CN116143995A - Polyphenol compound modified polyurethane elastomer and preparation method thereof - Google Patents

Polyphenol compound modified polyurethane elastomer and preparation method thereof Download PDF

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CN116143995A
CN116143995A CN202310125972.2A CN202310125972A CN116143995A CN 116143995 A CN116143995 A CN 116143995A CN 202310125972 A CN202310125972 A CN 202310125972A CN 116143995 A CN116143995 A CN 116143995A
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polyurethane elastomer
polyurethane
polyphenol compound
polyol
modified polyurethane
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苏醒
邹美帅
白子辰
李晓东
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

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  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention designs a polyphenol compound modified polyurethane elastomer and a preparation method thereof, belonging to the technical field of high-performance polymers. The polyphenol compound modified polyurethane is novel high-performance self-repairing polyurethane, and polyphenol substances in the polyphenol compound modified polyurethane can be crosslinked with a high molecular chain, so that the mechanical property of the polyurethane is improved; can generate dynamic chemical bonds with specific point positions of high molecular chains, and improves the self-repairing performance of polyurethane. In order to efficiently introduce polyphenols into the polyurethane, the method is used for crosslinking the polyphenols with polyurethane chain segments, a specific organic solvent N, N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran is used for introducing an organic phase into solid-phase polyurethane through a soaking method, and meanwhile, too little organic solvent cannot fully soak a polyurethane substrate, so that performance loss is caused, and too much tetrahydrofuran can cause waste of the organic phase, pollute the environment and increase production cost.

Description

Polyphenol compound modified polyurethane elastomer and preparation method thereof
Technical Field
The invention designs a polyphenol compound modified polyurethane elastomer and a preparation method thereof, belonging to the technical field of high-performance polymers
Background
Polyurethane is known as the fifth plastic because of its excellent mechanical properties, good deformability, high biocompatibility and solvent resistance, and various application ranges. Polyurethane materials are widely used in the fields of coal industry, traffic construction, mechanical engineering, electronics, electricity, biomedicine and the like. However, aiming at the research content in the current polyurethane field, there are still bottlenecks such as poor repairability, uneven cell size, to-be-improved ageing resistance, single material property, difficulty in adjustment in a simple manner and the like.
In order to prolong the service life of polyurethane and improve the mechanical properties of polyurethane, researchers usually adopt a spray coating layer and a surface film coating to modify the polyurethane. The sprayed coating can significantly improve the abrasion resistance of polyurethane but reduce the hardness adjustment capability of polyurethane. The surface coating can increase the application range of the polyurethane substrate while protecting the polyurethane substrate, but the coating film has single performance, so that the universality of the polyurethane is reduced.
In the prior art, dynamic disulfide bonds in 2-hydroxyethyl disulfide (HEDS), dynamic Diels-Alder bonds and dynamic borate bonds in polyurethane (IPDA-BA) produced by taking boric acid as a crosslinking agent are generally utilized, but the bond energy of the dynamic chemical bonds is lower, and the mechanical properties of the whole material are reduced after the dynamic chemical bonds are introduced into a polyurethane system. In addition, as most dynamic chemical bonds have strict requirements on the environmental temperature, the stability of the whole polymer chain can be damaged after the polyurethane material is heated, and the mechanical property and the service life of the polyurethane are reduced.
Disclosure of Invention
Aiming at the defects in the prior art, one of the purposes of the invention is to provide a polyphenol compound modified polyurethane elastomer, which comprises high bond energy dynamic chemical bonds and can improve the mechanical properties of the polyurethane elastomer when being influenced by high temperature. The self-repairing capability of the polyurethane material can be enhanced and the service life of the polyurethane can be prolonged on the premise of ensuring the mechanical property of the polyurethane material due to the strong hydrogen bonding effect between the polyphenol substance and the polar group in the macromolecule. Meanwhile, the natural polyphenols have various special functions such as ultraviolet resistance, metal chelation and the like, and the application range of polyurethane can be improved by selecting different polyphenols.
The second purpose of the invention is to provide a preparation method of the polyphenol compound modified polyurethane elastomer.
The aim of the invention is achieved by the following technical scheme.
The polyurethane elastomer consists of a hard segment and a soft segment, and intermolecular hydrogen bonds are formed between the polyphenol compound and the hard segment and the soft segment of the polyurethane elastomer; the structural formula of the polyphenol compound modified polyurethane elastomer is as follows:
Figure BDA0004082125720000021
wherein R 'and R' are respectively-H, -OH, C3-C5 alkyl, benzene ring, catechol or pyrogallol;
Figure BDA0004082125720000031
is intermolecular hydrogen bond; the value of x is 4-30.
Preferably, the mass fraction of the polyphenols in the polyphenols modified polyurethane elastomer is 5% -25%.
Preferably, the polyurethane elastomer is obtained by curing and molding an A component and a B component, wherein the total mass of raw materials for preparing the A component is 100%, and the raw materials comprise the following components in percentage by mass: 44-46% of diisocyanate substances and 54-56% of polyol; the total mass of the raw materials for preparing the component B is 100%, and the raw material components and mass fractions thereof are as follows: 70-74% of poly polyol, 18-22% of polyether 330N polyol (330N) and 4-8% of glycol chain extender.
Preferably, the polyol is one or more of polytetramethylene glycol (PTMG), polypropylene glycol (PPG) and polyethylene glycol (PEG).
Preferably, the diisocyanate is one or more of diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).
Preferably, the glycol chain extender is one or more of 1, 4-Butanediol (BDO), 1, 3-Propanediol (PDO), ethylene Glycol (EG) and 1, 5-Pentanediol (PTDO).
Preferably, the molecular weight of the polyol is 1760-2080, and the molecular weight of the polyether 330N polyol is 4600-4800.
Preferably, the polyurethane elastomer is prepared by the following method, which comprises the following steps:
(1) Under the protection of protective gas, the raw materials of the component A, namely diphenylmethane diisocyanate and polyol, are mixed, heated to 80-85 ℃, stirred and reacted for 4-5 hours, and cooled to obtain viscous polyurethane prepolymer;
(2) Under the condition of isolating air, preheating the viscous polyurethane prepolymer to 40-50 ℃, and preheating the polyol, polyether 330N polyol and glycol chain extender in the component B to 50-70 ℃;
(3) Stirring the preheated raw material in the step (2) at the speed of 2000r/min for 10-15 s, pouring the raw material into a polytetrafluoroethylene mold, and curing the raw material for 2-4 h at the temperature of 65-75 ℃ to obtain the polyurethane elastomer.
Preferably, the isocyanate content of the polyurethane prepolymer is determined by titration: adding the polyurethane prepolymer into isopropanol, heating and stirring at 45-55 ℃ to dissolve the polyurethane prepolymer to obtain a titration sample solution; and then using toluene solution of bromocreosote blue and di-n-butylamine as an indicator by a titration method, and titrating to obtain the isocyanate content in the prepolymer.
Preferably, the dosage ratio of the polyurethane prepolymer to the isopropanol is 3-4 g: 450-550 mL; the volume ratio of the titration sample solution to the toluene solution of di-n-butylamine is 2:1; the dosage ratio of the bromocreosote blue to the titration sample solution is 1g to 1000mL.
Preferably, the mass relation of the polyurethane prepolymer, the polyol in the component B, the polyether 330N polyol and the glycol chain extender satisfies the formula:
(m 1 ×a％)/42＝R×((m 2 /N 1 )×2+(m 3 /N 2 )×3+(m 4 /N 3 )×2)
m in the formula 1 、m 2 、m 3 、m 4 Respectively polyurethane prepolymer, the mass of the poly polyol in the component B, polyether 330N polyol and glycol chain extender; n (N) 1 、N 2 、N 3 The molecular weights of the polyatomic alcohol, the polyether 330N polyatomic alcohol and the glycol chain extender in the component B respectively; a is the isocyanate content of the polyurethane prepolymer; the R value is the number ratio of isocyanic acid radical to hydroxyl radical in the system, and R value=1.04-1.06.
The preparation method of the polyphenol compound modified polyurethane elastomer comprises the following steps:
placing the polyurethane elastomer into an organic solution of polyphenols, soaking and stirring for 18-24 hours, taking out a solid phase after the soaking is completed, and drying at 25-70 ℃ to obtain the polyphenols modified polyurethane elastomer; the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.
Preferably, the polyphenols are ellagic acid, punicalagin, gallic acid, tannic acid or tea polyphenols.
Preferably, the dosage ratio of the polyphenols and the organic solvent is 4-5 g: 200-250 mL; the soaking process is carried out at the temperature of 25-40 ℃ and the stirring speed is 200-500 r/min.
Advantageous effects
The invention provides a polyphenol compound modified polyurethane elastomer, which is novel high-performance self-repairing polyurethane, wherein polyphenol substances in the polyphenol compound modified polyurethane can be crosslinked with a high polymer chain, so that the mechanical property of the polyurethane is improved; can generate dynamic chemical bonds with specific point positions of high molecular chains, and improves the self-repairing performance of polyurethane.
The invention provides a polyphenol compound modified polyurethane elastomer, which consists of A, B two components, wherein the total mass of A, B raw materials is 100%, and the components in raw materials A and the mass fractions thereof are as follows: 44-46% of diisocyanate substances and 54-56% of polyol; the raw material B comprises the following components in percentage by mass: 70-74% of poly polyol, 18-22% of polyether 330N polyol (330N) and 4-8% of glycol chain extender, wherein the mass fraction can ensure the balance of-NCO groups and-OH groups in polyurethane, and ensure the deformation capability of the polyurethane while endowing the polyurethane with excellent mechanical properties.
The invention provides a polyphenol compound modified polyurethane elastomer, which is prepared by the steps that in the preparation of the polyurethane elastomer, isocyanate groups are contained at two ends of diisocyanate substances in the raw material composition of an A component, hydroxyl groups are contained at two ends of polyatomic alcohol, and the polyurethane elastomer and the polyatomic alcohol can be stored for a long time under the condition of room temperature after preliminary synthesis of a prepolymer. Different types of high molecular long chain segments (PTMG, PPG and the like), cross-linking agents (such as 330N and the like) and chain extenders (such as BDO, PDO and the like) can be added according to different production requirements, the raw materials can be polymerized to generate polyurethane elastomer under normal temperature, and then the polyurethane elastomer is dried after being treated by tetrahydrofuran solution of polyphenol substances, so that a finished product can be obtained; the method has simple steps, the experimental formula can be changed according to the production requirement, and industrial production can be carried out.
The invention provides a polyphenol compound modified polyurethane elastomer, wherein the reaction temperature of prepolymer synthesis in the preparation of the polyurethane elastomer is 80-85 ℃ which is an important condition for the prepolymer to be successfully carried out.
The invention provides a polyphenol compound modified polyurethane elastomer, wherein in the preparation of the polyurethane elastomer, the preheating temperature of a prepolymer is kept at 40-50 ℃ which is the key for preserving the prepolymer, and the prepolymer can be subjected to self-polymerization under the action of the temperature of 50-70 ℃. Both ends of the prepolymer are blocked by isocyanato (-NCO), and the prepolymer has a tendency to polymerize with hydroxyl groups in components such as chain extender, crosslinking agent and the like in main raw materials under normal temperature environment, and the forward reaction can be promoted and the reaction rate can be accelerated by the polymerization mode.
The invention provides a polyphenol compound modified polyurethane elastomer, wherein in the preparation of the polyurethane elastomer, the isocyanate content of a prepolymer needs to be controlled, and the excessive isocyanate content can cause the difficulty in molding a polyurethane structure and can not obtain the polyurethane elastomer; too many hydroxyl groups in the main raw materials can cause the mechanical property of polyurethane to be reduced.
The invention provides a preparation method of polyphenol compound modified polyurethane, which aims to introduce polyphenol compound efficiently to crosslink the polyphenol compound and polyurethane chain segments, and introduces a specific organic solvent N, N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran into solid-phase polyurethane through a soaking method, and meanwhile, too little organic solvent cannot completely permeate a polyurethane substrate, so that performance loss is caused, and too much tetrahydrofuran can cause waste of the organic phase, pollute the environment and increase production cost.
Drawings
FIG. 1 is an infrared spectrum of a polyurethane blank, a polyurethane sample treated with tannic acid at room temperature and 70℃and a polyurethane sample treated with tea polyphenols at room temperature and 70 ℃;
FIG. 2 is a graph showing the results of mechanical property tests of polyurethane blanks, polyurethane samples treated with tannic acid at room temperature, 50℃and 70℃and polyurethane samples treated with tea polyphenols at room temperature, 50℃and 70 ℃;
FIG. 3 is a graph showing the results of mechanical properties of polyurethane samples treated with tetrahydrofuran and N, N-dimethylformamide.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples, but is not intended to limit the scope of the patent.
Example 1
In this example, the molecular weight of polytetramethylene glycol was 1760 and the molecular weight of polyether 330N polyol was 4600.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.3995g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 12.89%;
the ratio of the mass (g) of the bromocreosote in the bromocreosote indicator to the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L.
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) Sequentially adding 35.86g of polytetramethylene glycol, 9.96g of polyether 330N polyol and 3.76g of 1, 4-butanediol in the step (3) into a container, adding 45.17g of prepolymer, and stirring the solution for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tea polyphenol, wherein the color of the solution is dark brown, taking out polyurethane after soaking for 12 hours, and drying at room temperature for 12 hours to obtain a tea polyphenol modified polyurethane elastomer, wherein the obtained tea polyphenol modified polyurethane is dark brown, and confirming that the tea polyphenol is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tea polyphenol to the volume (mL) of tetrahydrofuran is 5:250.
The polyurethane elastomer obtained in the step (4) was sampled for 1.2132g and 0.8901g, which were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tannic acid was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, the solid phase was taken out, dried at room temperature, and then weighed, the mass of sample 1 was 1.2963g, and the mass of sample 2 was 0.9055g. The mass fraction of tannic acid in the sample at this time was calculated to be 13.80%.
The structural formula of the tea polyphenol modified polyurethane is as follows:
Figure BDA0004082125720000081
example 2
In this example, the molecular weight of polytetramethylene glycol was 1760 and the molecular weight of polyether 330N polyol was 4750.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.3970g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 12.97 percent;
the proportional relation between the mass (g) of the bromocreosote in the bromocreosote indicator and the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L;
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) 36.61g of polytetramethylene glycol, 10.37g of polyether 330N polyol and 3.74g of 1, 4-butanediol in the step (3) are sequentially added into a container, 46.55g of prepolymer is added, and the solution is stirred for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tea polyphenol, wherein the color of the solution is dark brown, taking out polyurethane after soaking for 12 hours, and drying at room temperature for 12 hours to obtain a tea polyphenol modified polyurethane elastomer, wherein the obtained tea polyphenol modified polyurethane is dark brown, and confirming that the tea polyphenol is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tea polyphenol to the volume (mL) of tetrahydrofuran is 5:250.
The polyurethane elastomer obtained in the step (4) was sampled for 1.3950g and 1.0058g, which were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tannic acid was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, the solid phase was taken out, dried at room temperature, and then weighed, the mass of sample 1 was 1.4781g, and the mass of sample 2 was 1.0351g. The mass fraction of tannic acid in the sample at this time was calculated to be 10.62%.
The structural formula of the tea polyphenol modified polyurethane is the same as that of the example 1.
Example 3
In this example, the molecular weight of polytetramethylene glycol was 1760 and the molecular weight of polyether 330N polyol was 4800.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.4244g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 11.52%;
the ratio of the mass (g) of the bromocreosote in the bromocreosote indicator to the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L.
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) Sequentially adding 36.01g of polytetramethylene glycol, 9.91g of polyether 330N polyol and 3.74g of 1, 4-butanediol in the step (3) into a container, adding 46.12g of prepolymer, and stirring the solution for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tea polyphenol, wherein the color of the solution is dark brown, taking out polyurethane after soaking for 12 hours, and drying at room temperature for 12 hours to obtain a tea polyphenol modified polyurethane elastomer, wherein the obtained tea polyphenol modified polyurethane is dark brown, and confirming that the tea polyphenol is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tea polyphenol to the volume (mL) of tetrahydrofuran is 5:250.
The polyurethane elastomer obtained in the step (4) was sampled for 1.7923g and 0.8901g, which were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tannic acid was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, the solid phase was taken out, dried at room temperature, and then weighed, the mass of sample 1 was 1.8458g, and the mass of sample 2 was 0.9055g. The mass fraction of tannic acid in the sample at this time was calculated to be 5.01%.
The structural formula of the tea polyphenol modified polyurethane is the same as that of the example 1.
Example 4
The molecular weight of polytetramethylene glycol in this example was 2080 and the molecular weight of polyether 330N polyol was 4600.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.4036g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 10.84 percent;
the ratio of the mass (g) of the bromocreosote in the bromocreosote indicator to the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L.
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) Sequentially adding 36.06g of polytetramethylene glycol, 9.91g of polyether 330N polyol and 3.75g of 1, 4-butanediol in the step (3) into a container, adding 45.91g of prepolymer, and stirring the solution for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tannic acid, wherein the solution is yellow in color, taking out polyurethane after soaking for 12h and drying at room temperature for 12h to obtain a tannic acid modified polyurethane elastomer, wherein the tannic acid modified polyurethane is yellow, and confirming that tannic acid is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tannic acid to the volume (mL) of tetrahydrofuran is 5:250.
Samples 1.1152g and 1.0058g of the polyurethane elastomer obtained in the step (4) were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tea polyphenol was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, and the solid phase was taken out and dried at room temperature, and then weighed, the mass of sample 1 was 1.2380g, and the mass of sample 2 was 1.0351g. The mass fraction of tea polyphenols in the sample at this time was calculated to be 20.07%.
The tannic acid modified polyurethane has the following structural formula:
Figure BDA0004082125720000121
example 5
The molecular weight of polytetramethylene glycol in this example was 2080 and the molecular weight of polyether 330N polyol was 4750.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.4066g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 12.76%;
the ratio of the mass (g) of the bromocreosote in the bromocreosote indicator to the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L.
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) Sequentially adding 36.31g of polytetramethylene glycol, 10.03g of polyether 330N polyol and 3.74g of 1, 4-butanediol in the step (3) into a container, adding 45.02g of prepolymer, and stirring the solution for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tannic acid, wherein the solution is yellow in color, taking out polyurethane after soaking for 12h and drying at room temperature for 12h to obtain a tannic acid modified polyurethane elastomer, wherein the tannic acid modified polyurethane is yellow, and confirming that tannic acid is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tannic acid to the volume (mL) of tetrahydrofuran is 5:250.
Samples 1.3879g and 0.8901g of the polyurethane elastomer obtained in the step (4) were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tea polyphenol was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, and the solid phase was taken out and dried at room temperature, and then weighed, the mass of sample 1 was 1.5107g, and the mass of sample 2 was 0.9055g. The mass fraction of tea polyphenols in the sample at this time was calculated to be 23.00%.
The tannic acid modified polyurethane has the structural formula as in example 4.
Example 6
The molecular weight of the polytetramethylene glycol in this example was 2080 and the molecular weight of the polyether 330N polyol was 4800.
(1) 45g of diphenylmethane diisocyanate and 55g of polytetramethylene glycol are added into a 100mL three-neck flask, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
(2) Dissolving 0.3754g of the prepolymer obtained by the reaction in the step (1) in 50mL of isopropanol, heating at 50 ℃ for 10min to fully dissolve the prepolymer, dripping 4 drops of the bromcreosol blue indicator, and then adding 25mL of toluene solution of di-n-butylamine to fully dissolve the indicator; titration is carried out by using 0.1036mol/L of dilute hydrochloric acid to obtain that the isocyanate content in the prepolymer is 15.34%;
the ratio of the mass (g) of the bromocreosote in the bromocreosote indicator to the volume (mL) of the solvent sodium hydroxide is 1:1000, and the concentration of the sodium hydroxide is 0.1mol/L.
(3) Preheating the prepolymer titrated in the step (2) to 50 ℃, and preheating the main raw materials of polytetramethylene glycol, polyether 330N polyol and 1, 4-butanediol to 70 ℃ after dehydration.
(4) Sequentially adding 36.23g of polytetramethylene glycol, 10.14g of polyether 330N polyol and 3.75g of 1, 4-butanediol in the step (3) into a container, adding 36.02g of prepolymer, and stirring the solution for 12s at a stirring rate of 2000 r/min; pouring the polyurethane elastomer into a polytetrafluoroethylene container, and then placing the container into a 70 ℃ oven for curing for 4 hours to obtain the polyurethane elastomer.
(5) Soaking the polyurethane elastomer obtained in the step (4) in 250mL of tetrahydrofuran solution of tannic acid, wherein the solution is yellow in color, taking out polyurethane after soaking for 12h and drying at room temperature for 12h to obtain a tannic acid modified polyurethane elastomer, wherein the tannic acid modified polyurethane is yellow, and confirming that tannic acid is successfully introduced into the polyurethane elastomer;
the ratio of the mass (g) of tannic acid to the volume (mL) of tetrahydrofuran is 5:250.
Samples 1.0371g and 1.0058g of the polyurethane elastomer obtained in the step (4) were designated as sample 1 and sample 2, respectively, sample 1 was immersed in 18ml of tetrahydrofuran solvent in which 0.45g of tea polyphenol was dissolved, sample 2 was immersed in 18ml of tetrahydrofuran solvent, immersed for 2 hours at a stirring rate of 600r/min, and the solid phase was taken out and dried at room temperature, and then weighed, the mass of sample 1 was 1.1450g, and the mass of sample 2 was 1.0351g. The mass fraction of tea polyphenols in the sample at this time was calculated to be 17.27%.
The tannic acid modified polyurethane has the structural formula as in example 4.
As a result of infrared spectrum testing of the end products prepared in examples 1 to 6, as shown in FIG. 1, it can be seen that the infrared spectrum of the end product of example 1 does not contain off-hydrogen bonds, and is 1729cm in all, compared with the polyurethane elastomer -1 The carbonyl groups which are not hydrogen bonded are flowed from the group to 1700cm -1 The carbonyl groups forming hydrogen bonds are moved, so that it can be judged that the off carbonyl groups in the polyurethane are completely crosslinked after the tea polyphenol treatment and a large number of intermolecular hydrogen bonds are formed, which is helpful for forming a crosslinked network and improving the mechanical properties of the material. The infrared-indicating results of the end products obtained in examples 2 to 3 were similar to those of example 1. Furthermore, the infrared spectrum of the end product of example 4 contains only small amounts of off-flow hydrogen bonds, most 1729cm compared to the polyurethane elastomer -1 The carbonyl groups which are not hydrogen bonded are flowed from the group to 1700cm -1 The carbonyl groups forming hydrogen bonds are moved, so that the fact that the fluidized carbonyl groups in the polyurethane are greatly crosslinked and a large number of intermolecular hydrogen bonds are formed after tannic acid treatment can be judged, and the formation of a crosslinked network and the improvement of the mechanical properties of the material are facilitated. The infrared-indicating results of the end products obtained in examples 5 to 6 were similar to those of example 4.
The final products prepared in examples 1 to 6 were subjected to tensile test under the condition that a 500N mechanical sensor was used, and the size of the test sample was selected from a 4mm×50mm small test sample, and the test sample was subjected to a 20mm/min tensile rate, as shown in fig. 2, it was found that the mechanical properties of the polyurethane sample after the heat treatment (the mechanical properties of tannic acid treatment were about 22MPa and the mechanical properties of tea polyphenol treatment were about 24 MPa) were improved by 46.7% and 60% as compared with the mechanical properties of the ordinary polyurethane elastomer (about 15 MPa), which means that the polyphenol compound modified polyurethane can be used as a polyurethane elastomer modifier to greatly improve the mechanical properties of polyurethane.
The end products prepared in examples 1 to 6 were tested for the self-repairing performance by tensile testing in such a manner that a gap with a depth of 2mm was cut on the surface of the prepared polyphenol modified polyurethane by a knife, two drops of tetrahydrofuran were dropped into the gap, the two ends of the sample were drawn together, the sample was loosened after 10 seconds and the section was observed, at this time the sample had completed the self-repairing process and the self-repairing property was maintained in a short period of time, and the existence of self-repairing property of the sample was confirmed. The sample test results in examples 2 to 3 are similar to example 1, and the sample test results in examples 5 to 6 are similar to example 4.
Comparative example 1
The polyurethane elastomer described in example 1 was immersed in 250ml of an ethanol solution of tannic acid, at which time the solution appeared yellow in color, and after immersing for 12 hours, the polyurethane was taken out and dried at room temperature for 12 hours to obtain a tannic acid-modified polyurethane elastomer, at which time the tannic acid-modified polyurethane obtained appeared white in color, consistent with the polyurethane elastomer before modification, confirming that tannic acid was not successfully incorporated into the polyurethane elastomer.
Comparative example 2
The polyurethane elastomer described in example 1 was immersed in 250ml of deionized water of tannic acid, at which time the solution appeared pale yellow in color, after 12 hours of immersion, the polyurethane was taken out and dried at room temperature for 12 hours to obtain a tannic acid-modified polyurethane elastomer, at which time the tannic acid-modified polyurethane obtained appeared white in color, consistent with the polyurethane elastomer before modification, confirming that tannic acid was not successfully incorporated into the polyurethane elastomer.
Comparative example 3
The polyurethane elastomer described in example 1 is soaked in 250ml of tetrahydrofuran pure solvent, the solution is colorless and transparent, polyurethane is taken out after soaking for 12 hours and dried for 12 hours at room temperature to obtain tetrahydrofuran modified polyurethane elastomer, the mechanical property test is carried out on the sample at the moment, the test condition is that a small test sample with the size of 4mm multiplied by 50mm is adopted on the premise of using a 500N mechanical sensor, the test is carried out under the condition of 20mm/min stretching rate, the test structure is shown as figure 3, the normal tensile strength of the polyurethane sample is 13.11MPa, the tensile strength of the sample treated by tetrahydrofuran is reduced to 8.73MPa, and the obvious mechanical property reduction exists.
Comparative example 4
The polyurethane elastomer described in example 1 is soaked in 250ml of pure solvent of N, N-dimethylformamide, the solution is colorless and transparent, polyurethane is taken out after soaking for 12 hours and dried at room temperature for 12 hours, the tetrahydrofuran modified polyurethane elastomer is obtained, the mechanical property test is carried out on the sample at the moment, the test condition is that a small test sample with the size of 4mm multiplied by 50mm is adopted on the premise of using a 500N mechanical sensor, the test is carried out under the condition of 20mm/min stretching rate, the test structure is shown in figure 3, the normal tensile strength of the polyurethane sample is 13.11MPa, and the tensile strength of the sample treated by the N, N-dimethylformamide is reduced to 9.02MPa, so that the obvious mechanical property reduction exists.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.

Claims (10)

1. A polyphenol compound modified polyurethane elastomer is characterized in that: the polyurethane elastomer consists of a hard segment and a soft segment, and intermolecular hydrogen bonds are formed between the polyphenol compound and the hard segment and the soft segment of the polyurethane elastomer; the structural formula of the polyphenol compound modified polyurethane elastomer is as follows:
Figure FDA0004082125710000011
wherein R 'and R' are respectively-H, -OH, C3-C5 alkyl, benzene ring, catechol or pyrogallol;
Figure FDA0004082125710000012
is intermolecular hydrogen bond; the value of x is 4-30.
2. A polyphenol compound modified polyurethane elastomer as defined in claim 1 wherein: the mass fraction of the polyphenols in the polyphenols modified polyurethane elastomer is 5% -25%.
3. A polyphenol compound modified polyurethane elastomer as defined in claim 1 wherein: the polyurethane elastomer is obtained by curing and molding a component A and a component B, wherein the total mass of raw materials for preparing the component A is 100%, and the raw materials comprise the following components in percentage by mass: 44-46% of diisocyanate substances and 54-56% of polyol; the total mass of the raw materials for preparing the component B is 100%, and the raw material components and mass fractions thereof are as follows: 70-74% of poly polyol, 18-22% of polyether 330N polyol and 4-8% of glycol chain extender.
4. A polyphenol compound modified polyurethane elastomer as defined in claim 3 wherein: the polyatomic alcohol is more than one of polytetramethylene glycol, polypropylene glycol and polyethylene glycol;
the diisocyanate is more than one of diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;
the diol chain extender is more than one of 1, 4-butanediol, 1, 3-propanediol, ethylene glycol and 1, 5-pentanediol;
the molecular weight of the polyatomic alcohol is 1760-2080, and the molecular weight of the polyether 330N polyatomic alcohol is 4600-4800.
5. A polyphenol compound modified polyurethane elastomer as defined in claim 3 wherein: the polyurethane elastomer is prepared by the following steps:
(1) Under the protection of protective gas, the raw materials of the component A, namely diphenylmethane diisocyanate and polyol, are mixed, heated to 80-85 ℃, stirred and reacted for 4-5 hours, and cooled to obtain viscous polyurethane prepolymer;
(2) Under the condition of isolating air, preheating the viscous polyurethane prepolymer to 40-50 ℃, and preheating the polyol, polyether 330N polyol and glycol chain extender in the component B to 50-70 ℃;
(3) Stirring the preheated raw material in the step (2) at the speed of 2000r/min for 10-15 s, pouring the raw material into a polytetrafluoroethylene mold, and curing the raw material for 2-4 h at the temperature of 65-75 ℃ to obtain the polyurethane elastomer.
6. A polyphenol compound modified polyurethane elastomer as defined in claim 5 wherein: the isocyanate content of the polyurethane prepolymer is determined by titration: adding the polyurethane prepolymer into isopropanol, heating and stirring at 45-55 ℃ to dissolve the polyurethane prepolymer to obtain a titration sample solution; then using toluene solution of bromocreosote blue and di-n-butylamine as an indicator by a titration method, and titrating to obtain the isocyanate content in the prepolymer;
the dosage ratio of the polyurethane prepolymer to the isopropanol is 3-4 g: 450-550 mL; the volume ratio of the titration sample solution to the toluene solution of di-n-butylamine is 2:1; the dosage ratio of the bromocreosote blue to the titration sample solution is 1g to 1000mL.
7. A polyphenol compound modified polyurethane elastomer as defined in claim 3 wherein: the mass relation among the polyurethane prepolymer, the polyol in the component B, the polyether 330N polyol and the glycol chain extender satisfies the formula:
(m 1 ×a％)/42＝R×((m 2 /N 1 )×2+(m 3 /N 2 )×3+(m 4 /N 3 )×2)
m in the formula 1 、m 2 、m 3 、m 4 Respectively polyurethane prepolymer, the mass of the poly polyol in the component B, polyether 330N polyol and glycol chain extender; n (N) 1 、N 2 、N 3 The molecular weights of the polyatomic alcohol, the polyether 330N polyatomic alcohol and the glycol chain extender in the component B respectively; a is the isocyanate content of the polyurethane prepolymer; the R value is the number ratio of isocyanic acid radical to hydroxyl radical in the system, and R value=1.04-1.06.
8. A process for producing the polyphenol compound-modified polyurethane elastomer according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
placing the polyurethane elastomer into an organic solution of polyphenols, soaking and stirring for 18-24 hours, taking out a solid phase after the soaking is completed, and drying at 25-70 ℃ to obtain the polyphenols modified polyurethane elastomer; the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.
9. The method for preparing the polyphenol compound modified polyurethane elastomer according to claim 8, which is characterized in that: the polyphenols are ellagic acid, punicalagin, gallic acid, tannic acid or tea polyphenols.
10. The method for preparing the polyphenol compound modified polyurethane elastomer according to claim 8, which is characterized in that: the dosage ratio of the polyphenols to the organic solvent is 4-5 g: 200-250 mL; the soaking process is carried out at the temperature of 25-40 ℃ and the stirring speed is 200-500 r/min.
CN202310125972.2A 2023-02-17 2023-02-17 Polyphenol compound modified polyurethane elastomer and preparation method thereof Pending CN116143995A (en)

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