A single-end type dihydroxylalkylamine-modified polysiloxane, a method for preparing the same, and an application thereof

Abstract

The application relates to the technical field of high polymer materials, and discloses a single-end type dihydroxyalkylamine modified polysiloxane as well as a preparation method and application thereof, and the structure is shown in formula I, wherein the value range of n is a natural number of 10-65. The preparation process is as follows: diethanolamine, hexamethyldisilazane, allyl bromide and alpha-(trimethylsilyl)-omega-dimethylsilyl polydimethylsiloxane shown in formula M1 are used as raw materials, and a single-end trimethylsilyl group and a dihydroxyalkylamine group are substituted at the other end under the catalysis of a Karstedt catalyst, the dihydroxyalkylamine modified polysiloxane has excellent stability and hydrophilicity, and the emulsion prepared by using the dihydroxyalkylamine modified polysiloxane has high hydrophilicity and good yellowing resistance when treating fabric.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular materials, in particular to a single-end type dihydrocarbylamine-modified polysiloxane and a preparation method and application thereof. BACKGROUND

[0002] Polysiloxane material is a polymer with a main chain of repeating Si-O bonds and organic groups directly connected to silicon atoms. The main chain of polysiloxane with common organic groups such as methyl is very flexible, and the energy required for rotation around the Si-O bond is almost zero, giving the polysiloxane chain segment freedom, so that the polysiloxane chain can rotate freely by 360°. Benefiting from the rotation freedom of Si-O-Si bond and the low interaction energy between methyl groups on silicon atoms, organosiloxane has good low surface tension, electrical properties, softness and thermal oxidative stability, which makes organosiloxane an excellent fabric finishing agent. The unique structure of polysiloxane applied to fabric finishing agents provides good stress resilience and flexibility to fabrics. The introduction of other functional groups into the organosilicon chain segment can further improve the application performance of the organosilicon softener. Compared with other functional group modifications, the aminoalkyl group is commonly used to chemically modify the polysiloxane main chain, which can give the polysiloxane so-called "super soft" treatment effect.

[0003] When amino-modified organosilicon is arranged on the fabric, the hydrophobic end Si-CH3 group extends outward into the air, while the Si-O dipole bond and the polar amino group point to the interface between amino silicon and cellulose, and tightly bind with the original hydroxyl group on the fiber surface. When the amino-modified organosilicon softener is used to treat the fabric, it will be fixed on or in the cellulose structure, accompanied by the formation of a semi-interpenetrating network structure, thereby improving the crosslinking and networking degree. There is also a self-condensation phenomenon between amino-modified organosilicon and fibers. Due to the good activity of amino groups, they will react with carbonic acid (water molecules react with carbon dioxide to form carbonic acid) in the air to form a highly polymerized elastic crosslinked network structure, which not only can give the fabric super soft effect, smoothness, but also can increase the wash resistance of the fabric. The fabric treated by amino-modified organosilicon generally exhibits good softness, flexibility, tensile strength and color fastness.

[0004] Amino-modified organosilicon refers to a class of polydimethylsiloxanes with amino groups on the side chains and / or end groups. Amino-modified organosilicon not only has the properties of general polysiloxanes such as non-toxicity, non-corrosiveness, and low surface tension, but also the amino functional groups can improve the orientation and affinity of polysiloxane segments on the substrate, making it easy for amino-modified polysiloxanes to spread and form a film on the fiber surface, forming a polymer coating and reducing the roughness of the fiber surface. However, amino-modified polysiloxanes still have the following problems when used as organosilicon softeners: (1) Poor hydrophilicity. The hydrophilic oxygen atoms in polysiloxanes 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 resistance to yellowing. This is because amino groups are easily oxidized, and long-term exposure to air will combine with oxygen to generate yellowing groups such as azo groups or oxyazo groups, which will cause changes 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 organosiloxanes, emulsified them, applied them to fabric finishing, and tested their properties. The emulsion (solid content 25%, pH 6-7, viscosity 60 mPa·s) still maintained thermal stability, alkali stability, and dielectric stability at 80℃. The performance test showed that the amino-modified organosilicone softener had little effect on the fabric strength and no significant effect on the color fastness of the dyed fabric, and could give the fabric good wash resistance. After multiple washes, the color retention rate was 60%, the softness test rating reached 5, and the hand feel rating of the original cotton fabric was 4.5.

[0006] Monofunctional silicone softeners, due to the differences in the properties of their functional groups, can only meet specific or partial needs in fabric processing. To obtain silicone finishing agents with better overall performance, multifunctional modified silicone softeners are crucial. The shortcomings of amino silicone oils can be improved by introducing other functional groups onto amino-modified silicone. Summary of the Invention

[0007] This invention addresses the problems of insufficient hydrophilicity and poor yellowing resistance of amino-modified polysiloxanes by providing an emulsifiable dihydroxyalkylamine-modified polysiloxane material. This polysiloxane has one end substituted with trimethyl and the other end substituted with dihydroxyalkylamine, exhibiting excellent weather resistance, softness, and breathability, as well as good thermal stability. Fabrics treated with emulsions prepared using this material show strong hydrophilicity and good yellowing resistance.

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

[0009] A single-terminal dihydroxyalkylamine-modified polysiloxane, the structure of which is shown in Formula I:

[0010]

[0011] Where n is a natural number ranging from 10 to 65.

[0012] The bishydroxyalkylamine-modified polysiloxane in this invention transforms the primary amine group of amino silicone oil into a bishydroxyalkyl group. The resulting tertiary amine structure exhibits better resistance to oxidative yellowing than the primary amine. Furthermore, the introduced hydroxyl groups can form hydrogen bonds with water molecules, which can provide better moisture absorption for fabrics and improve the yellowing and poor hydrophilicity problems of amino silicone oil.

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

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

[0015] Step 1: Diethanolamine and hexamethyldisilazane are refluxed to give bis[2-(trimethylsiloxy)ethyl]amine;

[0016] Step 2: Allyl bromide is added dropwise to bis[2-(trimethylsiloxy)ethyl]amine, and the reaction continues to obtain N,N-bis[2-(trimethylsiloxy)ethyl]allylamine;

[0017] Step 3: N,N-bis[2-(trimethylsiloxy)ethyl]allylamine is reacted with the single-ended hydrogen-containing silicone oil (α-(trimethylsilyl)-ω-dimethylsilyl polydimethylsiloxane) shown in Formula M2 via a hydrosilylation reaction to obtain α-methyl-ω-N,N-bis[2-(trimethylsiloxy)ethyl]aminopropyl polydimethylsiloxane. After hydroxyl deprotection, the single-ended dihydroxylamine-modified polysiloxane material shown in Formula I is obtained.

[0018]

[0019] Where n is a natural number ranging from 10 to 65.

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

[0021]

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

[0023] Step 3, the hydrosilylation reaction, includes a catalyst, specifically a Castrol catalyst, wherein the total amount of Pt is 0.5% mol of N,N-bis[2-(trimethylsiloxy)ethyl]allylamine, plus 10–40 × 10⁻⁶ mol of the total mass of the two raw materials for the hydrosilylation reaction. -6 Since nitrogen-containing feedstocks can deactivate catalysts, the amount of nitrogen-containing feedstocks must be considered when adding catalysts to combat catalyst poisoning, which also leads to higher reaction yields.

[0024] The reaction temperature in step 1 is 120-160℃, and the reaction time is 20-35h;

[0025] In step 2, the temperature during the dropwise addition of allyl bromide is -5 to 5℃, and after the dropwise addition is completed, the reaction is carried out at -5 to 45℃ for 1 to 4 hours.

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

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

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

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

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

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

[0032] The preparation method of the amino silicone oil emulsion specifically involves mixing and inverting a mixture of 2 parts of the single-terminated dihydroxylamine-modified polysiloxane as described in claim 1 or 2 with 0.6 parts of emulsifier, 0.1 parts of 33% acetic acid, and 7.3 parts of water. The inverted emulsion with a 20% solids content is then diluted with water at a mass ratio of 5-7:200 to obtain the amino silicone oil emulsion.

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

[0034] Specifically, the method for using the amino silicone oil emulsion to finish fabrics includes the following steps: immersing cut woven fabric in the amino silicone oil emulsion, performing a dip-and-roll process followed by preliminary shaping, drying, and rehydration to obtain the finished fabric. The amino silicone oil emulsion of this invention can improve the hydrophilicity and yellowing resistance of fabrics.

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

[0036] (1) The polysiloxane in this invention has a trimethylsilyl group at one end, which has excellent thermal stability and solvent resistance. The resulting emulsion is placed in a padding machine for padding process, which greatly improves the hydrophilicity of the woven fabric and slightly improves its yellowing resistance.

[0037] (2) The polysiloxane preparation process in this invention uses a cassiterite catalyst and strictly controls the amount of catalyst, catalyst poisoning rate, raw material conversion rate, product success rate and yield. Attached Figure Description

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

[0039] Figure 2 The mono-terminated dihydroxyalkyl modified amino polysiloxane of Formula I prepared in Example 1 1 H NMR spectrum.

[0040] Figure 3 The mono-terminated dihydroxyalkyl modified amino polysiloxane of Formula II prepared in Example 2 1H NMR spectrum.

[0041] Figure 4 The amino polysiloxane material with dihydroxyl-terminated ends as shown in Formula III, prepared in Example 3. 1 H NMR spectrum.

[0042] Figure 5 TGA images of the single- and double-ended dihydroxyalkyl modified amino polysiloxane materials prepared in Examples 1 and 3. Detailed Implementation

[0043] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Modifications or equivalent substitutions made by those skilled in the art based on their understanding of the technical solutions of this invention, without departing from the spirit and scope of the invention, should be covered within the protection scope of this invention.

[0044] All raw materials used in the following specific implementation methods were purchased from the market.

[0045] Example 1

[0046] S1: 158 g (1.5 mol) of diethanolamine was added to a dry 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, condenser, thermometer, and constant-pressure dropping funnel. 314 g (1.95 mol) of hexamethyldisilazane was slowly added dropwise over 225 min with stirring under reflux at 100 °C. After the addition was complete, the temperature was increased to 140 °C at a rate of 10 °C / h, and the mixture was refluxed and stirred for 30 h before the heating was turned off. The product, bis[2-(trimethylsiloxy)ethyl]amine, was distilled off under reduced pressure (100 kPa) at 140 °C as a clear liquid, with a yield of 93%.

[0047] S2: 49.8 g of bis[2-(trimethylsiloxy)ethyl]amine was added to a dry 250 mL three-necked round-bottom flask equipped with a magnetic stirrer, condenser, thermometer, and constant-pressure dropping funnel. 25.4 g of allyl bromide was slowly added dropwise in an ice bath at 5 °C. After the addition, the yellow color of the solution became more pronounced. After removing the ice, the temperature was gradually raised to room temperature and then placed in a 40 °C oil bath. A 20% NaOH solution was slowly added dropwise to bring the entire system to a weakly alkaline state, allowing the reaction to proceed in the forward direction. The reaction was stopped 2 hours after all the addition was completed. The oil phase was extracted with dichloromethane, and after solvent removal, it was distilled under reduced pressure of 100 kPa. The N,N-bis[2-(trimethylsiloxy)ethyl]allylamine product, a single-end hydrogen-containing silicone oil, was collected at 140 °C. 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 × 10⁻⁶) to a 100 ml three-necked flask under dry nitrogen protection. -3 0.38 g of 1 wt% Kerstedt catalyst (effective content 230 ppm) of N,N-bis[2-(trimethylsiloxy)ethyl]allylamine and 0.38 g of 1 wt% Kerstedt catalyst were stirred and heated to 70 °C, and activated at this temperature for 30 min. 15.5 g of single-ended hydrogen-containing silicone oil was uniformly added to the reaction system using a syringe pump over 1.5 h. After injection, the reaction was continued at 70 °C for 10 h, then cooled to room temperature. The system was left open to deactivate the catalyst. The product was subjected to vacuum distillation to remove low-boiling points, yielding α-methyl-ω-N,N-bis[2-(trimethylsiloxy)ethyl]aminopropyl polydimethylsiloxane, whose 1H NMR spectrum is shown below. Figure 1 As shown.

[0049] Taking the synthesis of α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane with a molecular weight Mn of 1000 as an example, the raw material conversion rate is greater than 90%. After adding an acetic acid-methanol (1:50) mixture and refluxing for 6 hours to remove low-boiling substances, the target single-terminal dihydroxyalkyl modified amino polysiloxane (α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane) shown in Formula I is obtained.

[0050] Calculation and Testing: Using single-ended hydrogen-containing silicone oil as the key component, calculations were performed on the product with a molecular weight of approximately 1000 prepared by hydrosilylation in Example 1. 1 1H NMR analysis, results as follows Figure 1 As shown, the double addition bond formation rate of the emulsifiable single-terminated dihydroxyalkyl-modified aminopolysiloxane is close to 100%, with a yield of 90%. After deprotection, the target single-terminated dihydroxyalkyl-modified aminopolysiloxane material was obtained, and the NMR spectrum results are shown below. Figure 2 As shown.

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

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

[0053] Table 1. Data on amino polysiloxanes with different molecular weights and single-terminated dihydroxyl groups.

[0054] Sample name Mn / g-mol -1 ]] 25 / cP]]> ​ nD 25 ]]> 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] Following the process steps in Example 1, in step 3, the single-ended hydrogen-containing silicone oil α-(trimethylsilyl)-ω-dimethylsilylpolydimethylsiloxane was replaced with an equimolar mass of butyl-substituted single-ended hydrogen-containing silicone oil of formula M3. The other steps were the same to obtain α-butyl-ω-N,N-dihydroxyethylaminopropylpolydimethylsiloxane of formula II. The NMR spectrum of the product is shown below. Figure 3 As shown.

[0057]

[0058] Comparative Example 2

[0059] Following the process steps in Example 1, in step 3, the single-ended hydrogen-containing silicone oil α-(trimethylsilyl)-ω-dimethylsilylpolydimethylsiloxane was replaced with an equimolar mass of the double-ended hydrogen-containing silicone oil α,ω-dimethylsilylpolydimethylsiloxane shown in Formula M4. The other steps remained the same, yielding α,ω-N,N-dihydroxyethylaminopropylpolydimethylsiloxane as shown in Formula III. The NMR spectrum of the product is as follows. Figure 4 As shown.

[0060]

[0061] Application Example 1

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

[0063] Calculation and Testing:

[0064] Fabric cutting: Use machine-woven fabric and cut to the size of two A4 sheets of paper.

[0065] Impregnation: The cut woven fabric is immersed in the emulsion for 10 seconds. The wetted woven fabric is initially shaped by a padding machine through a one-dip-one-pad process. After shaping, the fabric is passed through a shaping machine and dried for 1 minute at a speed of 4 m / min. The fabric that has passed through the shaping machine is placed in a dry and dark place to rehydrate for 1 hour.

[0066] Testing: The whiteness of the rehydrated woven fabric will be tested, followed by tests on hydrophilicity, mechanical properties, etc.

[0067] Hydrophilicity test: Fix the rehydrated fabric sample onto a stretching loop. Use a dropper to drop a drop of water 1 cm above the fabric surface and start timing. Stop timing when the water droplet shrinks to a non-reflective watermark. Hydrophilicity can also be expressed by the water contact angle of the fabric after padding. Under the same padding process, compare the absorption time; the longer the absorption time, the worse the water absorption.

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

[0069] Whiteness test: After the fabric has been rolled and re-moistened, place it in a colorimeter for whiteness testing. Fold the fabric into four layers and test four times. The values ​​of the four tests are automatically averaged.

[0070] Antistatic test: A resistance electrostatic tester was used. Before the test, the instrument was preheated. The woven fabric after impregnation was cut into 45mm×45mm pieces and placed in an environment with a humidity of 29.6%RH and a temperature of 20.2℃ for 5 hours before the test.

[0071] The fabric properties after emulsion treatment with the polysiloxane prepared in Example 1 are shown in Table 2, where the original fabric refers to the untreated woven fabric. It can be seen that the static water absorption time of the fabric treated with the emulsion of single-terminated dihydroxyalkylamine polydimethylsiloxane (I) is in the range of 10-35 s. Compared with the static water absorption time of 180 s for the original fabric, the emulsion of single-terminated dihydroxyalkylamine polydimethylsiloxane (I) exhibits excellent hydrophilicity when applied to fabrics. The softness rating of the fabric treated with the emulsion of single-terminated dihydroxyalkylamine polydimethylsiloxane (I) is 3.2-4.2, which is a certain degree of improvement compared with the original fabric's 2.0.

[0072] The emulsification effect is influenced by the molecular weight of the silicone oil. Emulsification conditions for different molecular weights were investigated. When the molecular weight of the prepared single-terminated dihydroxylamine-modified polydimethylsiloxane was less than 1000 g / mol, poor adhesion to the fabric surface occurred, potentially leading to decreased wash resistance. At a molecular weight of approximately 5000 g / mol, emulsification became difficult, with excessively high viscosity during phase inversion, making it difficult to obtain a homogeneous emulsion and hindering effective padding of the fabric. Experimental results determined that the optimal molecular weight for the single-terminated dihydroxylamine-modified polysiloxane used is between 1000 and 5000 g / mol. -1 Within a certain range, fabrics with a uniform surface coating of single-ended dihydroxyalkylamine-modified polysiloxane can be tested for properties such as hydrophilicity and yellowing.

[0073] Table 2. Fabric properties of the emulsion prepared in Example 1 with a single-terminated dihydroxyalkylamine polydimethylsiloxane.

[0074]

[0075] Application Example 2

[0076] Following the process steps of Application Example 1, an emulsion of butyl-modified dihydroxyamino polysiloxane from Comparative Example 1 was prepared and applied to treat fabrics. The fabric test results 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 to α-methyl-ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane (I) in Example 1, the structurally inert methyl group at the end furthest from the fabric is changed to butyl, which has virtually no effect on the fabric's softness. However, differences in hydrophilicity and yellowing are observable. As shown in Table 3, the fabric treated with the butyl-modified dihydroxyaminopolydimethylsiloxane emulsion has a static water absorption time of less than 10 seconds. Compared to the fabric treated with the polysiloxane emulsion in Example 1 (Table 3), it exhibits better hydrophilicity than the original fabric, but worse water absorption than the fabric treated with the polysiloxane emulsion in Example 1. Its whiteness is also significantly worse than the original fabric and that of Example 1, and yellowing is very pronounced.

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

[0079]

[0080] Application Example 3

[0081] Following the process steps of Application Example 1, an emulsion of bi-terminated dihydroxyalkylamine polydimethylsiloxane (PDMS) from Comparative Example 2 was prepared and applied to treat fabrics. The fabric test results are shown in Table 4. Different sample names D in Table 4...OH -1~D OH -3 represents polydimethylsiloxane samples with different molecular weights, such as α,ω-N,N-dihydroxyethylaminopropyl polydimethylsiloxane (III).

[0082] As shown in Table 4, the static water absorption time of the fabric treated with the emulsion of dihydroxyalkylamine polydimethylsiloxane (III) is less than 20s. The emulsion applied to the fabric shows good hydrophilicity and improved softness compared to the original fabric.

[0083] Table 4 Fabric properties of dual-terminated dihydroxyalkylamine polydimethylsiloxane (III) emulsions

[0084]

[0085] In further investigation, the thermal stability of the Formula I single-terminated dihydroxyalkylamine polydimethylsiloxane prepared in Example 1 and the Formula III double-terminated dihydroxyalkylamine polydimethylsiloxane prepared in Comparative Example 2 were tested, and the results are as follows: Figure 5 As shown, T of the single-ended polysiloxane represented by Formula I 5％ The temperature at that time was 396℃, and the T of the double-ended polysiloxane shown in Formula III was... 5％ At 308℃, single-ended polysiloxanes exhibit superior thermal stability.

Claims

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

2. The single-terminal dihydroxyalkylamine-modified polysiloxane according to claim 1, characterized in that, The single-terminal dihydroxyamino-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 single-terminal dihydroxyalkylamine-modified polysiloxane according to claim 1 or 2, characterized in that, Including the following steps: Step 1: Diethanolamine and hexamethyldisilazane are refluxed to give bis[2-(trimethylsiloxy)ethyl]amine; Step 2: Allyl bromide is added dropwise to bis[2-(trimethylsiloxy)ethyl]amine, and the reaction continues to obtain N,N-bis[2-(trimethylsiloxy)ethyl]allylamine; Step 3: N,N-bis[2-(trimethylsiloxy)ethyl]allylamine and the single-ended hydrogen-containing silicone oil shown in Formula M2 are reacted via hydrosilylation to obtain α-methyl-ω-N,N-bis[2-(trimethylsiloxy)ethyl]aminopropyl polydimethylsiloxane, which is then deprotected by hydroxyl groups to obtain the single-ended dihydroxyalkylamine-modified polysiloxane shown in Formula I. Where n is a natural number ranging from 10 to 65.

4. The method for preparing single-terminal dihydroxylamine-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-(trimethylsiloxy)ethyl]allylamine to the Si-H group in the single-ended hydrogen-containing silicone oil shown in formula M2 is 1-1.2:

1.

5. The method for preparing single-terminal dihydroxyalkylamine-modified polysiloxane according to claim 3, characterized in that, The hydrosilylation reaction in step 3 includes a catalyst, which is a Castel catalyst.

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

7. The method for preparing single-terminal dihydroxyalkylamine-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-(trimethylsiloxy)ethyl]allylamine is first activated by a catalyst, and then single-ended hydrogen-containing silicone oil as shown in formula M2 is injected into the reaction system to continue the reaction and obtain the product.

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

9. An amino silicone oil emulsion, characterized in that, The raw material composition includes 1-5 parts of the single-ended dihydroxyalkylamine modified polysiloxane as described in claim 1 or 2, 0.1-2 parts of 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 process includes the following steps: mixing and inverting a single-ended dihydroxylamine-modified polysiloxane according to claim 1 or 2 with 0.1-2 parts of emulsifier, 0.1-0.5 parts of acetic acid and 5-10 parts of water; diluting the inverted emulsion with water at a mass ratio of 5-10:200 to obtain the amino silicone oil emulsion.

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