A polybutadiene silicone diol, a method for preparing the same, and a thermoplastic silicone polyurethane elastomer

Abstract

The present application relates to the field of polyurethane elastomer material, and particularly relates to a polybutadiene silicone diol, a preparation method thereof and a thermoplastic silicone polyurethane elastomer. The polybutadiene silicone diol with the structure of formula (I) has a moderate solubility parameter, the thermoplastic silicone polyurethane elastomer prepared from the polybutadiene silicone diol has a small degree of phase separation in the molecular chain of the elastomer, the product has unexpectedly good transparency, and in addition, the elastomer has the characteristics of PDMS and CTPB, and has excellent mechanical properties, outstanding low-temperature resilience, aging resistance, surface hydrophobicity and smoothness and other properties.

Description

Technical Field

[0001] This invention relates to the field of polyurethane elastomer materials, specifically to a polybutadiene organosilicon diol, its preparation method, and a thermoplastic organosilicon polyurethane elastomer. Background Technology

[0002] Thermoplastic polyurethane elastomer (TPU) is a high-performance polymer synthetic material with excellent comprehensive properties. It has excellent mechanical properties such as high strength, high elasticity, high abrasion resistance and high flexibility, as well as oil resistance, solvent resistance and chemical resistance. There are many types of TPU materials such as films, pipes, shoe materials, wires, cables, sheets, etc., so it can be widely used in various fields.

[0003] Although TPU has many excellent properties, its low-temperature resistance and surface inertness are not satisfactory. Many scholars have studied this issue. Polydimethylsiloxane (PDMS) in the organosilicon series has excellent flexibility, with a Tg of less than -100℃. In addition, it has extremely low surface energy and is prone to surface migration. Therefore, some scholars have used PDMS to synthesize and modify TPU to improve its low-temperature resistance and surface inertness.

[0004] Patent CN 106565933A discloses a method for preparing silicone thermoplastic polyurethane. This invention uses polyester / polyether polyol, two-terminal reactive PDMS, chain extender, and diisocyanate as raw materials, and prepares a silicone-containing TPU (Si-TPU) material with a PDMS structure in the molecular backbone by different feeding sequences. Patent CN109485826A uses single-terminal mono / bifunctional reactive silicone as a raw material to prepare a Si-TPU with silicone segments distributed at the ends / side chains of the product molecule. Compared to the silicone segments in the chain, the silicone segments at the ends / side chains are more prone to surface migration, giving the Si-TPU elastomer good surface hydrophobicity and low-temperature resistance. US Patent 006313254B1 discloses the preparation, composition, and properties of a polyurethane elastomer containing polysiloxane. This invention uses MDI / BDO as the hard segment and at least one polysiloxane macromolecular diol and at least one polyether / polycarbonate macromolecular diol as the soft segment, resulting in a Si-TPU product with PDMS in its molecular backbone. Patent CN104448231A uses a polyether-organic silicone block polymer PEO-PDMS-PEO as a raw material to prepare a Si-TPU elastomer, which exhibits good mechanical properties, low-temperature resistance, and surface hydrophobicity.

[0005] In the field of transparent TPU films, there are high requirements for transparency and surface adhesion (i.e., surface inertness). For example, air cushion materials in footwear also have high requirements for transparency and low-temperature resilience (i.e., low-temperature resistance). Although the above methods can effectively improve the low-temperature resistance and surface inertness of TPU, due to the extremely low solubility parameter of organosilicon and its high incompatibility, it is easy to cause severe phase separation in the product. Introducing organosilicon into the TPU molecular chain will make the product completely opaque or have very low light transmittance, thus limiting the application of this type of Si-TPU. Currently, there are few reports on the preparation of transparent Si-TPU. Summary of the Invention

[0006] Therefore, the purpose of this invention is to provide a polybutadiene silicone diol, its preparation method, and a thermoplastic silicone polyurethane elastomer. The polybutadiene silicone diol of formula (I) has a suitable solubility parameter, and the Si-TPU prepared from it exhibits low phase separation and good product transparency. This elastomer combines the characteristics of polydimethylsiloxane (PDMS) and carboxyl-terminated polybutadiene (CTPB), and also possesses excellent mechanical properties, outstanding low-temperature resilience, surface hydrophobicity, and slip properties.

[0007] To achieve the above-mentioned objectives, the technical solution provided by this invention is as follows:

[0008] A polybutadiene organosilicon diol, the structural formula of which is shown in formula (I):

[0009]

[0010] Where m is an integer from 1 to 23, x is an integer from 1 to 17, y is an integer from 1 to 8, n is an integer from 2 to 12, and R1 is one of alkyl, ether, or ester groups containing 1 to 8 carbon atoms.

[0011] Furthermore, m is an integer from 2 to 15; and / or x is an integer from 2 to 9; and / or y is an integer from 2 to 6; and / or n is an integer from 4 to 10.

[0012] Furthermore, R1 can be -CH2-, -CH2CH2-, -CH2CH2CH2-, #-CH2OCH2CH2-*, -CH2CH2OCH2CH2-, *-CH2CH2OCH2CH2CH2-#, #-CH2COOCH2CH2-*, or #-CH2CH2CH2COOCH2CH2CH2CH2-*, where the * terminal is connected to an oxygen atom and the # terminal is connected to a silicon atom.

[0013] Furthermore, the polybutadiene organosilicon diol has a hydroxyl value of 5.3-29.1 mgKOH / g and an acid value of 0.01-0.5 mgKOH / g.

[0014] On the other hand, the present invention provides a method for preparing polybutadiene organosilicon diol, comprising the following steps: mixing carboxyl-terminated polybutadiene and hydroxyl-terminated polydimethylsiloxane, and subjecting the mixture to a polycondensation reaction to obtain polybutadiene organosilicon diol, wherein the structural formula of the carboxyl-terminated polybutadiene is shown in formula (II), and the structure of the hydroxyl-terminated polydimethylsiloxane is shown in formula (III).

[0015]

[0016]

[0017] In Equations (II) and (III), m, x, and y are defined as above, and R1 in Equation (III) is defined as above.

[0018] Furthermore, the molar ratio of the hydroxyl-terminated polydimethylsiloxane to the carboxyl-terminated polybutadiene is 1–2.5:1; and / or, during the polycondensation reaction, the system is first heated to 140–230°C for 2–6 h under inert gas protection, and then the temperature is continuously raised to 210–280°C for another 2–8 h. Afterward, the vacuum system is turned on, and the reaction continues under vacuum conditions (until the hydroxyl value and acid value are qualified).

[0019] On the other hand, the present invention also provides a thermoplastic silicone polyurethane elastomer, the raw materials of which include the polybutadiene silicone diol or the polybutadiene silicone diol prepared by the preparation method described above; preferably, based on 100 parts by weight of the total raw materials, the raw materials for preparing the thermoplastic silicone polyurethane elastomer include the following components:

[0020] (1) Diisocyanate: 19-42 parts, preferably 28-38 parts;

[0021] (2) The polybutadiene organosilicon diol: 28-57 parts, preferably 34-47 parts;

[0022] (3) Other diols: 6-44 parts, preferably 15-27 parts;

[0023] (4) Chain extender: 4 to 15 parts, preferably 5 to 9 parts.

[0024] Furthermore, the thermoplastic silicone polyurethane elastomer also satisfies at least one of the following conditions (1)-(4):

[0025] (1) The diisocyanate is one or more of aliphatic, alicyclic and aromatic diisocyanates; preferably at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, terephthalic diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, phenylmethylene diisocyanate, cyclohexane diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl-methylene diisocyanate, norbornene diisocyanate, dimethyl biphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate, and lysine diisocyanate;

[0026] (2) The number average molecular weight of the other diols is 800-8000 g / mol, preferably 1000-6000 g / mol;

[0027] (3) The other diols are other macromolecular diols having two terminal hydroxyl groups; preferably, the other diols are one or more of aliphatic or aromatic polyester diols, aliphatic or aromatic polyether diols, aliphatic or aromatic polycarbonate diols, aliphatic or aromatic polylactic acid diols, and aliphatic or aromatic polyolefin diols; more preferably, the other diols are one or more of polytetrahydrofuran diol, polybutylene adipate diol, polycarbonate diol, poly(1,6-hexanediol terephthalate) diol, polypropylene oxide diol, and polyethylene adipate diol.

[0028] (4) The chain extender is a small molecule chain extender, preferably an aliphatic and / or aromatic small molecule chain extender; more preferably ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, butyl ethylpropanediol, diethylpentanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, trimethylpentanediol, 1,5-pentanediol, 1,2-pentanediol, hydroxyl neopentanediol, etc. Hydroxypentyl valerate, 2-ethyl-1,3-hexanediol, dodecanediol, 1,4-dihydroxymethylcyclohexane, 1,4-cyclohexanediol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, resorcinol dihydroxypropyl ether, resorcinol dihydroxypropyl ethyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, 3-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, bisphenol A dihydroxyethyl ether, bisphenol A dihydroxypropyl ether, 1,4-cyclohexanediamine, diaminodicyclohexylmethane, trimethylhexanediamine, dimethyldiaminodicyclohexylmethane.

[0029] In some more preferred embodiments, the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and terephthalic diisocyanate.

[0030] In some more preferred embodiments, the other diol is one or more of polytetrahydrofuran diol, polybutylene adipate diol, polycarbonate diol, poly(1,6-hexanediol terephthalate) diol, and polypropylene oxide diol.

[0031] In some more preferred embodiments, the chain extender is one or more selected from ethylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, 1,3-propanediol, dipropylene glycol, 1,5-pentanediol, and 1,4-cyclohexanediamine.

[0032] On the other hand, the present invention also provides a method for preparing the aforementioned thermoplastic silicone polyurethane elastomer, comprising the following steps:

[0033] Polybutadiene silicone diol, other diols and chain extender are mixed to obtain a mixture; the mixture is then mixed with diisocyanate and reacted to obtain thermoplastic silicone polyurethane elastomer;

[0034] Optionally, the reaction temperature is 80–160°C.

[0035] On the other hand, the present invention provides the application of the above-mentioned thermoplastic silicone polyurethane elastomer or the thermoplastic silicone polyurethane elastomer prepared by the above-described preparation method in medical supplies, clothing, protective equipment, smart wearable devices, cables, and automotive supplies, such as for use on the surface of bags, electronic product cases, medical devices, wires and cables, and car seats.

[0036] The technical solution of this invention has the following advantages:

[0037] 1. The polybutadiene organosilicon diol provided by the present invention has a moderate solubility parameter. The thermoplastic organosilicon polyurethane elastomer prepared from it has a small degree of phase separation in the molecular chain containing the elastomer. The product has unexpectedly good transparency. In addition, the elastomer has the characteristics of both PDMS and CTPB. Therefore, the thermoplastic organosilicon polyurethane elastomer prepared by the present invention has not only good transparency, but also excellent mechanical properties, outstanding low temperature resilience, aging resistance, surface hydrophobicity and slip properties.

[0038] 2. The preparation method of polybutadiene organosilicon diol provided by this invention is simple, convenient to operate, and suitable for industrial production. Polybutadiene organosilicon diol is obtained through a polycondensation reaction of carboxyl-terminated polybutadiene and hydroxyl-terminated polydimethylsiloxane. During the reaction, the carboxyl groups of the carboxyl-terminated polybutadiene and the hydroxyl groups of the hydroxyl-terminated polydimethylsiloxane undergo an esterification reaction.

[0039] 3. The thermoplastic organosilicon polyurethane elastomer provided by the present invention is made by using polybutadiene organosilicon diol with the structure of formula (I) as raw material. The elastomer has significantly improved transparency, and has the characteristics of both PDMS and CTPB. It also has excellent mechanical properties, outstanding low-temperature resilience, surface hydrophobicity and slip properties.

[0040] The overall properties of the prepared elastomer can be further improved by controlling the values ​​of m, x, y, or n in the structure of formula (I) to be within a preferred range or by selecting the preferred type of R1. The overall properties of the prepared elastomer can also be further improved by controlling the weight proportions of polybutadiene silicone diol, other diols, chain extenders, and diisocyanates to be within a preferred range and by selecting the preferred types of these substances. Detailed Implementation

[0041] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Where specific experimental steps or conditions are not specified in the examples, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0043] Example 1

[0044] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps:

[0045] Carboxyl-terminated polybutadiene (CTPB) (x = 8, y = 3), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is -CH2CH2CH2-, m is 10) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.5:1. Under inert gas protection, the system was heated to 180℃ and reacted for 4 hours, then the temperature was continuously increased to 250℃ and the reaction continued for 5 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value were within acceptable limits. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 14.9 mgKOH / g, and the acid value was 0.05 mgKOH / g.

[0046] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0047]

[0048] Where m is 10, x is 8, y is 3, and R1 is -CH2CH2CH2-.

[0049] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0050] (1) Diisocyanate: Diphenylmethane diisocyanate, 32 parts;

[0051] (2) Polybutadiene organosilicon diol prepared in this embodiment: 38 parts;

[0052] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 22 parts;

[0053] (4) Small molecule chain extender: 1,4-butanediol, 8 parts.

[0054] The preparation method includes the following steps:

[0055] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0056] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0057] Example 2

[0058] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps:

[0059] Carboxyl-terminated polybutadiene (CTPB) (x = 17, y = 8), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is *-CH2CH2OCH2CH2CH2-#, where the * end is connected to an oxygen atom and the # end is connected to a silicon atom, and m is 15) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.2:1. Under inert gas protection, the system was heated to 140℃ and reacted for 6 hours, then the temperature was continuously increased to 210℃ and the reaction continued for 8 hours. Subsequently, a vacuum system was activated, and the reaction continued under vacuum until the hydroxyl value and acid value were qualified. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value of the polybutadiene organosilicon diol was 11.2 mgKOH / g, and the acid value was 0.01 mgKOH / g.

[0060] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0061]

[0062] Where m is 15, x is 17, y is 8, and R1 is *-CH2CH2OCH2CH2CH2-#, where the * end is connected to an oxygen atom and the # end is connected to a silicon atom.

[0063] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0064] (1) Diisocyanate: Hexamethylene diisocyanate, 25 parts;

[0065] (2) Polybutadiene organosilicon diol prepared in this embodiment: 47 parts;

[0066] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 8000 g / mol, 23 parts;

[0067] (4) Small molecule chain extender: 1,6-hexanediol, 5 parts.

[0068] The preparation method includes the following steps:

[0069] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0070] 2) Add diisocyanate to the mixture in step 1) and react at 120°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0071] Example 3

[0072] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 2, y = 1), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is #-CH2CH2CH2COOCH2CH2CH2CH2-*, where the * end is connected to an oxygen atom, the # end is connected to a silicon atom, and m is 2) PDMS-OH / CTPB was added to the reactor at a molar ratio of 2:1. Under inert gas protection, the system was heated to 230℃ and reacted for 2 hours, then the temperature was continuously increased to 280℃ and the reaction continued for another 2 hours. Subsequently, a vacuum system was activated, and the reaction continued under vacuum until the hydroxyl value and acid value were qualified. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value of the polybutadiene organosilicon diol was 29.1 mgKOH / g, and the acid value was 0.31 mgKOH / g.

[0073] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0074]

[0075] Where m is 2, x is 2, y is 1, and R1 is #-CH2CH2CH2COOCH2CH2CH2CH2-*, where the * end is connected to an oxygen atom and the # end is connected to a silicon atom.

[0076] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0077] (1) Diisocyanate: phenyl diisocyanate, 42 parts;

[0078] (2) Polybutadiene organosilicon diol prepared in this embodiment: 28 parts;

[0079] (3) Other macromolecular diols: Polybutylene adipate diol, number average molecular weight of 1000 g / mol, 15 parts;

[0080] (4) Small molecule chain extender: 1,4-butanediol, 15 parts.

[0081] The preparation method includes the following steps:

[0082] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0083] 2) Add diisocyanate to the mixture in step 1) and react at 80°C for 1 min to obtain thermoplastic polyurethane elastomer.

[0084] Example 4

[0085] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 14, y = 9), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is -CH2-, m is 23) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1:1. Under inert gas protection, the system was heated to 160℃ and reacted for 3 hours, then the temperature was continuously increased to 230℃ and the reaction continued for 4 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value met the requirements. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 5.3 mgKOH / g, and the acid value was 0.35 mgKOH / g.

[0086] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0087]

[0088] Where m is 23, x is 14, y is 9, and R1 is -CH2-.

[0089] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0090] (1) Diisocyanate: terephthalic diisocyanate, 19 parts;

[0091] (2) Polybutadiene organosilicon diol prepared in this embodiment: 52 parts;

[0092] (3) Other macromolecular diols: polycarbonate diol, number average molecular weight of 2000 g / mol, 24 parts;

[0093] (4) Small molecule chain extender: dipropylene glycol, 5 parts.

[0094] The preparation method includes the following steps:

[0095] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0096] 2) Add diisocyanate to the mixture in step 1) and react at 160°C for 1 min to obtain thermoplastic polyurethane elastomer.

[0097] Example 5

[0098] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 9, y = 6), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is -CH2CH2-, m is 6) PDMS-OH / CTPB was added to the reactor at a molar ratio of 2.5:1. Under inert gas protection, the system was heated to 200℃ and reacted for 5 hours, then the temperature was continuously increased to 250℃ and the reaction continued for 6 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value met the requirements. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 7 mgKOH / g, and the acid value was 0.5 mgKOH / g.

[0099] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0100]

[0101] Where m is 6, x is 9, y is 6, and R1 is -CH2CH2-.

[0102] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0103] (1) Diisocyanate: Isophorone diisocyanate, 38 parts;

[0104] (2) Polybutadiene organosilicon diol prepared in this embodiment: 44 parts;

[0105] (3) Other macromolecular diols: Poly(1,6-hexanediol terephthalate) diol, number average molecular weight 6000 g / mol, 9 parts;

[0106] (4) Small molecule chain extender: hydroquinone dihydroxyethyl ether, 9 parts.

[0107] The preparation method includes the following steps:

[0108] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0109] 2) Add diisocyanate to the mixture in step 1) and react at 90°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0110] Example 6

[0111] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 3, y = 2), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is #-CH2COOCH2CH2-*, where the * end is connected to an oxygen atom, the # end is connected to a silicon atom, and m is 5) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.8:1. Under inert gas protection, the system was heated to 150℃ and reacted for 4 hours, then the temperature was continuously increased to 220℃ and the reaction continued for 5 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value were within acceptable limits. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 23.2 mgKOH / g, and the acid value was 0.22 mgKOH / g.

[0112] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0113]

[0114] Where m is 5, x is 3, y is 2, and R1 is #-CH2COOCH2CH2-*, where the * end is connected to an oxygen atom and the # end is connected to a silicon atom.

[0115] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0116] (1) Diisocyanate: Cyclohexanedimethyl diisocyanate, 24 parts;

[0117] (2) Polybutadiene organosilicon diol prepared in this embodiment: 34 parts;

[0118] (3) Other macromolecular diols: Polyethylene adipate diol, number average molecular weight of 3000 g / mol, 38 parts;

[0119] (4) Small molecule chain extender: 1,4-cyclohexanediol, 4 parts.

[0120] The preparation method includes the following steps:

[0121] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0122] 2) Add diisocyanate to the mixture in step 1) and react at 120°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0123] Example 7

[0124] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 1, y = 4), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is -CH2CH2OCH2CH2-, m is 12) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.4:1. Under inert gas protection, the system was heated to 190℃ and reacted for 3 hours, then the temperature was continuously increased to 240℃ and the reaction continued for 6 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value met the requirements. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 8.4 mgKOH / g, and the acid value was 0.27 mgKOH / g.

[0125] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0126]

[0127] Where m is 12, x is 1, y is 4, and R1 is -CH2CH2OCH2CH2-.

[0128] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0129] (1) Diisocyanate: Toluene diisocyanate, 20 parts;

[0130] (2) Polybutadiene organosilicon diol prepared in this embodiment: 29 parts;

[0131] (3) Other macromolecular diols: polyoxypropylene glycol, number average molecular weight of 5000 g / mol, 44 parts;

[0132] (4) Small molecule chain extender: 1,3-propanediol, 7 parts.

[0133] The preparation method includes the following steps:

[0134] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0135] 2) Add diisocyanate to the mixture in step 1) and react at 130°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0136] Example 8

[0137] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 2, y = 1), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is #-CH2OCH2CH2-*, where the * end is connected to an oxygen atom, the # end is connected to a silicon atom, and m is 1) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.5:1. Under inert gas protection, such as nitrogen, the system was heated to 170℃ and reacted for 5 hours. The temperature was then continuously increased to 230℃ and the reaction continued for another 4 hours. Subsequently, a vacuum system was activated, and the reaction continued under vacuum until the hydroxyl value and acid value met the requirements. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 15.5 mgKOH / g, and the acid value was 0.38 mgKOH / g.

[0138] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0139]

[0140] Where m is 1, x is 2, y is 1, and R1 is #-CH2OCH2CH2-*, where the * end is connected to an oxygen atom and the # end is connected to a silicon atom.

[0141] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0142] (1) Diisocyanate: phenyl diisocyanate, 28 parts;

[0143] (2) Polybutadiene organosilicon diol prepared in this embodiment: 57 parts;

[0144] (3) Other macromolecular diols: Polyethylene adipate diol, with a number average molecular weight of 800 g / mol, 6 parts;

[0145] (4) Small molecule chain extender: tripropylene glycol, 9 parts.

[0146] The preparation method includes the following steps:

[0147] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0148] 2) Add diisocyanate to the mixture in step 1) and react at 120°C for 3 min to obtain thermoplastic polyurethane elastomer.

[0149] Example 9

[0150] This embodiment provides a method for preparing polybutadiene organosilicon diol, including the following steps: preparing carboxyl-terminated polybutadiene (CTPB). (x = 6, y = 4), hydroxyl-terminated polydimethylsiloxane (PDMS-OH) (R1 is -CH2CH2CH2-, m is 8) PDMS-OH / CTPB was added to the reactor at a molar ratio of 1.6:1. Under inert gas protection, the system was heated to 180℃ and reacted for 3 hours, then the temperature was continuously increased to 240℃ and the reaction continued for 5 hours. A vacuum system was then activated, and the reaction continued under vacuum until the hydroxyl value and acid value met the requirements. The product was then cooled and discharged to obtain polybutadiene organosilicon diol. The hydroxyl value was 14 mgKOH / g, and the acid value was 0.06 mgKOH / g.

[0151] The structural formula of the prepared polybutadiene organosilicon diol is as follows:

[0152]

[0153] Where m is 8, x is 6, y is 4, and R1 is -CH2CH2CH2-.

[0154] This embodiment provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0155] (1) Diisocyanate: Diphenylmethane diisocyanate, 31 parts;

[0156] (2) Polybutadiene organosilicon diol prepared in this embodiment: 35 parts;

[0157] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 27 parts;

[0158] (4) Small molecule chain extender: ethylene glycol, 7 parts.

[0159] The preparation method includes the following steps:

[0160] 1) Mix polybutadiene organosilicon diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0161] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0162] Comparative Example 1

[0163] This comparative example provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0164] (1) Diisocyanate: Diphenylmethane diisocyanate, 32 parts;

[0165] (2) Polybutadiene diol: 38 parts, purchased from Lanzhou Petrochemical Company, structural formula is: (x1 is 22, y1 is 12);

[0166] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 22 parts;

[0167] (4) Small molecule chain extender: 1,4-butanediol, 8 parts.

[0168] The preparation method includes the following steps:

[0169] 1) Mix polybutadiene diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0170] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic butadiene polyurethane elastomer.

[0171] Comparative Example 2

[0172] This comparative example provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0173] (1) Diisocyanate: Diphenylmethane diisocyanate, 32 parts;

[0174] (2) Polydimethylsiloxane diol: 38 parts, purchased from WACKER, structural formula is... (m1 is 24);

[0175] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 22 parts;

[0176] (4) Small molecule chain extender: 1,4-butanediol, 8 parts.

[0177] The preparation method includes the following steps:

[0178] 1) Mix polydimethylsiloxane diol, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0179] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic silicone polyurethane elastomer.

[0180] Comparative Example 3

[0181] This comparative example provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0182] (1) Diisocyanate: Diphenylmethane diisocyanate, 32 parts;

[0183] (2) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 60 parts;

[0184] (4) Small molecule chain extender: 1,4-butanediol, 8 parts.

[0185] The preparation method includes the following steps:

[0186] 1) Mix other macromolecular diols and small molecule chain extenders evenly to obtain a mixture;

[0187] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0188] Comparative Example 4

[0189] This comparative example provides a thermoplastic silicone polyurethane elastomer, the raw materials of which, based on a total weight of 100 parts, include:

[0190] (1) Diisocyanate: Diphenylmethane diisocyanate, 32 parts;

[0191] (2) A mixture of PDMS-OH and CTPB in a molar ratio of 1.5:1, totaling 38 parts, wherein the structures of PDMS-OH and CTPB are the same as those of PDMS-OH and CTPB in Example 1;

[0192] (3) Other macromolecular diols: polytetrahydrofuran diol, number average molecular weight of 2000 g / mol, 22 parts;

[0193] (4) Small molecule chain extender: 1,4-butanediol, 8 parts.

[0194] The preparation method includes the following steps:

[0195] 1) Mix PDMS-OH and CTPB, other macromolecular diols, and small molecule chain extenders evenly to obtain a mixture;

[0196] 2) Add diisocyanate to the mixture in step 1) and react at 100°C for 2 min to obtain thermoplastic polyurethane elastomer.

[0197] Test case

[0198] The properties of the thermoplastic polyurethane elastomers prepared in each embodiment and comparative example were tested; the results are shown in Table 1.

[0199] Table 1 Properties of thermoplastic polyurethane elastomers

[0200]

[0201]

[0202] Because PDMS-OH has an extremely low solubility parameter and very poor compatibility, the Si-TPU prepared with it exhibits severe phase separation and is opaque. In contrast, CTPB has a relatively high solubility parameter, and its reaction with PDMS-OH yields a polybutadiene silicone diol with a suitable solubility parameter. However, the thermoplastic polyurethane elastomer prepared in Comparative Example 4 from the combination of PDMS-OH, CTPB, and diisocyanate exhibits severe phase separation, poor mechanical properties, and is unfavorable for subsequent processing. Furthermore, it suffers from high haze and poor transparency, affecting product usability. In contrast, the Si-TPU prepared from the polybutadiene silicone diol provided in Examples 1-9 of this invention exhibits less phase separation, better mechanical properties, and good product transparency.

[0203] Furthermore, compared to the comparative examples, the tensile strength, elongation at break, and hardness of the thermoplastic polyurethane elastomers provided in Examples 1-9 of this invention are significantly improved, indicating that the thermoplastic polyurethane elastomers also possess excellent mechanical properties. Compared to the comparative examples, the glass transition temperature and static water contact angle of the thermoplastic polyurethane elastomers provided in Examples 1-9 of this invention are significantly reduced, indicating that the thermoplastic polyurethane elastomers also possess outstanding low-temperature resilience and surface hydrophobicity. The thermoplastic polyurethane elastomer prepared in Example 1 exhibits the best overall performance.

[0204] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polybutadiene organosilicon diol, characterized in that, Its structural formula is shown in equation (I): （I）； Wherein, R1 is one of alkyl, ether, or ester groups containing 1-8 carbon atoms, the hydroxyl value of the polybutadiene organosilicon diol is 14-23.2 mgKOH / g, and the acid value is 0.01-0.22 mgKOH / g; m is an integer from 5 to 10; x is an integer from 3 to 8; y is an integer from 2 to 4; and n is an integer from 4 to 5.

2. The polybutadiene organosilicon diol according to claim 1, characterized in that, R1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, #-CH2OCH2CH2- -CH2CH2OCH2CH2- -CH2CH2OCH2CH2CH2-#, #-CH2COOCH2CH2- Or #-CH2CH2CH2COOCH2CH2CH2CH2- ,in The terminal is connected to an oxygen atom, and the # symbol is connected to a silicon atom.

3. A method for preparing the polybutadiene organosilicon diol according to claim 1 or 2, characterized in that, The process includes the following steps: mixing carboxyl-terminated polybutadiene and hydroxyl-terminated polydimethylsiloxane, followed by a polycondensation reaction to obtain polybutadiene organosilicon diol; the structural formula of the carboxyl-terminated polybutadiene is shown in formula (II), and the structure of the hydroxyl-terminated polydimethylsiloxane is shown in formula (III). Formula (II); Formula (III); In formulas (II) and (III), m, x, and y are as defined in claim 1 or 2, and R1 in formula (III) is as defined in claim 1 or 2.

4. The method for preparing polybutadiene organosilicon diol according to claim 3, characterized in that, The molar ratio of the hydroxyl-terminated polydimethylsiloxane to the carboxyl-terminated polybutadiene is 1~2.5:

1. During the polycondensation reaction, the system is first heated to 140-230℃ and reacted for 2-6 hours under inert gas protection, and then the temperature is continuously raised to 210-280℃ and reacted for another 2-8 hours. After that, the vacuum system is turned on and the reaction is carried out under vacuum conditions.

5. A thermoplastic silicone polyurethane elastomer, characterized in that, The raw materials for its preparation include the polybutadiene organosilicon diol as described in claim 1 or 2, or the polybutadiene organosilicon diol prepared by the preparation method described in claim 3 or 4.

6. The thermoplastic silicone polyurethane elastomer according to claim 5, characterized in that, Based on a total weight of 100 parts, the raw materials for preparing the thermoplastic silicone polyurethane elastomer include the following components: (1) Diisocyanate: 19-42 parts; (2) The polybutadiene organosilicon diol: 28~57 parts; (3) Other diols: 6-44 parts; (4) Chain extender: 4-15 parts.

7. The thermoplastic silicone polyurethane elastomer according to claim 5, characterized in that, Based on a total weight of 100 parts, the raw materials for preparing the thermoplastic silicone polyurethane elastomer include the following components: (1) Diisocyanate: 28-38 parts; (2) The polybutadiene organosilicon diol: 34~47 parts; (3) Other diols: 15-27 parts; (4) Chain extender: 5-9 parts.

8. The thermoplastic silicone polyurethane elastomer according to claim 6 or 7, characterized in that, The thermoplastic silicone polyurethane elastomer also satisfies at least one of the following conditions (1)-(4): (1) The diisocyanate is one or more of aliphatic, alicyclic and aromatic diisocyanates; (2) The number average molecular weight of the other diols is 800~8000 g / mol; (3) The other diols are other macromolecular diols with two terminal hydroxyl groups; (4) The chain extender is a small molecule chain extender.

9. The thermoplastic silicone polyurethane elastomer according to claim 8, characterized in that, The diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, terephthalic diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, phenylenediamine diisocyanate, cyclohexane diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl-m-phenylenediamine diisocyanate, norbornene diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, and lysine diisocyanate. And / or, the number average molecular weight of the other diols is 1000-6000 g / mol; And / or, the other diol is one or more of aliphatic or aromatic polyester diol, aliphatic or aromatic polyether diol, aliphatic or aromatic polycarbonate diol, aliphatic or aromatic polylactic acid diol, and aliphatic or aromatic polyolefin diol. And / or, the chain extender is an aliphatic and / or aromatic small molecule chain extender.

10. The thermoplastic silicone polyurethane elastomer according to claim 9, characterized in that, The other diols are one or more of the following: polytetrahydrofuran diol, polybutylene adipate diol, polycarbonate diol, poly(1,6-hexanediol terephthalate) diol, polypropylene oxide diol, and polyethylene adipate diol. And / or, the chain extender is ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, butyl ethylpropanediol, diethylpentanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, trimethylpentanediol, 1,5-pentanediol, 1,2-pentanediol, hydroxyneopentyl hydroxypentanoate, 2-ethyl-1 One or more of the following: 3-hexanediol, dodecanediol, 1,4-dihydroxymethylcyclohexane, 1,4-cyclohexanediol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, resorcinol dihydroxypropyl ether, resorcinol dihydroxypropyl ethyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, 3-hydroxyethyloxyethyl-1-hydroxyethylphenyl diether, bisphenol A dihydroxyethyl ether, bisphenol A dihydroxypropyl ether, 1,4-cyclohexanediamine, diaminodicyclohexylmethane, trimethylhexanediamine, and dimethyldiaminodicyclohexylmethane.

11. A method for preparing the thermoplastic organosilicon polyurethane elastomer according to any one of claims 5-10, characterized in that, Includes the following steps: Polybutadiene silicone diol, other diols and chain extender are mixed to obtain a mixture; the mixture is then mixed with diisocyanate and reacted to obtain thermoplastic silicone polyurethane elastomer.

12. The method for preparing the thermoplastic organosilicon polyurethane elastomer according to claim 11, characterized in that, The reaction temperature is 80~160℃.

13. The application of a thermoplastic silicone polyurethane elastomer according to any one of claims 5-10 or a thermoplastic silicone polyurethane elastomer prepared by the preparation method according to claim 11 or 12 in medical supplies, clothing, protective equipment, smart wearable devices, cables, and automotive supplies.

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