Diisocyanate composition, diisocyanate prepolymer, organosilicon polyurethane elastomer and preparation method thereof

Abstract

The invention relates to the field of high polymer materials, and discloses a diisocyanate composition which comprises 15-40 parts of diisocyanate, 0.5-20 parts of hydroxyl-terminated siloxane and 50-80 parts of a compound containing reactive hydrogen. The invention also relates to a diisocyanate prepolymer prepared from the diisocyanate composition, an organic silicon polyurethane elastomer and a preparation method of the diisocyanate prepolymer and the organic silicon polyurethane elastomer. When the organic silicon polyurethane elastomer is prepared, diisocyanate, hydroxyl-terminated siloxane and a compound containing reactive hydrogen react to generate a diisocyanate prepolymer, and then the diisocyanate prepolymer and a mixture of a chain extender and a catalyst are mixed and cured. Silicon contained in the obtained organic silicon polyurethane elastomer has the characteristic of low polarity, so that the non-slip effect of the material is effectively improved, and the main chain contains siloxane which is connected with a covalent bond and has high strength, so that the organic silicon polyurethane elastomer has excellent wear resistance and non-slip property; and the coating can be widely applied to the fields of shoe outsoles, fabrics, clothes weaving coatings and the like.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and particularly to a diisocyanate composition, a diisocyanate prepolymer, an organosilicon polyurethane elastomer and a preparation method thereof. The organosilicon polyurethane elastomer described herein is a material with both wear resistance and anti-slip performance, and can be used in the fields of clothing, shoes and hats. Background Art

[0002] At present, polyurethane (PU) materials are often used in the shoe and clothing industries. For example, most sole materials are made of PU. PU soles have a low density, a soft texture, and are light and comfortable to wear. The PU coating is a common coating for clothing fabrics. After coating, the fabric feels plump, soft and elastic, smooth and comfortable to touch, and can improve the wear-resistant wearing experience of specific parts of the clothing.

[0003] At present, the PU materials used for preparing sole materials or clothing fabrics, although having certain wear resistance and anti-slip effects, have limited wear resistance. If higher wear strength is required, the PU materials are far from meeting the special functional requirements. At the same time, due to the high polarity and hydrophilicity of PU, the wet anti-slip effect of the shoe outsole is not good, and the static friction coefficient is 0.30 - 0.45, which does not meet the use requirements of professional sports shoes.

[0004] Therefore, there is a continuous need in the art to develop a polyurethane elastomer with more excellent wear resistance and dry and wet anti-slip effects. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide an organosilicon polyurethane elastomer with more excellent wear resistance and dry and wet anti-slip effects. The present application also provides a diisocyanate composition, a diisocyanate prepolymer and a preparation method of the organosilicon polyurethane elastomer. Specifically, the diisocyanate prepolymer described herein is made from a diisocyanate, a hydroxyl-terminated siloxane and a compound containing active hydrogen. By introducing Si - O bonds into the main chain of the diisocyanate prepolymer, the wear resistance of the finally obtained organosilicon polyurethane elastomer is improved. The side chain of the prepolymer synthesized from the diisocyanate and the hydroxyl-terminated siloxane described herein can be a long-chain group, and the long silane is located on the side chain, increasing the molecular swing space, and thus enhancing the reactivity with the glue when sticking to the bottom and increasing the adhesion of sticking to the bottom.

[0006] To achieve the above purpose, the present application provides the following technical solutions.

[0007] In the first aspect, the present application provides a diisocyanate composition, which comprises the following components: 15 - 40 parts of a diisocyanate, 0.5 - 20 parts of a hydroxyl-terminated siloxane, and 50 - 80 parts of a compound containing active hydrogen;

[0008] The structural formula of the active hydrogen-containing compound is HO-R-OH, where R is at least one of aliphatic polyester, aromatic polyester, polyether, polycarbonate, polycyclic ester, polylactic acid, and polyolefin group.

[0009] In one embodiment of the first aspect, the diisocyanate is at least one of aliphatic diisocyanate, cycloaliphatic diisocyanate, and aromatic diisocyanate. Preferably, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and benzenedimethyl diisocyanate;

[0010] and / or, the hydroxyl-terminated siloxane has a structure represented by the following general formula (I):

[0011]

[0012] wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z is an integer from 0 to 6; p is an integer from 2 to 10; preferably, p is 6 or 8, and the average molecular weight of the hydroxyl-terminated siloxane is 1000-2500 g / mol;

[0013] and / or, in the structural formula of the active hydrogen-containing compound, R is at least one of polytetrahydrofuran, polypropylene oxide, poly-1,6-hexanediol terephthalate, polyethylene adipate, and polybutylene adipate. Preferably, the average molecular weight of the active hydrogen-containing compound is 600-8000 g / mol.

[0014] In the second aspect, the present application provides a diisocyanate prepolymer, which is made from the diisocyanate composition as described in the first aspect.

[0015] In one embodiment of the second aspect, the diisocyanate prepolymer has a structure represented by the following general formula (II):

[0016]

[0017] wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z is an integer from 0 to 6; p is an integer from 2 to 10; i is 1-50.

[0018] In the third aspect, the present application provides a method for preparing a diisocyanate prepolymer, the method comprising:

[0019] Step (1): Uniformly mix the hydroxyl-terminated siloxane and the active hydrogen-containing compound, preheat, then add the diisocyanate, gradually raise the temperature, continue the constant-temperature reaction after the reaction system turns from turbid to transparent, and degas after the NCO content in the reaction system is qualified to obtain the diisocyanate prepolymer.

[0020] In a specific embodiment, the preheating temperature is 50 °C, gradually raise the temperature to 70 - 110 °C, the constant-temperature reaction temperature is 70 - 110 °C, the constant-temperature reaction time is 0.5 - 5 h, and the NCO content in the reaction system being less than 6.5% is qualified.

[0021] In a fourth aspect, the present application provides a silicone polyurethane elastomer, which is made from the diisocyanate prepolymer, chain extender and catalyst as described in the first aspect, and the raw materials for preparing the silicone polyurethane elastomer include the following components: 20 - 50 parts of diisocyanate, 0.5 - 20 parts of hydroxyl-terminated siloxane, 50 - 80 parts of active hydrogen-containing compound; 3 - 10 parts of chain extender and 0.2 parts of catalyst.

[0022] In an embodiment of the fourth aspect, the chain extender is at least one of an aliphatic chain extender and an aromatic chain extender. Preferably, the chain extender is at least one of ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-cyclohexanediol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, resorcinol bis(hydroxypropyl)ether, resorcinol bis(hydroxypropyl)ethyl ether, 4-(hydroxyethyloxyethyl)-1-(hydroxyethyl)benzene diether, 3-(hydroxyethyloxyethyl)-1-(hydroxyethyl)benzene diether, bisphenol A dihydroxyethyl ether;

[0023] And / or, the catalyst is at least one of bismuth neodecanoate, chelated bismuth, zinc octoate, 1,4-diazabicyclooctane, acid-blocked triethylenediamine, 1,8-diazabicycloundec-7-ene. Preferably, the catalyst is a mixture of bismuth neodecanoate and zinc octoate.

[0024] In a fifth aspect, the present application provides a method for preparing a silicone polyurethane elastomer, and the method includes:

[0025] Step (2): Uniformly mix the chain extender and the catalyst to obtain a mixture;

[0026] Step (3): Uniformly mix the diisocyanate prepolymer with the mixture obtained in step (2) and cure to obtain the silicone polyurethane elastomer.

[0027] In a specific embodiment, the chain extender and the catalyst in step (2) are mixed at 60°C - 70°C;

[0028] And / or, based on the terminal NCO groups of the diisocyanate prepolymer and the terminal OH groups of the chain extender, the molar ratio of the diisocyanate prepolymer to the chain extender in step (3) is 107:100;

[0029] And / or, in step (3), the diisocyanate prepolymer and the mixture are mixed and degassed under vacuum using a centrifugal mixer to be uniformly mixed;

[0030] And / or, after the diisocyanate prepolymer and the mixture are uniformly mixed in step (3), they are poured into a standard test piece mold or a casting machine for curing;

[0031] And / or, the curing temperature in step (3) is 25 - 100°C;

[0032] And / or, the curing time in step (3) is 16 - 24 h.

[0033] The silicone polyurethane elastomer described herein has excellent wear-resistant and anti-slip properties and can be used in the clothing, shoes, and hats industry, widely applied to the soles and fabrics of shoes, coatings for clothing fabrics, etc., and can be used to prepare more wear-resistant and anti-slip clothing, shoes, and hats, meeting higher usage requirements.

[0034] Compared with the prior art, the beneficial effects of this application are as follows: The raw materials for preparing the silicone polyurethane elastomer described herein contain specific weight parts of diisocyanate, hydroxyl-terminated siloxane, active hydrogen-containing compounds, chain extender, and catalyst. During preparation, the diisocyanate, hydroxyl-terminated siloxane, and active hydrogen-containing compounds are first reacted to form a diisocyanate prepolymer, and then the diisocyanate prepolymer is mixed and cured with a mixture of chain extender and catalyst, making the prepared material contain silicon and having a siloxane structure on the structure. Silicon has the characteristic of low polarity, which can balance the high polarity of PU, thereby effectively improving the wet anti-slip effect of the prepared material. And Si-O has a high-strength covalent bond connection, which can significantly improve the wear resistance of the material. Therefore, the wear-resistant and anti-slip material of the present invention has excellent wear resistance and anti-slip performance and can meet the higher anti-slip and wear-resistant usage requirements of the soles and fabrics of shoes and coatings for clothing fabrics. The preparation method of the wear-resistant and anti-slip material of the present invention has simple process steps, is convenient for industrial promotion and application, and has great commercial prospects. The application of the wear-resistant and anti-slip material of the present invention in clothing, shoes, and hats provides a material choice with more excellent wear resistance and anti-slip performance for the soles and fabrics of shoes and coatings for clothing fabrics. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1Schematic diagram of the synthesis reaction process of the diisocyanate prepolymer in the preparation process of a silicone polyurethane elastomer according to an embodiment of the present invention.

[0036] Figure 2 Comparison diagram of the appearance of the reaction system before and after the synthesis of the diisocyanate prepolymer in the preparation process of a silicone polyurethane elastomer according to an embodiment of the present invention.

[0037] Figure 3 For the Fourier transform infrared spectrum FT-IR diagrams of the silicone polyurethane elastomers of Examples 3 and 6 of the present invention and TPU in the scanning range of 400 - 4000 cm -1 In Figure 3 Si Cura represents the silicone polyurethane elastomer of Example 3, and SiCura 20 represents the silicone polyurethane elastomer of Example 6.

[0038] Figure 4 For Figure 3 For the Fourier transform infrared spectrum FT-IR diagrams of the silicone polyurethane elastomers of Examples 3 and 6 of the present invention and TPU in the scanning range of 500 - 2000 cm -1 In Figure 3 Si Cura represents the silicone polyurethane elastomer of Example 3, and Si Cura 20 represents the silicone polyurethane elastomer of Example 6. Detailed implementation manners

[0039] To better illustrate the purpose, technical solution and advantages of the present invention, the present invention will be further described below with reference to the drawings and specific embodiments.

[0040] All substances used in the following examples are common substances in the art and can be prepared by known methods or directly purchased from the market.

[0041] The present invention provides a material with more excellent wear resistance and anti-slip effect. The preparation raw materials of the silicone polyurethane elastomer include the following components in parts by weight: 15 - 40 parts of diisocyanate, 0.5 - 20 parts of hydroxyl-terminated siloxane, 50 - 80 parts of active hydrogen-containing compound, 3 - 10 parts of chain extender, and 0.2 part of catalyst;

[0042] The structural formula of the active hydrogen-containing compound is HO-R-OH, where R is at least one of aliphatic polyester, aromatic polyester, polyether, polycarbonate, polycyclic ester, polylactic acid, and polyolefin group.

[0043] In the silicone polyurethane elastomer, a diisocyanate prepolymer is first prepared by reacting a diisocyanate, a hydroxyl-terminated siloxane, and a compound containing active hydrogen. Then, the diisocyanate prepolymer is cured by mixing it with a chain extender and a catalyst. The silicon contained in the product has the characteristic of low polarity, which can balance the high polarity of the PU, thereby effectively improving the wet anti-slip effect of the prepared material. In addition, the main chain of the obtained product contains siloxane. Due to the high-strength covalent bond connection of Si-O, the wear resistance of the material can be significantly improved. Therefore, the silicone polyurethane elastomer described in the present invention, the product obtained after certain reactions of its preparation raw materials, has significantly improved anti-slip performance and wear resistance compared with the PU widely used in clothing and footwear at present, and can meet higher anti-slip and wear requirements.

[0044] The diisocyanate is at least one of an aliphatic diisocyanate, an alicyclic diisocyanate, and an aromatic diisocyanate. Specifically, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and xylylene diisocyanate.

[0045] The hydroxyl-terminated siloxane has a structure represented by the following general formula (I):

[0046]

[0047] Wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z takes an integer from 0 to 6; p is an integer between 2 and 10; preferably, p is 6 or 8, and the average molecular weight of the hydroxyl-terminated siloxane is 1000-2500 g / mol.

[0048] The hydroxyl-terminated siloxane can be selected from at least one of the above structural formulas. In the structural formula, m and n are each independently an integer between 2 and 200, for example, they can be any value among 2, 5, 10, 20, 30, 40, 50, 100, 150, or 200, or an integer within the range formed by two point values. p can be an integer between 1 and 10, for example, p is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and more preferably, p is 6 or 8. The long side chain connected to the silicon atom can serve as a hydrophobic group, increasing the surface flexibility and hydrophobicity of the coating, and further improving the wet anti-slip performance.

[0049] The hydroxyl-terminated siloxane is one or a mixture of two or more of the above structural formulas, a copolymer, etc. The hydroxyl-terminated siloxane, as an important raw material for preparing the organosilicon polyurethane elastomer of the present invention, provides silicon that can balance the high polarity of the PU, thereby improving the wet anti-slip performance of the prepared material. Moreover, the siloxane therein can make the main chain of the final material contain siloxane. Utilizing the high-strength covalent bond connection of Si-O can significantly improve the wear resistance of the material. Preferably, the average molecular weight of the hydroxyl-terminated siloxane is 1000-2500 g / mol. More preferably, the average molecular weight of the hydroxyl-terminated siloxane is 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500 g / mol or the range or sub-range between any two of these values.

[0050] In some specific embodiments, the hydroxyl-terminated siloxane is a mixture or copolymer of at least two compounds in the above structural formula. For example, the hydroxyl-terminated siloxane is a copolymer of the compound with p = 6 and the compound with p = 8 in the above structural formula, and the average molecular weight of the copolymer is 500-6000 g / mol. When the hydroxyl-terminated siloxane is a copolymer of the compound with p = 6 and the compound with p = 8 in the above structural formula, the product obtained by the reaction and curing of the hydroxyl-terminated siloxane with other raw materials can more significantly improve the wear resistance and anti-slip property of the material.

[0051] In the structural formula of the active hydrogen-containing compound, R is at least one of an aliphatic polyester, an aromatic polyester, and a polyether. Specifically, in the structural formula of the active hydrogen-containing compound, R is at least one of polytetrahydrofuran, polypropylene oxide, poly(1,6-hexanediol terephthalate), polyethylene adipate, and polybutylene adipate.

[0052] The active hydrogen-containing compound undergoes a chemical reaction with the hydroxyl-terminated siloxane to form a diisocyanate prepolymer with a specific structure for preparing the organosilicon polyurethane elastomer of the present invention. Preferably, the average molecular weight of the active hydrogen-containing compound is 600-8000 g / mol.

[0053] The chain extender is at least one of aliphatic chain extenders and aromatic chain extenders. Specifically, the chain extender is at least one of ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-cyclohexanediol, hydroquinone bis(2-hydroxyethyl) ether, resorcinol bis(2-hydroxyethyl) ether, resorcinol bis(2-hydroxypropyl) ether, resorcinol bis(2-hydroxypropyl ethyl) ether, 4-(2-hydroxyethoxyethyl)-1-(2-hydroxyethyl)benzene diether, 3-(2-hydroxyethoxyethyl)-1-(2-hydroxyethyl)benzene diether, bisphenol A bis(2-hydroxyethyl) ether. In some preferred embodiments, the chain extender is at least one of ethylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, 1,3-propanediol.

[0054] The catalyst is at least one of bismuth neodecanoate, chelated bismuth, zinc isooctanoate, 1,4-diazabicyclooctane (DABCO), acid-blocked triethylenediamine, 1,8-diazabicycloundec-7-ene (DBU). In some preferred embodiments, the catalyst is a mixture of bismuth neodecanoate and zinc isooctanoate. When the catalyst is a mixture of bismuth neodecanoate and zinc isooctanoate, the bismuth neodecanoate and zinc isooctanoate can be in any mass ratio, for example, including but not limited to the mass ratio of bismuth neodecanoate to zinc isooctanoate being 1:2.

[0055] In a specific embodiment, the diisocyanate prepolymer has a structure represented by the following general formula (II):

[0056]

[0057] Wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z takes an integer from 0 to 6; p is an integer between 2 and 10; i is from 1 to 50. The definitions of m, n, R1 and p are as described above. The value range of i depends on the molecular weight of the compound containing active hydrogen and can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or the range or sub-range between any two of these values.

[0058] When preparing the organosilicon polyurethane elastomer of the present invention, the preparation method includes the following steps:

[0059] Step (1): Uniformly mix a hydroxyl-terminated siloxane and a compound containing active hydrogen, preheat, then add a diisocyanate, gradually raise the temperature, continue the constant-temperature reaction after the reaction system changes from turbid to transparent, and degas after the NCO content in the reaction system is qualified to obtain a diisocyanate prepolymer;

[0060] Step (2): Uniformly mix a chain extender and a catalyst to obtain a mixture;

[0061] Step (3): Uniformly mix the diisocyanate prepolymer obtained in step (1) with the mixture obtained in step (2) and cure to obtain a silicone polyurethane elastomer.

[0062] In step (1) of the present invention, the color change of the reaction system is used as a judgment on whether the siloxane group is incorporated into the main chain. When the siloxane group is incorporated into the main chain, the generated PU is transparent. On the contrary, if the siloxane group is not attached to the main chain, the reaction system is turbid. In step (1), whether the NCO content is qualified is used as the reaction end point. The test method for the NCO% content in the reaction system is GB / T 601 HG / T 2409-92 "Determination of Isocyanate Group Content in Polyurethane Prepolymer". Specifically, when the NCO content is less than 6.5%, it can be considered qualified. In other embodiments, when the NCO content is less than 6.5%, 6%, 5%, 4%, 3%, it can be considered qualified.

[0063] In step (1), after the hydroxyl-terminated siloxane and the compound containing active hydrogen are mixed, preheating is required. In some preferred embodiments, the preheating temperature in step (1) is 50°C.

[0064] After adding the diisocyanate to the mixture of the hydroxyl-terminated siloxane and the compound containing active hydrogen, the temperature needs to be further raised to enable them to react. In some preferred embodiments, the temperature is gradually raised to 70-110°C in step (1); for example, in step (1), the temperature is gradually raised to any point value or range value formed by two point values among 70°C, 80°C, 90°C, 100°C, 110°C.

[0065] After the reaction system changes from turbid to transparent, it is necessary to continue the reaction at a constant temperature to ensure sufficient reaction. In some preferred embodiments, the constant-temperature reaction temperature in step (1) is 70-110°C; more preferably, the constant-temperature reaction temperature in step (1) is 80°C. The time of the constant-temperature reaction in step (1) is not particularly limited, and generally 0.5-5 h is appropriate. More preferably, the time of the constant-temperature reaction in step (1) is 2 h.

[0066] In step (1), the content of NCO in the final reaction system needs to be controlled. Specifically, when the NCO content in the reaction system is less than the designed value, it is qualified.

[0067] In step (2), the chain extender and the catalyst are preferably mixed at a certain temperature. In a preferred embodiment, the mixing temperature is 60°C.

[0068] In step (3), the diisocyanate prepolymer and the mixture need to be mixed and cured in a certain quantitative ratio. In a preferred embodiment, calculated based on the terminal NCO groups of the diisocyanate prepolymer and the terminal OH groups of the chain extender, the molar ratio of the diisocyanate prepolymer to the chain extender is 107:100.

[0069] In step (3), the diisocyanate prepolymer and the mixture can be mixed uniformly by conventional methods in the prior art. For example, but not limited to, centrifugal mixer vacuum degassing can be preferably used for mixing uniformly.

[0070] After the diisocyanate prepolymer and the mixture in step (3) are mixed uniformly, curing is required. The curing preferably, but not limited to, is carried out by pouring into a standard test piece mold.

[0071] In step (3), curing needs to be carried out at a certain temperature. The curing temperature is preferably, but not limited to, 25 - 100°C. The curing time is not strictly limited. For example, but not limited to, 16 h.

[0072] In the preparation method of the silicone polyurethane elastomer, first, the specific quantitative ratio of diisocyanate, hydroxyl-terminated siloxane, and active hydrogen-containing compound are reacted under certain conditions. The process of the three reacting is exemplified as shown in the appendix. Figure 1 As shown in the appendix. Figure 1 It can be seen that the diisocyanate, hydroxyl-terminated siloxane, and active hydrogen-containing compound undergo a polymerization reaction at a specific temperature. The diisocyanate and the active hydrogen-containing compound are respectively grafted at both ends of the hydroxyl-terminated siloxane. The resulting diisocyanate prepolymer contains silicon and has a siloxane on the main chain. The low polarity of silicon is used to balance the high polarity of PU, thereby improving the wet anti-slip performance. The siloxane on the main chain, through the high-strength covalent bond connection of Si - O, can significantly improve the wear resistance of the material. The long silane is located on the side chain and has a functional group designed at the end, which can increase the adhesion between the bottom and the glue. At the same time, the diisocyanate prepolymer has a silane long side chain, which can reduce the crystallization of the polymer, effectively reduce the problem of stress concentration points generated when the material is bent due to crystallization, resulting in easy cracking, and make the material have more excellent transparency and bend resistance.

[0073] When the diisocyanate, hydroxyl-terminated siloxane, and active hydrogen-containing compound react, the reaction system will gradually change from turbid to transparent. The comparison diagrams of the mixed state before the reaction and the synthesized diisocyanate prepolymer after the reaction are shown in the appendix.Figure 2 As shown in the appended Figure 2 As can be seen from the right figure in the appendix, before the reaction, the raw material mixture is in a turbid state. At this time, each raw material has not reacted yet, and the siloxane groups have not been attached to the main chain; as shown in the appended Figure 2 As can be seen from the left figure in the appendix, after the reaction raw materials react under specific conditions, the reaction system becomes semi-transparent, indicating that SiO has been attached to the main chain.

[0074] The diisocyanate prepolymer formed by the reaction of the described diisocyanate, hydroxyl-terminated siloxane, and compound containing active hydrogen is mixed with the mixture obtained by mixing the chain extender and the catalyst. After the two are mixed in a certain proportion and cured, the organosilicon polyurethane elastomer of the present invention can be obtained, named Si Cura TM .

[0075] In the following examples, the hydroxyl-terminated siloxane used has the structure shown by the general formula (III):

[0076]

[0077] The average molecular weight of this hydroxyl-terminated siloxane is 1750 g / mol, the appearance is a light yellow transparent liquid, the hydroxyl content is 2.0%, the kinematic viscosity at 25 °C is 30 - 100 cSt, and the refractive index at 25 °C is 1.4260 ± 0.0050.

[0078] In the following examples, the molar ratio of the diisocyanate prepolymer to the mixture is calculated based on the terminal NCO groups of the diisocyanate prepolymer and the terminal OH groups of the chain extender.

[0079] Example 1

[0080] This example is an example of the organosilicon polyurethane elastomer of the present invention. The preparation raw materials of the organosilicon polyurethane elastomer described in this example include the following components in parts by weight: 35 parts of diphenylmethane diisocyanate, 0.5 part of hydroxyl-terminated siloxane, 60 parts of adipic acid-1,4-butanediol ester diol, 4.5 parts of ethylene glycol, and 0.2 part of catalyst;

[0081] The average molecular weight of the described adipic acid-1,4-butanediol ester diol is 2000 g / mol;

[0082] The catalyst is a mixture of bismuth neodecanoate and zinc isooctanoate in a mass ratio of 1:2.

[0083] The preparation method of the organosilicon polyurethane elastomer described in this example includes the following steps:

[0084] Step (1): Mix the hydroxyl-terminated siloxane and adipic acid-1,4-butanediol ester diol evenly, preheat to 50 °C, then add diphenylmethane diisocyanate, gradually raise the temperature to 80 °C, and continue to react at a constant temperature of 80 °C for 2 hours after the reaction system turns from turbid to transparent. After the NCO content in the reaction system reaches 6.5%, defoam to obtain the diisocyanate prepolymer;

[0085] Step (2): At 60 °C, mix ethylene glycol and the catalyst evenly to obtain a mixture;

[0086] Step (3): Mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) evenly by vacuum defoaming using a centrifugal mixer according to the molar ratio of diisocyanate prepolymer:ethylene glycol = 107:100, pour it into a standard test piece mold, and cure at 100 °C for 16 hours to obtain the organosilicon polyurethane elastomer of this example.

[0087] Example 2

[0088] This example is an example of the organosilicon polyurethane elastomer of the present invention. The preparation raw materials of the organosilicon polyurethane elastomer in this example include the following components in parts by weight: 16 parts of toluene diisocyanate, 2 parts of hydroxyl-terminated siloxane, 76 parts of polyether diol, 6 parts of 1,4-butanediol, and 0.2 part of catalyst;

[0089] The average molecular weight of the polyether diol is 3000 g / mol;

[0090] The catalyst is a mixture of bismuth neodecanoate and zinc isooctanoate in a mass ratio of 1:1.

[0091] The preparation method of the organosilicon polyurethane elastomer in this example includes the following steps:

[0092] Step (1): Mix the hydroxyl-terminated siloxane and polyether diol evenly, preheat to 50 °C, then add toluene diisocyanate, gradually raise the temperature to 110 °C, and continue to react at a constant temperature of 110 °C for 0.5 hour after the reaction system turns from turbid to transparent. After the NCO content in the reaction system reaches 3.1%, defoam to obtain the diisocyanate prepolymer;

[0093] Step (2): At 60 °C, mix 1,4-butanediol and the catalyst evenly to obtain a mixture;

[0094] Step (3): Mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) evenly by vacuum defoaming using a centrifugal mixer according to the molar ratio of diisocyanate prepolymer:1,4-butanediol = 107:100, pour it into a standard test piece mold, and cure at 25 °C for 16 hours to obtain the organosilicon polyurethane elastomer of this example.

[0095] Example 3

[0096] This example is an example of the silicone polyurethane elastomer of the present invention. The raw materials for preparing the silicone polyurethane elastomer in this example include the following components in parts by weight: 22 parts of isophorone diisocyanate, 4 parts of hydroxyl-terminated siloxane, 68 parts of polycarbonate diol, 6 parts of diethylene glycol, and 0.2 part of chelated bismuth;

[0097] The average molecular weight of the polycarbonate diol is 2000 g / mol.

[0098] The preparation method of the silicone polyurethane elastomer in this example includes the following steps:

[0099] Step (1): Mix the hydroxyl-terminated siloxane and polycarbonate diol evenly, preheat to 50 °C, then add isophorone diisocyanate, gradually raise the temperature to 70 °C, continue to react at a constant temperature of 70 °C for 5 hours after the reaction system changes from turbid to transparent, and degas after the NCO content in the reaction system reaches 5.6% to obtain a diisocyanate prepolymer;

[0100] Step (2): At 60 °C, mix diethylene glycol and chelated bismuth evenly to obtain a mixture;

[0101] Step (3): Vacuum degas and mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) evenly according to the molar ratio of diisocyanate prepolymer:diethylene glycol = 107:100, pour it into a standard test piece mold, and cure at 80 °C for 16 hours to obtain the silicone polyurethane elastomer of this example.

[0102] Example 4

[0103] This example is an example of the silicone polyurethane elastomer of the present invention. The raw materials for preparing the silicone polyurethane elastomer in this example include the following components in parts by weight: 18 parts of hexamethylene diisocyanate, 8 parts of hydroxyl-terminated siloxane, 67 parts of polylactic acid diol, 7 parts of 1,6-hexanediol, and 0.2 part of stannous octoate (T-9);

[0104] The average molecular weight of the polylactic acid diol is 3000 g / mol.

[0105] The preparation method of the silicone polyurethane elastomer in this example includes the following steps:

[0106] Step (1): Mix the hydroxyl-terminated siloxane and polylactic acid diol evenly, preheat to 50 °C, then add hexamethylene diisocyanate, gradually raise the temperature to 90 °C, continue to react at a constant temperature of 90 °C for 2 hours after the reaction system changes from turbid to transparent, and degas after the NCO content in the reaction system reaches 6.3% to obtain a diisocyanate prepolymer;

[0107] Step (2): At 60°C, mix 1,6 - hexanediol and stannous octoate (T - 9) evenly to obtain a mixture.

[0108] Step (3): Use a centrifugal mixer to degas and mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) under vacuum in a ratio of diisocyanate prepolymer:1,6 - hexanediol = 107:100 (molar ratio), pour it into a standard test piece mold, and cure at 70°C for 24 hours to obtain the silicone polyurethane elastomer of this example.

[0109] Example 5

[0110] This example is an example of the silicone polyurethane elastomer of the present invention. The raw materials for preparing the silicone polyurethane elastomer in this example include the following components in parts by weight: 24.5 parts of dicyclohexylmethane diisocyanate, 12 parts of hydroxyl - terminated siloxane, 58 parts of polyester diol, 5.5 parts of 1,3 - propanediol, and 0.2 part of stannous octoate (T - 9).

[0111] The average molecular weight of the polyester diol is 2200 g / mol.

[0112] The preparation method of the silicone polyurethane elastomer in this example includes the following steps:

[0113] Step (1): Mix the hydroxyl - terminated siloxane and polyester diol evenly, preheat to 50°C, then add dicyclohexylmethane diisocyanate, gradually raise the temperature to 100°C, continue to react at a constant temperature of 100°C for 1 hour after the reaction system changes from turbid to transparent, and degas after the NCO content in the reaction system reaches 6.1% to obtain a diisocyanate prepolymer.

[0114] Step (2): At 60°C, mix 1,3 - propanediol and stannous octoate (T - 9) evenly to obtain a mixture.

[0115] Step (3): Use a centrifugal mixer to degas and mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) under vacuum in a ratio of diisocyanate prepolymer:1,3 - propanediol = 107:100 (molar ratio), pour it into a standard test piece mold, and cure at 80°C for 24 hours to obtain the silicone polyurethane elastomer of this example.

[0116] Example 6

[0117] This example is an example of the silicone polyurethane elastomer of the present invention. The raw materials for preparing the silicone polyurethane elastomer in this example include the following components in parts by weight: 16 parts of xylylene diisocyanate, 20 parts of hydroxyl-terminated siloxane, 56 parts of polybutadiene diol, 8 parts of resorcinol bis(2-hydroxyethyl) ether, and 0.2 part of acid-blocked triethylenediamine;

[0118] The average molecular weight of the polybutadiene diol is 2000 g / mol.

[0119] The preparation method of the silicone polyurethane elastomer in this example includes the following steps:

[0120] Step (1): Mix the hydroxyl-terminated siloxane and polybutadiene diol evenly, preheat to 50 °C, then add xylylene diisocyanate, gradually raise the temperature to 80 °C, and continue to react at a constant temperature of 80 °C for 3 hours after the reaction system changes from turbid to transparent. After the NCO content in the reaction system reaches 5.2%, defoam to obtain a diisocyanate prepolymer;

[0121] Step (2): At 60 °C, mix resorcinol bis(2-hydroxyethyl) ether and acid-blocked triethylenediamine evenly to obtain a mixture;

[0122] Step (3): Vacuum defoam and mix the diisocyanate prepolymer obtained in step (1) and the mixture obtained in step (2) evenly according to the molar ratio of diisocyanate prepolymer: resorcinol bis(2-hydroxyethyl) ether = 107:100. Pour it into a standard specimen mold and cure at 100 °C for 16 hours to obtain the silicone polyurethane elastomer of this example.

[0123] Comparative Example 1

[0124] This comparative example is a comparative example of the silicone polyurethane elastomer of the present invention. Compared with Example 1, the silicone polyurethane elastomer in this comparative example is only different in that hydroxyl-terminated siloxane is not added in the preparation raw materials, and the addition amounts of the other raw materials and the preparation method are the same.

[0125] Effect Example 1

[0126] This effect example relates to the Fourier transform infrared spectroscopy test of the silicone polyurethane elastomer of the present invention.

[0127] The organosilicon polyurethane elastomers prepared in Example 2 and Example 6 were subjected to Fourier transform infrared spectroscopy tests with TPU (produced by Yantai Wanhua, grade 1180). The test method was as follows: The organosilicon polyurethane elastomers of Example 2 and Example 6 and TPU were respectively mixed and ground evenly with anhydrous KBr powder. The organosilicon polyurethane elastomers of Example 2 and Example 6 and anhydrous KBr powder were respectively mixed at a ratio of 1:200 and 1:5 to obtain Si Cura (0.5%) samples and Si Cura 20 (20%) samples. TPU and anhydrous KBr powder were mixed at a ratio of 1:200 to obtain TPU group samples. Subsequently, they were pressed into transparent thin slices under high pressure as samples for infrared light to pass through. After instrument calibration and background scanning, the prepared samples were placed at the measurement position, and then the samples were scanned. The scanning range was 400 - 4000 cm -1 The results are shown in the attached Figure 3 as shown, and the scanning range was 500 - 2000 cm -1 The results are shown in the attached Figure 4 as shown. In the attached Figure 3 and 4 , A is the Fourier transform infrared spectrum (FT-IR) of TPU, B is the Fourier transform infrared spectrum (FT-IR) of the organosilicon polyurethane elastomer and anhydrous KBr powder at a ratio of 1:200, that is, the Fourier transform infrared spectrum (FT-IR) of the organosilicon polyurethane elastomer Si Cura with a content of 0.5%, and C is the Fourier transform infrared spectrum (FT-IR) of the organosilicon polyurethane elastomer and anhydrous KBr powder at a ratio of 1:5, that is, the Fourier transform infrared spectrum (FT-IR) of the organosilicon polyurethane elastomer Si Cura with a content of 20%.

[0128] In the attached Figure 3 and 4 , the smaller the transmittance, the higher the content. TPU has an absorption peak at a wavenumber of 1017 cm -1 , and if there is Si-O, the absorption will also be enhanced. For the Si-O bond, at a wavenumber of 1017 cm -1 , TPU does not contain Si-O, so the original transmittance is 52.11. As the Si-O content increases from Si Cura 0.5% to Si Cura 20 20%, the transmittance decreases from 49.18 to 40.95. At a wavenumber of 1063 - 1065 cm -1 , TPU does not contain Si-O and has no obvious absorption peak. As the Si-O content increases from Si Cura (0.5%) to SiCura 20 (20%), the transmittance decreases from 34.92 to 33.29. For the Si-C bond, at a wavenumber of 1256 - 1269 cm -1, the TPU without Si-C has no obvious absorption peak. For example, as the Si-C content increases from Si Cura(0.5%) to Si Cura 20(20%), its transmittance decreases from 53.27 to 50.47. At a wavelength of 801 cm -1 The absorption peak is weak. After overlapping with the TPU, the value of Si Cura(0.5%) changes from not obvious to 47.03 for Si Cura 20(20%).

[0129] Effect Example 2

[0130] This effect example relates to the wear resistance test of the silicone polyurethane elastomer of the present invention.

[0131] The silicone polyurethane elastomers of Examples 1-6 were respectively subjected to wear resistance tests. At the same time, polyester fiber PET was used as a control group. The test method was ASTM D3886-1999 "Standard Test Method for Abrasion Resistance of Textile Fabrics (Inflatable Diaphragm Method)", and the number of cycles required to wear a hole in each group of materials was tested.

[0132] The test results of each group are shown in Table 1.

[0133] Table 1 Wear Resistance Test Results of Each Group of Materials

[0134] Group Number of cycles required to grind out a hole Control group 400 times Example 1 800 times Example 2 2000 times Example 3 3500 times Example 4 5000 times Example 5 7500 times Example 6 10000 times Comparative example 1 600 times

[0135] It can be seen from the results in Table 1 that the wear resistance of the silicone polyurethane elastomer of the present invention is significantly better than that of the comparative example, and the number of cycles can be increased from 600 times to 10,000 times at most.

[0136] Effect Example 3

[0137] This effect example relates to the wear resistance experiment of the silicone polyurethane elastomer of the present invention.

[0138] The elastomers of Examples 1-6 and Comparative Example 1 were respectively subjected to wear resistance tests. At the same time, styrene-butadiene rubber was used as a control group. The test method was DIN53516 Rubber Abrasion Test, and the test results are shown in Table 2.

[0139] Table 2 Wear Resistance Test Results of Each Group of Materials

[0140]

[0141]

[0142] It can be seen from Table 2 that the wear amount of the silicone polyurethane elastomer of the present invention is significantly less than that of the rubber in Comparative Example 1, indicating good wear resistance.

[0143] Effect Example 4

[0144] This effect embodiment relates to the anti-slip effect experiment of the silicone polyurethane elastomer of the present invention.

[0145] The anti-slip performance of the silicone polyurethane elastomers of Examples 1-6 was tested respectively. At the same time, TPU was used as the control group. The test method was ASTM F609 "Standard Test Method for Using a Horizontal Pull Slipmeter (HPS)". The test result showed that the slip index was ten times the static friction coefficient, and the test result was converted into the static friction coefficient. The test results of each group are shown in Table 3.

[0146] Table 3 Test results of the anti-slip performance of each group of materials

[0147] Group Static dry anti-slip friction coefficient Static wet anti-slip friction coefficient Control group 0.90 0.35 Example 1 0.85 0.40 Example 2 0.75 0.48 Example 3 0.65 0.58 Example 4 0.60 0.62 Example 5 0.58 0.65 Example 6 0.55 0.68 Comparative example 1 0.90 0.35

[0148] From the data in Table 3, it can be seen that the dry-wet coefficient is a concept of the overall balance of the material. By adding silane oxygen, the hydrophobicity of the material is improved, the dry anti-slip coefficient can be reduced, and the wet anti-slip coefficient can be increased, making the dry and wet anti-slip more balanced, which is beneficial to the application of sports shoes in various occasions.

[0149] Effect Example 4

[0150] This effect embodiment relates to the adhesion of the long silane position in the silicone polyurethane elastomer of the present invention to the sole and glue.

[0151] In this effect embodiment, a test group and a control group were set up. In the test group, the silicone polyurethane elastomer Si Cura of Example 2 was adhered to EVA, and in the control group, TPU (Wanhua Chemical TPU A9084) was adhered to EVA.

[0152] The adhesion of the materials in the test group and the control group to the sole and glue was tested respectively. The test method was: ASTM D903-98(2017) "Standard Test Method for Adhesive Peel or Stripping Strength".

[0153] The test results of each group are shown in Table 4.

[0154] Table 4 Test results of the adhesion of each group of materials to the sole and glue

[0155]

[0156] From the results in Table 4, it can be seen that when the long silane is located in the side chain, the adhesion of the sole to the glue can be increased.

[0157] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A diisocyanate composition, characterized in that, The diisocyanate composition comprises the following components: 15 to 40 parts of diisocyanate, 0.5 to 20 parts of hydroxy-terminated siloxane, and 50 to 80 parts of active hydrogen-containing compound; The structural formula of the active hydrogen-containing compound is HO-R-OH, where R is at least one of aliphatic polyester, aromatic polyester, polyether, polycarbonate, polycyclic ester, polylactic acid, and polyolefin group.

2. The diisocyanate composition according to claim 1, wherein The diisocyanate is at least one of aliphatic diisocyanate, cycloaliphatic diisocyanate, and aromatic diisocyanate. Preferably, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and xylylene diisocyanate; and / or, the hydroxy-terminated siloxane has a structure represented by the following general formula (I): wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z is an integer from 0 to 6; p is an integer between 2 and 10; preferably, p is 6 or 8, and the average molecular weight of the hydroxyl-terminated siloxane is 1000-2500 g / mol; and / or, in the structural formula of the active hydrogen-containing compound, R is at least one of polytetrahydrofuran, polypropylene oxide, poly(1,6-hexanediol terephthalate), polyethylene adipate, polybutylene adipate. Preferably, the average molecular weight of the active hydrogen-containing compound is 600 to 8000 g / mol.

3. A diisocyanate prepolymer, characterized in that, The diisocyanate prepolymer is made from the diisocyanate composition as described in claim 1 or 2.

4. The diisocyanate prepolymer according to claim 3, characterized in that, The diisocyanate prepolymer has a structure represented by the following general formula (II): wherein, m and n are each independently an integer between 2 and 100; the structural formula of R1 is (CH2) z , then z is an integer from 0 to 6; p is an integer from 2 to 10; i is from 1 to 50.

5. The preparation method of the diisocyanate prepolymer according to claim 3, characterized in that, The method includes: Step (1): Mix the hydroxy-terminated siloxane and the active hydrogen-containing compound evenly, preheat, then add the diisocyanate, gradually raise the temperature, continue the constant-temperature reaction after the reaction system turns from turbid to transparent, and defoam after the NCO content in the reaction system is qualified to obtain the diisocyanate prepolymer.

6. The preparation method according to claim 5, characterized in that, The preheating temperature is 50 °C, gradually raise the temperature to 70 - 110 °C, the constant-temperature reaction temperature is 70 - 110 °C, the constant-temperature reaction time is 0.5 - 5 h, and it is qualified when the NCO content in the reaction system is less than 6.5%.

7. A silicone polyurethane elastomer, characterized in that, The organosilicon polyurethane elastomer is made from the diisocyanate prepolymer, chain extender, and catalyst as described in claim 1 or 2, and the raw materials for preparing the organosilicon polyurethane elastomer comprise the following components: 15 to 40 parts of diisocyanate, 0.5 to 20 parts of hydroxy-terminated siloxane, 50 to 80 parts of active hydrogen-containing compound; 3 to 10 parts of chain extender and 0.2 part of catalyst.

8. The organosilicon polyurethane elastomer according to claim 7, wherein The chain extender is at least one of aliphatic chain extender and aromatic chain extender. Preferably, the chain extender is at least one of ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-cyclohexanediol, hydroquinone bis(2-hydroxyethyl) ether, resorcinol bis(2-hydroxyethyl) ether, resorcinol bis(2-hydroxypropyl) ether, resorcinol bis(2-hydroxypropyl ethyl) ether, 4-(2-hydroxyethoxyethyl)-1-(2-hydroxyethyl)benzene diether, 3-(2-hydroxyethoxyethyl)-1-(2-hydroxyethyl)benzene diether, and bisphenol A bis(2-hydroxyethyl) ether; And / or, the catalyst is at least one of bismuth neodecanoate, chelated bismuth, zinc isooctanoate, 1,4-diazabicyclooctane, acid-blocked triethylenediamine, 1,8-diazabicycloundec-7-ene. Preferably, the catalyst is a mixture of bismuth neodecanoate and zinc isooctanoate.

9. The preparation method of the silicone polyurethane elastomer according to claim 7 or 8, characterized in that, The method includes: Step (2): Mix the chain extender and the catalyst evenly to obtain a mixture; Step (3): Mix the diisocyanate prepolymer with the mixture obtained in step (2) evenly and cure to obtain the organosilicon polyurethane elastomer.

10. The method according to claim 9, wherein In step (2), the chain extender and the catalyst are mixed at 60°C - 70°C; And / or, based on the terminal NCO groups of the diisocyanate prepolymer and the terminal OH groups of the chain extender, the molar ratio of the diisocyanate prepolymer to the chain extender in step (3) is 107:100; And / or, in step (3), the diisocyanate prepolymer and the mixture are mixed evenly by vacuum degassing using a centrifugal mixer or a casting machine; And / or, in step (3), after the diisocyanate prepolymer and the mixture are mixed evenly, they are poured into a standard test piece mold for curing; And / or, the curing temperature in step (3) is 25 - 100°C; And / or, the curing time in step (3) is 16 - 24 h.

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