Modified isocyanate monomer and preparation method thereof

Abstract

The present invention provides a modified isocyanate monomer having a rational molecular design obtained by reacting a diol or a diamine with a diisocyanate. The modified isocyanate monomer of the present invention is cured and polymerized with an oligomer diol to obtain a polyurethane elastomer having improved heat resistance and processing rheology, so that the polyurethane elastomer can meet the performance requirements of polyurethane in the fields of plates, rubber rollers, rubber wheels and tires.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a modified isocyanate monomer and a preparation method thereof. Background Art

[0002] Polyurethane is a type of multi-block copolymer with alternating hard and soft segments containing repeating urethane and / or urea bonds within its molecular chain. Due to the rich and diverse raw material composition, polyurethane elastomers possess a wide range of adjustable mechanical properties. By manipulating the raw material structure and component ratios, polyurethanes can be endowed with numerous advantages, including excellent toughness, elasticity, wear resistance, solvent resistance, and corrosion resistance. The microphase separation structure of alternating hard and soft segments in polyurethane has led to its widespread application in a wide range of fields, including the metal industry, artificial intelligence, biomedicine, construction engineering, aerospace, and emerging materials.

[0003] Chain extenders are used in the synthesis of polyurethanes, and their structure significantly influences the properties of polyurethane elastomers. Commonly used chain extenders include alcohols and amines. Alcohol chain extenders react with isocyanates to form urethane bonds, while amine chain extenders react with isocyanates to form urea bonds. Both urethane and urea bonds can form hydrogen bonds between polymer molecules, inducing microphase separation. The degree of microphase separation is a key factor influencing the performance of polyurethane materials. Given the same molecular structure and composition, the better and more ordered the microphase separation, the better the physical and mechanical properties of the material. Compared to small molecule amine chain extenders, diol chain extenders have relatively moderate reactivity and are the primary raw material for preparing polyurethane elastomers. The rich variety and adjustable chemical structure of small molecule diols endow polyurethane elastomers with a wide range of adjustable properties, enabling the preparation of materials with excellent properties such as wear resistance, high load-bearing capacity, fatigue resistance, thermal insulation, and good biocompatibility to meet the needs of diverse applications. Although polyurethane elastomer materials prepared using small molecule amine chain extenders can form more hydrogen bonding structures in their molecular structure, inducing more complete microphase separation in the material, thereby improving the material's physical and mechanical properties, their rapid reactivity generally limits their application to cast polyurethane materials and makes them difficult to use in the production of thermoplastic polyurethane elastomers, thus reducing the application range of polyurethane materials. To address this issue, some researchers have introduced electron-withdrawing structures, halogen atoms, or large steric hindrance groups into the molecular structure of diamines to reduce the activity of amine chain extenders. However, the relatively high reactivity of aromatic diamines makes them difficult to directly apply to the production of thermoplastic polyurethane elastomers.

[0004] Among existing methods for producing thermoplastic polyurethane elastomers, the one-step method or prepolymer method is the most commonly used. When using the one-step method, since the reaction occurs simultaneously between the oligomer diol, chain extender, and isocyanate monomer, this results in a disordered structure of the resulting polymer molecular chain, which affects the microphase separation of the material and thus the processability of the material and the mechanical properties of the product. In addition, with the advancement of science and technology, thermoplastic polyurethane elastomers produced by existing processes can no longer meet the physical and mechanical performance requirements of elastomer materials in some new applications such as screen plates, rubber rollers, rubber wheels, and tires. Therefore, developing a method for synthesizing polyurethane elastomer materials with a modified isocyanate monomer structure is of great significance for improving the performance of elastomer materials. Summary of the Invention

[0005] To address the above-mentioned issues, the present invention provides a modified isocyanate monomer obtained by reacting a diol or diamine with a diisocyanate. The polyurethane prepared from this modified cyanate monomer and oligomeric diol exhibits a regular molecular structure, improved heat resistance, and enhanced processing rheology. The resulting elastomeric material exhibits significantly improved performance, thus meeting the performance requirements of polyurethanes in applications such as screen plates, rubber rollers, rubber wheels, and tires.

[0006] The first aspect of the present invention is to provide a modified isocyanate monomer having the following structure:

[0007]

[0008] Among them, R1 is selected from an alkylene group or a diphenol alkyl group, preferably an alkylene group containing 4 to 6 carbon atoms or diethyl hydroquinone, and more preferably a butylene group (-(CH2)4-), a hexylene group (-(CH2)6-) or diethyl hydroquinone.

[0009] Hydroquinone diethyl is:

[0010] R3 and R4 are selected from aromatic sub-groups, preferably selected from benzene sub-groups, more preferably:

[0011]

[0012] R2 is selected from aromatic groups, preferably substituted phenyl groups or 4,4'-methylenedianiline compounds, more preferably:

[0013]

[0014] Here, X is a halogen, preferably bromine or chlorine, more preferably chlorine.

[0015] The second aspect of the present invention aims to provide a modified isocyanate monomer, wherein the modified isocyanate monomer is obtained by reacting a diol or a diamine with a diisocyanate.

[0016] The diol is selected from one or more of an alkane diol and a diphenolic hydroxyl alkanol, preferably one or more of an alkane diol having a carbon number of 4-6 and hydroquinone dihydroxyethyl ether, more preferably 1,4-butanediol (BDO), 1,6-hexanediol (HDO) or hydroquinone dihydroxyethyl ether (HQEE).

[0017] The diamine is selected from one or more aromatic diamines, preferably one or more phenylenediamine compounds and 4,4'-methylenedianiline compounds, more preferably 3,5-diethyltoluenediamine (DETDA), 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) or 3,5-dimethylthiotoluenediamine (DMTDA).

[0018] The diisocyanate is selected from one or more diisocyanates containing an aromatic structure, preferably selected from one or more of phenyl diisocyanate compounds, alkylphenyl diisocyanate compounds, naphthalene diisocyanate and diphenyl alkane diisocyanate, more preferably 2,4-toluene diisocyanate (TDI), meta-xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI) or para-phenylene diisocyanate (PPDI).

[0019] A third aspect of the present invention provides a method for preparing the modified isocyanate monomer. The method comprises adding a diol or diamine solution to a diisocyanate monomer solution under an oxygen-free protective atmosphere, preferably dropwise, and allowing the mixture to react at room temperature to obtain a reaction solution containing the modified isocyanate monomer. The modified isocyanate monomer is then obtained through precipitation, washing, separation, and drying.

[0020] The fourth aspect of the present invention aims to provide a method for preparing a polyurethane elastomer using the modified isocyanate monomer, wherein the method uses the modified isocyanate monomer and oligomer diol as raw materials to prepare the polyurethane elastomer.

[0021] The modified isocyanate monomer provided in the present invention has the following beneficial effects:

[0022] (1) The present invention introduces a diol or diamine chain segment into a modified isocyanate monomer by reacting a diol or diamine with a diisocyanate, thereby adjusting the reaction activity so that the reaction rate is controlled during the preparation of the polyurethane, thereby achieving controlled microphase separation of the polyurethane.

[0023] (2) The modified isocyanate monomer of the present invention has a reasonable molecular design, a simple preparation process, and is easy to control the synthesis, which is conducive to its promotion and application in industrial production.

[0024] (3) The polyurethane prepared by using the modified isocyanate monomer and oligomer diol obtained in the present invention has a regular molecular structure, better heat resistance and processing rheology, and the performance of the obtained elastomeric material is effectively improved, thereby being able to meet the requirements of polyurethane performance in fields such as screen plates, rubber rollers, rubber wheels and tires. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The infrared spectrum of the modified isocyanate monomer THT of the present invention is shown;

[0026] Figure 2 The infrared spectrum of the modified isocyanate monomer TBT of the present invention is shown;

[0027] Figure 3 The infrared spectrum of the modified isocyanate monomer XBX of the present invention is shown;

[0028] Figure 4 The infrared spectrum of the modified isocyanate monomer XHX of the present invention is shown;

[0029] Figure 5 The infrared spectrum of the modified isocyanate monomer TMT of the present invention is shown;

[0030] Figure 6 The infrared spectrum of the modified isocyanate monomer MBM of the present invention is shown;

[0031] Figure 7 The infrared spectrum of the modified isocyanate monomer PBP of the present invention is shown;

[0032] Figure 8 The infrared spectrum of the modified isocyanate monomer PHP of the present invention is shown;

[0033] Figure 9 The infrared spectrum of the modified isocyanate monomer XDEX of the present invention is shown;

[0034] Figure 10 The infrared spectrum of the modified isocyanate monomer XMCX of the present invention is shown;

[0035] Figure 11 Shown is an infrared spectrum of the modified isocyanate monomer XDMX of the present invention;

[0036] Figure 12 The infrared spectrum of the modified isocyanate monomer PHDP of the present invention is shown;

[0037] Figure 13The complex viscosity |η*|-temperature curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' of the present invention are shown;

[0038] Figure 14 The complex viscosity |η*|-frequency curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' of the present invention are shown;

[0039] Figure 15 The tan δ-temperature curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' of the present invention are shown;

[0040] Figure 16 The storage modulus-temperature curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' of the present invention are shown. DETAILED DESCRIPTION

[0041] The present invention will be described in detail below through specific embodiments, and the features and advantages of the present invention will become clearer and more distinct with these descriptions.

[0042] The invention provides a modified isocyanate monomer obtained by reacting diol or diamine with diisocyanate.

[0043] The diol is selected from one or more of an alkane diol and a diphenolic hydroxyl alkanol, preferably one or more of an alkane diol having a carbon number of 4-6 and hydroquinone dihydroxyethyl ether, more preferably 1,4-butanediol (BDO), 1,6-hexanediol (HDO) or hydroquinone dihydroxyethyl ether (HQEE).

[0044] The diamine is selected from one or more aromatic diamines, preferably one or more phenylenediamine compounds and 4,4'-methylenedianiline compounds, more preferably 3,5-diethyltoluenediamine (DETDA), 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) or 3,5-dimethylthiotoluenediamine (DMTDA).

[0045] The diisocyanate is selected from one or more diisocyanates containing aromatic groups, preferably selected from one or more of phenyl diisocyanate compounds, alkylphenyl diisocyanate compounds, naphthalene diisocyanate and diphenyl alkane diisocyanate, more preferably 2,4-toluene diisocyanate (TDI), meta-xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI) or para-phenylene diisocyanate (PPDI).

[0046] The modified isocyanate monomer has the following structure:

[0047]

[0048] Among them, R1 is selected from an alkylene group or a diphenol alkyl group, preferably an alkylene group containing 4 to 6 carbon atoms or diethyl hydroquinone, and more preferably a butylene group (-(CH2)4-), a hexylene group (-(CH2)6-) or diethyl hydroquinone.

[0049] Hydroquinone diethyl is:

[0050] R3 and R4 are selected from aromatic sub-groups, preferably selected from benzene sub-groups, more preferably:

[0051]

[0052] R2 is selected from arylene groups, preferably substituted phenylene groups or 4,4'-methylenebisphenyl groups, more preferably:

[0053]

[0054] Here, X is a halogen, preferably bromine or chlorine, more preferably chlorine.

[0055] Preferably, the modified isocyanate monomer is:

[0056]

[0057]

[0058] More preferably, the modified isocyanate monomer is:

[0059]

[0060] The present invention also provides a method for preparing the modified isocyanate monomer. The method comprises adding a diol or diamine solution to a diisocyanate monomer solution under an oxygen-free atmosphere, preferably dropwise, and allowing the mixture to react at room temperature to obtain a reaction solution containing the modified isocyanate monomer. The reaction solution is then precipitated, washed, separated, and dried to obtain the modified isocyanate monomer.

[0061] Preferably, the reaction is carried out in the presence of a catalyst, and the catalyst is selected from one or more organotin compounds, preferably one or more tetraalkyltin compounds and stannous carboxylate compounds, more preferably one or more dibutyltin diacetate, stannous octoate and dibutyltin dilaurate.

[0062] The ratio of the mass of the catalyst to the total mass of the diisocyanate monomer and the alcohol or amine monomer is (0.0005-0.003):1, preferably (0.0005-0.0015):1, and more preferably (0.0007-0.0012):1.

[0063] The molar ratio of the diol or diamine to the diisocyanate monomer is 1:(1.5-7.5), preferably 1:(2-6.5), and more preferably 1:(2.5-5.5).

[0064] The reaction temperature is 30-60° C., preferably 35-55° C., more preferably 40-50° C. The dropwise addition time is 1-3 h, and the reaction time is 3-8 h, preferably 3.5-7 h, more preferably 4-6 h.

[0065] The solvent of the diisocyanate monomer solution is selected from one or more of cyclic ether solvents, alkane solvents, halogenated aromatic solvents and ester solvents, preferably one or more of tetrahydrofuran, dioxane, chlorobenzene, o-dichlorobenzene, tert-butyl acetate, ethyl butyrate and ethyl acetate, more preferably one or more of tetrahydrofuran, dioxane, chlorobenzene and ethyl acetate.

[0066] The concentration of the diisocyanate monomer solution is 0.15-7.5 mol / L, preferably 0.25-6.5 mol / L, and more preferably 0.35-5.5 mol / L.

[0067] The solvent of the diol or diamine solution is selected from one or more of cyclic ether solvents, alkane solvents, halogenated aromatic solvents and ester solvents, preferably one or more of tetrahydrofuran, dioxane, chlorobenzene, o-dichlorobenzene, tert-butyl acetate, ethyl butyrate and ethyl acetate, more preferably one or more of tetrahydrofuran, dioxane, chlorobenzene and ethyl acetate.

[0068] The concentration of the diol or diamine solution is 0.05-1.8 mol / L, preferably 0.08-1.5 mol / L, and more preferably 0.1-1.2 mol / L.

[0069] The oxygen-free protective atmosphere is selected from nitrogen and / or argon.

[0070] The present invention also provides a method for preparing a polyurethane elastomer using the modified isocyanate monomer. The method uses the modified isocyanate monomer and oligomer diol as raw materials to prepare the polyurethane elastomer.

[0071] The oligomer diol is selected from one or more of polycarbonate diol (PCD), polytetramethylene glycol (PTMEG), polycaprolactone diol (PCL) and polypropylene glycol (PPG), preferably polycarbonate diol (PCD) and / or polytetramethylene glycol (PTMEG), more preferably polycarbonate diol (PCD) or polytetramethylene glycol (PTMEG).

[0072] The weight average molecular weight (M w) is 600-3000 g / mol, preferably 700-2000 g / mol, more preferably 800-1200 g / mol.

[0073] In the present invention, the modified isocyanate monomer is added to the oligomer diol preheated to 70-100° C., stirred and mixed to form a uniform liquid, and heated and cured to obtain a polyurethane elastomer.

[0074] The curing temperature is 65-145° C., preferably 75-135° C., more preferably 85-125° C. The curing time is 16-32 hours, preferably 18-30 hours, more preferably 20-28 hours.

[0075] Preferably, the curing is carried out at 80-95°C for 2-3 hours, at 95-105°C for 2-3 hours, at 105-115°C for 2-3 hours, and at 115-125°C for 16-20 hours.

[0076] The modified isocyanate monomers of the present invention are obtained by reacting diols or diamines with diisocyanates. They feature a rational molecular design and a simple and easily controllable preparation process, facilitating widespread application in large-scale production. Curing polymerization of the modified isocyanate monomers of the present invention with oligomeric diols yields polyurethane elastomers with enhanced heat resistance and processing rheology, improving their performance. This broadens the application areas of polyurethane elastomers and enables them to meet the performance requirements of polyurethane in applications such as sheet metal, rubber rollers, rubber wheels, and tires.

[0077] Example

[0078] Example 1

[0079]

[0080] 1.98 g of hydroquinone dihydroxyethyl ether (HQEE) and 40 mL of dry tetrahydrofuran (THF) were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 8.71 g of 2,4-toluene diisocyanate (TDI), 25 mL of dioxane, and 0.0086 g of dibutyltin dilaurate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 50°C. Under stirring and nitrogen, the mixed HQEE solution was slowly added to the reaction container over a period of 3 hours. After stirring and reacting at 50°C for 5 hours, a reaction solution of the modified isocyanate monomer THT was obtained.

[0081] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated, and dried to obtain the modified isocyanate monomer THT. The structure of the obtained modified isocyanate monomer THT is accurately analyzed using FT-IR (Fourier transform infrared spectroscopy). The infrared spectrum is shown in FIG. Figure 1 As shown, its characteristic peak position is -NCO: 2276cm -1 , -NH-: 3298cm -1 , CN:1512cm -1 , -CH2-: 2943cm -1 , -CH3: 2873cm -1 , C=O:1701cm -1 , COC: 1226cm -1 and 1068cm -1 .

[0082] 10.00 g of THT and 17.43 g of polycarbonate diol (PCD1000, Shanghai Jide Chemical Co., Ltd., model NIPPOLLAN981, M W =1000 g / mol, hydroxyl value = 112 ± 4 KOH mg / g) was added to a reaction vessel and rapidly stirred until a uniform liquid state was achieved. Finally, the mixed material was placed in an oven and gradually heated for curing. The curing conditions were: heating to 90°C and holding for 2 hours, then to 100°C and holding for 2 hours, then to 110°C and holding for 2 hours, and finally to 120°C and holding for 18 hours. After natural cooling, a polyurethane elastomer PU-1 with regularly alternating soft and hard segments was obtained.

[0083] The infrared spectrum analysis of the polyurethane elastomer PU-1 shows that its characteristic peak is -NH: 3300cm -1 and 1530cm -1 , C=O:1700cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0084] Example 2

[0085] The polyurethane elastomer PU-2 was prepared according to the method for preparing PU-1 in Example 1, except that 17.76 g of polytetramethylene glycol (PTMEG, Shanghai Jide Chemical Co., Ltd., model PolyTHF 1000 (S)) was added. W =1000 g / mol, hydroxyl value =112±4 KOH mg / g) was used to replace 17.43 g of polycarbonate diol (PCD1000).

[0086] The infrared spectrum analysis of the polyurethane elastomer PU-2 shows that its characteristic peak is -NH: 3300cm -1 and 1530cm -1, C=O:1690cm -1 and 1720cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0087] Example 3

[0088]

[0089] 0.90 g of 1,4-butanediol (BDO) and 15 mL of dry THF were stirred and mixed in a container until uniformly mixed and set aside. Under a nitrogen atmosphere, 10.45 g of 2,4-toluene diisocyanate (TDI) and 30 mL of n-hexane were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 60°C. The uniformly mixed BDO solution was slowly added to the reaction container under stirring and nitrogen over a period of 2 hours. The reaction was continued at 60°C with stirring for 6 hours to obtain a reaction solution containing the modified isocyanate monomer TBT.

[0090] Under stirring conditions, the obtained reaction solution was added to dry THF, and the precipitate was washed, separated and dried to obtain the modified isocyanate monomer TBT. The structure of the obtained monomer was accurately analyzed by characterization methods such as FT-IR, and its infrared spectrum is shown in the figure below. Figure 2 shown.

[0091] The polyurethane elastomer PU-6 was prepared according to the method for preparing PU-1 in Example 1, except that 10.00 g of TBT was added instead of THT, 22.14 g of polytetramethylene glycol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF 1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g) was used to replace 17.43 g of polycarbonate diol (PCD1000).

[0092] The infrared spectrum analysis of the polyurethane elastomer PU-6 shows that its characteristic peak is -NH: 3300cm -1 and 1530cm -1 , C=O:1690cm -1 and 1720cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0093] Example 4

[0094]

[0095] 0.90 g of 1,4-butanediol (BDO) and 10 mL of dry tetrahydrofuran (THF) were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 5.65 g of m-xylylene diisocyanate (XDI), 15 mL of n-hexane, and 0.0066 g of stannous octoate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 40°C. The mixed BDO solution was slowly added to the reaction container under stirring and nitrogen over a period of 1 hour. The reaction was continued at 40°C with stirring for 5 hours to obtain a reaction solution of the modified isocyanate monomer XBX.

[0096] The obtained reaction solution is added to dry THF under stirring, and the precipitate is washed, separated, and dried to obtain the modified isocyanate monomer XBX. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR.

[0097] The polyurethane elastomer PU-9 was prepared according to the method for preparing PU-1 in Example 1, except that 10 g of modified isocyanate monomer XBX was added instead of THT, 21.01 g of polytetramethylene glycol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF 1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g) was used to replace 17.43 g of polycarbonate diol (PCD1000).

[0098] The infrared spectrum analysis of the polyurethane elastomer PU-9 shows that its characteristic peak is NH: 3300cm -1 , C=O:1690cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1

[0099] Example 5

[0100]

[0101] 1.98 g of hydroquinone dihydroxyethyl ether (HQEE) and 40 mL of dry THF were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 7.53 g of XDI, 15 mL of dioxane, and 0.0095 g of dibutyltin diacetate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 50°C. The mixed HQEE solution was slowly added to the reaction container under stirring and nitrogen over a period of 3 hours. The reaction was continued at 50°C with stirring for 4 hours to obtain a reaction solution of the modified isocyanate monomer XHX.

[0102] The obtained reaction solution is added to dry n-hexane under stirring, and the modified isocyanate monomer XHX is obtained by precipitation, washing, separation, and drying. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR.

[0103] PU-13 was prepared according to the preparation method of PU-1 in Example 1, except that 10 g of modified isocyanate monomer XHX was used instead of THT, 17.06 g of polytetrahydrofuran diol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g).

[0104] The infrared spectrum analysis of the polyurethane elastomer PU-13 shows that its characteristic peak is -NH: 3300cm -1 , C=O:1690cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0105] Example 6

[0106]

[0107] 2.67 g of 3,3-dichloro-4,4-diaminodiphenylmethane (MOCA) and 20 mL of dry chlorobenzene were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 6.97 g of TDI and 20 mL of chlorobenzene were added to the reaction container and stirred to mix thoroughly. The temperature was maintained at 20°C. The mixed MOCA solution was slowly added to the reaction container under stirring and nitrogen conditions over a period of 2 hours. After stirring and reacting at 20°C for 5 hours, a reaction solution of the modified isocyanate monomer TMT was obtained.

[0108] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer TMT. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 5 shown.

[0109] PU-29 was prepared according to the preparation method of PU-1 in Example 1, except that 10 g of modified isocyanate monomer TMT was used instead of THT, 15.77 g of polytetramethylene glycol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g).

[0110] The infrared spectrum analysis of the polyurethane elastomer PU-29 shows that its characteristic peak is -NH: 3300cm -1 and 1530cm -1 , C=O:1650cm -1 and 1720cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0111] Example 7

[0112]

[0113] 0.90 g of BDO and 15 mL of dry THF were stirred and mixed in a container until uniformly mixed and set aside. Under a nitrogen atmosphere, 10.01 g of diphenylmethane diisocyanate (MDI), 30 mL of THF solvent, and 0.0109 g of dibutyltin dilaurate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 50°C. The uniformly mixed BDO solution was slowly added to the reaction container under stirring and nitrogen over a period of 2 hours. The reaction was continued at 50°C with stirring for 6 hours to obtain a reaction solution of the modified isocyanate monomer MBM.

[0114] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer MBM. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 6 shown.

[0115] PU-33 was prepared according to the preparation method of PU-1 in Example 1, except that 10 g of modified isocyanate monomer MBM was used instead of THT, 16.44 g of polytetrahydrofuran diol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF1000 (S) was added, and M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g).

[0116] The infrared spectrum analysis of the polyurethane elastomer PU-33 shows that its characteristic peak is -NH: 3300cm -1 and 1530cm -1 , C=O:1700cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0117] Example 8

[0118]

[0119] 0.90 g of BDO and 15 mL of dry THF were stirred and mixed in a container until uniformly mixed and set aside. Under a nitrogen atmosphere, 6.41 g of p-phenylene diisocyanate (PPDI) and 60 mL of THF were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 40°C. The uniformly mixed BDO solution was slowly added to the reaction container under stirring and nitrogen over a period of 1 hour. The reaction was continued with stirring at 40°C for 5 hours to obtain a reaction solution of the modified isocyanate monomer PBP.

[0120] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer PBP. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 7 shown.

[0121] PU-37 was prepared according to the preparation method of PU-1 in Example 1, except that 10 g of modified isocyanate monomer PBP was used instead of THT, 23.65 g of polytetramethylene glycol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g).

[0122] The infrared spectrum analysis of the polyurethane elastomer PU-37 shows that its characteristic peak is -NH: 3300cm -1 , C=O:1690cm-1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0123] Example 9

[0124]

[0125] 1.98 g of HQEE and 65 mL of dry THF were stirred and mixed in a container until uniformly mixed and set aside. Under a nitrogen atmosphere, 6.41 g of p-phenylene diisocyanate (PPDI) and 50 mL of THF were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 45°C. The uniformly mixed HQEE solution was slowly added to the reaction container under stirring and nitrogen over a period of 3 hours. The reaction was continued at 45°C with stirring for 6 hours to obtain a reaction solution of the modified isocyanate monomer PHP.

[0126] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer PHP. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 8 shown.

[0127] PU-45 was prepared according to the preparation method of PU-1 in Example 1, except that 10 g of modified isocyanate monomer PHP was used instead of THT, and 19.29 g of polytetrahydrofuran diol (PTMEG) (Shanghai Jide Chemical Co., Ltd., model PolyTHF1000 (S), M W =1000 g / mol, hydroxyl value =112±4 KOH mg / g).

[0128] The infrared spectrum analysis of the polyurethane elastomer PU-45 shows that its characteristic peak is -NH: 3300cm -1 , C=O:1690cm -1 , CN:1520cm -1 , -COC-:1230cm -1 and 1160cm -1 .

[0129] Example 10

[0130]

[0131] 1.78 g of 3,5-diethyltoluenediamine (DETDA) and 25 mL of dry dioxane were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 7.53 g of XDI, 15 mL of dioxane, and 0.0093 g of dibutyltin dilaurate were added to the reaction container and stirred until mixed. The temperature was maintained at 40°C. The mixed DETDA solution was slowly added to the reaction container under stirring and nitrogen over a period of 2 hours. After stirring and reacting at 40°C for 4 hours, a reaction solution of the modified isocyanate monomer XDEX was obtained.

[0132] Under stirring conditions, the obtained reaction solution is added to dry THF, precipitated, washed, separated and dried to obtain the modified isocyanate monomer XDEX. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 9 shown.

[0133] Example 11

[0134]

[0135] 3.79 g of 4,4-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) and 40 mL of dry chlorobenzene were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 9.41 g of XDI, 20 mL of chlorobenzene, and 0.0132 g of dibutyltin dilaurate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 30°C. Under stirring and nitrogen, the mixed MCDEA solution was slowly added to the reaction container over a 2-hour period. After stirring and reacting at 40°C for 4 hours, a reaction solution of modified isocyanate monomer XMCX was obtained.

[0136] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer XMCX. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 10 shown.

[0137] Example 12

[0138]

[0139] 2.14 g of 3,5-dimethylthiotoluenediamine (DMTDA) and 30 mL of dry ethyl acetate were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 13.17 g of XDI, 40 mL of ethyl acetate, and 0.0153 g of dibutyltin dilaurate were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 50°C. Under stirring and nitrogen conditions, the mixed DMTDA solution was slowly added to the reaction container over a period of 2 hours. After stirring and reacting at 50°C for 5 hours, a reaction solution of the modified isocyanate monomer XDMX was obtained.

[0140] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer XDMX. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 11 shown.

[0141] Example 13

[0142]

[0143] 1.18 g of 1,6-hexanediol (HDO) and 15 mL of dry THF were stirred and mixed in a container and set aside. Under a nitrogen atmosphere, 8.10 g of p-phenylene diisocyanate (PPDI) and 65 mL of THF were added to the reaction container and stirred until uniformly mixed. The temperature was maintained at 45°C. The mixed HDO solution was slowly added to the reaction container under stirring and nitrogen over a period of 1 hour. The reaction was continued at 45°C with stirring for 5 hours to obtain a reaction solution of the modified isocyanate monomer PHDP.

[0144] Under stirring conditions, the obtained reaction solution is added to dry n-hexane, precipitated, washed, separated and dried to obtain the modified isocyanate monomer PHDP. The structure of the obtained monomer is accurately analyzed by characterization methods such as FT-IR, as shown in the following example: Figure 12 shown.

[0145] Comparative Example

[0146] Comparative Example 1

[0147] 7.50g of TDI was added to a reaction vessel containing 17.43g of PCD1000, which had been dehydrated and preheated to 60°C. The temperature was maintained at 60°C under a nitrogen atmosphere with mechanical stirring for 1 hour. After heating to 110°C, 2.69g of HQEE was added and stirred for 10 minutes. Finally, the mixture was poured into a preheated tray and cured under the following conditions: heating to 90°C for 2 hours, then to 100°C for 2 hours, then to 110°C for 2 hours, and finally to 120°C for 18 hours. This yielded polyurethane elastomer PU-1'.

[0148] Comparative Example 2

[0149] Polyurethane elastomer PU-2' was prepared according to the method of Comparative Example 1, except that 21.76 g of PTMEG was added instead of 17.43 g of PCD1000.

[0150] Comparative Example 3

[0151] Polyurethane elastomer PU-6' was prepared according to the method of Comparative Example 1, except that 21.76 g of PTMEG was added instead of 17.43 g of PCD1000, and 1.22 g of BDO was added instead of 2.69 g of HQEE.

[0152] Comparative Example 4

[0153] Polyurethane elastomer PU-9' was prepared according to the method of Comparative Example 1, except that 15.34 g of XBX was added instead of TDI, 20 g of PTMEG was added instead of 17.43 g of PCD1000, and 5.43 g of BDO was added instead of 2.69 g of HQEE.

[0154] Comparative Example 5

[0155] Polyurethane elastomer PU-13' was prepared according to the method of Comparative Example 1, except that 15.34 g of XDI was added instead of TDI, 20 g of PTMEG was added instead of 17.43 g of PCD1000, and 6.76 g of HQEE was added.

[0156] Comparative Example 6

[0157] Polyurethane elastomer PU-29' was prepared according to the method of Comparative Example 1, except that 21.76 g of PTMEG was added instead of 17.43 g of PCD1000, and 3.39 g of MOCA was added instead of 2.69 g of HQEE.

[0158] Comparative Example 7

[0159] Polyurethane elastomer PU-33' was prepared according to the method of Comparative Example 1, except that 10.79 g of MDI was added instead of TDI, 21.76 g of PTMEG was added instead of 17.43 g of PCD1000, and 1.22 g of BDO was added instead of 2.69 g of HQEE.

[0160] Comparative Example 8

[0161] Polyurethane elastomer PU-37' was prepared according to the method of Comparative Example 1, except that 6.91 g of PPDI was added instead of TDI, 21.76 g of PTMEG was added instead of 17.43 g of PCD1000, and 1.22 g of BDO was added instead of 2.69 g of HQEE.

[0162] Comparative Example 9

[0163] The polyurethane elastomer PU-45' was prepared according to the method of Comparative Example 1, except that 6.91 g of PPDI was added instead of TDI, and 21.76 g of PTMEG was added instead of 17.43 g of PCD1000.

[0164] Experimental example

[0165] Experimental Example 1

[0166] The dynamic mechanical analyzer TA-Q800 (test mode is tensile mode, frequency is 1 Hz, strain amplitude is 20 μm, heating range is -80~150℃, heating rate is 5℃ / min) and the advanced rheometer AR200ex (test mode is oscillation mode in air environment) of TA company in the United States were used to analyze the mechanical properties of the product. procedure, the diameter of the rheometer plate is 25 mm, and the distance between the plates is 1 mm. During the dynamic temperature scanning test, the scanning frequency is fixed at 1 Hz, the test temperature is 150-210 ° C, the scanning method is from high temperature to low temperature, and the heating rate is 5 ° C / min. During the dynamic frequency scanning test, the strain is 0.1-15%, the test temperature is fixed at 180 ° C, the scanning method is from low frequency to high frequency, and the scanning frequency range is 0.01-100 Hz. ), the polyurethane elastomer PU-1 prepared in Example 1 and the polyurethane elastomer PU-1' prepared in Comparative Example 1 were subjected to dynamic temperature test, dynamic frequency test, mechanical loss (tanδ) test, and storage modulus test, and the complex viscosity |η*|-temperature curve, complex viscosity |η*|-frequency curve, tanδ-temperature curve, and storage modulus-temperature curve were obtained, respectively, as shown in detail. Figure 13 、 Figure 14 、 Figure 15 and Figure 16 shown.

[0167] Depend on Figure 13 and Figure 14 It can be seen that under different temperature or frequency conditions, the complex viscosity of polyurethane elastomer PU-1 is always lower than that of polyurethane elastomer PU-1', indicating that the polyurethane elastomer prepared in Example 1 has better melt processing performance than the polyurethane elastomer prepared in Comparative Example 1.

[0168] Depend on Figure 15 and Figure 16The analysis showed that the transition temperature (T g ) is 33.9 ° C, the storage modulus is 2231 MPa, and the polyurethane elastomer PU-1 prepared in Example 1 has a higher glass transition temperature (T g )(44.3℃) and storage modulus (2543MPa). This is because the polyurethane elastomer PU-1 has a regular alternating arrangement of soft segments and hard segments, forming a better microphase separation structure and higher crystallinity, and the interaction between the two phases is also improved.

[0169] Experimental Example 2

[0170] The glass transition temperature and storage modulus of polyurethane elastomers PU-2, PU-2', PU-6, PU-6', PU-9, PU-9', PU-13, PU-13', PU-29, PU-29', PU-33, PU-33', PU-37, PU-37', PU-45, and PU-45' were tested according to the method of Experimental Example 1. The test results are shown in Table 1.

[0171] Table 1:

[0172] polyurethane elastomer <![CDATA[T g (℃)]]> Storage modulus (MPa) PU-2 8.7 2860 PU-2' -7.7 2450 PU-6 0 2040 PU-6' -8 1600 PU-9 -31 2420 PU-9' -42 2160 PU-13 -28 2510 PU-13' -36 2250 PU-29 11 2780 PU-29' -7 2405 PU-33 -8 2470 PU-33' -19 2200 PU-37 -22 3560 PU-37' -41 3310 PU-45 -26 3770 PU-45' -35 3430

[0173] From the data in Table 1, it can be seen that the storage modulus of the polyurethane elastomer prepared by using the modified isocyanate monomer provided in the present invention is significantly improved, and the glass transition temperature (T g ) has also improved to a certain extent.

[0174] The present invention has been described in detail above with reference to specific embodiments and / or exemplary examples and the accompanying drawings. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A modified isocyanate monomer, characterized in that It has the following structure: in, R4 is: R2 is: Wherein, X is bromine or chlorine, The modified isocyanate monomer is obtained by reacting diamine with diisocyanate.

2. The modified isocyanate monomer according to claim 1, characterized in that X is chlorine.

3. The modified isocyanate monomer according to claim 1, characterized in that The modified isocyanate monomer is: Wherein, the diamine is 3,3-dichloro-4,4-diaminodiphenylmethane, and the diisocyanate is 2,4-toluene diisocyanate.

4. The modified isocyanate monomer according to claim 1, characterized in that The diamine is 3,5-diethyltoluenediamine, 4,4'-methylenebis(3-chloro-2,6-diethylaniline) or 3,5-dimethylthiotoluenediamine. The diisocyanate is 2,4-toluene diisocyanate, m-xylylene diisocyanate or p-phenylene diisocyanate.

5. A method for preparing a modified isocyanate monomer according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: adding a diamine solution to a diisocyanate monomer solution under an oxygen-free protective atmosphere, and carrying out a reaction at a temperature-insulating state to obtain a reaction solution containing a modified isocyanate monomer; and then precipitating, washing, separating, and drying to obtain a modified isocyanate monomer. The molar ratio of the diamine to the diisocyanate monomer is 1:(2-6.5), The reaction temperature is 35-55°C, The concentration of the diisocyanate monomer solution is 0.25-6.5 mol / L, The concentration of the diamine solution is 0.08-1.5 mol / L.

6. The preparation method according to claim 5, characterized in that The molar ratio of the diamine to the diisocyanate monomer is 1:(2.5-5.5), The reaction temperature is 40-50°C.

7. The preparation method according to claim 5, characterized in that The concentration of the diisocyanate monomer solution is 0.35-5.5 mol / L, The concentration of the diamine solution is 0.1-1.2 mol / L.

8. A method for preparing a polyurethane elastomer using the modified isocyanate monomer according to any one of claims 1 to 4, characterized in that: The method uses modified isocyanate monomers and oligomer diols as raw materials to prepare polyurethane elastomers. The oligomer diol is selected from one or more of polycarbonate diol, polytetramethylene glycol, polycaprolactone diol and polypropylene glycol.

9. The method for preparing a polyurethane elastomer according to claim 8, wherein The oligomer diol is polycarbonate diol and / or polytetramethylene glycol, The modified isocyanate monomer is added to the oligomer diol preheated to 70-100° C., stirred and mixed to form a uniform liquid, and heated for curing reaction to obtain a polyurethane elastomer.

Images