Self-repairing polyurea waterproof anticorrosion coiled material and preparation method thereof

Abstract

The application discloses a kind of self-repairing polyurea waterproof anticorrosion coiled material and preparation method, by following component constitutes: IPDI, PPG, APD and MOF derived NiO / CeO2 Compound;MOF derived NiO / CeO2 Compound MOF ligand is H3BTC.In the application, NiO and CeO2 have certain oxidation resistance and corrosion resistance, their synergistic effect in the compound, and by introducing MOF framework, the anticorrosive effect of NiO and CeO2 when used alone is improved while maintaining good tensile strength and tensile recovery rate.The specific mass ratio range of IPDI, PPG, APD and MOF derived NiO / CeO2 Compound is defined, and the further preferred ratio is helpful to accurately control the performance of coiled material, so that it reaches the best balance in waterproof, anticorrosion and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a self-repairing polyurea waterproof and anticorrosion coiled material and a preparation method. BACKGROUND

[0002] Polyurea, as a specific branch of polyurethane material system, is generated by chemical reaction of isocyanate (-NCO) and polyamine (-NH2), and belongs to block copolymer. Its molecular chain structure presents the characteristics of alternating arrangement of soft segment and hard segment, which gives the material high designability. With this unique molecular structure, polyurea exhibits excellent physical and chemical properties and is widely used in many fields such as military equipment protection, building structure maintenance and aerospace component manufacturing.

[0003] However, in the actual processing and service process, polyurea materials are inevitably subjected to the coupling erosion of various external factors such as light radiation, heat and mechanical stress. Long-term effects of these factors often lead to micro and even macro damage on the surface of polyurea materials, such as scratches, cracks and other defects. These surface damages not only destroy the appearance integrity of the materials, but also seriously affect the durability and reliability of the materials, thereby reducing the actual availability of polyurea materials and greatly increasing the maintenance and replacement costs. This phenomenon not only causes a large amount of waste of valuable resources, but also has potential negative effects on the ecological environment, such as environmental pollution problems in the process of waste material treatment.

[0004] In view of the above challenges, it is of great scientific and practical significance to develop polyurea materials with self-repairing function. Such intelligent polyurea materials can spontaneously restore the original structure and performance of the materials after being damaged through the internal pre-set repair mechanism. This not only can significantly prolong the service life of polyurea materials and reduce resource consumption, but also has far-reaching strategic significance for promoting the construction of resource-saving and environment-friendly society and achieving the sustainable development goals of human society. SUMMARY

[0005] In order to solve the problems in the prior art, the present application provides a self-repairing polyurea waterproof and anticorrosion coiled material and a preparation method.

[0006] The present application is realized by the following technical scheme:

[0007] A self-repairing polyurea waterproof and anticorrosion coiled material is composed of the following components: IPDI, PPG, APD and MOF derived NiO / CeO2 composite.

[0008] The ligand of MOF in the MOF derived NiO / CeO2 composite is H3BTC.

[0009] Further, the mass ratio of the IPDI, PPG, APD and MOF derived NiO / CeO2 composite is: 4~8:18~24:7:10:0.2~0.8.

[0010] Further, the mass ratio of the IPDI, PPG, APD and MOF derived NiO / CeO2 composite is: 5:20:8:0.2~0.8.

[0011] Further, the preparation method of the MOF derived NiO / CeO2 composite is:

[0012] H3BTC, PVP (K30), citric acid, Ni(NO3)2·6H2O and Ce(NO3)2·6H2O are added to a mixed solution composed of ethanol, deionized water and DMF, and then stirred vigorously for 30 min;

[0013] Then the mixed solution is transferred to a stainless steel reaction kettle, heated at 150 degrees Celsius for 10 h, after the reaction is completed, centrifuged after natural cooling to room temperature, the obtained precipitate is washed with ethanol for 5 times, and then the washed precipitate is vacuum dried at 60 degrees Celsius overnight; then the dried precipitate is heated from 25 degrees Celsius to 600 degrees Celsius, the heating rate is 2 degrees Celsius / min, when the temperature rises to 600 degrees Celsius, it is kept for 3 h under normal pressure air atmosphere.

[0014] Further, the mass ratio of the H3BTC, PVP, citric acid, Ni(NO3)2·6H2O is 1.5:15:2:5.

[0015] Further, the molar ratio of the Ni / Ce is 1:0.1~0.4.

[0016] Further, the volume ratio of ethanol, deionized water and DMF in the mixed solution composed of ethanol, deionized water and DMF is 1:1:1.

[0017] Further, the PPG has a molecular weight of 2000 and a functionality of 2.

[0018] The application also provides a preparation method of the self-repairing polyurea waterproof and anticorrosion coiled material, characterized by comprising the following steps:

[0019] Accurately weigh 5g of IPDI and dissolve it in 20mL of THF, stir at room temperature for 20min to obtain solution A;

[0020] Accurately weigh 20g of PPG-2000 and 8g of APD and dissolve them in 30mL of THF, stir at room temperature for 20min to obtain solution B;

[0021] Add 0.5g of MOF-derived NiO / CeO2 complex to solution A and stir for 20min. Then, slowly add solution B to solution A while stirring at room temperature. After the addition is complete, stir at room temperature for 1h, let stand at room temperature for 12h, and then let stand at 80 degrees Celsius for 24h.

[0022] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0023] NiO and CeO2 possess certain antioxidant and corrosion-resistant properties. Their synergistic effect in the composite, and the introduction of the MOF framework, enhances the corrosion protection effect when NiO and CeO2 are used alone, while maintaining good tensile strength and tensile recovery. The specific mass ratio ranges of NiO / CeO2 composites derived from IPDI, PPG, APD, and MOF were clarified, and further optimized ratios were developed. This helps to precisely control the performance of the roll material, achieving an optimal balance in terms of waterproofing and corrosion resistance. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0025] In this invention, IPDI is isophorone diisocyanate, PPG-2000 is amino-terminated polyoxypropylene ether with a molecular weight of 2000 and a functionality of 2, APD is 2,2'-diaminodiphenyl disulfide, and THF is tetrahydrofuran.

[0026] Example 1: A self-healing polyurea waterproof and corrosion-resistant roll material, the preparation method of which is as follows: accurately weigh 5g of IPDI and dissolve it in 20mL of THF, stir at room temperature for 20min to obtain solution A; accurately weigh 20g of PPG-2000 and 8g of APD and dissolve them in 30mL of THF, stir at room temperature for 20min to obtain solution B; add 0.5g of MOF-derived NiO / CeO2 composite to the above solution A, stir for 20min, and then slowly add solution B dropwise to solution A while stirring at room temperature. After the addition is complete, stir at room temperature for 1h, place at room temperature for 12h, and then place at 80 degrees Celsius for 24h.

[0027] The synthesis method of the MOF-derived NiO / CeO2 complex is as follows: 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, 500 mg Ni(NO3)2·6H2O, and Ce(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1, and then the mixture is stirred vigorously for 30 min, wherein the molar ratio of Ni / Ce is 1:0.1.

[0028] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0029] Example 2: A self-healing polyurea waterproof and corrosion-resistant roll material, the preparation method of which is as follows: accurately weigh 5g of IPDI and dissolve it in 20mL of THF, stir at room temperature for 20min to obtain solution A; accurately weigh 20g of PPG-2000 and 8g of APD and dissolve them in 30mL of THF, stir at room temperature for 20min to obtain solution B; add 0.5g of MOF-derived NiO / CeO2 composite to the above solution A, stir for 20min, and then slowly add solution B dropwise to solution A while stirring at room temperature. After the addition is complete, stir at room temperature for 1h, place at room temperature for 12h, and then place at 80 degrees Celsius for 24h.

[0030] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is different. Specifically, 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, 500 mg Ni(NO3)2·6H2O, and Ce(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1. The solution is then stirred vigorously for 30 min, wherein the molar ratio of Ni / Ce is 1:0.2.

[0031] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0032] Example 3: A self-healing polyurea waterproof and corrosion-resistant roll material, the preparation method of which is as follows: accurately weigh 5g of IPDI and dissolve it in 20mL of THF, stir at room temperature for 20min to obtain solution A; accurately weigh 20g of PPG-2000 and 8g of APD and dissolve them in 30mL of THF, stir at room temperature for 20min to obtain solution B; add 0.5g of MOF-derived NiO / CeO2 composite to the above solution A, stir for 20min, and then slowly add solution B dropwise to solution A while stirring at room temperature. After the addition is complete, stir at room temperature for 1h, place at room temperature for 12h, and then place at 80 degrees Celsius for 24h.

[0033] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is different. Specifically, 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, 500 mg Ni(NO3)2·6H2O, and Ce(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1. The solution is then stirred vigorously for 30 min, wherein the molar ratio of Ni / Ce is 1:0.3.

[0034] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0035] Example 4: A self-healing polyurea waterproof and corrosion-resistant roll material, the preparation method of which is as follows: accurately weigh 5g of IPDI and dissolve it in 20mL of THF, stir at room temperature for 20min to obtain solution A; accurately weigh 20g of PPG-2000 and 8g of APD and dissolve them in 30mL of THF, stir at room temperature for 20min to obtain solution B; add 0.5g of MOF-derived NiO / CeO2 composite to the above solution A, stir for 20min, and then slowly add solution B dropwise to solution A while stirring at room temperature. After the addition is complete, stir at room temperature for 1h, place at room temperature for 12h, and then place at 80 degrees Celsius for 24h.

[0036] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is different. Specifically, 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, 500 mg Ni(NO3)2·6H2O, and Ce(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1. The solution is then stirred vigorously for 30 min, wherein the molar ratio of Ni / Ce is 1:0.4.

[0037] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0038] Example 5: The difference between this example and Example 3 is the content of the MOF-derived NiO / CeO2 complex.

[0039] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.2g of MOF-derived NiO / CeO2 composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0040] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is the same as that in Example 3.

[0041] Example 6: The difference between this example and Example 3 is the content of the MOF-derived NiO / CeO2 complex.

[0042] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.3g of MOF-derived NiO / CeO2 composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0043] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is the same as that in Example 3.

[0044] Example 7: The difference between this example and Example 3 is the content of the MOF-derived NiO / CeO2 complex.

[0045] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.6g of MOF-derived NiO / CeO2 composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0046] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is the same as that in Example 3.

[0047] Example 8: The difference between this example and Example 3 is the content of the MOF-derived NiO / CeO2 complex.

[0048] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.8g of MOF-derived NiO / CeO2 composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0049] The synthesis method of the MOF-derived NiO / CeO2 complex described in this embodiment is the same as that in Example 3.

[0050] Comparative Example 1

[0051] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.5g of the composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0052] The preparation method of the complex does not involve adding H3BTC. Specifically, 1.5g of PVP(K30), 200mg of citric acid, 500mg of Ni(NO3)2·6H2O, and Ce(NO3)2·6H2O are added to 30mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1. The solution is then stirred vigorously for 30min, wherein the molar ratio of Ni / Ce is 1:0.3.

[0053] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0054] Comparative Example 2

[0055] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.5g of the composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0056] The preparation method of the complex does not add CeO2. Specifically, 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, and 500 mg Ni(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1, and then the mixture is stirred vigorously for 30 min.

[0057] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0058] Comparative Example 3

[0059] A self-healing polyurea waterproof and corrosion-resistant membrane is prepared as follows: 5g of IPDI is accurately weighed and dissolved in 20mL of THF, and stirred at room temperature for 20min to obtain solution A; 20g of PPG-2000 and 8g of APD are accurately weighed and dissolved in 30mL of THF, and stirred at room temperature for 20min to obtain solution B; 0.5g of the composite is added to solution A and stirred for 20min; then solution B is slowly added dropwise to solution A while stirring at room temperature. After the addition is complete, the mixture is stirred at room temperature for 1h, left to stand at room temperature for 12h, and then placed at 80 degrees Celsius for 24h.

[0060] The preparation method of the complex does not add NiO2. Specifically, 150 mg H3BTC, 1.5 g PVP (K30), 200 mg citric acid, and 5223.8 mg Ce(NO3)2·6H2O are added to 30 mL of a solution composed of ethanol, deionized water, and DMF in a volume ratio of 1:1:1, and then the mixture is stirred vigorously for 30 min.

[0061] The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

[0062] Test Example 1

[0063] The tensile strength recovery rate is the ratio of the tensile strength of the cut samples after they have been in contact with each other for 8 hours at 120°C to the initial tensile strength.

[0064] Acid resistance was tested according to the relevant test methods in GB / T 9274-1988 "Determination of resistance to liquid media in paints and varnishes".

[0065]

[0066] As shown in Table 1, Examples 1-8 above confirm that the self-healing polyurea waterproof and corrosion-resistant membrane prepared by the method of the present invention has good tensile strength, tensile strength recovery rate and acid resistance.

[0067] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A self-healing polyurea waterproof and corrosion-resistant membrane, characterized in that, It consists of the following components: isophorone diisocyanate, amino-terminated polyoxypropylene ether, 2,2'-diaminodiphenyl disulfide and MOF-derived NiO / CeO2 complex. The MOF ligand in the MOF-derived NiO / CeO2 composite is H3BTC; The preparation method of the MOF-derived NiO / CeO2 complex is as follows: H3BTC, PVP, citric acid, Ni(NO3)2·6H2O and Ce(NO3)2·6H2O are added to a mixed solution composed of ethanol, deionized water and DMF, and then stirred vigorously for 30 min. The mixed solution was then transferred to a stainless steel reactor and heated at 150°C for 10 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and then centrifuged. The resulting precipitate was washed five times with ethanol and then vacuum dried at 60°C overnight. The dried precipitate was then heated from 25°C to 600°C at a rate of 2°C / min. After reaching 600°C, the temperature was maintained at atmospheric pressure in air for 3 hours.

2. The self-healing polyurea waterproof and corrosion-resistant membrane according to claim 1, characterized in that, The mass ratio of isophorone diisocyanate, amino-terminated polyoxypropylene ether, 2,2'-diaminodiphenyl disulfide, and MOF-derived NiO / CeO2 composite is 5:20:8:0.2~0.

8.

3. The self-healing polyurea waterproof and corrosion-resistant membrane according to claim 1, characterized in that, The mass ratio of H3BTC, PVP, citric acid, and Ni(NO3)2·6H2O is 1.5:15:2:

5.

4. The self-healing polyurea waterproof and corrosion-resistant membrane according to claim 3, characterized in that, The molar ratio of Ni / Ce is 1:0.1~0.

4.

5. The self-healing polyurea waterproof and corrosion-resistant membrane according to claim 1, characterized in that, The volume ratio of ethanol, deionized water and DMF in the mixed solution is 1:1:

1.

6. The self-healing polyurea waterproof and corrosion-resistant membrane according to claim 1, characterized in that, The terminal amino polyoxypropylene ether has a molecular weight of 2000 and a functionality of 2.

7. The method for preparing self-healing polyurea waterproof and corrosion-resistant membrane according to any one of claims 1 to 6, characterized in that, The steps include: accurately weighing 5g of isophorone diisocyanate and dissolving it in 20mL of tetrahydrofuran, stirring at room temperature for 20min to obtain solution A; accurately weighing 20g of terminal amino polyoxypropylene ether-2000 and 8g of 2,2'-diaminodiphenyl disulfide and dissolving them in 30mL of tetrahydrofuran, stirring at room temperature for 20min to obtain solution B; adding 0.5g of MOF-derived NiO / CeO2 complex to solution A, stirring for 20min, and then slowly adding solution B dropwise to solution A while stirring at room temperature. After the addition is complete, stirring at room temperature for 1h, standing at room temperature for 12h, and then standing at 80 degrees Celsius for 24h.

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