Polyester modified organic silicon softening agent as well as low-temperature synthesis method and application thereof

Abstract

The invention belongs to the technical field of fine chemical engineering, and particularly provides a polyester modified organic silicon softening agent and a low-temperature synthesis method and application of the polyester modified organic silicon softening agent. A carboxyl group-containing polyester; the modified dehydrating agent is obtained by modifying through a silane coupling agent; and a catalyst. The low-temperature synthesis method of the polyester modified organic silicon softener comprises the following step: carrying out reaction on hydroxyl-containing polysiloxane and carboxyl-containing polyester in the presence of a modified dehydrating agent and a catalyst at the reaction temperature not higher than 80 DEG C to obtain the polyester modified organic silicon softener. According to the softening agent, through the introduction of polyester, the yellowing phenomenon of the softening agent under a high-temperature condition is effectively avoided; meanwhile, by adding the polyester, the compatibility of the organic silicon softening agent and conventional resin is remarkably improved, higher softness and smoothness are given to the organic silicon softening agent, and the organic silicon softening agent can be widely applied to the fields of fibers, leather, textiles and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemicals, and particularly relates to a polyester-modified organosilicon softener and a low-temperature synthesis method and application thereof. Background Art

[0002] Silicone softeners are widely used in textile finishing and other fields due to their excellent softness, heat resistance and hydrophobic properties. Currently, traditional silicone softeners mainly include the following types: (1) amino silicone oil, which contains amino groups and can bind to the fiber surface to provide long-lasting softness; (2) hydroxy silicone oil, which contains hydroxy groups and is suitable for high-temperature setting processes and can be used on synthetic fiber products; (3) epoxy-modified silicone oil, which contains epoxy groups and can provide better water-washing resistance and outstanding antistatic properties.

[0003] However, these traditional silicone softeners have problems such as poor yellowing resistance and insufficient durability. In addition, many of them are prepared using high-temperature polycondensation processes, which have problems such as high energy consumption and many side reactions, which can easily lead to poor product stability and stiff fabric feel after application.

[0004] Polyester-modified silicone combines the high elasticity of polyester segments with the flexibility of silicone, and is biodegradable, offering great application potential and environmental friendliness. However, polyester-modified silicone is currently rarely used in textile finishing. This is partly because existing polyester modification technologies mostly rely on high-temperature reactions or complex catalytic systems, and silicone oil itself has poor compatibility with resin systems, which can easily lead to problems such as polyester segment degradation and uneven silicone cross-linking. Furthermore, the synthesis process of polyester-modified silicone often requires the use of toxic solvents, which significantly restricts the product's environmental friendliness and process economics. Furthermore, the development of low-temperature synthesis processes still faces technical bottlenecks, such as insufficient reaction activity and low functional group grafting efficiency, making it difficult to achieve low-temperature energy conservation while simultaneously maintaining a balance in product performance.

[0005] In summary, developing an efficient, environmentally friendly, low-temperature synthesis method to prepare polyester-modified silicone softeners with excellent softness, yellowing resistance, and good processing adaptability has become a key issue that urgently needs to be broken through in this field. Summary of the Invention

[0006] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a polyester-modified silicone softener and a low-temperature synthesis method and application thereof. The polyester-modified silicone softener provided by the present invention is synthesized by using carboxyl-containing polyester as a polyester modification raw material and hydroxyl-containing silicone oil as a silicone raw material. It has both the high elasticity of polyester segments and the compliance of silicone, and can give fabrics a good feel and slippery feel. On the other hand, the present invention has developed a method for preparing a silicone softener by copolymerizing carboxyl polyester and hydroxyl silicone oil under low temperature conditions. This method has the characteristics of low energy consumption and green environmental protection, and the prepared silicone softener has few by-products, excellent compatibility with conventional resin materials, excellent yellowing resistance, and is suitable for use in the fields of textiles, leather, and coatings, and has significant practical value.

[0007] To achieve this object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a polyester-modified silicone softener, wherein the raw materials for preparing the polyester-modified silicone softener include the following components: (a) a hydroxyl-containing polysiloxane containing at least one hydroxyl group; (b) a carboxyl-containing polyester containing at least one carboxyl group; (c) a modified dehydrating agent, which is obtained by modification with a silane coupling agent; (d) Catalyst.

[0008] Hydroxyl silicone oil and carboxyl polyester serve as the primary reactive monomers, a silane coupling agent-modified dehydrating agent is used to promote carboxylic acid condensation and improve the system's compatibility, and a catalyst is used to regulate reaction activity. The polyester-modified silicone softener prepared using these raw materials contains few byproducts and exhibits excellent softness, yellowing resistance, and hand feel, as well as good compatibility with other resins.

[0009] Preferably, the molar ratio between the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1: (0.2-8): (1-8.8): (0.001-0.8); Among them, (0.2~8) can take values ​​of 0.3, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, etc.; Among them, (1~8.8) can take values ​​of 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, etc.; Among them, (0.001~0.8) can take values ​​of 0.005, 0.008, 0.01, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, etc.

[0010] More preferably, the molar ratio of the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1:(0.2-4):(1-4.4):(0.004-0.1).

[0011] More preferably, the molar ratio of the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1:(0.2-2):(1-4.4):(0.004-0.1).

[0012] Preferably, the carboxyl-containing polyester comprises carboxyl-containing polycaprolactone.

[0013] Preferably, the molecular weight of the carboxyl-containing polycaprolactone is 1000~8000g / mol; for example, it can be 1500g / mol, 2000g / mol, 2500g / mol, 3000g / mol, 3500g / mol, 4000g / mol, 4500g / mol, 5000g / mol, 5500g / mol, 6000g / mol, 6500g / mol, 7000g / mol, 7500g / mol, 7500g / mol, etc.

[0014] Preferably, the carboxyl-containing polycaprolactone includes one or more of monocarboxyl polycaprolactone, dicarboxyl polycaprolactone and polycarboxyl polycaprolactone.

[0015] Preferably, the silane coupling agent comprises epoxy-containing silane.

[0016] Preferably, the epoxy group-containing silane includes γ-glycidyloxypropyltrimethoxysilane and / or γ-glycidyloxypropyltriethoxysilane.

[0017] Preferably, the modified dehydrating agent comprises a modified carbodiimide dehydrating agent.

[0018] Preferably, the modified dehydrating agent comprises modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) and / or modified N,N'-dicyclohexylcarbodiimide (DCC).

[0019] Preferably, the hydroxyl-containing polysiloxane includes one or more of monohydroxyl polysiloxane, dihydroxyl polysiloxane and polyhydroxyl polysiloxane.

[0020] Preferably, the molecular weight of the monohydroxy polysiloxane is 500-3500 g / mol; for example, it can be 800 g / mol, 1000 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2500 g / mol, 3000 g / mol, 3200 g / mol, etc.

[0021] More preferably, the molecular weight of the monohydroxy polysiloxane is 1300-3000 g / mol.

[0022] Preferably, the molecular weight of the dihydroxy polysiloxane is 1500-6000 g / mol; for example, it can be 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, 5500 g / mol, etc.

[0023] Preferably, the molecular weight of the polyhydroxy polysiloxane is 3000~20000 g / mol, for example, it can be 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, 5500 g / mol, 6000 g / mol, 6500 g / mol, 7000 g / mol, 7500 g / mol, 8000 g / mol, 8500 g / mol, 9000 g / mol, 9500 g / mol, 10000 g / mol, 15000 g / mol, 18000 g / mol, etc.

[0024] Preferably, the catalyst comprises an organic base catalyst.

[0025] Preferably, the catalyst comprises any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, stannous chloride dihydrate, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2.2.2]octane, N-methylimidazole and tetramethylguanidine.

[0026] More preferably, the catalyst comprises a combination of any one or more of pyridine, 4-dimethylaminopyridine, stannous chloride dihydrate, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2.2.2]octane, N-methylimidazole and tetramethylguanidine and triethylamine.

[0027] In a second aspect, the present invention provides a low-temperature synthesis method for the above-mentioned polyester-modified silicone softener, the method comprising the following steps: The hydroxyl-containing polysiloxane and the carboxyl-containing polyester are reacted in the presence of a modified dehydrating agent and a catalyst at a reaction temperature not higher than 80° C. to obtain the polyester-modified organic silicone softener.

[0028] The present invention uses a silane coupling agent to modify the dehydrating agent, resulting in a modified dehydrating agent that significantly improves the compatibility of the system and promotes the polycondensation reaction. In combination with the modified dehydrating agent and catalyst, hydroxyl-containing polysiloxane and carboxyl-containing polyester achieve efficient copolymerization under low-temperature conditions.

[0029] Preferably, the reaction temperature is 40-80°C, for example, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, etc.

[0030] Preferably, the reaction time is 4 to 10 h; for example, it can be 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, etc.

[0031] Preferably, the method further comprises the following steps: filtering the mixed solution after the reaction is completed while hot, collecting the filtrate, and obtaining the polyester-modified silicone softener.

[0032] Preferably, the modification method of the modified dehydrating agent comprises the following steps: preparing a pre-hydrolysis product from a silane coupling agent, ethanol and acetic acid, mixing the pre-hydrolysis product and the dehydrating agent, and then performing stirring, heating, ultrasonication, aging, filtering, washing and drying steps to obtain the modified dehydrating agent.

[0033] Preferably, the mass ratio between the silane coupling agent and the dehydrating agent is 1:(1.2-1.5).

[0034] Preferably, the stirring and heating temperature is 35-40° C., and the stirring and heating time is 1-2 h.

[0035] In a third aspect, the present invention provides a use of the polyester-modified silicone softener or the polyester-modified silicone softener obtained by the low-temperature synthesis method as an auxiliary agent or textile finishing agent.

[0036] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The present invention uses carboxyl-containing polyester and hydroxyl silicone oil as synthetic monomers, and obtains a polyester-modified silicone softener having both polyester segments and silicone segments in the presence of a modified dehydrating agent and a catalyst. The polyester segment has high elasticity, heat stability and excellent compatibility, so that the prepared silicone softener not only has softness, but also has good yellowing resistance and compatibility, and has extremely high practical value.

[0037] 2. The present invention uses carboxyl polyester and hydroxy silicone oil to prepare silicone softener under low temperature conditions below 80 degrees. Since high temperature reaction is avoided, it not only reduces energy consumption, but also reduces the risk of by-products and uneven reaction problems; it also overcomes the problems of insufficient reaction activity and low functional group grafting efficiency, achieving low temperature reaction while ensuring product performance. DETAILED DESCRIPTION

[0038] The technical scheme of the present invention is further described below by specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention. Unless otherwise specified, the raw materials and methods used in the following examples are all raw materials and methods well known in the art.

[0039] The following hydroxyl-containing polysiloxane is sourced from Guangzhou Siloke New Materials Co., Ltd.

[0040] Synthesis example 1 This synthesis example provides a preparation method of KH560 modified N,N'-dicyclohexylcarbodiimide (DCC), which comprises the following steps: 100 g of KH560 was mixed with ethanol / acetic acid buffer solution (pH = 5.0-6.0) in a volume ratio of 1:10, and then stirred at 40 ° C for 40 min to complete partial hydrolysis. Subsequently, 135 g of DCC powder was slowly added to the above hydrolysis solution (controlled at 35 ° C). After stirring evenly, it was ultrasonically treated for 20 min and then allowed to stand for 2 h. The aged reaction solution was vacuum filtered and the filter residue was washed three times with ethanol. The filter residue was then dried in a vacuum environment at 40 ° C for 2 h to obtain white KH560-modified N, N'-dicyclohexylcarbodiimide (DCC) powder.

[0041] Synthesis example 2 This synthesis example provides a preparation method of KH560 modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC), which comprises the following steps: 100 g of KH560 was mixed with ethanol / acetic acid buffer solution (pH = 5.0-6.0) in a volume ratio of 1:10, and then stirred at 40 ° C for 40 minutes to complete partial hydrolysis. Subsequently, 123 g of EDC.HCl powder was slowly added to the above hydrolysis solution (the temperature was controlled at 35 ° C). After stirring evenly, it was ultrasonically treated for 30 minutes and then allowed to stand for 1 hour. The obtained reaction solution was vacuum filtered and the filter residue was washed three times with ethanol. The filter residue was then dried in a vacuum environment at 40 ° C for 2 hours to obtain white KH560-modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) powder.

[0042] The silane coupling agent-modified N,N'-dicyclohexylcarbodiimide (DCC) and the silane coupling agent-modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) used in the following examples are KH560-modified N,N'-dicyclohexylcarbodiimide (DCC) obtained in Synthesis Example 1 and KH560-modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) obtained in Synthesis Example 2, respectively. Example 1

[0043] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 0.5 mol monohydroxy silicone oil (Guangzhou Silok 8861), 0.5 mol monocarboxyl polycaprolactone (Anhui Huaihai Biological, HPA-001), 0.6 mol silane coupling agent modified N, N'-dicyclohexylcarbodiimide (DCC), 0.025 mol triethylamine (TEA) and 0.025 mol 4-dimethylaminopyridine (DMAP).

[0044] The preparation method of the polyester modified silicone softener comprises the following steps: Monohydroxy silicone oil (Silok 8861, Guangzhou), monocarboxyl polycaprolactone (HPA-001, Anhui Huaihai Biological), silane coupling agent modified DCC, triethylamine (TEA) and 4-dimethylaminopyridine (DMAP) were mixed evenly, stirred, and the system was slowly heated to 40°C and kept warm for 4 hours. After the reaction was completed, insoluble impurities were filtered out to obtain a polyester-modified silicone softener. Example 2

[0045] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 1 mol monohydroxy silicone oil (Silok 8861, Guangzhou), 0.5 mol dicarboxyl polycaprolactone (HPA-002, Anhui Huaihai Biological), 1.2 mol silane coupling agent modified DCC, 0.05 mol triethylamine (TEA) and 0.05 mol 1,8-diazabicycloundec-7-ene (DBU).

[0046] The preparation method of the polyester modified silicone softener comprises the following steps: Monohydroxy silicone oil (Silok 8861, Guangzhou), dicarboxyl polycaprolactone (HPA-002, Anhui Huaihai Biological), silane coupling agent modified DCC, triethylamine (TEA) and 1,8-diazabicycloundec-7-ene (DBU) were mixed evenly, stirred, and the system was slowly heated to 60 °C and kept warm for 6.5 h. After the reaction was completed, insoluble impurities were removed by filtration to obtain a polyester-modified silicone softener. Example 3

[0047] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 0.5 mol dihydroxy silicone oil (Silok 8812 F2, Guangzhou), 1.0 mol monocarboxyl polycaprolactone (HPA-002, Anhui Huaihai Biological), 2.2 mol silane coupling agent modified DCC, 0.005 triethylamine (TEA) and 0.005 g tetramethylguanidine (TMG).

[0048] The preparation method of the polyester modified silicone softener comprises the following steps: Dihydroxy silicone oil (Silok 8812 F2, Guangzhou), monocarboxyl polycaprolactone (HPA-001, Anhui Huaihai Biological), silane coupling agent modified DCC, triethylamine (TEA) and tetramethylguanidine (TMG) were mixed evenly, stirred, and the system was slowly heated to 50 °C and kept warm for 5 h. After the reaction was completed, insoluble impurities were filtered out to obtain a polyester-modified silicone softener. Example 4

[0049] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 0.5 mol dihydroxy silicone oil (Guangzhou Silok 8812 F2), 0.5 mol monocarboxyl polycaprolactone (Anhui Huaihai Biological, HPA-001), 1.2 mol silane coupling agent modified 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC), 0.001 mol pyridine and 0.001 mol 4-dimethylaminopyridine (DMAP).

[0050] The preparation method of the polyester modified silicone softener comprises the following steps: Monohydroxy silicone oil (Silok 8812 F2, Guangzhou), monocarboxyl polycaprolactone (HPA-001, Anhui Huaihai Biological), silane coupling agent modified EDC, pyridine and 4-dimethylaminopyridine (DMAP) were mixed evenly, stirred, and the system was slowly heated to 45°C and kept warm for 5.5 hours. After the reaction was completed, insoluble impurities were filtered out to obtain a polyester-modified silicone softener. Example 5

[0051] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 0.5 mol monohydroxy silicone oil (Guangzhou Silok 8841), 0.1 mol tetracarboxyl polycaprolactone (Anhui Huaihai Biological, HPA-004), 0.5 mol silane coupling agent modified EDC, 0.001 mol pyridine and 0.001 mol stannous chloride dihydrate (SnCl2.2H2O).

[0052] The preparation method of the polyester modified silicone softener comprises the following steps: Monohydroxy silicone oil (Silok 8841, Guangzhou), tetracarboxyl polycaprolactone (HPA-004, Anhui Huaihai Biological), silane coupling agent modified EDC, pyridine and stannous chloride dihydrate (SnCl2.2H2O) were mixed evenly, stirred, and the system was slowly heated to 70°C and kept warm for 8 hours. After the reaction was completed, insoluble impurities were filtered out to obtain a polyester-modified silicone softener. Example 6

[0053] This embodiment provides a polyester-modified silicone softener, the raw materials for its preparation include: 0.5 mol polyhydroxy silicone oil (Guangzhou Silok 8827 F4), 0.12 mol dicarboxyl polycaprolactone (Anhui Huaihai Biological, HPA-002), 0.75 mol silane coupling agent modified DCC, 0.002 mol 1,4-diazabicyclo[2.2.2]octane (DABCO) and 0.002 mol 4-dimethylaminopyridine (DMAP).

[0054] The preparation method of the polyester modified silicone softener comprises the following steps: Monohydroxy silicone oil (Silok 8827 F4, Guangzhou), dicarboxyl polycaprolactone (HPA-002, Anhui Huaihai Biological), silane coupling agent modified DCC, 1,4-diazabicyclo[2.2.2]octane (DABCO) and 4-dimethylaminopyridine (DMAP) were mixed evenly, stirred, and the system was slowly heated to 80°C and kept warm for 8 hours. After the reaction was completed, the insoluble impurities were filtered out to obtain a polyester-modified silicone softener. Example 7

[0055] The only difference between this embodiment and embodiment 1 is that the monohydroxy silicone oil in this embodiment is replaced with monohydroxy silicone oil (Silok 8871) of the same molar number. Example 8

[0056] The only difference between this embodiment and embodiment 1 is that the monohydroxy silicone oil in this embodiment is replaced with monohydroxy silicone oil (Silok 8821 F2) of the same molar number. Example 9

[0057] The only difference between this example and Example 1 is that the catalyst used in the preparation of this example does not contain triethylamine (TEA), and triethylamine is replaced by an equal molar amount of 4-dimethylaminopyridine, while the amounts of other raw materials remain unchanged. Example 10

[0058] The only difference between this embodiment and embodiment 1 is that the carboxyl-modified polyester used in this embodiment is monocarboxyl poly (neopentyl adipate) with the same molecular weight. Example 11

[0059] The only difference between this embodiment and embodiment 1 is that the carboxyl-modified polyester used in this embodiment is monocarboxyl poly(hexanediol adipate) of the same molecular weight. Example 12

[0060] The only difference between this embodiment and embodiment 1 is that the amount of carboxyl-modified polycaprolactone added in this embodiment is changed to 4 mol.

[0061] Comparative Example 1 The only difference between this comparative example and Example 1 is that the dehydrating agent used in this comparative example is N,N'-dicyclohexylcarbodiimide (DCC) which has not been modified with KH560, and the weights and amounts of other raw materials remain unchanged.

[0062] Comparative Example 2 The only difference between this comparative example and Example 1 is that in this comparative example, the carboxyl-modified polycaprolactone is replaced by a styrene-maleic anhydride copolymer SMA50 (Shenzhen Pasteur New Material Technology Co., Ltd.) with the same molar amount of carboxyl groups.

[0063] Comparative Example 3 The only difference between this comparative example and Example 1 is that the reaction temperature of the system is changed to 100°C in this comparative example.

[0064] Application Examples 1 to 12 A fabric coating finishing agent comprises 1 g of the polyester silicone softener obtained in Examples 1 to 12, 100 g of solvent-based polyurethane (Guangzhou Siluoke New Materials, CJ-10), and 0.1 g of a thickener.

[0065] Comparative Application Examples 1~3 A fabric coating finishing agent comprises 1 g of the polyester silicone softener obtained in Comparative Examples 1 to 3, 100 g of solvent-based polyurethane (Guangzhou Siluoke New Materials, CJ-10), and 0.1 g of a thickener.

[0066] Performance testing: 1 g of the polyester silicone softener obtained in Examples 1 to 12 and Comparative Examples 1 to 3, 100 g of solvent-based polyurethane (Guangzhou Siluoke New Materials, CJ-10) and 0.1 g of thickener were mixed to prepare a fabric finishing coating. After air bubbles were removed by ultrasonication, the coating was treated on cotton fabric according to the following finishing process: coating (coating thickness: 10 μm) - baking (30 min, 60°C), and the following tests were performed. The specific test methods are as follows: (1) Softness: Cut the treated fabric into 10×10 cm size and measure the softness using a computer softness meter. The smaller the test force required, the better the softness of the fabric.

[0067] (2) Yellowing resistance: Test the fabric samples according to GB / T 30669-2014 “Textiles—Tests for colour fastness—Colour fastness to yellowing from light”.

[0068] (3) Friction resistance: The treated fabric was cut into 30 mm × 28 mm and 30 mm × 77 mm sizes. The long sample was placed in the clamp of the basic workbench, and the short sample was covered on top with the same fabric surface direction. The friction performance of the fabric was tested using a YG821L style meter under the conditions of temperature (22 ± 2°C) and relative humidity 68% ± 2%.

[0069] The specific test results are shown in Table 1, and the fabric sample not treated with polyester modified silicone softener was used as a blank sample for comparison.

[0070] Table 1

[0071] As can be seen from the data in Table 1, the polyester-modified silicone softener provided in the embodiments of the present invention, prepared via a low-temperature synthesis process, can impart excellent softness, yellowing resistance, and smoothness to textiles when applied to textile finishing. This softener has broad application prospects in the field of textile softening and finishing. It is suitable for use with a variety of fiber materials, such as cotton, linen, silk, and chemical fibers, significantly improving fabric quality and wearing comfort. It provides a new technological option for the textile finishing industry, driving the industry's development towards high-performance, environmentally friendly products.

[0072] It can be seen from Example 1 of the present invention and Comparative Example 1 that when unmodified N,N'-dicyclohexylcarbodiimide (DCC) is used as a dehydrating agent, all properties of the obtained polyester silicone softener are degraded.

[0073] It can be seen from Example 1 of the present invention and Comparative Example 2 that the performance of the polyester silicone softener obtained by using non-polyester raw materials for modification is reduced in various aspects.

[0074] The applicant states that the present invention specifically illustrates the polyester-modified silicone softener, its low-temperature synthesis method, and its application through the aforementioned embodiments. However, the present invention is not limited to the aforementioned embodiments, nor does it necessarily rely on these specific examples for implementation. Those skilled in the art should understand that any improvements to the present invention, including but not limited to equivalent substitutions of raw materials, addition of auxiliary components, and selection of specific implementation methods, should be considered part of the scope of protection and disclosure of the present invention.

Claims

1. A polyester modified silicone softener, characterized in that: The raw materials for preparing the polyester modified silicone softener include the following components: (a) a hydroxyl-containing polysiloxane containing at least one hydroxyl group; (b) a carboxyl-containing polyester containing at least one carboxyl group; (c) a modified dehydrating agent, which is obtained by modification with a silane coupling agent; (d) Catalyst.

2. The polyester modified silicone softener according to claim 1, characterized in that: The molar ratio of the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1: (0.2-8): (1-8.8): (0.001-0.8); Preferably, the molar ratio between the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1:(0.2-4):(1-4.4):(0.004-0.1); More preferably, the molar ratio of the hydroxyl-containing polysiloxane, the carboxyl-containing polyester, the modified dehydrating agent and the catalyst is 1:(0.2-2):(1-4.4):(0.004-0.1).

3. The polyester modified silicone softener according to claim 1, characterized in that: The carboxyl-containing polyester includes carboxyl-containing polycaprolactone; Preferably, the molecular weight of the carboxyl-containing polycaprolactone is 1000-8000 g / mol; Preferably, the carboxyl-containing polycaprolactone includes one or more of monocarboxyl polycaprolactone, dicarboxyl polycaprolactone and polycarboxyl polycaprolactone.

4. The polyester modified silicone softener according to claim 1, characterized in that The silane coupling agent includes epoxy-containing silane; Preferably, the epoxy-containing silane comprises γ-glycidyloxypropyltrimethoxysilane and / or γ-glycidyloxypropyltriethoxysilane; Preferably, the modified dehydrating agent comprises a modified carbodiimide dehydrating agent.

5. The polyester modified silicone softener according to claim 1, characterized in that: The hydroxyl-containing polysiloxane includes one or more of monohydroxy polysiloxane, dihydroxy polysiloxane, and polyhydroxy polysiloxane; Preferably, the molecular weight of the monohydroxy polysiloxane is 500-3500 g / mol; more preferably 1300-3000 g / mol; Preferably, the molecular weight of the dihydroxy polysiloxane is 1500-6000 g / mol; Preferably, the molecular weight of the polyhydroxy polysiloxane is 3000-20000 g / mol.

6. The polyester modified silicone softener according to claim 1, characterized in that: The catalyst includes an organic base catalyst; Preferably, the catalyst comprises any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, stannous chloride dihydrate, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2.2.2]octane, N-methylimidazole and tetramethylguanidine; More preferably, the catalyst comprises a combination of any one or more of pyridine, 4-dimethylaminopyridine, stannous chloride dihydrate, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2.2.2]octane, N-methylimidazole and tetramethylguanidine and triethylamine.

7. A low-temperature synthesis method for a polyester-modified silicone softener according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: The hydroxyl-containing polysiloxane and the carboxyl-containing polyester are reacted in the presence of a modified dehydrating agent and a catalyst at a reaction temperature not higher than 80° C. to obtain the polyester-modified organic silicone softener.

8. The method according to claim 7, characterized in that The reaction temperature is 40-80°C, and the reaction time is 4-10 h; Preferably, the method further comprises the following steps: filtering the mixed solution after the reaction is completed while hot, collecting the filtrate, and obtaining the polyester-modified silicone softener.

9. The method according to claim 7, characterized in that The modification method of the modified dehydrating agent comprises the following steps: preparing a pre-hydrolyzed product from a silane coupling agent, ethanol and acetic acid, mixing the pre-hydrolyzed product with a dehydrating agent, and sequentially performing stirring and heating, ultrasonication, aging, filtering, washing and drying steps to obtain the modified dehydrating agent; Preferably, the stirring and heating temperature is 35-40°C, and the stirring and heating time is 1-2 h; Preferably, the mass ratio between the silane coupling agent and the dehydrating agent is 1:(1.2-1.5).

10. Use of the polyester-modified silicone softener according to claims 1 to 6 or the polyester-modified silicone softener prepared by the low-temperature synthesis method according to claims 7 to 9 in textile finishing, fiber or leather.

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