a 1000mL four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen tube, add 124g of 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 500g of single-ended amino polyether (M=1000g / mol, Huntsman M-1000), and 60g of isopropanol. The temperature is kept at 80-85°C for 2h, and the low molecular weight substances are removed by vacuum to obtain a slightly yellow and transparent amino polyether silane with a non-volatile matter content of ≥99.5% (110°C / 3h).

[0076] Step 2, preparation of polyether / amino silicone oil:

[0077] In a 1000mL four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen tube, add 400g of hydroxyl-terminated linear silicone oil with a viscosity of 40cs, 32g of aminoethylaminopropylmethyldimethoxysilane hydrolyzate, and 170g of aminopolyether silane obtained in step 1, stir and heat to 85-90°C, add 1g of lithium hydroxide, stir and react for 30min, control the reaction temperature at 105-110°C, keep the temperature for 4h, and vacuumize to remove low molecular weight substances. After cooling, filter out the solid insoluble matter with a filter to obtain a slightly yellowish transparent intermediate polyether / amino silicone oil with a viscosity of 2758mPa.S and a non-volatile matter content of ≥99.2% (110°C / 3h).

[0078] Step 3, preparation of silicone polymer:

[0079] In a 1000mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 360g of the intermediate polyether / amino silicone oil synthesized in step 2, 22g of 2,3-epoxypropyltrimethylammonium chloride, and 128g of isopropanol were added, and refluxed at 80°C-90°C until the reactant became transparent, and then the temperature was kept for two hours. Finally, the temperature was lowered and the pressure was reduced to remove the isopropanol to obtain a yellow transparent viscous liquid with a detected viscosity of 3329mPa.s and a non-volatile matter content of 90% (110°C / 3h). The relevant characterization spectra are shown in Figure 1 shown.

[0080] The organosilicon polymer prepared in this example was used to prepare a 25% microemulsion:

[0081] 372 g of deionized water and 3 g of glacial acetic acid were added to a 1000 ml beaker and stirred evenly. Then, 125 g of the organosilicon polymer prepared above was slowly added under stirring. After stirring for 30 minutes, a transparent liquid with blue light was obtained.

[0082] The properties of the above microemulsion are as follows:

[0083] Appearance: blue transparent liquid;

[0084] Solid content: 20%;

[0085] Ionic type: cationic;

[0086] pH value: 6.2;

[0087] Stability: No stratification or oil floating after centrifugal separation at 3000r / min for 30min.

[0088] application:

[0089] The 25% microemulsion prepared above was used to treat white pure cotton plain cloth, and a blank experiment was performed at the same time.

[0090] 1. Hand feel finishing process

[0091]

[0092] Natural moisture recovery for 24 hours.

[0093] Application effect evaluation: softness and hydrophilicity.

[0094] (a) Softness:

[0095] Five trained people evaluated the fabrics and took the average value, 1-5 points, with 1 being the worst and 5 being the best.

[0096] (b) Hydrophilicity:

[0097] The evaluation standard refers to AATCC79:1995 Absorbency of Bleached Textiles.

[0098] 2. Performance comparison:

[0099] 1) The softness and hydrophilicity of the fabric are shown in Table 1.

[0100] Table 1 Softness and hydrophilicity of hydrophilic antibacterial softening finishing agent

[0101] Finishing agent Softness Hydrophilicity / s blank Difference 1 Diamino silicone emulsion excellent 62 Hydrophilic amino silicone emulsion good 2 25% microemulsion of Example 1 excellent 2

[0102] As can be seen from Table 1, the fabric finished with 25% microemulsion has excellent hydrophilic properties, and its softness is comparable to that of diamino silicone emulsion (Dow Corning DC8040), and is much better than that of single hydrophilic amino silicone emulsion (Jiangsu Aoshijia L-3327). This is the result of the synergistic effect of the two components in the finishing agent.

[0103] 2) Antibacterial properties of fabrics, see Table 2.

[0104] Table 2 Antibacterial effect of hydrophilic antibacterial softening finishing agent

[0105] Antibacterial rate against Escherichia coli / % Antibacterial rate against Staphylococcus aureus / % Blank - unfinished grey fabric 2.33 4.92 Finished cotton (unwashed) 99.63 99.52 After washing 10 times 97.75 96.02

[0106] Note: The above data is provided by the Antimicrobial Laboratory of Soochow University.

[0107] As can be seen from Table 2, the antibacterial rates of the finished fabric samples against Escherichia coli and Staphylococcus aureus reached 99.63% and 99.52% respectively. After the fabric was washed 10 times with 2g / L AEO9 solution (fatty alcohol polyoxyethylene ether, purchased from Jiangsu Hai'an Petrochemical Plant), the antibacterial rates against Escherichia coli and Staphylococcus aureus could still reach 97.75% and 96.02% respectively.

[0108] From the comparison results, it can be seen that the hydrophilic, antibacterial and soft silicone polymer and its emulsion prepared by the present invention are hygienic finishing agents with very significant antibacterial effects and good washability. At the same time, the finished fabric also has multiple excellent properties such as hydrophilicity and softness, so it is an ideal functional finishing agent for fabric post-finishing.

[0109] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An organosilicon polymer, characterized in that: The structural formula of the organosilicon polymer is as follows: Among them: A, B, C, D are all positive integers; and A>B≥C≥D, A＝0～2000； B＝0～60； C＝0～50； D＝0～40； R is selected from: -OH, -CH3 or -OCH3; R1 is selected from: -C3H6NHC2H4NH2 or -C3H6NHC3H6N(CH3)2 or R2 is selected from: R3 is selected from: Wherein m and n are positive integers, m=3~29, n=1~31.

2. A method for synthesizing an organosilicon polymer as claimed in claim 1, characterized in that: The following steps are involved: Step 1, preparation of aminopolyether silane: 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane and single-terminated amino polyether are stirred and heated under the action of a solvent, the reaction temperature is controlled at 80-85°C, the reaction is kept warm for 2h-3h, and low molecular weight substances are removed by vacuum to obtain amino polyether silane. The reaction formula is as follows: Step 2, preparation of polyether / amino silicone oil: The hydroxyl-terminated linear silicone oil, the amino polyether silane obtained in step 1 and the amino coupling agent are used as reaction raw materials, the temperature is raised to 85-90° C. with stirring, a catalyst is added, and the reaction is stirred for 30 minutes, the reaction temperature is controlled at 105-110° C., the reaction is kept warm for 4-6 hours, low molecular weight substances are removed by vacuuming, and solid insolubles are filtered out with a filter after cooling to obtain an intermediate product polyether / amino silicone oil, wherein the solid insolubles are the catalyst; Step 3, preparation of silicone polymer: In the reactor, the intermediate product polyether / amino silicone oil and 2,3-epoxypropyltrimethylammonium chloride obtained in the above reaction are added in proportion, and then an organic solvent is added. The mixture is stirred and heated to 80-90°C for reflux reaction. After the reaction is kept warm for 3h-5h, low molecular weight substances are removed by vacuum to obtain the desired silicone polymer.

3. The method for synthesizing an organosilicon polymer according to claim 2, characterized in that: The hydroxyl-terminated linear silicone oil in step 2 has a non-volatile matter content of ≥99.5%, a water content of ≤0.1%, a viscosity of 20 to 120 mPa.S, and an amount thereof accounting for 60% to 85% of the total weight of the reaction system in step 2.

4. The method for synthesizing an organosilicon polymer according to claim 2, characterized in that: The amino polyether siloxane has a structural formula containing R3, and the amount of the amino polyether siloxane used accounts for 2% to 15% of the total weight of the reaction system in step 2; the amino coupling agent has a structural formula containing R1, and the amount of the amino coupling agent used accounts for 1% to 10% of the total weight of the reaction system in step 2.

5. The method for synthesizing an organosilicon polymer according to claim 2, characterized in that: The catalyst in step 2 is lithium hydroxide, and its usage accounts for 50-500ppm of the total weight of the reaction system in step 2.

6. The method for synthesizing an organosilicon polymer according to claim 2, characterized in that: In step 3, the amount of polyether / amino silicone oil used accounts for 50% to 85% of the total weight of the reaction system in step 3; the amount of organic solvent used accounts for 20% to 40% of the total weight of the reaction system in step 3; the amount of 2,3-epoxypropyltrimethylammonium chloride used accounts for 5% to 40% of the total weight of the reaction system in step 3.

7. The method for synthesizing an organosilicon polymer according to claim 2, characterized in that: The solvent used in step 1 and the organic solvent used in step 3 are selected from one or a mixture of isopropanol, ethanol, ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.

8. An organosilicon polymer microemulsion, characterized in that: Prepared by the following steps: After adding deionized water and neutralizing acid into the reactor and stirring evenly, the organosilicon polymer according to claim 1 or the organosilicon polymer prepared by the synthesis method of the organosilicon polymer according to any one of claims 2 to 7 is slowly added under stirring, and stirred for 20-40 minutes to obtain the desired organosilicon polymer microemulsion.

9. The organosilicon polymer microemulsion according to claim 8, characterized in that: The neutralizing acid is selected from formic acid, glacial acetic acid or aminosulfonic acid, and its usage is 0.1% to 4.0% of the total weight of the reaction system.

10. Use of the organosilicon polymer microemulsion according to claim 8 in textile printing and dyeing smoothing finishing agents and daily chemical care agents.

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