Organic silicon copolymer, preparation method, foam stabilizer and polyurethane shoe sponge

Abstract

The invention discloses an organosilicon copolymer, a preparation method, a foam stabilizer and a polyurethane shoe sponge, and relates to the technical field of organosilicon surfactants. The structural formula of the organosilicon copolymer is as follows: wherein m is 1-10, n is 1-4, and m+n is 2-14; the chemical structural formula of R1 is as follows: -CH2CH2CH2(OCH2CH2) a (OCH2CHCH3) b R2; wherein a is 1-10, b is 1-6; the chemical structure of R2 is as follows: The present invention not only provides antifungal properties for the organosilicon copolymer by introducing allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether and limiting the values ​​of m, n, a and b, but also improves the pore size and pore complex structure of the polyurethane shoe sponge, thereby improving the air permeability of the polyurethane shoe sponge. The above-mentioned organosilicon copolymer can be widely used in the preparation of foam stabilizers.

Description

Technical Field

[0001] The invention relates to the technical field of organosilicon surfactants, and in particular to an organosilicon copolymer, a preparation method, a foam stabilizer and a polyurethane shoe sponge. Background Art

[0002] The traditional production of insoles is a molding process, and the density of the insoles is generally 300kg / m 3 Although it has good elasticity and comfort, its breathability is very poor.

[0003] Polyurethane materials have excellent physical and processing properties and are widely used in footwear. Polyurethane insoles have better rebound force, compression resistance and shock absorption. For example, polyurethane insoles with arch support completely support the arch of the foot, which can improve physiological characteristics, be soft and comfortable, and greatly reduce fatigue or pain when walking. However, with the improvement of living standards, people have higher and higher requirements for polyurethane insoles. On the premise of meeting the basic load-bearing requirements of insoles, they must also be lightweight (density between 100-150kg / m 3 Between), high resilience, sweat absorption and breathability, mildew and antibacterial, and washable performance.

[0004] Invention patent CN116731503A relates to a polyurethane sponge for shoe materials and a preparation method thereof. In order to make the shoe sponge have antibacterial properties, an antibacterial agent is invented by reacting polyhexamethyleneguanidine hydrochloride with terminal carboxyl hyperbranched polyester and then reacting with zinc ions and calcium ions. The polyurethane shoe material prepared by adding the antibacterial agent has improved antibacterial ability, but the added antibacterial agent is prone to migration, causing a decrease in antibacterial performance; and the antifungal ability of polyhexamethyleneguanidine hydrochloride is weak.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The purpose of the present invention is to provide an organosilicon copolymer, a preparation method, a foam stabilizer and a polyurethane shoe sponge.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides an organosilicon copolymer, the structural formula of which is as follows:

[0009]

[0010] Wherein, m is 1-10, n is 1-4, and m+n is 2-14;

[0011] The chemical structure of R1 is as follows: -CH2CH2CH2(OCH2CH2) a (OCH2CHCH3) bR2; wherein a is 1-10, and b is 1-6;

[0012] The chemical structure of R2 is:

[0013]

[0014] In a second aspect, the present invention provides a method for preparing an organosilicon copolymer as described in the aforementioned embodiment, comprising: reacting allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether with hydrogen-containing silicone oil to form an organosilicon copolymer.

[0015] In an optional embodiment, the preparation method of the allyl-terminated triazole polyoxyethylene polyoxypropylene ether comprises: reacting triazole, ethylene oxide and propylene oxide to obtain triazole polyoxyethylene polyoxypropylene ether; reacting the triazole polyoxyethylene polyoxypropylene ether with propylene monochloride to obtain the allyl-terminated triazole polyoxyethylene polyoxypropylene ether;

[0016] Preferably, the oxadiazole includes any one of diniconazole, tebuconazole and hexaconazole.

[0017] In an optional embodiment, the step of reacting azodiazole, ethylene oxide and propylene oxide comprises: adding the azodiazole and the first catalyst into a reaction kettle, introducing the ethylene oxide and the propylene oxide and reacting them at 110-130° C. for 1-5 hours to obtain the azodiazole polyoxyethylene polyoxypropylene ether;

[0018] Preferably, the molar ratio of the oxadiazole, the ethylene oxide and the propylene oxide is 1:(1-10):(1-6);

[0019] Preferably, the first catalyst comprises at least one of sodium hydroxide and potassium hydroxide;

[0020] Preferably, the amount of the first catalyst is 0.2-0.5% of the total mass of the oxadiazole, the ethylene oxide and the propylene oxide;

[0021] Preferably, the molecular weight of the azodiazole polyoxyethylene polyoxypropylene ether is 400-1200 g / mol.

[0022] In an optional embodiment, the step of reacting the azolidinone polyoxyethylene polyoxypropylene ether with the monochloropropylene comprises: adding the azolidinone polyoxyethylene polyoxypropylene ether and a second catalyst into a reaction kettle, introducing the monochloropropylene at 30-60° C., and reacting for 1-5 hours to obtain the allyl-terminated azolidinone polyoxyethylene polyoxypropylene ether;

[0023] Preferably, the second catalyst comprises at least one of sodium, potassium and sodium hydride;

[0024] Preferably, the molar ratio of the azodiazole polyoxyethylene polyoxypropylene ether to the second catalyst is 1:0.9-1.1;

[0025] Preferably, the molar ratio of the azolidinone polyoxyethylene polyoxypropylene ether to the monochloropropylene is 1:1-1.5.

[0026] In an optional embodiment, after the azolidinone polyoxyethylene polyoxypropylene ether reacts with the monochloropropylene, the process further comprises adsorbing and filtering the reactants using an adsorbent to obtain the azolidinone polyoxyethylene polyoxypropylene ether terminated with the allyl group;

[0027] Preferably, the adsorbent is at least one of magnesium silicate, aluminum silicate and diatomaceous earth;

[0028] Preferably, the amount of the adsorbent used is 0.5-2% of the total mass of the azolidinone polyoxyethylene polyoxypropylene ether and the monochloropropylene.

[0029] In an optional embodiment, the step of reacting the allyl-terminated triazole polyoxyethylene polyoxypropylene ether with the hydrogen-containing silicone oil comprises: reacting the hydrogen-containing silicone oil, the allyl-terminated triazole polyoxyethylene polyoxypropylene ether and a third catalyst at 80-130° C. for 2-5 hours;

[0030] Preferably, the molar ratio of the allyl bond in the allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether to the silicon-hydrogen bond in the hydrogen-containing silicone oil is 1.3-1.8:1;

[0031] Preferably, the hydrogen-containing silicone oil is low-hydrogen-containing silicone oil;

[0032] Preferably, the hydrogen content in the hydrogen-containing silicone oil is 0.2-0.4%;

[0033] Preferably, the third catalyst is a metal catalyst, preferably a chloroplatinic acid catalyst;

[0034] Preferably, the third catalyst is used in an amount of 10-20 ppm of the total mass of the allyl-terminated azoles polyoxyethylene polyoxypropylene ether and the hydrogen-containing silicone oil.

[0035] In a third aspect, the present invention provides a foam stabilizer, which includes the organosilicon copolymer as described in the aforementioned embodiment or the organosilicon copolymer prepared by the preparation method of the organosilicon copolymer as described in any one of the aforementioned embodiments.

[0036] In a fourth aspect, the present invention provides a polyurethane shoe sponge, which is prepared by using the foam stabilizer as described in the above embodiment.

[0037] In an optional embodiment, the foam stabilizer is added in an amount of 1-3% of the total mass of the polyurethane shoe sponge.

[0038] The present invention has the following beneficial effects:

[0039] The organosilicon copolymer provided by the present invention is introduced into the side chain of hydrogen silicone oil by introducing the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether. The present invention defines the m of the organosilicon copolymer as 1-10, n as 1-4, and further defines the values ​​of polyoxyethylene and polyoxypropylene in the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether, so that the organosilicon copolymer has a good comb-shaped structure. In the present invention, by utilizing the H in the -OH of dinadiazole, tebuconazole or hexaconazole to be grafted onto the polyoxyethylene polyoxypropylene ether, an excellent antifungal effect can be provided for the organosilicon copolymer. Moreover, the introduction of the R2 group not only provides antifungal properties for the organosilicon copolymer, but also, since dinadiazole, tebuconazole or hexaconazole all have good hydrophobicity and complex stereo configuration, it can further improve the pore size and pore complex structure of the polyurethane shoe sponge, thereby improving the air permeability of the polyurethane shoe sponge. The preparation method of the organosilicon copolymer provided by the present invention is to prepare azodiazole polyoxyethylene polyoxypropylene ether by first using azodiazole, ethylene oxide and propylene oxide, then allyl-terminate the azodiazole polyoxyethylene polyoxypropylene ether, and finally graft the allyl-terminated azodiazole polyoxyethylene polyoxypropylene ether onto hydrogen-containing silicone oil. In the present invention, by introducing azodiazole, excellent antifungal effect can be provided for the organosilicon copolymer. The preparation method of the organosilicon copolymer provided by the present invention is simple and easy to implement. The above-mentioned organosilicon copolymer can be widely used in the preparation of foam stabilizers. The polyurethane shoe sponge prepared by the foam stabilizer has good antibacterial properties and air permeability. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0041] The present invention provides an organosilicon copolymer, the structural formula of which is as follows:

[0042]

[0043] Wherein, m is 1-10, n is 1-4, and m+n is 2-14;

[0044] The chemical structure of R1 is as follows: -CH2CH2CH2(OCH2CH2) a (OCH2CHCH3) b R2; wherein a is 1-10, and b is 1-6;

[0045] The chemical structure of R2 is:

[0046]

[0047] The chemical structure of R2 is that H in -OH of diniconazole, tebuconazole or hexaconazole is grafted onto polyoxyethylene polyoxypropylene ether, wherein diniconazole, tebuconazole or hexaconazole are all used as bactericides to provide excellent antifungal effect for the silicone copolymer.

[0048] The structural formula of diniconazole is It is a systemic broad-spectrum fungicide with protective, therapeutic and eradication effects; it inhibits 14α-demethylation in the biosynthesis of ergosterol in fungi and acts on the fungal cell membrane, thereby exerting a bactericidal effect.

[0049] The structural formula of tebuconazole is It is a highly effective, broad-spectrum, systemic triazole fungicide with three functions: protection, treatment, and eradication. It has a broad fungicide spectrum and a long lasting effect. Like all triazole fungicides, tebuconazole can inhibit the biosynthesis of ergosterol in fungi.

[0050] The structural formula of hexaconazole is It is a triazole fungicide and a sterol demethylation inhibitor. It has a broad spectrum of protective and therapeutic effects on fungi, especially diseases caused by Basidiomycetes and Ascomycetes. It destroys and prevents the biosynthesis of ergosterol, an important component of the cell membrane of pathogens, resulting in the inability to form cell membranes and the death of pathogens.

[0051] In the present invention, by introducing allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether on the side chain of hydrogen-containing silicone oil, the present invention defines m of the silicone copolymer as 1-10, n as 1-4, and further defines the values ​​of polyoxyethylene and polyoxypropylene in the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether, so that the silicone copolymer has a good comb-shaped structure. In the present invention, by utilizing the H in the -OH of oxadiazole, tebuconazole or hexaconazole to be grafted onto the polyoxyethylene polyoxypropylene ether, an excellent antifungal effect can be provided for the silicone copolymer. Moreover, the introduction of the R2 group not only provides antifungal properties for the silicone copolymer, but also, since oxadiazole, tebuconazole or hexaconazole all have good hydrophobicity and complex stereo configuration, they can further increase the pore size and pore complex structure of the polyurethane shoe sponge, thereby increasing the air permeability of the polyurethane shoe sponge.

[0052] The present invention also provides a method for preparing the above-mentioned organosilicon copolymer, which comprises: reacting allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether with hydrogen-containing silicone oil to form the organosilicon copolymer.

[0053] The specific steps include:

[0054] (1) Preparation of oxadiazole polyoxyethylene polyoxypropylene ether.

[0055] The oxadiazole, ethylene oxide and propylene oxide are reacted to prepare the oxadiazole polyoxyethylene polyoxypropylene ether.

[0056] Specifically, azodiazole and a first catalyst are added into a reaction kettle, and ethylene oxide and propylene oxide are introduced to react at 110-130° C. for 1-5 hours to obtain azodiazole polyoxyethylene polyoxypropylene ether with a molecular weight of 400-1200 g / mol;

[0057] Among them, the oxadiazoles include any one of diniconazole, tebuconazole and hexaconazole. Diniconazole, tebuconazole and hexaconazole are all common antibacterial agents. By preparing oxadiazole polyoxyethylene polyoxypropylene ether, good antifungal properties can be provided for the subsequent silicone copolymer.

[0058] The molar ratio of azodiazole, ethylene oxide and propylene oxide is 1:(1-10):(1-6). By limiting the above molar ratio, the amount of azodiazole, ethylene oxide and propylene oxide in the azodiazole polyoxyethylene polyoxypropylene ether can be limited, thereby regulating the molecular structure of azodiazole, ethylene oxide and propylene oxide, which is beneficial to regulating the structure of the subsequent organosilicon copolymer, thereby obtaining better air permeability.

[0059] The first catalyst includes but is not limited to at least one of sodium hydroxide and potassium hydroxide; the dosage of the first catalyst is 0.2-0.5% of the total mass of oxadiazole, ethylene oxide and propylene oxide; in the present invention, the first catalyst is used to catalyze the reaction of oxadiazole, ethylene oxide and propylene oxide, and the catalytic effect is good.

[0060] (2) Preparation of allyl-terminated azoles polyoxyethylene polyoxypropylene ether.

[0061] The oxadiazole polyoxyethylene polyoxypropylene ether is reacted with propylene monochloride to obtain the oxadiazole polyoxyethylene polyoxypropylene ether terminated with allyl group.

[0062] Specifically, azodiazole polyoxyethylene polyoxypropylene ether and a second catalyst are added into a reaction kettle, and the molar ratio of azodiazole polyoxyethylene polyoxypropylene ether to the second catalyst is 1:0.9-1.1; monochloropropylene is introduced, and the molar ratio of azodiazole polyoxyethylene polyoxypropylene ether to monochloropropylene is 1:1-1.5, and the reaction is carried out at 30-60°C for 1-5h to obtain allyl-terminated azodiazole polyoxyethylene polyoxypropylene ether.

[0063] The second catalyst includes but is not limited to at least one of sodium, potassium, and sodium hydride. The present invention utilizes azodiazole polyoxyethylene polyoxypropylene ether to react with propylene monochloride to achieve allyl end-capping, which is convenient for subsequent grafting onto hydrogen-containing silicone oil.

[0064] After the azodiazole polyoxyethylene polyoxypropylene ether reacts with propylene monochloride, the method further comprises using an adsorbent to perform adsorption filtration on the reactants to obtain the azodiazole polyoxyethylene polyoxypropylene ether terminated with allyl groups; the adsorbent includes but is not limited to at least one of magnesium silicate, aluminum silicate and diatomaceous earth; the amount of the adsorbent is 0.5-2% of the total mass of the azodiazole polyoxyethylene polyoxypropylene ether and propylene monochloride. In the present invention, the purity of the reactants can be improved by performing adsorption filtration with the adsorbent.

[0065] (3) Preparation of organosilicon copolymers.

[0066] The hydrogen-containing silicone oil, the allyl-terminated azoles polyoxyethylene polyoxypropylene ether and the third catalyst are reacted at 80-130° C. for 2-5 hours.

[0067] The molar ratio of the allyl bond in the allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether to the silicon-hydrogen bond in the hydrogen-containing silicone oil is 1.3-1.8:1.

[0068] Among them, the hydrogen-containing silicone oil is low-hydrogen-containing silicone oil; the hydrogen content in the hydrogen-containing silicone oil is 0.2-0.4%; the third catalyst is a metal catalyst, preferably a chloroplatinic acid catalyst; the amount of the third catalyst is 10-20ppm of the total mass of the allyl-terminated azoles polyoxyethylene polyoxypropylene ether and the hydrogen-containing silicone oil.

[0069] The preparation method of the organosilicon copolymer provided by the present invention is to prepare the oxadiazole polyoxyethylene polyoxypropylene ether by first using oxadiazole, ethylene oxide and propylene oxide, then allyl-terminate the oxadiazole polyoxyethylene polyoxypropylene ether, and finally graft the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether onto the hydrogen-containing silicone oil. In the present invention, by introducing oxadiazole, the organosilicon copolymer can be provided with excellent antifungal effect. Moreover, the introduction of the R2 group not only provides antifungal properties for the organosilicon copolymer, but also, since oxadiazole, tebuconazole or hexaconazole all have good hydrophobicity and complex stereo configuration, they can further improve the pore size and pore complex structure of the polyurethane shoe sponge, thereby improving the air permeability of the polyurethane shoe sponge. The preparation method of the organosilicon copolymer provided by the present invention is simple and easy to implement.

[0070] The above-mentioned organosilicon copolymer can be widely used in the preparation of foam stabilizers. Correspondingly, the present invention provides a foam stabilizer, which comprises the above-mentioned organosilicon copolymer or the organosilicon copolymer prepared by the preparation method of the above-mentioned organosilicon copolymer.

[0071] In addition, the present invention also provides a polyurethane shoe material sponge, which is prepared by the above foam stabilizer. The amount of the foam stabilizer added is 1-3% of the total mass of the polyurethane shoe material sponge. The addition of the foam stabilizer can provide the polyurethane shoe material sponge with good antibacterial properties and air permeability.

[0072] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0073] Example 1

[0074] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0075] (1) 163.00 g of diniconazole and 0.61 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 110.00 g of ethylene oxide and 29.00 g of propylene oxide were slowly added, and the reaction was carried out at 130° C. for 3 h. After the reaction was completed, diniconazole polyoxyethylene polyoxypropylene ether was obtained.

[0076] (2) 201 g of diniconazole polyoxyethylene polyoxypropylene ether and 6.90 g of sodium were put into a reaction kettle, and 25.30 g of monochloropropylene was slowly added. The mixture was reacted at 50° C. for 3 h, and then 1.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated diniconazole polyoxyethylene polyoxypropylene ether.

[0077] (3) 74.93 g of the allyl-terminated diniconazole polyoxyethylene polyoxypropylene obtained in step (2) and 25.07 g of low-hydrogen silicone oil were put into a reaction kettle, 15 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 110° C. for 3 h to obtain an organosilicon copolymer.

[0078] The structural formula of the organosilicon copolymer is as follows:

[0079]

[0080] R1 structural formula: -CH2CH2CH2(OCH2CH2)5(OCH2CHCH3)1R2;

[0081] R2 is

[0082] Example 2

[0083] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0084] (1) 153.50 g of tebuconazole and 1.20 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 110° C., and then 176.00 g of ethylene oxide and 87.00 g of propylene oxide were slowly added, and the reaction was carried out at 110° C. for 4 h. After the reaction was completed, tebuconazole polyoxyethylene polyoxypropylene ether was obtained.

[0085] (2) 277.00 g of tebuconazole polyoxyethylene polyoxypropylene ether and 14.20 g of potassium were put into a reaction kettle, 34.20 g of monochloropropylene was slowly added, and the mixture was reacted at 40° C. for 2.5 h. Then 3.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated tebuconazole polyoxyethylene polyoxypropylene ether.

[0086] (3) 72.43 g of the allyl-terminated tebuconazole polyoxyethylene polyoxypropylene obtained in step (2) and 27.57 g of low-hydrogen silicone oil were put into a reaction kettle, 10 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 90° C. for 2 h to obtain an organosilicon copolymer.

[0087] The structural formula of the organosilicon copolymer is as follows:

[0088]

[0089] R1 structural formula: -CH2CH2CH2(OCH2CH2)8(OCH2CHCH3)3OR2;

[0090] R2 is

[0091] Example 3

[0092] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0093] (1) 157.00 g of hexaconazole and 2.20 g of potassium hydroxide were put into a reaction kettle, the temperature was raised to 120° C., and then 198.00 g of ethylene oxide and 174.00 g of propylene oxide were slowly added, and the reaction was carried out at 120° C. for 5 h. After the reaction was completed, hexaconazole polyoxyethylene polyoxypropylene ether was obtained.

[0094] (2) 352.00 g of hexaconazole polyoxyethylene polyoxypropylene ether and 7.92 g of sodium hydride were put into a reaction kettle, 30.20 g of monochloropropylene was slowly added, and the mixture was reacted at 60° C. for 3 h, and then 7.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated hexaconazole polyoxyethylene polyoxypropylene ether.

[0095] (3) 86.90 g of the allyl-terminated hexaconazole polyoxyethylene polyoxypropylene ether obtained in step (2) and 13.10 g of low-hydrogen silicone oil were put into a reaction kettle, 20 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 120° C. for 5 h to obtain an organosilicon copolymer.

[0096] The structural formula of the organosilicon copolymer is as follows:

[0097]

[0098] R1 structural formula: -CH2CH2CH2(OCH2CH2)9(OCH2CHCH3)6OR2;

[0099] R2 is

[0100] Example 4

[0101] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0102] (1) 163 g of diniconazole and 0.49 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 22.00 g of ethylene oxide and 58.00 g of propylene oxide were slowly added, and the reaction was carried out at 130° C. for 1 hour. After the reaction was completed, diniconazole polyoxyethylene polyoxypropylene ether was obtained.

[0103] (2) 243.00 g of diniconazole polyoxyethylene polyoxypropylene ether and 10.4 g of sodium were put into a reaction kettle, 38.03 g of monochloropropylene was slowly added, and the mixture was reacted at 50° C. for 1 h. Then 1.50 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated diniconazole polyoxyethylene polyoxypropylene ether.

[0104] (3) 69.80 g of the allyl-terminated diniconazole polyoxyethylene polyoxypropylene obtained in step (2) and 30.20 g of low-hydrogen silicone oil were put into a reaction kettle, 10 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 110° C. for 2 h to obtain an organosilicon copolymer.

[0105] The structural formula of the organosilicon copolymer is as follows:

[0106]

[0107] R1 structural formula: -CH2CH2CH2(OCH2CH2)1(OCH2CHCH3)2OR2;

[0108] R2 is

[0109] Example 5

[0110] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0111] (1) 153.50 g of tebuconazole and 3.00 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 110° C., and then 220.00 g of ethylene oxide and 145.00 g of propylene oxide were slowly added, and the reaction was carried out at 110° C. for 5 h. After the reaction was completed, tebuconazole polyoxyethylene polyoxypropylene ether was obtained.

[0112] (2) 345.00 g of tebuconazole polyoxyethylene polyoxypropylene ether and 19.50 g of potassium were put into a reaction kettle, 32.10 g of monochloropropylene was slowly added, and the mixture was reacted at 60° C. for 5 h, and then 7.90 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated tebuconazole polyoxyethylene polyoxypropylene ether.

[0113] (3) 88.61 g of the allyl-terminated tebuconazole polyoxyethylene polyoxypropylene obtained in step (2) and 11.39 g of low-hydrogen silicone oil were put into a reaction kettle, 20 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 130° C. for 4 h to obtain an organosilicon copolymer.

[0114] The structural formula of the organosilicon copolymer is as follows:

[0115]

[0116] R1 structural formula: -CH2CH2CH2(OCH2CH2) 10 (OCH2CHCH3)5OR2;

[0117] R2 is

[0118] Example 6

[0119] This embodiment provides an organosilicon copolymer, and the preparation method thereof comprises the following steps:

[0120] (1) 157.00 g of hexaconazole and 2.20 g of potassium hydroxide were put into a reaction kettle, the temperature was raised to 125° C., and then 88.00 g of ethylene oxide and 116.00 g of propylene oxide were slowly added, and the reaction was carried out at 125° C. for 3.5 hours. After the reaction was completed, hexaconazole polyoxyethylene polyoxypropylene ether was obtained.

[0121] (2) 361.00 g of hexaconazole polyoxyethylene polyoxypropylene ether and 10.80 g of sodium hydride were put into a reaction kettle, 42.80 g of monochloropropylene was slowly added, and the mixture was reacted at 45° C. for 2 h, and then 4.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated hexaconazole polyoxyethylene polyoxypropylene ether.

[0122] (3) 72.60 g of the allyl-terminated hexaconazole polyoxyethylene polyoxypropylene obtained in step (2) and 27.40 g of low-hydrogen silicone oil were put into a reaction kettle, 10 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 100° C. for 3 h to obtain an organosilicon copolymer.

[0123] The structural formula of the organosilicon copolymer is as follows:

[0124]

[0125] R1 structural formula: -CH2CH2CH2(OCH2CH2)4(OCH2CHCH3)4OR2;

[0126] R2 is

[0127] Comparative Example 1

[0128] (1) 16.00 g of methanol and 0.46 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 120° C., and then 110.00 g of ethylene oxide and 29.00 g of propylene oxide were slowly added, and the reaction was carried out at 120° C. for 2 h. After the reaction was completed, polyoxyethylene polyoxypropylene monomethyl ether was obtained.

[0129] (2) 155.00 g of polyoxyethylene polyoxypropylene monomethyl ether and 10.40 g of sodium were put into a reaction kettle, 40.10 g of propylene monochloride was slowly added, and the mixture was reacted at 50° C. for 3 h, and then 1.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated polyoxyethylene polyoxypropylene monomethyl ether.

[0130] (3) 65.00 g of the allyl-terminated polyoxyethylene-polyoxypropylene monomethyl ether obtained in step (2) and 35.00 g of low-hydrogen silicone oil were put into a reaction kettle, 10 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 110° C. for 3 h to obtain an organosilicon copolymer.

[0131] The structural formula of the organosilicon copolymer is as follows:

[0132]

[0133] R1 structural formula: -CH2CH2CH2(OCH2CH2)5(OCH2CHCH3)1OCH3.

[0134] Comparative Example 2

[0135] (1) 23.00 g of ethanol and 0.90 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 110° C., and then 176.00 g of ethylene oxide and 87.00 g of propylene oxide were slowly added, and the reaction was carried out at 110° C. for 4 hours. After the reaction was completed, polyoxyethylene polyoxypropylene monoethyl ether was obtained.

[0136] (2) 286.00 g of polyoxyethylene polyoxypropylene monoethyl ether and 17.60 g of potassium were put into a reaction kettle, 39.20 g of monochloropropylene was slowly added, and the mixture was reacted at 40° C. for 2.5 h. Then 3.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated polyoxyethylene polyoxypropylene monoethyl ether.

[0137] (3) 67.50 g of the allyl-terminated polyoxyethylene polyoxypropylene monoethyl ether obtained in step (2) and 32.50 g of low-hydrogen silicone oil were put into a reaction kettle, 10 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 90° C. for 2 h to obtain an organosilicon copolymer.

[0138] The structural formula of the organosilicon copolymer is as follows:

[0139]

[0140] R1 structural formula: -CH2CH2CH2(OCH2CH2)8(OCH2CHCH3)3OC2H5.

[0141] Comparative Example 3

[0142] (1) 30.00 g of isopropanol and 1.20 g of potassium hydroxide were put into a reaction kettle, the temperature was raised to 120° C., and then 198.00 g of ethylene oxide and 174.00 g of propylene oxide were slowly added. The reaction was carried out at 120° C. for 5 h. After the reaction was completed, polyoxyethylene polyoxypropylene monoisopropyl ether was obtained.

[0143] (2) 402.00 g of polyoxyethylene polyoxypropylene monoisopropyl ether and 13.20 g of sodium hydride were put into a reaction kettle, 45.90 g of monochloropropylene was slowly added, and the mixture was reacted at 60° C. for 3 h. Then 5.00 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated polyoxyethylene polyoxypropylene monoisopropyl ether.

[0144] (3) 75.90 g of the allyl-terminated polyoxyethylene polyoxypropylene monoisopropyl ether obtained in step (2) and 24.10 g of low-hydrogen silicone oil were put into a reaction kettle, 15 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 120° C. for 5 h to obtain an organosilicon copolymer.

[0145] The structural formula of the organosilicon copolymer is as follows:

[0146]

[0147] R1 structural formula: -CH2CH2CH2(OCH2CH2)9(OCH2CHCH3)6OC3H7.

[0148] Comparative Example 4

[0149] (1) 38.00 g of butanol and 0.49 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 22.00 g of ethylene oxide and 58.00 g of propylene oxide were slowly added, and the reaction was carried out at 130° C. for 3 h. After the reaction was completed, polyoxyethylene polyoxypropylene monobutyl ether was obtained.

[0150] (2) 118.00 g of polyoxyethylene polyoxypropylene monobutyl ether and 11.50 g of sodium were put into a reaction kettle, 45.90 g of propylene monochloride was slowly added, and the mixture was reacted at 50° C. for 1.5 h. Then 2.00 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated polyoxyethylene polyoxypropylene monobutyl ether.

[0151] (3) 52.55 g of the allyl-terminated polyoxyethylene polyoxypropylene monobutyl ether obtained in step (2) and 47.45 g of low-hydrogen silicone oil were put into a reaction kettle, 15 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 110° C. for 4 h to obtain an organosilicon copolymer.

[0152] The structural formula of the organosilicon copolymer is as follows:

[0153]

[0154] R1 structural formula: -CH2CH2CH2(OCH2CH2)1(OCH2CHCH3)2OC4H9.

[0155] Comparative Example 5

[0156] (1) 29.00 g of allyl alcohol and 1.60 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 220.00 g of ethylene oxide and 145.00 g of propylene oxide were slowly added, and the reaction was carried out at 110° C. for 5 h. After the reaction was completed, allyl polyoxyethylene polyoxypropylene ether was obtained.

[0157] (2) 83.33 g of the allyl polyoxyethylene polyoxypropylene ether obtained in step (1) and 16.67 g of low-hydrogen silicone oil were put into a reaction kettle, 20 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 130° C. for 4 h to obtain an organosilicon copolymer.

[0158] The structural formula of the organosilicon copolymer is as follows:

[0159]

[0160] R1 structural formula: -CH2CH2CH2(OCH2CH2) 10 (OCH2CHCH3)5OH.

[0161] Comparative Example 6

[0162] (1) 51.00 g of n-hexanol and 0.80 g of potassium hydroxide were put into a reaction kettle, the temperature was raised to 125° C., and then 88.00 g of ethylene oxide and 116.00 g of propylene oxide were slowly added. The reaction was carried out at 125° C. for 3.5 hours. After the reaction was completed, polyoxyethylene polyoxypropylene n-hexyl ether was obtained.

[0163] (2) 255.00 g of polyoxyethylene polyoxypropylene n-hexyl ether and 12.00 g of sodium hydride were put into a reaction kettle, and 49.70 g of monochloropropylene was slowly added. The mixture was reacted at 45° C. for 3 h, and then 3.20 g of aluminum silicate was added and stirred for 2 h. The mixture was refined and filtered to obtain allyl-terminated polyoxyethylene polyoxypropylene n-hexyl ether.

[0164] (3) 78.19 g of the allyl-terminated hexaconazole polyoxyethylene polyoxypropylene obtained in step (2) and 21.81 g of low-hydrogen silicone oil were put into a reaction kettle, 15 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 105° C. for 3 h to obtain an organosilicon copolymer.

[0165] The structural formula of the organosilicon copolymer is as follows:

[0166]

[0167] R1 structural formula: -CH2CH2CH2(OCH2CH2)4(OCH2CHCH3)4OC6H 13 .

[0168] Comparative Example 7

[0169] (1) 29.00 g of allyl alcohol and 3.50 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 264.00 g of ethylene oxide and 290.00 g of propylene oxide were slowly added, and the reaction was carried out at 110° C. for 5 h. After the reaction was completed, allyl polyoxyethylene polyoxypropylene ether was obtained.

[0170] (2) 85.24 g of the allyl polyoxyethylene polyoxypropylene ether obtained in step (1) and 14.76 g of low-hydrogen silicone oil were put into a reaction kettle, 20 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 130° C. for 4 h to obtain an organosilicon copolymer.

[0171] The structural formula of the organosilicon copolymer is as follows:

[0172]

[0173] R1 structural formula: -CH2CH2CH2(OCH2CH2) 12 (OCH2CHCH3) 10 OH.

[0174] Comparative Example 8

[0175] (1) 163.00 g of diniconazole and 3.11 g of sodium hydroxide were put into a reaction kettle, the temperature was raised to 130° C., and then 440.00 g of ethylene oxide and 435.00 g of propylene oxide were slowly added, and the reaction was carried out at 130° C. for 3 h. After the reaction was completed, diniconazole polyoxyethylene polyoxypropylene ether was obtained.

[0176] (2) 519.00 g of diniconazole polyoxyethylene polyoxypropylene ether and 5.75 g of sodium were put into a reaction kettle, 19.13 g of monochloropropylene was slowly added, and the mixture was reacted at 50° C. for 3 h. Then, 5.44 g of aluminum silicate was added and stirred for 2 h, and the mixture was refined and filtered to obtain allyl-terminated diniconazole polyoxyethylene polyoxypropylene ether.

[0177] (3) 89.76 g of the allyl-terminated diniconazole polyoxyethylene polyoxypropylene obtained in step (2) and 10.24 g of low-hydrogen silicone oil were put into a reaction kettle, 15 ppm of chloroplatinic acid catalyst was added, and the mixture was reacted at 110° C. for 3 h to obtain an organosilicon copolymer.

[0178] The structural formula of the organosilicon copolymer is as follows:

[0179]

[0180] R1 structural formula: -CH2CH2CH2(OCH2CH2) 20 (OCH2CHCH3) 15 R2;

[0181] R2 is

[0182] Experimental example

[0183] The organosilicon copolymers provided in the above examples and comparative examples were used as foam stabilizers to prepare polyurethane shoe sponges and the antifungal and breathable properties of the polyurethane shoe sponges were evaluated. Specifically, the polyurethane shoe sponges were prepared with reference to the formula in Table 1.

[0184] Table 1. Polyurethane shoe sponge formula

[0185] raw material Proportion Polyether 360N 50 Polyether ED28 25 Polyether 2045 25 Ethylene glycol 5 Polyether 2047 2 Foam stabilizer 1.7 water 1.8 C225 0.2 1027 0.2 MDI 70

[0186] The performance tests were carried out on the polyurethane shoe sponge prepared in the above embodiment. The air permeability was tested according to the test method in ASTM D737-04 "Standard Test Method for Air Permeability of Textile Fabrics", and the antibacterial rate was tested according to the test method in GB / T 20944.3 "Textiles. Evaluation of Antibacterial Properties". The results are shown in Table 2.

[0187] Table 2. Air permeability and antibacterial rate test results

[0188]

[0189] It can be seen from the above table that the polyurethane shoe sponge prepared by using the organosilicon copolymer provided by Examples 1-6 of the present invention as a foam stabilizer has excellent air permeability and antifungal properties. Before washing, the antibacterial rate of Candida albicans is greater than 99.1%, and the antibacterial rate of Candida albicans after washing 30 times is still greater than 98.2%; and the air permeability of the polyurethane of the present application is 30cm 3 / s / cm 2 This indicates that the polyurethane shoe sponge of the present application has good air permeability and excellent antifungal performance.

[0190] In Comparative Example 1, no R2 group was introduced, but a methoxy group was introduced through methanol. It can be seen that the air permeability and antibacterial properties of the polyurethane shoe sponge obtained therefrom are significantly reduced. Similarly, in Comparative Example 2, an ethoxy group was introduced through ethanol, a propoxy group was introduced through isopropanol in Comparative Example 3, a butoxy group was introduced through butanol in Comparative Example 4, and a hexoxy group was introduced through n-hexanol in Comparative Example 6. The alcohols in Comparative Examples 1-4 and 6 cannot improve the air permeability and antibacterial properties of the polyurethane shoe sponge. Although ethanol can be used as a bactericide, its effect is still significantly worse than that of Example 1.

[0191] In Comparative Examples 5 and 7, only allyl polyoxyethylene polyoxypropylene ether was grafted. It can be seen that the air permeability and antibacterial properties of the polyurethane shoe sponge obtained therefrom are significantly reduced. Among them, the value of m in the structural formula of Comparative Example 7 is 20, and n is 9, which exceeds the value range of the present invention. At the same time, the values ​​of a and b in the R1 substituent also exceed the value range of the present invention, and the air permeability and antibacterial effect are poor. Although the bactericide of the present invention is introduced in Comparative Example 8, the air permeability and antibacterial effect are poor because the values ​​of m, n, a and b in its structural formula exceed the value range of the present invention.

[0192] In summary, the organosilicon copolymer provided by the present invention is introduced into the side chain of hydrogen silicone oil by introducing the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether. The present invention defines the m of the organosilicon copolymer as 1-10, n as 1-4, and further defines the values ​​of polyoxyethylene and polyoxypropylene in the allyl-terminated oxadiazole polyoxyethylene polyoxypropylene ether, so that the organosilicon copolymer has a good comb-shaped structure. In the present invention, by utilizing the H in the -OH of oxadiazole, tebuconazole or hexaconazole to be grafted onto the polyoxyethylene polyoxypropylene ether, an excellent antifungal effect can be provided for the organosilicon copolymer. Moreover, the introduction of the R2 group not only provides antifungal properties for the organosilicon copolymer, but also, since oxadiazole, tebuconazole or hexaconazole all have good hydrophobicity and complex stereo configuration, it can further improve the pore size and pore complex structure of the polyurethane shoe sponge, thereby improving the air permeability of the polyurethane shoe sponge. The preparation method of the organosilicon copolymer provided by the present invention is to prepare azodiazole polyoxyethylene polyoxypropylene ether by first using azodiazole, ethylene oxide and propylene oxide, then allyl-terminate the azodiazole polyoxyethylene polyoxypropylene ether, and finally graft the allyl-terminated azodiazole polyoxyethylene polyoxypropylene ether onto hydrogen-containing silicone oil. In the present invention, by introducing azodiazole, excellent antifungal effect can be provided for the organosilicon copolymer. The preparation method of the organosilicon copolymer provided by the present invention is simple and easy to implement. The above-mentioned organosilicon copolymer can be widely used in the preparation of foam stabilizers. The polyurethane shoe sponge prepared by the foam stabilizer has good antibacterial properties and air permeability.

[0193] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An organosilicon copolymer, characterized in that: Its structural formula is as follows: Wherein, m is 1-10, n is 1-4, and m+n is 2-14; The chemical structure of R1 is as follows: -CH2CH2CH2(OCH2CH2) a (OCH2CHCH3) b R2; wherein a is 1-10, and b is 1-6; The chemical structure of R2 is as follows:

2. A method for preparing an organosilicon copolymer as claimed in claim 1, characterized in that: It includes: The allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether is reacted with hydrogen-containing silicone oil to form an organosilicon copolymer.

3. The method for preparing the organosilicon copolymer according to claim 2, characterized in that: The preparation method of the allyl-terminated triazole polyoxyethylene polyoxypropylene ether comprises: reacting triazole, ethylene oxide and propylene oxide to obtain triazole polyoxyethylene polyoxypropylene ether; reacting the triazole polyoxyethylene polyoxypropylene ether with propylene monochloride to obtain the allyl-terminated triazole polyoxyethylene polyoxypropylene ether; Preferably, the oxadiazole includes any one of diniconazole, tebuconazole and hexaconazole.

4. The method for preparing the organosilicon copolymer according to claim 3, characterized in that: The step of reacting azodiazole, ethylene oxide and propylene oxide comprises: adding the azodiazole and the first catalyst into a reaction kettle, introducing the ethylene oxide and the propylene oxide and reacting them at 110-130° C. for 1-5 hours to obtain the azodiazole polyoxyethylene polyoxypropylene ether; Preferably, the molar ratio of the oxadiazole, the ethylene oxide and the propylene oxide is 1:(1-10):(1-6); Preferably, the first catalyst comprises at least one of sodium hydroxide and potassium hydroxide; Preferably, the amount of the first catalyst is 0.2-0.5% of the total mass of the oxadiazole, the ethylene oxide and the propylene oxide; Preferably, the molecular weight of the azodiazole polyoxyethylene polyoxypropylene ether is 400-1200 g / mol.

5. The method for preparing the organosilicon copolymer according to claim 3, characterized in that: The step of reacting the azolidinone polyoxyethylene polyoxypropylene ether with the monochloropropylene comprises: adding the azolidinone polyoxyethylene polyoxypropylene ether and a second catalyst into a reaction kettle, introducing the monochloropropylene at 30-60° C., and reacting for 1-5 hours to obtain the allyl-terminated azolidinone polyoxyethylene polyoxypropylene ether; Preferably, the second catalyst comprises at least one of sodium, potassium, and sodium hydride; Preferably, the molar ratio of the azodiazole polyoxyethylene polyoxypropylene ether to the second catalyst is 1:0.9-1.1; Preferably, the molar ratio of the azolidinone polyoxyethylene polyoxypropylene ether to the monochloropropylene is 1:1-1.

5.

6. The method for preparing an organosilicon copolymer according to claim 5, characterized in that: After the azodiazole polyoxyethylene polyoxypropylene ether reacts with the monochloropropylene, the process further comprises: using an adsorbent to perform adsorption filtration on the reactants to obtain the allyl-terminated azodiazole polyoxyethylene polyoxypropylene ether; Preferably, the adsorbent is at least one of magnesium silicate, aluminum silicate and diatomaceous earth; Preferably, the amount of the adsorbent used is 0.5-2% of the total mass of the azolidinone polyoxyethylene polyoxypropylene ether and the monochloropropylene.

7. The method for preparing an organosilicon copolymer according to claim 2, characterized in that: The step of reacting the allyl-terminated triazole polyoxyethylene polyoxypropylene ether with the hydrogen-containing silicone oil comprises: reacting the hydrogen-containing silicone oil, the allyl-terminated triazole polyoxyethylene polyoxypropylene ether and a third catalyst at 80-130° C. for 2-5 hours; Preferably, the molar ratio of the allyl bond in the allyl-terminated azole alcohol polyoxyethylene polyoxypropylene ether to the silicon-hydrogen bond in the hydrogen-containing silicone oil is 1.3-1.8:1; Preferably, the hydrogen-containing silicone oil is low-hydrogen-containing silicone oil; Preferably, the hydrogen content in the hydrogen-containing silicone oil is 0.2-0.4%; Preferably, the third catalyst is a metal catalyst, preferably a chloroplatinic acid catalyst; Preferably, the third catalyst is used in an amount of 10-20 ppm of the total mass of the allyl-terminated azoles polyoxyethylene polyoxypropylene ether and the hydrogen-containing silicone oil.

8. A foam stabilizer, characterized in that The organic silicon copolymer comprises the organic silicon copolymer as claimed in claim 1 or the organic silicon copolymer prepared by the method for preparing the organic silicon copolymer as claimed in any one of claims 2 to 6.

9. A polyurethane shoe sponge, characterized in that: The foam stabilizer is prepared by the foam stabilizer as claimed in claim 7.

10. The polyurethane shoe sponge according to claim 9, characterized in that: The added amount of the foam stabilizer is 1-3% of the total mass of the polyurethane shoe material sponge.

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