Carbon-sequestration bio-based polyurethane composite material and preparation method thereof

Abstract

The invention provides a carbon-sequestration bio-based polyurethane composite material and a preparation method thereof, and the carbon-sequestration bio-based polyurethane composite material is prepared by adopting an initiator with hydroxyl or amino, CO2 and an epoxy monomer as raw materials to synthesize carbon dioxide-based polyester diol, and then reacting with isocyanate and a chain extender to prepare the carbon-sequestration bio-based polyurethane composite material. The number-average molecular weight of the prepared bio-based polyurethane composite material is 70000-200000, the glass transition temperature (Tg) is 30 DEG C below zero to 7 DEG C below zero, the tensile strength is 20-35 MPa, the tan delta max is 1.02-1.14, and good thermal stability, mechanical properties, wet skid resistance and the like are achieved. Meanwhile, various properties of the material can be directly controlled by regulating and controlling the proportion of the raw materials, and the material serving as a damping material is energy-saving and emission-reducing and has important significance on environmental protection.

Description

Technical Field

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

[0002] With globalization and the development of modern industry, noise pollution has become increasingly serious. To address this problem, damping materials have emerged. These materials can absorb the mechanical energy generated during vibration and convert it into heat energy, thus reducing resonance amplitude and structural noise. Polyurethane elastomers (PU) are widely used in vibration reduction and noise reduction due to their advantages such as high damping, high modulus, corrosion resistance, and good adhesion. PU is mainly divided into three types: compounded, castable, and thermoplastic. It is typically composed of hard segments (isocyanate and chain extender) and soft segments (oligomeric polyols). The significant difference in thermodynamic properties between the hard and soft segments creates a unique microphase separation structure, increasing inter-chain friction during molecular motion. When subjected to vibration and deformation, it can convert vibrational kinetic energy into heat energy for dissipation, thus giving PU excellent damping performance. Simultaneously, the interaction between the hard segments of PU molecules plays a dominant role in its mechanical properties; strengthening the intermolecular forces between hard segments can significantly improve its mechanical properties. However, the main raw materials for PU, isocyanate and polyol, are usually derived from non-renewable petroleum resources. On the one hand, the use of petroleum-based and coal-based fossil fuels releases large amounts of carbon dioxide and various volatile organic compounds, harming the environment and human health. On the other hand, the price of fossil fuels fluctuates greatly, and oil is projected to be depleted within the next 50 years. Therefore, from both environmental and economic perspectives, developing renewable raw materials as green alternatives to fossil fuels has become an urgent issue. Among renewable resources, bio-based raw materials are an ideal choice to replace fossil fuels due to their abundance, high availability, and high functionality. Biomass absorbs carbon dioxide and performs photosynthesis during its growth, and is therefore generally considered a carbon-neutral material. Through chemical modification or biotransformation, bio-based raw materials can enable corresponding bio-based polyurethane damping materials to achieve the performance required for different application scenarios, continuously expanding their application scope.

[0003] Polyurethane (PU) viscoelastic damping materials, as functional materials, exhibit significant viscoelasticity and internal friction. High damping and high strength can be achieved through molecular structure design and the addition of functional fillers. Blending PU with fillers to prepare composite materials can improve the performance of PU. Composite materials prepared by uniformly dispersing fillers within a PU matrix not only maintain the properties of PU itself but also incorporate the special properties of the fillers (such as ultralight conductivity, microwave absorption, photocatalysis, degradation, bioactivity, and antibacterial properties). Commonly used nanofillers include montmorillonite (MMT), nano-TiO2, carbon nanotubes (CNTs), and graphene. Wajeeh Ur Rehman et al. (Thermoplastic polyurethane / rutile titaniumdioxide composites tuned for hydrophobicity with effective reinforcement[J]. Journal of Polymer Research, 2022, Vol.29(5).) Furthermore, the above-mentioned technical solutions improve the mechanical and other properties of materials by blending PU with fillers. However, these technical solutions modify PU based on petroleum, which is a non-renewable resource. Petroleum-based polyurethane is difficult to degrade, and the fillers used are non-biological fillers, which have a significant impact on the environment and greatly limit the application of polyurethane products. Summary of the Invention

[0004] Existing damping materials largely rely on petroleum resources, making the development of novel, petroleum-independent damping materials a crucial research topic. This invention utilizes hydroxyl- or amino-containing initiators to synthesize carbon dioxide-based polyester diols. These carbon dioxide-based polyester diols are then used as soft segments in the design and synthesis of polyurethane, with the addition of bio-based fillers to obtain carbon-fixing bio-based polyurethane elastomers. Furthermore, while traditional PU raw materials depend on petroleum resources, the production of alternating copolymers of carbon dioxide and epoxy monomers can utilize carbon dioxide, which is biodegradable after use, thus benefiting environmental protection and attracting widespread attention. This invention achieves excellent thermal stability and mechanical properties in the synthesis of polyurethane using carbon dioxide-based polyester diols, facilitating industrial production and enabling the application of carbon dioxide-based polyester diols in green tires, reducing dependence on petroleum resources.

[0005] One of the objectives of this invention is to provide a carbon-fixing bio-based polyurethane composite material, comprising a mixture of carbon dioxide-based polyurethane material, bio-based filler and / or its reaction products.

[0006] In this context, based on 100 parts by weight of the carbon dioxide-based polyurethane material, the bio-based filler is 1 to 40 parts, preferably 10 to 30 parts.

[0007] The carbon dioxide-based polyurethane material further comprises additives; preferably, based on 100 parts by weight of the carbon dioxide-based polyurethane material, the additives are 1.5 to 6 parts. The additives can be commonly used additive components in 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), and 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.

[0008] The bio-based filler is selected from at least one of lignin, tannic acid, cellulose, starch, phytic acid, gallic acid, and chitosan.

[0009] The carbon dioxide-based polyurethane material uses the reaction product of an initiator with hydroxyl or amino groups and CO2 and epoxy monomers as soft segments, and segments containing isocyanate compounds and chain extenders as hard segments.

[0010] The hydroxyl or amino-containing initiator 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 diol (PTMEG), polypropylene oxide diol (PPG), polytrimethylene ether diol (PO3G), tetrahydrofuran-propylene oxide copolyol, polycaprolactone (PCDL), polyhexyl adipate diol (PHA), polyethylene adipate diol (PEA), poly(1-4-butylpentyl adipate diol) (PBA), and poly... Neopentyl adipate diol (PNA), polybutylene adipate, polybutylene succinate, polybutylene succinate, ethylene glycol (EG), 1,4-butanediol (BDO), 1,6-hexanediol (HG), diethylene glycol (DEG), 1,2-propanediol, 1,3-propanediol, 1,2-octanediol, 2,3-butanediol, 1,4-cyclohexanediol, hexamethylenediamine, o-phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, p-phenylenediamine, m-phenylenediamine, 1,3-propanediamine, 1,5-pentanediamine, and 1,3-cyclohexanedimethylamine;

[0011] The epoxy monomer is at least one of ethylene oxide, propylene oxide (PO), 1,2-epoxybutane (BO), hexane oxide, allyl glycidyl epoxide (AGE), tetrahydrofuran (THF), cycloethylene oxide (CHO), 4-vinylcyclohexene-1,2-epoxide (VCHO), and cyclopentene oxide (CPO).

[0012] The isocyanate 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).

[0013] The chain extender is selected from at least one of trimethylolpropane monoallyl ether, glyceryl allyl ether, trimethylolpropane, 1,4-butenediol, 3-allyloxy-1,2-propanediol, and glyceryl monomethacrylate.

[0014] The second objective of this invention is to provide a method for preparing the above-mentioned carbon-fixable bio-based polyurethane composite material, comprising: mixing components including carbon dioxide-based polyurethane material and bio-based filler, and then vulcanizing to obtain the bio-based polyurethane composite material.

[0015] The vulcanization conditions are: vulcanization temperature 130-150℃, vulcanization time 20-30min;

[0016] Additives are also added during the mixing process. These additives can be commonly used components in vulcanizates, such as 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.

[0017] The carbon dioxide-based polyurethane material is prepared by the following steps:

[0018] (1) A carbon dioxide-based polyester diol is obtained by reacting an initiator with hydroxyl or amino groups, CO2 and an epoxy monomer under the action of catalyst C1.

[0019] (2) The carbon dioxide-based polyester diol and isocyanate compounds obtained in step (1) are subjected to a prepolymerization reaction under the action of catalyst C2 to obtain polyurethane prepolymer;

[0020] (3) Add a chain extender to the polyurethane prepolymer obtained in step (1) and carry out a chain extension reaction, then cure to obtain the carbon dioxide-based polyurethane material.

[0021] In the preparation of the carbon dioxide-based polyurethane material, step (1) includes:

[0022] The molar ratio of the initiator with hydroxyl or amino groups to the epoxy monomer is (1-2.5):1, preferably (1-1.7):1;

[0023] The catalyst C1 is selected from at least one of Zn-Fe bimetallic cyanide, Zn-Co bimetallic cyanide, Salen-Co(III) catalyst, Salen-Co(III) complex of quaternary ammonium salt, citrate complex, zinc glutarate, and Zn3[Co(CN)6]2-based bimetallic cyanide complex;

[0024] The amount of catalyst C1 used is 0.1 to 7 wt% of the epoxy monomer, preferably 0.1 to 2 wt%.

[0025] The reaction conditions are as follows: carbon dioxide pressure is maintained at 0.1–10 MPa, reaction temperature is 40–80 °C, and reaction time is 12–24 h.

[0026] In the preparation of the aforementioned carbon dioxide-based polyurethane material:

[0027] The molar ratio of the carbon dioxide-based polyester diol, isocyanate compound, and chain extender is 1:(1.01-8):(0.01-7), preferably 1:(1.52-6.82):(0.52-5.82);

[0028] 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.

[0029] The amount of catalyst C2 used is 0.001 to 0.09 wt% of carbon dioxide-based polyester diol;

[0030] The conditions for the prepolymerization reaction are: 65–100°C for 20–50 min;

[0031] The chain extension reaction conditions are: 80–120°C for 10–60 min;

[0032] The curing conditions are: 80-110℃ for 10-24 hours.

[0033] The carbon-fixable bio-based polyurethane composite material obtained by the above preparation method,

[0034] The number-average molecular weight of the bio-based polyurethane composite material is 70,000 to 200,000.

[0035] The glass transition temperature of the bio-based polyurethane composite material is -30 to -7°C.

[0036] The tensile strength of the bio-based polyurethane composite material is 20–35 MPa;

[0037] The tanδ of the bio-based polyurethane composite material max It ranges from 1.02 to 1.14.

[0038] This invention proposes using hydroxyl or amino initiators and CO2 and epoxy monomers as raw materials to synthesize carbon dioxide-based polyester diols under the action of a catalyst. These diols are then used as soft segments to react with isocyanates and unsaturated chain extenders to obtain compounded polyurethane elastomers. Based on this, bio-based fillers are added to modify the polyurethane to obtain high-performance polyurethane elastomers.

[0039] Existing polyurethane raw materials largely rely on petroleum resources. In contrast, this invention uses hydroxyl or amino-containing initiators and CO2 and epoxy monomers as raw materials to synthesize carbon dioxide-based polyester diols. These carbon dioxide-based polyester diols are then reacted with isocyanates and chain extenders to modify the hard segment content. By adding bio-based fillers, a series of carbon-fixing bio-based compounded polyurethanes were prepared. The synthesized compounded polyurethanes have a number-average molecular weight of 70,000–200,000 and a glass transition temperature (T0). g At -30 to -7℃, the tensile strength is 20 to 35 MPa, tanδ max Within the range of 1.02 to 1.14, good thermal stability, mechanical properties, and anti-slip properties are achieved. Furthermore, the various properties of the material can be directly controlled by adjusting the raw material ratio. As a damping material, it contributes to energy conservation and emission reduction, which is of great significance for environmental protection. Attached Figure Description

[0040] Figure 1 The infrared spectra of the carbon dioxide-based polyurethanes prepared in Comparative Example 1 and Examples 1-2 are shown at 3345 cm⁻¹. -1 The characteristic absorption peak of NH in the -NH-COO- group appeared at 2250 cm⁻¹. -1The absence of characteristic peaks for -NCO groups at the specified location indicates that the reaction between the -NCO groups and the hydroxyl groups at both ends of the unsaturated chain extender is complete, demonstrating that carbon dioxide-based polyurethane was successfully prepared.

[0041] Figure 2 The DSC curves of the bio-based polyurethane composites obtained in Comparative Example 1 and Examples 1-2 were obtained by... Figure 2 The glass transition temperature T of the visible sample g Within the temperature range of -30 to -7℃, there is no melting absorption peak and no crystallization.

[0042] Figure 3 The DMA curves of the bio-based polyurethane composites obtained in Comparative Example 1 and Examples 1-2 are shown, with tanδ values ​​for the samples. max The tanδ values ​​are 1.02, 0.99, and 1.14, respectively. max It has a relatively high damping capacity and good damping performance. Detailed Implementation

[0043] 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.

[0044] The testing instruments and conditions used in this embodiment are as follows:

[0045] Infrared testing: The prepared self-healing elastomer 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.

[0046] 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.

[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] Comparative Example 1

[0050] Preparation of carbon dioxide-based polyester diol (PPC, Mn = 2000):

[0051] 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 5.62g of propylene oxide and 235.18g of polytrimethylene ether glycol (PO3G, Mn=2000). The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 70℃ oil bath, where 8MPa of CO2 was introduced, and stirring was initiated. If the pressure dropped by more than 0.2MPa during the reaction, CO2 was promptly added to restore the set pressure. After 8 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.

[0052] Preparation of carbon dioxide-based polyurethane materials:

[0053] Using PPC with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPC:PPDI:TME ratio of 1:2.02:1.02 (molar ratio) was designed, with a hard segment content of 20%. A compounded polyurethane elastomer raw rubber was prepared via the prepolymer method.

[0054] (1) Remove water from 140g PPC (Mn=2000) for 1.5h under mechanical stirring at -0.095MPa, 120℃ and 120r / min. This step removes water from the raw material.

[0055] (2) After the system is cooled to 85°C, 22.6g 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.

[0056] (3) Add 112.4 g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500 r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20 min, take out the product and place it in an oven at 90℃ for 18 h to obtain the compounded polyurethane raw rubber product PU1.

[0057] Preparation of bio-based polyurethane composite materials:

[0058] Add 100 parts of polyurethane raw rubber PU1, 1 part of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, and 1 part of sulfur to a two-roll 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 PU / Filler-1.

[0059] Example 1

[0060] Preparation of carbon dioxide-based polyester diol (PPC, Mn = 2000):

[0061] A 15mL stainless steel autoclave was dried in an oven at 80℃ for 5 hours, then transferred to an argon-atmosphere 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 5.3g of propylene oxide and 221.5g of polypropylene glycol (PPG). The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 70℃ oil bath, where 8MPa of CO2 was introduced, and stirring was started. If the pressure dropped by more than 0.2MPa during the reaction, CO2 was added promptly to restore the set pressure. After 8 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.

[0062] Preparation of carbon dioxide-based polyurethane materials:

[0063] Using PPC with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPC:PPDI:TME ratio of 1:2.51:1.51 (molar ratio) was designed, with a hard segment content of 25%. A compounded polyurethane elastomer raw rubber was prepared via the prepolymer method.

[0064] (1) Remove water from 131g PPC (Mn=2000) for 1.5h under mechanical stirring at -0.095MPa, 120℃ and 120r / min. This step removes water from the raw material.

[0065] (2) After the system is cooled to 85°C, 26g 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.

[0066] (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 the compounded polyurethane raw rubber product PU2 with a number average molecular weight of 83000.

[0067] Preparation of bio-based polyurethane composite materials:

[0068] In a two-roll mill, add 100 parts of polyurethane raw rubber PU2, 1 part of stearic acid, 11 parts of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, 1 part of sulfur, and 20 parts of tannic acid according to the mass ratio. Mix thoroughly and cut into thin sheets. Vulcanize in a flat vulcanizing machine at 150℃ for 20 minutes, and release gas 3 to 8 times to obtain vulcanized rubber sample PU / Filler-2.

[0069] Example 2

[0070] Preparation of carbon dioxide-based polyester diol (PPC, Mn = 2000)

[0071] A 15 mL stainless steel autoclave was dried in an oven at 80 °C for 5 hours, then transferred while still hot to an argon-atmospheric glove box. After the autoclave cooled to room temperature, 0.01 g of Zn-Co bimetallic cyanide (Zn-Co-DMC) catalyst was added, followed by 7.4 g of propylene oxide and 5.0 g of 1,3-propanediamine. The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 70 °C oil bath, where 8 MPa of CO2 was introduced, and stirring was initiated. If the pressure dropped by more than 0.2 MPa during the reaction, CO2 was promptly added to restore the set pressure. After 8 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.

[0072] Preparation of carbon dioxide-based polyurethane materials:

[0073] Using PPC with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPC:PPDI:TME ratio of 1:3.74:2.74 (molar ratio) was designed, with a hard segment content of 30%. A compounded polyurethane elastomer raw rubber was prepared via the prepolymer method.

[0074] (1) Remove water from 113.75g PPC (Mn=2000) for 1.5h under mechanical stirring at -0.095MPa, 120℃ and 120r / min. This step removes water from the raw material.

[0075] (2) After the system is cooled to 85°C, 34.08 g of terephthalic diisocyanate (PPDI) and 0.02 g of dibutyltin dilaurate catalyst are added. The rotation speed is adjusted to 300 r / min. After the system is heated to 90°C and the reaction is carried out for 1 h, the diisocyanate-terminated polyurethane prepolymer is obtained.

[0076] (3) Add 27.17 g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500 r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20 min, take out the product and place it in an oven at 90℃ for 18 h to obtain the compounded polyurethane raw rubber product PU3 with a number average molecular weight of 76000.

[0077] Preparation of bio-based polyurethane composite materials:

[0078] Add 100 parts of polyurethane raw rubber, 1 part of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, 1 part of sulfur, and 10 parts of lignin to a two-roll mill according to the following mass ratio, mix thoroughly, and sheet out in a thin pass; vulcanize in a flat vulcanizing machine at 150℃ for 20 minutes, and release gas 3 to 8 times to obtain vulcanized rubber sample PU / Filler-3.

[0079] Example 3

[0080] Preparation of carbon dioxide-based polyester diol (PPC, Mn = 2000)

[0081] A 15 mL stainless steel autoclave was dried in an oven at 80 °C for 5 hours, then transferred while still hot to an argon-atmospheric glove box. After the autoclave cooled to room temperature, 0.01 g of Zn-Co bimetallic cyanide (Zn-Co-DMC) catalyst was added, followed by 7.4 g of propylene oxide and 5.0 g of 1,3-propanediamine. The autoclave was then sealed. The autoclave was removed from the glove box and placed in a 70 °C oil bath, where 8 MPa of CO2 was introduced, and stirring was initiated. If the pressure dropped by more than 0.2 MPa during the reaction, CO2 was promptly added to restore the set pressure. After 8 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.

[0082] Preparation of carbon dioxide-based polyurethane materials:

[0083] Using PPC with Mn=2000 as the soft segment and terephthalic diisocyanate (PPDI) and trimethylpropane monoallyl ether (TME) as the hard segments, a PPC:PPDI:TME ratio of 1:3.74:2.74 (molar ratio) was designed, with a hard segment content of 30%. A compounded polyurethane elastomer raw rubber was prepared via the prepolymer method.

[0084] (1) Remove water from 113.75g PPC (Mn=2000) for 1.5h under mechanical stirring at -0.095MPa, 120℃ and 120r / min. This step removes water from the raw material.

[0085] (2) After the system is cooled to 85°C, 34.08 g of terephthalic diisocyanate (PPDI) and 0.02 g of dibutyltin dilaurate catalyst are added. The rotation speed is adjusted to 300 r / min. After the system is heated to 90°C and the reaction is carried out for 1 h, the diisocyanate-terminated polyurethane prepolymer is obtained.

[0086] (3) Add 27.17 g of chain extender trimethylpropane monoallyl ether under mechanical stirring at 500 r / min to ensure that the molar ratio of -NCO:-OH in the system is 1:1. After reacting at 95℃ for 20 min, take out the product and place it in an oven at 90℃ for 18 h to obtain the compounded polyurethane raw rubber product PU3 with a number average molecular weight of 81000.

[0087] Preparation of bio-based polyurethane composite materials:

[0088] Add 100 parts of polyurethane raw rubber, 1 part of stearic acid, 1 part of accelerator D, 2 parts of accelerator DM, 1 part of NH-2, 1 part of sulfur, and 20 parts of lignin to a two-roll mill according to the following mass ratio. Mix thoroughly and cut into thin sheets. Vulcanize in a flat vulcanizing machine at 150℃ for 20 minutes, and release gas 3 to 8 times to obtain vulcanized rubber sample PU / Filler-4.

[0089] The compounded polyurethanes synthesized in Examples 1-3 have a number-average molecular weight of over 70,000 and a glass transition temperature (T0). g At -30 to -7℃, the tensile strength is 20 to 35 MPa, tanδ max Within the range of 1.02 to 1.14, good thermal stability, mechanical properties, and anti-slip properties are achieved.

Claims

1. A carbon sequestration capable bio-based polyurethane composite comprising a mixture of a carbon dioxide-based polyurethane material, a bio-based filler and / or a reaction product thereof.

2. The bio-based polyurethane composite according to claim 1, wherein, the bio-based filler is 1 to 40 parts, preferably 10 to 30 parts, based on 100 parts by weight of the carbon dioxide-based polyurethane material; and / or, the carbon dioxide-based polyurethane material further comprises an auxiliary; preferably, the auxiliary is 1.5 to 6 parts, based on 100 parts by weight of the carbon dioxide-based polyurethane material.

3. The bio-based polyurethane composite according to claim 1, wherein, the carbon dioxide-based polyurethane material comprises a reaction product of a hydroxyl or amino group-containing initiator, CO2 and an epoxy monomer as a soft segment, and a segment comprising an isocyanate compound and a chain extender as a hard segment; and / or, the bio-based filler is selected from at least one of lignin, tannin, cellulose, starch, phytic acid, gallic acid, chitosan.

4. The bio-based polyurethane composite according to claim 3, wherein, the hydroxyl or amino group-containing initiator is selected from at least one of polycaprolactone diol, polycaprolactone carbonate copolydiol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated butadiene styrene rubber, polylactic acid diol, polytetramethylene ether glycol, polypropylene oxide glycol, polytrimethylene ether glycol, tetrahydrofuran-propylene oxide copolydiol, polycaprolactone, polyhexylene adipate diol, polyethylene adipate diol, poly-1-4 butylene 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, hexamethylenediamine, o-phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, p-phenylenediamine, m-phenylenediamine, 1,3-propanediamine, 1,5-pentanediamine, 1,3-cyclohexanedimethylamine; and / or, the epoxy monomer is at least one of oxirane, propylene oxide, 1,2-epoxybutane, oxepane, epoxy allyl glycidyl ether, tetrahydrofuran, oxacyclopentene, 4-vinylcyclohexene-1,2-epoxide, cyclopentene oxide; and / or, the isocyanate compound is at least one 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. ​ ​ ​ ​ ​ ​ ​ The chain extender is at least one selected from trimethylolpropane monoallyl ether, glycerol allyl ether, trimethylolpropane, 1,4-butenediol, 3-allyloxy-1,2-propanediol, and glycerol monomethacrylate.

5. A method of producing the carbon sequestering, bio-based polyurethane composite of any one of claims 1-4, comprising: The components including a carbon dioxide-based polyurethane material and a bio-based filler are mixed to obtain the bio-based polyurethane composite material after vulcanization.

6. The preparation method according to claim 5, characterized in that, the vulcanization is performed at a temperature of 130-150 ℃ for 20-30 min; and / or an auxiliary agent is added during the mixing.

7. The preparation method according to claim 5, characterized in that, The carbon dioxide-based polyurethane material is prepared by the following steps: (1) reacting a hydroxyl- or amino-containing initiator, CO2 and an epoxy monomer in the presence of a catalyst C1 to obtain a carbon dioxide-based polyester diol; (2) pre-polymerizing the carbon dioxide-based polyester diol obtained in step (1) and an isocyanate compound in the presence of a catalyst C2 to obtain a polyurethane prepolymer; (3) adding a chain extender to the polyurethane prepolymer obtained in step (1) to perform chain extension and curing to obtain the carbon dioxide-based polyurethane material.

8. The preparation method according to claim 7, characterized in that, In step (1), the molar ratio of the hydroxyl- or amino-containing initiator to the epoxy monomer is (1-2.5):1, preferably (1-1.7):1; 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, and Zn3[Co(CN)6]2-based double metal cyanide complex; and / or the amount of the catalyst C1 is 0.1-7 wt% of the epoxy monomer, preferably 0.1-2 wt%; and / or the reaction is performed at a carbon dioxide pressure of 0.1-10 MPa, a temperature of 40-80 ℃, and for 12-24 h.

9. The preparation method according to claim 7, characterized in that, the molar ratio of the carbon dioxide-based polyester diol, the isocyanate compound and the chain extender is 1:(1.01-8):(0.01-7), preferably 1:(1.52-6.82):(0.52-5.82); and / or the catalyst C2 is at least one selected from organotin catalysts, organozinc catalysts, and organobismuth catalysts, preferably at least one selected from stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis(dodecylthioate), zinc isooctoate, and bismuth isooctoate; and / or the amount of the catalyst C2 is 0.001-0.09 wt% of the carbon dioxide-based polyester diol; and / or the pre-polymerization is performed at 65-100 ℃ for 20-50 min; and / or the chain extension is performed at 80-120 ℃ for 10-60 min; and / or the curing is performed at 80-110 ℃ for 10-24 h.

10. The carbon sequesterable bio-based polyurethane composite material prepared according to the method of any one of claims 5-9, characterized in that, the number average molecular weight of the bio-based polyurethane composite material is 70,000-200,000; and / or, the glass transition temperature of the bio-based polyurethane composite material is -30 to -7°C; and / or, the tensile strength of the bio-based polyurethane composite material is 20-35 MPa; and / or, The tan delta of the bio-based polyurethane composite max is 1.02-1.14.

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