Carbon dioxide-based polyurethane material as well as preparation method and application thereof

Abstract

The invention provides a carbon dioxide-based polyurethane material as well as a preparation method and application thereof. The carbon dioxide-based polyurethane material provided by the invention takes a chain segment containing carbon dioxide-based polypropylene carbonate diol as a soft segment, and takes a chain segment containing a diisocyanate compound and a chain extender as a hard segment; and proper isocyanate and chain extender are selected to prepare the mixed polyurethane vulcanized rubber with high number-average molecular weight, good thermal stability and good mechanical properties. Compared with a thermoplastic polyurethane tire, the mixing type polyurethane vulcanized rubber can realize the bonding of a polyurethane tread and a rubber tire body through co-vulcanization, and is suitable for the existing tire processing equipment and process.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology, specifically relating to a carbon dioxide-based polyurethane material, its preparation method, and its application. Background Technology

[0002] Rubber tires are typical rubber nanocomposite products, facing the "magic triangle" problem of balancing low rolling resistance, high wet skid resistance, and high wear resistance. Low rolling resistance translates to fuel efficiency, high wear resistance to long service life, and high wet skid resistance to high safety; tire rolling resistance consumes more than 20% of a car's fuel. Therefore, developing green tires with low rolling resistance and fuel efficiency is crucial for the dual-carbon strategy and environmental protection. Traditional nanofiller-reinforced rubber systems have limited potential in balancing the "magic triangle" and are dependent on petroleum resources. In conclusion, designing novel self-assembling, self-reinforcing elastomers that do not rely on petroleum resources and developing higher-performance, green, and energy-saving tires have gradually become a focus of social attention.

[0003] Polyurethane elastomers are a potential green tire tread material. They possess high strength without the need for nano-reinforcement and exhibit high wear resistance and low rolling resistance. Further achieving a balance between low rolling resistance and high wet grip could potentially solve the "magic triangle" problem in tires. Compared to traditional rubber tires, polyurethane tires offer advantages in cut resistance, tear resistance, low rolling resistance, and high wear resistance. An ideal polyurethane tire is more fuel-efficient, wear-resistant, and environmentally friendly than traditional rubber tires. Composite tires, which combine the wear-resistant, puncture-resistant, and fuel-efficient polyurethane tread with a traditional rubber tire carcass, represent a new approach to green tire technology. Hu Shikai et al. (Self-repairable, recyclable, and heat-resistant polyurethane for high-performance automobile tires, NanoEnergy, Vol. 95) synthesized polyurethane as a tire tread material using polyhexylene carbonate diol (PCDL). Their research found that the polarity of the carbonate groups in PCDL and their interaction with the hard segments can balance the "magic triangle" performance of tires to some extent, but its wet-skid resistance still cannot compare to that of green tire treads. This is because PCDL only possesses the characteristics of polycarbonate, making it difficult to further adjust the wet-skid resistance of polyurethane by modifying its structure. Summary of the Invention

[0004] Currently, most green tire raw materials rely on petroleum resources, making the development of petroleum-independent green tire materials a crucial research topic. Existing technicians use polyhexylene carbonate diol (PU) to synthesize PU materials for tires. However, PU only possesses the characteristics of polycarbonate, making it difficult to further adjust its structure to modify the anti-skid properties of polyurethane. In contrast, carbon dioxide-based polypropylene carbonate diol (PPD) possesses the dual characteristics of both polycarbonate and polyether. Its molecular structure can be designed and controlled by altering the structure and molecular weight of the initiator diol. The resulting polyurethane elastomer exhibits greater adjustability in anti-skid properties compared to PPD-based PPD elastomers. Furthermore, since the raw material is CO2, it is not dependent on petroleum resources, thus contributing to energy conservation, emission reduction, and sustainable development.

[0005] One of the objectives of this invention is to provide a carbon dioxide-based polyurethane material, which uses segments containing carbon dioxide-based polypropylene carbonate diol as soft segments and segments containing diisocyanate compounds and chain extenders as hard segments.

[0006] In the carbon dioxide-based polyurethane material provided by this invention:

[0007] The number average molecular weight of the carbon dioxide-based polypropylene carbonate diol is 1000-5000, preferably 1500-3000.

[0008] The diisocyanate compound is selected from at least one of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), 1,5-naphthalene diisocyanate (NDI), terephthalic diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), and dimethylbiphenyl diisocyanate (TODI).

[0009] The chain extender is a hydroxyl-containing compound with unsaturated double bonds, preferably at least one selected from trimethylolpropane monoallyl ether, glyceryl allyl ether, trimethylolpropane, 1,4-butenediol, 3-allyloxy-1,2-propanediol, and glyceryl monomethacrylate.

[0010] According to the present invention, the carbon dioxide-based polypropylene carbonate diol (PPCD) is obtained by reacting an initiator diol and / or a diamine, carbon dioxide, and an epoxy monomer in the presence of a catalyst C1.

[0011] The initiator diol is selected from polycaprolactone diol, polycaprolactone carbonate copolyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated styrene-butadiene rubber, polylactic acid diol, polytetramethylene ether glycol (PTMEG), polypropylene oxide glycol (PPG), polytrimethylene ether glycol (PO3G), tetrahydrofuran-propylene oxide copolyol, polycaprolactone (PCDL), and polycaprolactone diol. Hexanediol adipate diol (PHA), polyethylene adipate diol (PEA), poly(1,4-butylpentylene adipate) diol (PBA), poly(neoprene glycol adipate) diol (PNA), polybutylene succinate, polybutylene succinate, polybutylene succinate, ethylene glycol (EG), 1,4-butanediol (BDO), 1,6-hexanediol (HG), diethylene glycol (DEG), 1,2-propanediol The diol is selected from at least one of the following: alcohol, 1,3-propanediol, 1,2-octanediol, 2,3-butanediol, and 1,4-cyclohexanediol; preferably, the initiator diol is selected from polycaprolactone diol, polycaprolactone carbonate copolydiol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated styrene-butadiene rubber, polylactic acid diol, polytetramethylene ether diol (PTMEG), and polypropylene glycol (PPG). At least one of the following: polytrimethylene ether glycol (PO3G), tetrahydrofuran-propylene oxide copolymer glycol, polycaprolactone (PCDL), polyhexanediol adipate diol (PHA), polyethylene adipate diol (PEA), poly(1-4-butylpentanediol adipate) diol (PBA), polyneoprene adipate diol (PNA), polybutylene succinate, polybutylene succinate, and polybutylene succinate.

[0012] The initiator diamine is selected from at least one of 1,3-propanediamine, 1,5-pentanediamine, hexanediamine, o-phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, p-phenylenediamine, m-phenylenediamine, and 1,3-cyclohexanedimethylamine;

[0013] The epoxy monomer is selected from at least one of C2 to C10 epoxy compounds, preferably from at least one of propylene oxide (PO), 1,2-epoxybutane (BO), hexane oxide, allyl glycidyl ether (AGE), tetrahydrofuran (THF), cycloethylene oxide (CHO), 4-vinylcyclohexene-1,2-epoxide (VCHO), cyclopentene oxide (CPO), and ethylene oxide.

[0014] The molar ratio of the initiator diol and / or diamine to the epoxy monomer is (1-2.1):1, preferably (1-1.6):1;

[0015] The catalyst C1 is selected from at least one of Zn-Fe bimetallic cyanide (Zn-Fe-DMC), Zn-Co bimetallic cyanide (Zn-Co-DMC), Salen-Co(III) catalyst, Salen-Co(III) complex of quaternary ammonium salt, citrate complex, zinc glutarate (ZnGA), and Zn3[Co(CN)6]2-based bimetallic cyanide complex;

[0016] The amount of catalyst C1 can be added according to the commonly used amount in the prior art. For example, the amount of catalyst C1 is 0.1 to 5 wt% of the epoxy monomer, preferably 0.1 to 2 wt%.

[0017] The reaction conditions are as follows: carbon dioxide pressure is maintained at 0.1-5 MPa, reaction temperature is 40-80℃, and reaction time is 1-12 h.

[0018] The reaction process further includes steps of dissolving, filtering, washing, and drying the reaction product; wherein, the solvent for dissolution can be a solvent such as dichloromethane, the solvent for washing can be a solvent such as ethanol, and the drying can be carried out under common drying conditions, such as room temperature vacuum drying.

[0019] According to a specific embodiment of the present invention, the carbon dioxide-based polypropylene carbonate diol can be prepared by the following specific process: After heating and drying a stainless steel autoclave, it is transferred to a glove box under an argon atmosphere while still hot. After the autoclave cools to room temperature, catalyst C1 is added, followed by epoxy monomer and initiator. The autoclave is then sealed. The autoclave is removed from the glove box and placed in an oil bath. CO2 is introduced, and the reaction is started with stirring. If the pressure drops by more than 0.2 MPa during the reaction, CO2 needs to be added in time. After the reaction, the autoclave is placed in an ice-water bath to cool to room temperature. The valve is opened to slowly release the remaining CO2. The product is dissolved in dichloromethane and filtered to remove the catalyst. Then, dichloromethane is removed by rotary evaporation. The product is washed with ethanol, dissolved again, and the process is repeated three times. The product is then vacuum dried at room temperature. The obtained polymer is stored in a cool, dry place for later use.

[0020] The carbon dioxide-based polypropylene carbonate diol (PPCD) used in this invention is an oligomeric polyol prepared from CO2 as a raw material, which is generated by copolymerization of carbon dioxide, epoxy monomers and initiators under the action of a catalyst.

[0021]

[0022] PPCD molecular chains primarily contain carbonate bonds formed by the alternating copolymerization of carbon dioxide and epoxy monomers, along with a small amount of ether bonds formed by the homopolymerization of epoxy monomers. The molecular chains are terminal hydroxyl groups, and the molecular structure contains repeating carbonate group structural units, making it a polycarbonate-polyether polyol. Therefore, carbon dioxide polyol can be considered a polyether polyol modified with carbonate structural units. Its polyurethane products combine the advantages of both polyether-type and polycarbonate-type polyurethanes, exhibiting excellent overall performance. PPCD production represents a direction for CO2 recovery and utilization, an effective way to achieve the goals of "carbon peaking" and "carbon neutrality." Furthermore, utilizing CO2 to synthesize high-molecular polymer materials and developing an artificial carbon cycle can reduce the use of traditional petroleum-based raw materials, alleviating dependence on petroleum resources and possessing significant socio-economic value. In addition, carbon dioxide resources are abundant and widely available, largely unaffected by cost. As an environmentally friendly material with great development potential, PPCD has broad application prospects. Therefore, polyurethane materials prepared using PPCD as raw material can replace traditional petroleum-based raw materials, reducing dependence on petroleum resources. In addition, the prepared products have high strength and hydrolysis resistance, exhibiting significant performance advantages.

[0023] A second objective of this invention is to provide a method for preparing the carbon dioxide-based polyurethane material described in one objective of this invention, comprising: reacting components including the carbon dioxide-based polypropylene carbonate diol, diisocyanate compounds and chain extenders to obtain the carbon dioxide-based polyurethane material.

[0024] Preferably, the preparation method of the carbon dioxide-based polyurethane material specifically includes the following steps:

[0025] (1) The carbon dioxide-based polypropylene carbonate diol and diisocyanate compound are subjected to a prepolymerization reaction under the action of catalyst C2 to obtain a polyurethane prepolymer.

[0026] (2) After adding a chain extender to the polyurethane prepolymer obtained in step (1) and carrying out a chain extension reaction, the carbon dioxide-based polyurethane material is obtained.

[0027] In the preparation method of the carbon dioxide-based polyurethane material:

[0028] The molar ratio of the carbon dioxide-based polypropylene carbonate diol, the diisocyanate compound, and the chain extender is 1:(1.01-7):(0.01-6), preferably 1:(1.57-6.76):(0.57-5.76).

[0029] The catalyst C2 is selected from at least one of organotin catalysts, organozinc catalysts, and organobismuth catalysts, preferably from at least one of stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, di(dodecyl sulfide)dibutyltin, zinc isooctanoate, and bismuth isooctanoate.

[0030] The amount of catalyst C2 can be added according to the commonly used amount in the prior art. For example, the amount of catalyst C2 is 0.001 to 0.08 wt% of carbon dioxide-based polypropylene carbonate diol, preferably 0.005 to 0.03 wt%.

[0031] The conditions for the prepolymerization reaction are: 70–95°C for 20–60 min;

[0032] The chain extension reaction conditions are: 80-110℃ for 15-60 min.

[0033] This invention synthesizes PPCD using hydroxyl or amino initiators, CO2, and epoxy monomers as raw materials in the presence of a catalyst. Using this PPCD as the soft segment, and selecting suitable isocyanates and chain extenders, a compounded polyurethane with high number-average molecular weight (approximately 90,000-200,000), good thermal stability, and excellent mechanical properties is prepared. Compared to thermoplastic polyurethane tires, this compounded polyurethane can achieve bonding between the polyurethane tread and the rubber carcass through co-vulcanization, making it compatible with existing tire processing equipment and processes.

[0034] A third objective of this invention is to provide a compounded polyurethane vulcanizate comprising a mixture of carbon dioxide-based polyurethane material, additives, and / or reaction products. The carbon dioxide-based polyurethane material is either the carbon dioxide-based polyurethane material described in one objective of this invention or a carbon dioxide-based polyurethane material obtained by the preparation method described in another objective of this invention. The compounded polyurethane vulcanizate exhibits a glass transition temperature of -29 to -17°C, an initial thermal decomposition temperature of 364 to 440°C, a tensile strength of 23.4 to 48.8 MPa, and a tanδ of 0°C of 0.28 to 0.82.

[0035] In the compounded polyurethane vulcanizate provided by this invention, the additives can be selected from commonly used additive components of vulcanizates. For example, the additives include activators, accelerators, and vulcanizing agents. The activator is selected from at least one of stearic acid and activator NH-2 (a complex of chromium chloride / zinc chloride and DM). The accelerator is selected from at least one of 2-mercaptobenzothiazole (accelerator M), dibenzothiazole disulfide (accelerator DM), diphenylguanidine accelerator (accelerator D), and N-cyclohexyl-2-benzothiazole sulfenamide (accelerator CZ). The vulcanizing agent can be commonly used sulfur. Based on 100 parts by weight of the carbon dioxide-based polyurethane material, the amount of each activator, accelerator, and vulcanizing agent is independently 0.5 to 2 parts. Other commonly used additive components may also be added to the additives.

[0036] This invention uses hydroxyl or amino initiators, CO2, and epoxy monomers as raw materials to synthesize PPCD. The PPCD is then reacted with isocyanate compounds and chain extenders to modify the hard segment content (e.g., 15%–50%), resulting in a series of polycarbonate-based compounded polyurethanes. The synthesized compounded polyurethane vulcanizates exhibit glass transition temperatures (Tg) of -29 to -17°C, initial thermal decomposition temperatures above 364–440°C, tensile strengths above 23.4–48.8 MPa, and tanδ at 0°C of 0.28–0.82, achieving excellent thermal stability, mechanical properties, and wet skid resistance. Furthermore, the various properties of the material can be directly controlled by adjusting the raw material ratios, making it suitable as a green tire tread material, contributing to energy conservation and emission reduction, and holding significant importance for environmental protection.

[0037] The fourth objective of this invention is to provide a method for preparing the compounded polyurethane vulcanizate described in the third objective of this invention, comprising: vulcanizing the components including carbon dioxide-based polyurethane material and additives to obtain the compounded polyurethane vulcanizate; preferably, the vulcanization conditions are: vulcanization at 130-150°C for 10-50 minutes.

[0038] Compared to polyhexylene carbonate diol, carbon dioxide-based polypropylene carbonate diol (PPCD) possesses the dual characteristics of polycarbonate and polyether. Its molecular structure can be designed and controlled by altering the structure and molecular weight of the initiator diol, resulting in polyurethane elastomers with greater adjustability in wet skid resistance compared to those synthesized from polyhexylene carbonate diol. Therefore, this invention utilizes initiators containing hydroxyl or amino groups to synthesize PPCD. Using this PPCD as the soft segment, carbon dioxide-based self-assembled, self-reinforced polyurethane elastomers with high wet skid resistance, high wear resistance, and low rolling resistance can be designed and synthesized. Furthermore, traditional polyurethane (PU) raw materials rely on petroleum resources. The production of PPCD, an alternating copolymer of carbon dioxide and epoxy monomers, can utilize carbon dioxide, and its post-use biodegradability is beneficial to environmental protection, thus attracting widespread attention. This invention achieves excellent thermal stability and mechanical properties in the synthesis of polyurethane using PPCD, facilitating industrial production and enabling the application of PPCD in green tires, reducing dependence on petroleum resources, and perfectly aligning with the national sustainable development strategy. Attached Figure Description

[0039] Figure 1 The images show the infrared spectra of the carbon dioxide-based polyurethane materials synthesized in Examples 4-6, with curves A-C representing the infrared spectra of the carbon dioxide-based polyurethane materials synthesized in Examples 4-6, respectively. Figure 1 The display shows that at 3345cm -1 The characteristic absorption peak of NH in the -NH-COO- group appeared at 2250 cm⁻¹. -1 The absence of characteristic peaks for -NCO groups at the specified location proves that the -NCO groups and the hydroxyl groups at both ends of the unsaturated chain extender react completely, indicating that a carbon dioxide-based polyurethane material has been obtained.

[0040] Figure 2 The figures show the DSC curves of the compounded polyurethane vulcanizates synthesized in Examples 4 to 6, with curves A to C being the DSC curves of the compounded polyurethane vulcanizates synthesized in Examples 4 to 6, respectively. Figure 2 This indicates that the sample's Tg does not exhibit a melting absorption peak or crystallization within the range of -29 to -17℃.

[0041] Figure 3 The DMA curves are for the compounded polyurethane vulcanizates synthesized in Examples 4-6, with curves A-C being the DMA curves of the compounded polyurethane vulcanizates synthesized in Examples 4-6, respectively. Figure 3 The tanδ values ​​of the samples at 0℃ were 0.28–0.82, and at 60℃ were 0.11–0.23, indicating that the compounded polyurethane vulcanizate has good rolling resistance and wet skid resistance. Detailed Implementation

[0042] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0043] The testing instruments and conditions used in this embodiment are as follows:

[0044] Infrared testing: The prepared polyurethane material was analyzed using a Bruker TENSOR 27 Fourier transform infrared spectroscopy system, with a testing range of 4000-500 cm⁻¹. -1 The chemical structure of the polyurethane elastomer was tested using ATR-IR mode. The sample preparation method was as follows: cut a 3×3×1cm sample... 3 The elastomer samples were dried in an infrared oven before being tested directly.

[0045] DSC testing: Differential scanning calorimetry (DSC) analysis was performed using the STARe system from Mettler Toledo, Switzerland. The heating and cooling rates were set to 10 K / min, the sample mass was approximately 10 mg, and a nitrogen atmosphere was used for protection. The temperature scan range was 193 K to 353 K.

[0046] Mechanical property testing: The tensile strength and elongation at break of the polyurethane vulcanizate were tested according to GB / T528-2009 standard using an Instron 5567 universal tensile testing machine from Instron Corporation, USA. Dumbbell-shaped specimens (25mm × 6mm × 1mm) were cut using a cutter and tested at room temperature. The tensile rate was set to 500mm / min, and at least five specimens were tested for each sample under the same conditions.

[0047] DMA test: The model used is GABO The 500 Dynamic Thermomechanical Analysis (DMA) was performed under the following conditions: strain 1%, frequency 1 Hz, and heating rate 3 °C / min. -1 The test temperature range is -70 to 100℃ for tensile testing.

[0048] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0049] Example 1: Synthesis of carbon dioxide-based polypropylene carbonate diol (PPCD-1)

[0050] A 15mL stainless steel autoclave was dried in an oven at 80℃ for 5 hours, then transferred while still hot to an argon-atmosphere glove box. After the autoclave cooled to room temperature, 0.01g of Zn-Fe bimetallic cyanide (Zn-Fe-DMC) catalyst was added, followed by 5.81g of propylene oxide and 260.00g of polytrimethylene ether glycol (PO3G, Mn=2000). The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 65℃ oil bath, where 5MPa of CO2 was introduced, and stirring was initiated. If the pressure dropped by more than 0.2MPa during the reaction, CO2 was added to bring the pressure back to 5MPa. After 5 hours of reaction, the autoclave was cooled in an ice-water bath to terminate the reaction at room temperature. The remaining CO2 was slowly released by opening the valve. The product was dissolved in dichloromethane and filtered to remove the catalyst. Dichloromethane was then removed by rotary evaporation. The product was washed with ethanol, dissolved again, and the process was repeated three times. The product was then vacuum dried at room temperature. The resulting polymer was stored in a cool, dry place for later use.

[0051] Example 2: Synthesis of carbon dioxide-based polypropylene carbonate diol (PPCD-2)

[0052] A 15mL stainless steel autoclave was dried in an oven at 80℃ for 5 hours, then transferred to an argon-atmospheric glove box while still hot. After the autoclave cooled to room temperature, 0.01g of Zn-Co bimetallic cyanide (Zn-Co-DMC) catalyst was added, followed by 7.20g of propylene oxide and 247.93g of polypropylene glycol (PPG, Mn=2000). The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 65℃ oil bath, where 5MPa of CO2 was introduced, and stirring was started. If the pressure dropped by more than 0.2MPa during the reaction, CO2 was added to bring the pressure back to 5MPa. After 4.5 hours of reaction, the autoclave was cooled in an ice-water bath to terminate the reaction at room temperature. The remaining CO2 was slowly released by opening the valve. The product was dissolved in dichloromethane and filtered to remove the catalyst. The dichloromethane was then removed by rotary evaporation. The product was washed with ethanol, dissolved again, and the process was repeated three times. The product was then vacuum dried at room temperature. The resulting polymer was stored in a cool, dry place for later use.

[0053] Example 3: Synthesis of carbon dioxide-based polypropylene carbonate diol (PPCD-3)

[0054] A 15mL stainless steel autoclave was dried in an oven at 80℃ for 5 hours, then transferred while still hot to an argon-atmospheric glove box. After the autoclave cooled to room temperature, 0.01g of Zn-Fe bimetallic cyanide (DMC) catalyst was added, followed by 5.81g of propylene oxide and 7.41g of 1,3-propanediamine. The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 65℃ oil bath, where 5MPa of CO2 was introduced, and stirring was initiated. If the pressure dropped by more than 0.2MPa during the reaction, CO2 was added to bring the pressure back to 5MPa. After 6 hours of reaction, the autoclave was cooled in an ice-water bath to terminate the reaction at room temperature. The remaining CO2 was slowly released by opening the valve. The product was dissolved in dichloromethane and filtered to remove the catalyst. Dichloromethane was then removed by rotary evaporation. The product was washed with ethanol, dissolved again, and the process was repeated three times. The product was then vacuum dried at room temperature. The resulting polymer was stored in a cool, dry place for later use.

[0055] Example 4

[0056] Polyurethane was synthesized using PPCD-1 synthesized in Example 1.

[0057] Using PPCD-1 with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPCD-1:PPDI:TME ratio of 1:1.58:0.58 (molar ratio) was designed, with a hard segment content of 15%. A carbon dioxide-based polyurethane material was prepared via a prepolymer method.

[0058] (1) Remove water from 148g PPCD-1 (Mn=2000) under mechanical stirring at -0.095MPa, 120℃ and 120r / min for 1.5h. This step removes water from the raw material.

[0059] (2) After the system is cooled to 85°C, 18g of terephthalic diisocyanate (PPDI) and 0.02g of dibutyltin dilaurate catalyst are added. The rotation speed is adjusted to 300r / min. After the system is heated to 90°C and the reaction is carried out for 1h, the diisocyanate-terminated polyurethane prepolymer is obtained.

[0060] (3) Add 7g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20min, take out the product and place it in an oven at 90℃ for 18h to obtain carbon dioxide-based polyurethane material with a number average molecular weight of 96000.

[0061] Preparation of compounded polyurethane vulcanizate MPU-1:

[0062] Add 100 parts of carbon dioxide-based polyurethane material, 0.5 parts of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, and 1 part of sulfur to an open mill according to the mass ratio, mix thoroughly, and cut into thin sheets; vulcanize at 150℃ for 20 minutes in a flat vulcanizing machine, and release gas 3 to 8 times to obtain vulcanized rubber sample MPU-1.

[0063] Example 5

[0064] Polyurethane was synthesized using PPCD-1 synthesized in Example 1.

[0065] Using PPCD-1 with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPCD-1:PPDI:TME ratio of 1:2.51:1.51 (molar ratio) was designed, with a hard segment content of 25%. A carbon dioxide-based polyurethane material was prepared via a prepolymer method.

[0066] (1) Remove water from 131g PPCD-1 (Mn=2000) under mechanical stirring at -0.095MPa, 120℃ and 120r / min for 1.5h. This step removes water from the raw material.

[0067] (2) After the system is cooled to 85°C, 26g of terephthalic diisocyanate (PPDI) and 0.01g of dibutyltin dilaurate catalyst are added. The rotation speed is adjusted to 300r / min. After the system is heated to 90°C and the reaction is carried out for 1h, the diisocyanate-terminated polyurethane prepolymer is obtained.

[0068] (3) Add 7g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20min, take out the product and place it in an oven at 90℃ for 18h to obtain carbon dioxide-based polyurethane material with a number average molecular weight of 92000.

[0069] Preparation of compounded polyurethane vulcanizate MPU-2:

[0070] Add 100 parts of carbon dioxide-based polyurethane material, 0.5 parts of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, and 1 part of sulfur to an open mill according to the mass ratio, mix thoroughly, and cut into thin sheets; vulcanize at 150℃ for 20 minutes in a flat vulcanizing machine, and release gas 3 to 8 times to obtain vulcanized rubber sample MPU-2.

[0071] Example 6

[0072] Polyurethane was synthesized using PPCD-2 synthesized in Example 2.

[0073] Using PPCD-2 with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPCD-2:PPDI:TME ratio of 1:3.08:2.08 (molar ratio) was designed, with a hard segment content of 30%. A carbon dioxide-based polyurethane material was prepared via a prepolymer method.

[0074] (1) Remove water from 245g PPCD-2 (Mn=2000) under mechanical stirring at -0.095MPa, 120℃ and 120r / min for 1.5h. This step removes water from the raw material.

[0075] (2) After the system is cooled to 85°C, 60g of terephthalic diisocyanate (PPDI) and 0.02g of dibutyltin dilaurate catalyst are added. The rotation speed is adjusted to 300r / min. After the system is heated to 90°C and the reaction is carried out for 1h, the diisocyanate-terminated polyurethane prepolymer is obtained.

[0076] (3) Add 45g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20min, take out the product and place it in an oven at 90℃ for 18h to obtain carbon dioxide-based polyurethane material with a number average molecular weight of 99000.

[0077] Preparation of compounded polyurethane vulcanizate MPU-3:

[0078] Add 100 parts of carbon dioxide-based polyurethane material, 0.5 parts of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, and 1 part of sulfur to an open mill according to the mass ratio, mix thoroughly, and cut into thin sheets; vulcanize at 150℃ for 20 minutes in a flat vulcanizing machine, and release gas 3 to 8 times to obtain vulcanized rubber sample MPU-3.

[0079] Preparation of Comparative Example 1: PCDL-TPU

[0080] Polyurethane material PCDL-TPU was prepared by using polycarbonate diol (PCDL), 1,5-naphthalene diisocyanate (NDI), and 1,4-butanediol (BDO) in a molar ratio of PCDL:NDI:BDO = 1:1.5:0.5.

[0081] (1) Dehydrate PCDL (Mn=2000) at 115℃ and vacuum dry for 1.5 hours. This step removes the moisture from the raw material.

[0082] (2) Add NDI and react with polyol (PCDL) to obtain a prepolymer at 100°C for 2 hours. This step yields a diisocyanate-terminated polyurethane prepolymer.

[0083] (3) Mix the prepolymer with BDO, pour it into a mold made of polytetrafluoroethylene, heat it to 100°C and react for 12 hours to obtain PCDL-TPU.

[0084] Table 1 shows the performance test results of the polyurethane vulcanizates prepared in Examples 4-5 and the polyurethane material prepared in Comparative Example 1.

[0085] Table 1

[0086]

[0087] As can be seen from the test results in Table 1, compared with the PCDL-TPU prepared in Comparative Example 1, the polyurethane materials synthesized using PPCD in Examples 4 to 6 have higher tensile strength. Furthermore, the PPCD type polyurethane material can achieve the bonding between the polyurethane tread and the rubber carcass through co-vulcanization, which is suitable for existing tire processing equipment and processes.

Claims

1. A carbon dioxide-based polyurethane material, wherein a segment comprising a carbon dioxide-based polypropylene carbonate diol is used as a soft segment, and a segment comprising a diisocyanate compound and a chain extender is used as a hard segment. 2.The carbon dioxide-based polyurethane material according to claim 1, wherein the number average molecular weight of the carbon dioxide-based polypropylene carbonate diol is 1000 to 5000, preferably 1500 to 3000; and / or the diisocyanate compound is at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, dimethyl diphenyl diisocyanate; and / or the chain extender is a hydroxyl-containing compound having an unsaturated double bond, and is at least one selected from the group consisting of trimethylolpropane monoallyl ether, glycerol allyl ether, trimethylolpropane, 1,4-butenediol, 3-allyloxy-1,2-propanediol, glycerol monomethacrylate; and / or the carbon dioxide-based polypropylene carbonate diol is obtained by reacting a starter diol and / or diamine, carbon dioxide, and an epoxy monomer in the presence of a catalyst C1. 4.The carbon dioxide-based polyurethane material according to claim 3, wherein the starter diol is at least one selected from the group consisting of polycaprolactone diol, polycaprolactone carbonate copolymer diol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated butadiene styrene rubber, polylactic acid diol, polytetramethylene ether diol, polypropylene oxide diol, polytrimethylene ether diol, tetrahydrofuran-propylene oxide copolymer diol, polycaprolactone, polyhexanediol adipate diol, polyethylene glycol adipate diol, poly-1,4-butyl glycol adipate diol, polyneopentyl glycol adipate diol, polybutylene succinate-adipate, polybutylene succinate-sebacate, polybutylene succinate, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-octanediol, 2,3-butanediol, 1,4-cyclohexanediol; and / or the starter diamine is at least one selected from the group consisting of 1,3-propanediamine, 1,5-pentanediamine, hexanediamine, o-phenylenediamine, 4,4'-diamino-2,2'-dimethyl diphenyl, p-phenylenediamine, m-phenylenediamine, 1,3-cyclohexanedimethylamine; and / or the epoxy monomer is at least one selected from the group consisting of C2 to C10 epoxy compounds, preferably at least one selected from the group consisting of propylene oxide, 1,2-epoxybutane, hexylene oxide, allyl glycidyl ether, tetrahydrofuran, ethylene oxide, 4-vinylcyclohexene-1,2-epoxide, cyclopentene oxide, oxirane; and / or the molar ratio of the starter diol and / or diamine to the epoxy monomer is (1 to 2.1) : 1, preferably (1 to 1.6) :

1. ​ ​ 3. The carbon dioxide-based polyurethane material of claim 1, wherein, ​ ​ ​ ​ ​ ​ The catalyst C1 is at least one selected from Zn-Fe double metal cyanide, Zn-Co double metal cyanide, Salen-Co(III) catalyst, Salen-Co(III) complex of quaternary ammonium salt, citrate complex, zinc glutarate, Zn3[Co(CN)6]2-based double metal cyanide complex; and / or, The catalyst C1 is at least one selected from Zn-Fe double metal cyanide, Zn-Co double metal cyanide, Salen-Co(III) catalyst, Salen-Co(III) complex of quaternary ammonium salt, citrate complex, zinc glutarate, Zn3[Co(CN)6]2-based double metal cyanide complex; and / or, The reaction conditions are as follows: the carbon dioxide pressure is maintained at 0.1-5 MPa, the reaction temperature is 40-80℃, and the reaction time is 1-12 h.

5. A process for the preparation of the carbon dioxide-based polyurethane material according to any one of claims 1 to 4, comprising: The components including the carbon dioxide-based polypropylene carbonate diol, diisocyanate compound and chain extender are reacted to obtain the carbon dioxide-based polyurethane material.

6. The production method according to claim 5, wherein The preparation method of the carbon dioxide-based polyurethane material specifically comprises the following steps: (1) The carbon dioxide-based polypropylene carbonate diol and diisocyanate compound are subjected to prepolymerization under the action of a catalyst C2 to obtain a polyurethane prepolymer; (2) The polyurethane prepolymer obtained in step (1) is added with a chain extender to perform chain extension reaction, thereby obtaining the carbon dioxide-based polyurethane material.

7. The preparation method according to claim 6, wherein, The molar ratio of the carbon dioxide-based polypropylene carbonate diol, diisocyanate compound and chain extender is 1:(1.01-7):(0.01-6), preferably 1:(1.57-6.76):(0.57-5.76); and / or, The catalyst C2 is at least one selected from organotin catalyst, organozinc catalyst, organobismuth catalyst, preferably at least one selected from stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis(dodecylthio), zinc isooctoate, bismuth isooctoate; and / or, The catalyst C2 is at least one selected from organotin catalyst, organozinc catalyst, organobismuth catalyst, preferably at least one selected from stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis(dodecylthio), zinc isooctoate, bismuth isooctoate; and / or, The prepolymerization conditions are as follows: 70-95℃ for 20-60 min; and / or, The chain extension reaction conditions are as follows: 80-110℃ for 15-60 min.

8. A mixed polyurethane vulcanizate comprising a mixture and / or reaction product of a carbon dioxide-based polyurethane material and an auxiliary agent, wherein the carbon dioxide-based polyurethane material is the carbon dioxide-based polyurethane material according to any one of claims 1-4 or obtained by the preparation method according to any one of claims 5-7.

9. The mixed polyurethane vulcanizate according to claim 8, wherein, The auxiliary agent comprises an active agent, an accelerator and a vulcanizing agent, and preferably, the amount of each of the active agent, accelerator and vulcanizing agent is independently 0.5-2 parts based on 100 parts by mass of the carbon dioxide-based polyurethane material.

10. A process for the preparation of the millable polyurethane vulcanizate of any one of claims 8 to 9, comprising: The components including the carbon dioxide-based polyurethane material and the auxiliary are vulcanized to obtain the mixing type polyurethane vulcanized rubber; preferably, the vulcanization condition is 130-150 °C for 10-50 min.

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