CN-119409923-B - Bio-based aliphatic polyguanidine urea material and preparation method and application thereof

Abstract

The invention discloses a bio-based aliphatic polyguanidine urea material, a preparation method and application thereof, and relates to the technical field of high polymer materials. The preparation method comprises the steps of enabling a uniformly mixed reaction system containing a bio-based aliphatic guanidyl amino acid monomer, a polyfunctional isocyanate compound and a solvent to be subjected to pre-reaction, removing the solvent, and then curing to obtain the remodelable polyguanidine urea material based on the bio-based aliphatic guanidyl amino acid. The technical scheme of the invention avoids excessive consumption of petrochemical resources, the preparation method is simple, a safer green preparation system without a catalyst is adopted, the catalyst is not needed through the multi-stage hydrogen bond and non-covalent bond in the structure, the reaction condition is mild, the operability is strong, the industrial production is easy to realize, the prepared material has good thermal stability, excellent mechanical property and high dynamic exchange speed, and the rapid remodelling and reprocessing can be realized through a simple hot-pressing method, so that the method has great application prospect.

Inventors

• TAO YUHONG
• YU ZHEN
• Fang Yajin
• LIU YANLIN
• TANG ZHAOBIN

Assignees

• 中国科学院宁波材料技术与工程研究所

Dates

Publication Date

20260512

Application Date

20241122

Claims (7)

1. 1. A preparation method of a bio-based aliphatic polyguanidine urea material is characterized in that a monomer containing bio-based aliphatic guanidyl amino acid and a polyfunctional isocyanate compound are subjected to a crosslinking reaction directly without a catalyst to obtain a remodelable bio-based aliphatic polyguanidine urea material; the method comprises the following specific steps: uniformly mixing a bio-based aliphatic guanidyl amino acid monomer, a polyfunctional isocyanate compound and a solvent to form a reaction system; Pre-reacting in flowing nitrogen atmosphere; Removing the solvent and then performing a curing reaction to obtain the aliphatic polyguanidine urea material; The biological aliphatic guanidyl amino acid monomer comprises any one or more than two of arginine, ornithine, 2-guanidyl succinic acid, 2-guanidyl ethyl mercapto succinic acid, guanidinoacetic acid, guanidyl propionic acid and 6-guanidyl caproic acid; and, the polyfunctional isocyanate compound includes any one or a combination of two or more of pentamethylene isocyanate, hexamethylene diisocyanate, L-lysine diisocyanate, 1, 5-pentanediol diisocyanate, and hexamethylene diisocyanate trimer; In the reaction system, the ratio of the sum of the mole numbers of the guanidine group, the carboxyl group and the water to the mole number of the isocyanate group is 1 (1-1.5), and the ratio of the mole number of the water to the mole number of the solvent is 1:50-200; and, the curing is gradient heating curing; and the curing times are 2-3 times; And curing for 1-3 hours under the condition of 95-150 ℃.
2. 2. The method for preparing a bio-based aliphatic polyguanidine urea material of claim 1, characterized in that the solvent comprises water or a mixture of water and any one or a combination of several of ethanol, dimethyl sulfoxide, N-dimethylformamide.
3. 3. The method for producing a biobased aliphatic polyguanidine urea material according to any one of claims 1 to 2, characterized in that, The pre-reaction comprises the step of reacting for 0.5-2 hours under the condition of 65-115 ℃ in a flowing nitrogen atmosphere.
4. 4. The method for producing a biobased aliphatic polyguanidine urea material according to any one of claims 1 to 2, characterized in that, The solvent removal comprises 0.5-2 h under vacuum at 65-90 ℃.
5. 5. A biobased aliphatic polyguanidine urea material prepared by the preparation method of any one of claims 1-4.
6. 6. The bio-based aliphatic polyguanidine urea material of claim 5, characterized in that the bio-based aliphatic polyguanidine urea material is hot pressed for 5-60 min at 100-140 ℃ to realize the remodeling; And/or the glass transition temperature of the bio-based aliphatic polyguanidine urea material is 90-120 ℃, the initial thermal degradation temperature is 200-270 ℃, the Young modulus is 980-1750 MPa, and the tensile strength is 40.1-97.6 MPa.
7. 7. Use of the biobased aliphatic polyguanidine urea material of any one of claims 5-6 in the field of waterproof and/or anticorrosive materials.

Description

Bio-based aliphatic polyguanidine urea material and preparation method and application thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a bio-based aliphatic polyguanidine urea material, a preparation method and application thereof. Background Thermosetting polymers are widely used in various fields of life and production due to their excellent mechanical properties, dimensional stability and chemical stability, but a series of problems such as difficult repair of defects in use, difficult disposal of wastes, high recovery and regeneration cost are also caused when the thermosetting polymers are endowed with excellent properties based on crosslinked networks inside the thermosetting polymers. Therefore, research on self-repairable thermosetting polymers has been developed, dynamic covalent bonds are used as crosslinking bonds in the thermosetting polymers, so that the materials can be made to be stable insoluble crosslinking polymers under certain conditions, and the materials have various excellent properties of the traditional thermosetting polymers, and dynamic exchange reaction can occur under certain conditions to enable the crosslinked network structure to be rearranged to realize self-repairing of the thermosetting materials, so that a wide-prospect road is opened up for effective circulation and reprocessing of the thermosetting polymers. The aliphatic polyurea material has excellent weather resistance, good mechanical strength and chemical stability, and is widely applied to the fields of corrosion resistance, water resistance and the like. However, in the preparation of conventional aliphatic polyurea materials, the catalytic action of a catalyst is often required to promote the reaction between the isocyanate and amine components to complete the curing process. CN110790888a discloses a preparation method of self-repairable polyurea elastomer, which is prepared by reacting polyfunctional polyetheramine and polyfunctional isocyanate under the catalysis of catalyst such as dibutyltin dilaurate, triethylamine, etc., and the self-repairable polyurea with high stretching and tearing resistance is prepared. However, the method still has the problem of complex preparation process, and the self-repairing speed of the obtained polyurea material is low. In addition, the method requires the use of a catalyst, with risks of catalyst precipitation, deactivation, and contamination. On the other hand, with the importance of green chemistry, higher requirements are put on the green nature of raw material sources, simplicity and convenience in reaction process, energy conservation and no pollution. The renewable biological source monomer is used as a raw material to replace petroleum-based materials to prepare the polymer, a safer and more convenient green preparation system without a catalyst is adopted, the influence on the environment is reduced, meanwhile, the renewable biological source monomer is used as the raw material to prepare the self-repairable polyurea material for repeated use, the recycling is not needed, the service life of the material is prolonged, and therefore technical support is provided for sustainable development of resources. Thus, providing a high strength, rapid remodeling bio-based polyurea material is one of the important directions in which polyurea materials are currently developed. Based on the analysis, the invention further improves the prior art, takes the monomer containing the biological aliphatic guanidyl amino acid and the polyfunctional isocyanate compound as raw materials, and obtains the remodelable biological aliphatic polyguanidine urea material based on the biological aliphatic guanidyl amino acid so as to solve the problems in the prior art. Disclosure of Invention In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a bio-based aliphatic polyguanidine urea material, thereby overcoming the defects in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions. The invention provides a preparation method of a bio-based aliphatic polyguanidine urea material, which is characterized in that a bio-based aliphatic guanidyl amino acid monomer and a polyfunctional isocyanate compound are subjected to a crosslinking reaction directly without a catalyst to obtain a remodelable bio-based aliphatic polyguanidine urea material based on the bio-based aliphatic guanidyl amino acid. In some specific embodiments, the method for preparing the bio-based aliphatic polyguanidine urea material comprises the following specific steps: uniformly mixing a bio-based aliphatic guanidyl amino acid monomer, a polyfunctional isocyanate compound and a solvent to form a reaction system; Heating to 65-115 ℃ in a nitrogen atmosphere to perform a pre-reaction; And removing the solvent and then performing a curing reaction to obtain