Single-ended dihydroxy hydrocarbon amino modified polysiloxane as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses single-ended dihydroxy hydrocarbon amino modified polysiloxane as well as a preparation method and application thereof, the structure of the single-ended dihydroxy hydrocarbon amino modified polysiloxane is shown as a formula I, and n is a natural number ranging from 10 to 65. According to the preparation process, diethanol amine, hexamethyldisilazane, allyl bromide and alpha-(trimethylsilyl)-omega-dimethylsilyl polydimethylsiloxane as shown in the formula M1 are used as raw materials, under the catalytic action of a Karst catalyst, single-ended trimethylsilyl is adopted, the other end is substituted by dihydroxy hydrocarbon amino, and excellent stability and hydrophilicity are achieved; woven cloth treated by using the emulsion prepared by the method is high in hydrophilicity and good in yellowing resistance. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a single-terminal dihydroxyalkylamine-modified polysiloxane and a preparation method and application thereof. Background Art

[0002] Polysiloxane materials are a class of polymers with repeated Si-O bonds as the main chain and organic groups directly connected to silicon atoms. The main chain of polysiloxane with methyl as the common organic group is very flexible, and the energy required to rotate around the Si-O bond is almost zero, giving the polysiloxane chain freedom, so that the polysiloxane chain can rotate 360 ​​degrees freely. Thanks to the rotational freedom of the Si-O-Si bond and the low interaction energy between the methyl groups on the silicon atoms, organosiloxane has good low surface tension, electrical properties, softness and thermal oxidation stability, which make organosiloxane an excellent fabric finishing agent. The unique structure of polysiloxane is applied to fabric finishing agents to provide fabrics with good force resilience and flexibility. Introducing other functional groups into the organosilicon chain can further improve the application performance of organosilicon softeners. Compared with other functional group modifications, aminoalkyl is often used to chemically modify the polysiloxane main chain, which can give polysiloxane the so-called "super soft" treatment effect.

[0003] When amino-modified silicone is arranged on the fabric, the Si-CH3 group at the hydrophobic end extends outward into the air, while the Si-O dipole bond and the polar amino group point to the interface between amino silicone and cellulose, and are tightly combined with the original hydroxyl groups on the fiber surface. When the amino-modified silicone softener treats the fabric, it will be fixed on or within the cellulose structure, accompanied by the formation of a semi-interpenetrating network structure, thereby improving the degree of cross-linking and networking. There is also a phenomenon of self-condensation between amino-modified silicone and the fiber. Due to the good activity of the amino group, it will react with carbonic acid in the air (water molecules react with carbon dioxide to form carbonic acid) to form a highly polymerized and elastic cross-linked network structure, which can not only give the fabric a super soft effect and smoothness, but also increase the fabric's washing resistance. Fabrics treated with amino-modified silicone generally show good softness, flexibility, tensile strength, and color fastness.

[0004] Amino-modified silicone refers to a type of polydimethylsiloxane with amino hydrocarbon groups on the side chain and / or end group. Amino-modified silicone not only has the properties of general polysiloxane such as non-toxicity, non-corrosiveness, and low surface tension, but also the amino functional group can improve the orientation and affinity of the polysiloxane chain segments on the substrate, making it easy for the amino-modified polysiloxane to spread on the fiber surface to form a film, forming a polymer coating and reducing the roughness of the fiber surface. However, the use of amino-modified polysiloxane as a silicone softener still has the following problems: (1) Poor hydrophilicity. The hydrophilic oxygen atoms in polysiloxane will react with the active functional groups on the fabric surface, and the hydrophobic methyl groups will cover the hydrophilic oxygen atoms, resulting in a hydrophobic state on the fabric surface; (2) Poor yellowing resistance. This is because the amino group is easily oxidized and will combine with oxygen to form yellowing groups such as azo or oxyazo groups when exposed to air for a long time, resulting in a change in the whiteness of the fabric.

[0005] Islam et al. (Islam MS, Lahiri SK, Nahar J, et al. Synthesis and application of amino-modified silicone oil on cotton fabric [J]. International Journal of Scientific and Engineering Research, 2015, 6 (5): 1195-1203.) prepared amino-modified organosiloxane, emulsified it and applied it to fabric finishing and tested its performance. The emulsion (solid content of 25%, pH of 6-7, viscosity of 60 mPa·s) can still have thermal stability, alkali stability and dielectric stability at a high temperature of 80°C. The test performance found that the amino-modified organosilicone softener has little effect on the strength of the fabric, and has no significant effect on the color fastness of the dyed fabric, which can give the fabric good wash resistance. After multiple washings, the color retention rate is 60%, the softness test rating reaches 5, and the feel rating of the original cotton fabric is 4.5.

[0006] Due to the difference in the properties of the functional groups, monofunctional silicone softeners can only meet the specific or partial requirements of fabric processing. In order to obtain silicone finishing agents with better comprehensive effects, multifunctional modified silicone softeners are essential. The insufficiency of amino silicone oil can be improved by introducing other functional groups on the basis of amino-modified silicone. Summary of the invention

[0007] Aiming at the problems of insufficient hydrophilicity and poor yellowing resistance of amino-modified polysiloxane, the present invention provides an emulsifiable bishydroxyalkylamine-modified polysiloxane material. The polysiloxane is substituted with trimethyl at one end and bishydroxyalkylamine at the other end, has excellent weather resistance, softness and breathability, and good thermal stability. The emulsion prepared by the polysiloxane has strong hydrophilicity and good yellowing resistance.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] A single-terminal bis-hydroxylamine-modified polysiloxane, wherein the structure of the single-terminal bis-hydroxylamine-modified polysiloxane is as shown in Formula I:

[0010]

[0011] The value of n is a natural number ranging from 10 to 65.

[0012] The dihydroxyalkylamine-modified polysiloxane in the present invention converts the primary amine group of the amino silicone oil into a dihydroxyalkyl group. The formed tertiary amine structure has better resistance to oxidative yellowing than the primary amine, and the introduced hydroxyl group can form hydrogen bonds with water molecules, which can bring better hygroscopicity to the fabric and improve the yellowing and poor hydrophilicity problems of the amino silicone oil.

[0013] The single-end bishydroxyalkylamine-modified polysiloxane has a number average molecular weight of 1000-5000 g / mol and a PDI value of 1.4-1.8.

[0014] The present invention also provides a method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane, comprising the steps of:

[0015] Step 1, reflux diethanolamine and hexamethyldisilazane to obtain bis[2-(trimethylsilyloxy)ethyl]amine;

[0016] Step 2, adding allyl bromide dropwise to bis[2-(trimethylsilyloxy)ethyl]amine, and continuing the reaction to obtain N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine;

[0017] Step 3, N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine is reacted with a single-terminal hydrogen-containing silicone oil (α-(trimethylsilyl)-ω-dimethylsilyl polydimethylsiloxane) represented by formula M2 through a hydrosilylation reaction to obtain α-methyl-ω-N,N-bis[2-(trimethylsilyloxy)ethyl]aminopropyl polydimethylsiloxane, and the single-terminal bishydroxyalkylamine-modified polysiloxane material represented by formula I is obtained through hydroxyl deprotection;

[0018]

[0019] The value of n is a natural number ranging from 10 to 65.

[0020] The structural formula of the N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine is shown below M1:

[0021]

[0022] In step 3, the molar ratio of the -CH2-CH=CH2 group in N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine to the Si-H group in the single-terminal hydrogen-containing silicone oil shown in formula M2 is about 1-1.2:1.

[0023] The hydrosilylation reaction in step 3 includes a catalyst, which is a Custer catalyst, wherein the total amount of Pt is 0.5 mol% of N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine, plus 10 to 40*10% of the total mass of the two raw materials for the hydrosilylation reaction. -6 Since N-containing raw materials can lead to catalyst deactivation, the amount of N-containing raw materials should be considered when adding the catalyst to resist catalyst poisoning, which also promotes a higher reaction yield.

[0024] In step 1, the reaction temperature is 120-160°C and the reaction time is 20-35h;

[0025] When allyl bromide is added dropwise in step 2, the temperature is -5-5°C, and after the addition is completed, the reaction is carried out at -5-45°C for 1-4h;

[0026] Step 3 specifically includes the following steps: under the protection of an inert gas, N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine is first activated by a catalyst, and then the single-terminal hydrogen-containing silicone oil shown in formula M2 is injected into the reaction system, and the reaction is continued to obtain a product.

[0027] In step 3, the activation temperature is 50-80°C and the activation time is 15-40min;

[0028] In step 3, the reaction temperature is 50-80°C and the reaction time is 8-15h;

[0029] The present invention also provides an amino silicone oil emulsion, which comprises 1-5 parts of the single-end dihydroxyalkylamine-modified polysiloxane according to claim 1 or 2, 0.1-2 parts of an emulsifier, 0.1-0.5 parts of acetic acid and 150-300 parts of water according to the raw material composition.

[0030] The emulsifier includes D-1, where D-1 is a mixture of fatty alcohol polyoxyethylene ether AE0-6 and AEO-9 in a mass ratio of 1:1.

[0031] The present invention also provides a method for preparing an amino silicone oil emulsion, comprising: mixing and phase-transforming 1 to 5 parts of the single-terminal dihydroxyalkylamine-modified polysiloxane according to claim 1 or 2 with 0.1 to 2 parts of an emulsifier, 0.1 to 0.5 parts of acetic acid and 5 to 10 parts of water according to a raw material composition; the emulsion after the phase transition is diluted with water at a mass ratio of 5 to 10:200 to obtain the amino silicone oil emulsion.

[0032] The preparation method of the amino silicone oil emulsion is specifically, according to the raw material composition, 2 parts of the single-terminal dihydroxylamine-modified polysiloxane according to claim 1 or 2 are mixed with 0.6 parts of emulsifier, 0.1 parts of 33% acetic acid and 7.3 parts of water for phase inversion. The 20% solid content emulsion after phase inversion is diluted with water at a mass ratio of 5-7:200 to obtain the amino silicone oil emulsion.

[0033] The invention also provides application of the amino silicone oil emulsion in fabric finishing.

[0034] Specifically, the method for using the amino silicone oil emulsion for fabric finishing comprises the steps of: soaking the cut woven fabric in the amino silicone oil emulsion, performing preliminary shaping, drying, and moisture regain after dipping and rolling to obtain the finished fabric. The amino silicone oil emulsion of the present invention can improve the hydrophilicity and yellowing resistance of the fabric.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The polysiloxane in the present invention has a trimethylsilyl group at one end and has excellent thermal stability and solvent resistance. The obtained emulsion and woven fabric are placed on a padder for a padding process, and the hydrophilicity of the woven fabric is greatly improved, and the yellowing resistance is also slightly improved.

[0037] (2) The polysiloxane preparation process of the present invention adopts a Custer catalyst, and strictly controls the amount of the catalyst, the catalyst poisoning rate, the conversion rate of the raw materials, the success rate of the product, and the yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The hydrosilylation product of S3 in Example 1 is α-methyl-ω-N,N-bis[2-(trimethylsilyloxy)ethyl]aminopropyl polydimethylsiloxane. 1 H NMR spectrum.

[0039] Figure 2 The single-terminal dihydroxyl-modified aminopolysiloxane of formula I prepared in Example 1 1 H NMR spectrum.

[0040] Figure 3 The single-terminal dihydroxyl-modified aminopolysiloxane of formula II prepared in Example 2 1H NMR spectrum.

[0041] Figure 4 The double-terminal dihydroxyl-modified aminopolysiloxane material of formula III prepared in Example 3 1 H NMR spectrum.

[0042] Figure 5 These are the TGA graphs of the single-terminal and double-terminal bishydroxyl-modified aminopolysiloxane materials prepared in Examples 1 and 3. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Those skilled in the art can make modifications or equivalent substitutions based on the understanding of the technical scheme of the present invention without departing from the spirit and scope of the technical scheme of the present invention, and all should be included in the protection scope of the present invention.

[0044] The raw materials used in the following specific embodiments are all purchased from the market.

[0045] Example 1

[0046] S1: Add 158g (1.5mol) of diethanolamine to a dry 500mL three-necked round-bottom flask equipped with a magnetic stirrer, a condenser, a thermometer and a constant pressure dropping funnel, and slowly add 314g (1.95mol) of hexamethyldisilazane under stirring and reflux at 100°C for 225min. After the addition is completed, the temperature is raised to 140°C at 10°C / h, and the heating is turned off after reflux and stirring for 30h. The product bis[2-(trimethylsilyloxy)ethyl]amine is distilled out at 140°C under reduced pressure of 100kpa as a transparent liquid with a yield of 93%.

[0047] S2: 49.8g of bis[2-(trimethylsilyloxy)ethyl]amine was added to a dry 250mL three-necked round-bottom flask with a magnetic stirrer, a condenser, a thermometer and a constant pressure dropping funnel. 25.4g of allyl bromide was slowly added dropwise under an ice bath at 5°C. After the addition, the yellow color of the solution became more obvious. After the ice cubes were removed, the temperature gradually returned to room temperature and was placed in a 40°C oil bath. A 20% NaOH solution was slowly added dropwise to make the whole system in a weakly alkaline state. The reaction proceeded in the positive direction. After all the additions were completed, the reaction was terminated after 2 hours. The oil phase extracted with dichloromethane was desolventized and distilled under a pressure reduction of 100kpa. The single-terminal hydrogenated silicone oil of the N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine product at 140°C was collected. The GC-MS purity was 99% and the yield was 51.2%.

[0048] S3: Add 15 ml of toluene with a water content of 200 ppm and 1.09 g (3.76 × 10 -3 mol) of N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine, 0.38g of 1wt% karstedt catalyst (effective content is 230ppm), stirred and heated to 70°C, and activated at this temperature for 30min; 15.5g of single-end hydrogenated silicone oil was uniformly added to the reaction system using a syringe pump, and the injection time was 1.5h. After the injection was completed, the reaction was continued at 70°C for 10h and then cooled to room temperature. The system was left open to deactivate the catalyst, and the product was subjected to reduced pressure distillation to remove low boiling points to obtain α-methyl-ω-N,N-bis[2-(trimethylsilyloxy)ethyl]aminopropyl polydimethylsiloxane, and its nuclear magnetic hydrogen spectrum is as follows Figure 1 shown.

[0049] Taking the synthesis of α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane with a molecular weight of Mn 1000 as an example, the raw material conversion rate is greater than 90%. A mixture of acetic acid and methanol (1:50) is added and refluxed for 6 hours, and after removing low boiling points, the target single-terminated dihydroxyl hydrocarbon modified amino polysiloxane (α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane) shown in formula I is obtained.

[0050] Calculation and test: With single-terminal hydrogen-containing silicone oil as the key component, the product with a molecular weight of about 1000 prepared by hydrosilylation in Example 1 was calculated and tested. 1 H NMR analysis, the results are as follows Figure 1 The double bond formation rate of the emulsifiable single-terminal dihydroxyl-modified aminopolysiloxane is close to 100%, and the yield is 90%. After deprotection, the target single-terminal dihydroxyl-modified aminopolysiloxane material is obtained, and the NMR spectrum results are as follows: Figure 2 shown.

[0051] Figure 1 The integral ratio of the characteristic peak of the hydroxyl group (~3.6ppm) to the structural characteristic peak (~0.5ppm) generated by the hydrosilylation reaction is 4.026:2.000, which is consistent with the structural characteristics of the single-terminal dihydroxyl group-modified aminopolysiloxane, and the double bond addition rate is close to 100%. 1 The degree of polymerization of the polymer was calculated from H NMR integration and was n≈12.

[0052] The data of α-methyl-ω-N,N-bis[2-(trimethylsiloxy)ethyl]aminopropyl polydimethylsiloxane with different molecular weights are shown in Table 1. OH-1 to OH-5 represent the sample numbers of α-methyl-ω-N,N-bis[2-(trimethylsiloxy)ethyl]aminopropyl polydimethylsiloxane (I) with different molecular weights. Mn / g·mol -1Refers to the relative number average molecular weight of the sample obtained by GPC test; η 25 / cP is the viscosity value of the test sample at 25°C; n D 25 Av is the refractive index of the test sample at 25°C; b / mmol·g -1 is the ammonia value obtained by titration, and b is the monomer containing a C=C bond. It can be seen that the higher the molecular weight, the more difficult it is to synthesize.

[0053] Table 1 Data of single-terminal dihydroxyl modified amino polysiloxanes with different molecular weights

[0054] Sample name <![CDATA[Mn / g·mol -1 ]]> <![CDATA[η 25 / cP]]> <![CDATA[nD 25 ]]> <![CDATA[Av b / mmol·g -1 ]]> Yield % OH-1 1000 111.5 1.4147 1.57 90％ OH-2 1500 142.6 1.4146 0.64 88％ OH-3 2500 204.3 1.4045 0.52 75％ OH-4 4000 207.5 1.4125 0.25 72％ OH-5 5000 245.0 1.4041 0.18 64％

[0055] Comparative Example 1

[0056] According to the process steps in Example 1, in step 3, the single-terminal hydrogen-containing silicone oil α-(trimethylsilyl)-ω-dimethylsilyl polydimethylsiloxane is replaced with a butyl-substituted single-terminal hydrogen-containing silicone oil of formula M3 of equal molar mass, and the other steps are consistent to obtain α-butyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane of formula II. The NMR spectrum of the product is shown in Figure 3 shown.

[0057]

[0058] Comparative Example 2

[0059] According to the process steps in Example 1, in step 3, the single-terminal hydrogen-containing silicone oil α-(trimethylsilyl)-ω-dimethylsilyl polydimethylsiloxane is replaced with a double-terminal hydrogen-containing silicone oil α,ω-dimethylsilyl polydimethylsiloxane shown in formula M4 of equal molar mass, and the other steps are the same to obtain α,ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane shown in formula III. The NMR spectrum of the product is shown as follows Figure 4 shown.

[0060]

[0061] Application Example 1

[0062] Prepare an emulsion with a solid content of 20% by taking 2 g of the polysiloxane of Example 1, 0.6 g of emulsifier D-1 (D-1 is a composite emulsifier prepared by mixing fatty alcohol polyoxyethylene ether AE0-6 and AEO-9 in a mass ratio of 1:1), 0.1 g of 33% acetic acid, and 7.3 g of water for preliminary phase inversion. After the phase inversion, 6 g of the emulsion is diluted with 200 g of water to obtain an O / W emulsion (O / W refers to oil-in-water state).

[0063] Calculation and testing:

[0064] Cutting fabric: The fabric should be woven fabric and the cutting size should be the size of two A4 papers.

[0065] Padding: Soak the cut woven fabric in the emulsion for 10 seconds, and use the process of dipping and padding to initially shape the soaked woven fabric through a padder. The shaped fabric passes through a setting machine with a drying time of 1 minute and a speed of 4m / min. Place the fabric that has passed the setting machine in a dry and dark place to regain moisture for 1 hour.

[0066] Test: The whiteness of the woven fabric after moisture regain is tested, followed by tests on hydrophilicity, mechanical properties, etc.

[0067] Hydrophilicity test: Fix the recovered fabric sample on the stretching ring, use a rubber-tipped dropper to drop a drop of water 1 cm above the fabric surface, and start timing. When the water drop is reduced to a non-reflective watermark, stop timing. Hydrophilicity can also be expressed by the water contact angle of the fabric after padding process. Under the same padding process, compare the length of water absorption time. The longer the water absorption time, the worse the water absorption.

[0068] Mechanical properties test: tear strength is tested according to GB / T 3917.1 standard using a drop weight fabric tear tester; sliding friction is tested according to GB / T 3925-2009 standard using a friction coefficient tester; breaking strength is tested according to ASTM D638 standard using a universal material testing machine.

[0069] Whiteness test: Place the fabric after moisture regain after rolling on the colorimeter for whiteness test. Fold the fabric into four layers and test four times. The average of the four values ​​is automatically read.

[0070] Antistatic test: Use a resistive static tester. Preheat the instrument before testing. Cut the woven fabric into 45mm×45mm after padding. Place it in an environment with a humidity of 29.6% RH and a temperature of 20.2℃ for 5 hours before testing.

[0071] The properties of the woven fabric after the emulsion treatment of the polysiloxane prepared in Example 1 are shown in Table 2, where the original fabric refers to the woven fabric that has not been treated in any way. It can be seen that the static water absorption time of the fabric treated with the emulsion of the single-terminal bishydroxyalkylamine polydimethylsiloxane (I) is in the range of 10-35s. The hydrophilicity is compared with the static water absorption time of the original fabric of 180s. It can be seen that the emulsion of the single-terminal bishydroxyalkylamine polydimethylsiloxane (I) shows good hydrophilicity when applied to the fabric. The softness rating of the fabric treated with the emulsion of the single-terminal bishydroxyalkylamine polydimethylsiloxane (I) is 3.2-4.2. Compared with the original fabric 2.0, the softness is improved to a certain extent.

[0072] The emulsification effect is affected by the molecular weight of silicone oil. The emulsification conditions of different molecular weights were explored. When the molecular weight of the prepared single-ended bis-hydroxylamine-modified polydimethylsiloxane is less than 1000g / mol, the bonding strength with the fabric surface will be poor, which may eventually cause the fabric's washability to deteriorate. When the molecular weight is about 5000g / mol, emulsification is more difficult, the viscosity is too high during phase transition, and it is difficult to obtain a homogeneous emulsion, which cannot complete the effective padding of the fabric. The experimental results determined that the molecular weight of the single-ended bis-hydroxylamine-modified polysiloxane used is between 1000-5000g·mol -1 Only within this range can the surface of the fabric uniformly coated with single-ended bishydroxyamine-modified polysiloxane be tested for hydrophilicity, yellowing and other properties.

[0073] Table 2 Fabric properties of the emulsion of single-terminated bis-hydroxylamine polydimethylsiloxane prepared in Example 1

[0074]

[0075] Application Example 2

[0076] According to the process steps of Application Example 1, the emulsion of butyl-modified bishydroxyalkylamine polysiloxane of Comparative Example 1 was prepared and applied to treat woven fabrics. The test results of the woven fabrics are shown in Table 3. In Table 3, different sample names C4H9-1 to C4H9-5 represent α-butyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane (II) with different molecular weights.

[0077] Compared with the α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane (I) of Example 1, the structurally inert methyl group far from one end of the fabric is changed to a butyl group, which has little effect on the softness of the fabric, but the hydrophilicity and yellowing properties can be observed to be different. As can be seen from Table 3, the static water absorption time of the fabric treated with the emulsion of butyl-modified dihydroxyalkylamino polydimethylsiloxane is less than 10s, but compared with the fabric treated with the polysiloxane emulsion of Example 1 in Table 3, it shows good hydrophilicity compared with the original fabric, but worse than the water absorption of the fabric treated with the polysiloxane emulsion of Example 1. Its whiteness is also much worse than that of the original fabric and Example 1, and the yellowing phenomenon is very obvious.

[0078] Table 3 Fabric properties of butyl-modified bis(hydroxylamine)polydimethylsiloxane (II) emulsion application

[0079]

[0080] Application Example 3

[0081] According to the process steps of Application Example 1, the emulsion of double-terminated bis-hydroxylamine polydimethylsiloxane of Comparative Example 2 was prepared and applied to treat woven fabrics. The test results of the woven fabrics are shown in Table 4.OH -1~D OH -3 represents double-terminated bis-hydroxyalkylamino polydimethylsiloxane samples with different molecular weights, α,ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane (III).

[0082] As can be seen from Table 4, the static water absorption time of the fabric treated with the emulsion of double-terminated bis-hydroxyalkylamine polydimethylsiloxane (III) is less than 20s. The emulsion applied to the fabric shows good hydrophilicity compared to the original fabric, and the softness is also improved.

[0083] Table 4 Fabric properties of double-terminal bis-hydroxylamine polydimethylsiloxane (III) emulsion

[0084]

[0085] In further research, the single-terminal bis-hydroxylamine polydimethylsiloxane of formula I prepared in Example 1 and the double-terminal bis-hydroxylamine polydimethylsiloxane of formula III prepared in Comparative Example 2 were subjected to thermal stability tests. The results are as follows: Figure 5 As shown, wherein the T of the single-terminal polysiloxane shown in Formula I 5％ The temperature is 396°C, and the T 5％ The single-ended polysiloxane exhibits better thermal stability.

Claims

1. A single-terminal bishydroxyalkylamine-modified polysiloxane, characterized in that: The structure of the single-terminal bis-hydroxyalkylamine-modified polysiloxane is shown in Formula I: The value of n is a natural number ranging from 10 to 65.

2. The single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 1, characterized in that: The single-end bishydroxyalkylamine-modified polysiloxane has a number average molecular weight of 1000-5000 g / mol and a PDI value of 1.4-1.

8.

3. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 1 or 2, characterized in that: Includes steps: Step 1, reflux diethanolamine and hexamethyldisilazane to obtain bis[2-(trimethylsilyloxy)ethyl]amine; Step 2, adding allyl bromide dropwise to bis[2-(trimethylsilyloxy)ethyl]amine, and continuing the reaction to obtain N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine; Step 3, N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine and the single-terminal hydrogen-containing silicone oil shown in formula M2 are subjected to a hydrosilylation reaction to obtain α-methyl-ω-N,N-bis[2-(trimethylsilyloxy)ethyl]aminopropyl polydimethylsiloxane, and the single-terminal bishydroxyalkylamine-modified polysiloxane shown in formula I is obtained by deprotecting the hydroxyl group; The value of n is a natural number ranging from 10 to 65.

4. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 3, characterized in that: In step 3, the molar ratio of the -CH2-CH=CH2 group in N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine to the Si-H group in the single-terminal hydrogen-containing silicone oil shown in formula M2 is about 1-1.2:

1.

5. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 3, characterized in that: The hydrosilylation reaction in step 3 includes a catalyst, which is a Custer catalyst, wherein the total amount of Pt is 0.5 mol% of N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine, plus 10 to 40*10% of the total mass of the two raw materials for the hydrosilylation reaction. -6 .

6. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 3, characterized in that: In step 1, the reaction temperature is 120-160°C and the reaction time is 20-35h; When allyl bromide is added dropwise in step 2, the temperature is -5-5°C, and after the addition is completed, the reaction is carried out at -5 to 45°C for 1-4 hours.

7. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 3, characterized in that: Step 3 specifically includes the following steps: under the protection of an inert gas, N,N-bis[2-(trimethylsilyloxy)ethyl]allylamine is first activated by a catalyst, and then the single-terminal hydrogen-containing silicone oil shown in formula M2 is injected into the reaction system, and the reaction is continued to obtain a product.

8. The method for preparing the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 7, characterized in that: In step 3, the activation temperature is 50-80°C and the activation time is 15-40min; In step 3, the reaction temperature is 50-80°C and the reaction time is 8-15h.

9. An amino silicone oil emulsion, characterized in that: The raw material composition comprises 1-5 parts of the single-terminal bishydroxyalkylamine-modified polysiloxane according to claim 1 or 2, 0.1-2 parts of an emulsifier, 0.1-0.5 parts of acetic acid and 150-300 parts of water.

10. The method for preparing the amino silicone oil emulsion according to claim 9, characterized in that: The method comprises the following steps: mixing 1-5 parts of the single-terminal dihydroxyalkylamine-modified polysiloxane according to claim 1 or 2 with 0.1-2 parts of an emulsifier, 0.1-0.5 parts of acetic acid and 5-10 parts of water for phase inversion according to the raw material composition; and diluting the emulsion after phase inversion with water at a mass ratio of 5-10:200 to obtain the amino silicone oil emulsion.

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