CN114957602A - Method for modifying polyurethane elastomer by using montmorillonite - Google Patents
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Abstract
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a method for modifying a polyurethane elastomer by utilizing montmorillonite. According to the invention, ammonium polyphosphate and boric acid are selected to be compounded to obtain the flame retardant, and the formula of the flame retardant is optimized to achieve the synergistic effects of high-efficiency flame retardance and smoke reduction and toxicity reduction on the polyurethane elastomer; sodium-based montmorillonite is prepared by a cation filling method, and then flower-like molybdenum disulfide grows in situ on the surface of the sodium-based montmorillonite by a hydrothermal method to obtain composite montmorillonite, and polyurethane is modified to achieve a synergistic flame-retardant effect; carrying out covalent grafting modification on the composite montmorillonite by adopting 4,4' -diphenylmethane diisocyanate to prepare the composite montmorillonite with high activity and high dispersibility and with isocyanate characteristics; modified isocyanated composite montmorillonite and toluene-2, 4-diisocyanate are used as hybrid reactants to prepare the grafted polyurethane elastomer, and the mechanical property and the thermal stability of polyurethane are obviously improved by adding the isocyanated composite montmorillonite.
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a method for modifying a polyurethane elastomer by utilizing montmorillonite.
Background
The thermoplastic polyurethane is a novel organic polymer synthetic material, belongs to a compound, has excellent performances, and has higher wear resistance and resilience than common polyurethane; in addition, the polyurethane elastomer has the advantages of high hardness, high strength, good elasticity, low temperature resistance, good oil resistance, chemical resistance, environmental resistance and the like, so that the thermoplastic polyurethane is widely applied to the fields of cables, automobiles, sanitation, pipes, films, sheets and the like. However, the linear thermoplastic polyurethane elastomer can generate creep deformation under dynamic load, and can generate serious endogenous heat, so that the rebound resilience is poor, the linear thermoplastic polyurethane elastomer is easy to age, is easy to burn and decompose when meeting fire, and generates a large amount of molten drops and toxic gases such as NO, CO, HCN and the like. The existing market generally adds fillers to thermoplastic polyurethanes to improve their properties.
Montmorillonite is a main mineral component of bentonite ore, is a natural mineral of expandable silicate formed in nature, has very strong rigidity, and can be used as a filler filled polymer to improve the mechanical property, heat insulation and flame retardant property and the like of the bentonite ore. However, montmorillonite particles composed of nano-sheets are micron-sized, and when the montmorillonite particles are directly applied to a polymer, the sheet structure is difficult to be completely opened, and the compatibility of the montmorillonite particles and the polymer is poor, so that the full play of the montmorillonite function is influenced.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a method for modifying a polyurethane elastomer using montmorillonite.
A method for modifying polyurethane elastomer by using montmorillonite comprises the following steps:
s1, adding isocyanated composite montmorillonite into polytetrahydrofuran ether glycol, then adding toluene-2, 4-diisocyanate, preserving heat for 1-2h at 80-90 ℃, and removing bubbles to obtain a polyurethane prepolymer;
s2, mixing the polyurethane prepolymer, dimethyl-sulfur-based toluene diamine, ultraviolet light stabilizer and flame retardant, stirring for 5-8min at 110-120 ℃, and vulcanizing to obtain the montmorillonite modified polyurethane elastomer.
Preferably, the preparation of the isocyanated composite montmorillonite comprises the following steps:
1) mixing montmorillonite and saturated sodium chloride solution, stirring at 65-70 deg.C for 22-24h, centrifuging, and oven drying to obtain sodium-based montmorillonite;
2) dissolving ammonium molybdate and thiourea in distilled water, stirring for 1-2h, adding sodium-based montmorillonite, continuing stirring for 1-2h, then keeping the temperature at 190-;
3): adding the composite montmorillonite into a solvent, and ultrasonically stirring to obtain montmorillonite suspension; adding 4,4' -diphenylmethane diisocyanate into a solvent, stirring and mixing, heating to 55 ℃, adding the montmorillonite suspension and a catalyst, keeping the temperature for 8-10h, washing and drying to obtain the isocyanated composite montmorillonite.
Preferably, the mass ratio of the montmorillonite to the ammonium molybdate to the thiourea is 4: 0.04: 0.05.
preferably, the mass ratio of the composite montmorillonite to the 4,4' -diphenylmethane diisocyanate is 0.1: 8.
preferably, the solvent is N, N-dimethylformamide and the catalyst is dibutyltin dilaurate.
Preferably, the flame retardant is obtained by compounding ammonium polyphosphate and boric acid, and the mass ratio of the ammonium polyphosphate to the boric acid is (4-6): 1.
preferably, the raw materials for preparing the montmorillonite modified polyurethane elastomer comprise the following components in parts by weight: 70-80 parts of polytetrahydrofuran ether glycol, 0.1-0.3 part of isocyanated composite montmorillonite, 20-22 parts of toluene-2, 4-diisocyanate, 8-10 parts of dimethylthiotoluenediamine, 0.5-1 part of ultraviolet light stabilizer and 0.5-1 part of flame retardant.
Preferably, the isocyanated composite montmorillonite accounts for 0.12-0.24% of the total mass of the raw materials for preparing the montmorillonite-modified polyurethane elastomer.
Preferably, the vulcanization is carried out under the following specific conditions: firstly, a vulcanizing machine is used for vulcanizing at the temperature of 100-105 ℃ for 1h, and the molded product is placed into an oven at the temperature of 100-105 ℃ for vulcanizing for 24-26 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the ammonium polyphosphate is independently used as a flame retardant, smoke toxic gas is generated during combustion, and the boron flame retardant has the characteristics of smoke suppression, good stability, environmental protection and the like, but has low solubility and is greatly influenced by temperature;
2. the sodium-based montmorillonite is prepared by a cation filling method, and then the flower-shaped molybdenum disulfide grows on the surface of the sodium-based montmorillonite in situ by a hydrothermal method to obtain the composite montmorillonite, so that the active sites of the composite montmorillonite are greatly improved, the polyurethane is modified, and the synergistic flame retardant effect is achieved; 4,4' -diphenylmethane diisocyanate is adopted to carry out covalent grafting modification on the composite montmorillonite to prepare the composite montmorillonite with isocyanate characteristics, high activity and high dispersibility, and the problem of agglomeration of the montmorillonite in a polyurethane matrix is better solved; the polyurethane elastomer prepared by using the isocyanated composite montmorillonite and the toluene-2, 4-diisocyanate as hybrid reactants has excellent mechanical property and thermal stability and higher conductivity.
Detailed Description
The invention is further described with reference to specific examples.
Source of raw materials
Polytetrahydrofuran ether glycol, number average molecular weight 2000, available from basf; dimethylthiotoluenediamine, available from Leling, Inc.; montmorillonite, purchased from Hubei energy chemical technology, Inc.; 2- (2' -hydroxy-3 ',5' -di-tert-amylphenyl) benzotriazole, available from Shanghai-derived PhylloBiotech, Inc.; ammonium polyphosphate A875114 (degree of polymerization: n < 20, water solubility > 90g/100mL), toluene-2, 4-diisocyanate T830062, available from Shanghai Michelin Biotech, Inc.; 4,4' -diphenylmethane diisocyanate, WANNATEMDI-100, Wanhua chemical Co., Ltd.
Example 1
A method for modifying a polyurethane elastomer by using montmorillonite comprises the following steps:
s1: heating 70g of polytetrahydrofuran ether glycol to 100 ℃, vacuumizing to remove water for 2h, cooling to 80 ℃, adding 0.24g of isocyanated composite montmorillonite, preserving heat for 0.5h, cooling to 50 ℃, adding 20g of toluene-2, 4-diisocyanate, heating to 90 ℃, preserving heat for 1h, vacuumizing to remove bubbles, and obtaining a polyurethane prepolymer;
s2: mixing the polyurethane prepolymer, 8g of dimethylthiotoluenediamine, 0.5g of ultraviolet light stabilizer and 0.5g of flame retardant, transferring the mixture into an internal mixer for mixing for 5min, pouring the mixture into a mold at the working temperature of 110 ℃, vulcanizing the mixture for 1.5h at the temperature of 100 ℃ by using a vulcanizing machine, and putting the mixture into a 100 ℃ oven for vulcanizing for 24h after molding to obtain the montmorillonite-modified polyurethane elastomer.
Wherein: the ultraviolet light stabilizer is 2- (2' -hydroxy-3 ',5' -di-tert-amyl phenyl) benzotriazole;
the flame retardant is obtained by compounding ammonium polyphosphate and boric acid, wherein the mass ratio of the ammonium polyphosphate to the boric acid is 4: 1;
the isocyanated composite montmorillonite accounts for 0.24 percent of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer;
the preparation of the isocyanated composite montmorillonite comprises the following steps:
1) mixing 4g of montmorillonite with 40mL of saturated sodium chloride solution, stirring for 24h at 65 ℃, centrifuging, and drying to obtain sodium-based montmorillonite;
2) dissolving 40mg of ammonium molybdate and 50mg of thiourea in distilled water, stirring for 1h, adding sodium-based montmorillonite, continuously stirring for 1h, transferring to an autoclave with a polytetrafluoroethylene lining, preserving heat at 190 ℃ for 24h, centrifuging, washing and drying to obtain composite montmorillonite;
3) mixing 100mg of composite montmorillonite and 25mLN, N-dimethylformamide, and then ultrasonically stirring to obtain montmorillonite suspension; mixing and stirring 8g of 4,4' -diphenylmethane diisocyanate and 15mLN, N-dimethylformamide, heating to 55 ℃, adding a montmorillonite suspension, then adding 2 drops of dibutyltin dilaurate, keeping the temperature for 8 hours, centrifuging, washing and drying to obtain the isocyanated composite montmorillonite.
Example 2
A method for modifying polyurethane elastomer by using montmorillonite comprises the following steps:
s1: heating 75g of polytetrahydrofuran ether glycol to 102 ℃, vacuumizing to remove water for 1.5h, cooling to 82 ℃, adding 0.23g of isocyanated composite montmorillonite, preserving heat for 0.8h, cooling to 50 ℃, adding 21g of toluene-2, 4-diisocyanate, heating to 85 ℃, preserving heat for 1.5h, vacuumizing to remove bubbles, and obtaining a polyurethane prepolymer;
s2: mixing the polyurethane prepolymer, 9g of dimethylthiotoluenediamine, 0.7g of ultraviolet light stabilizer and 0.8g of flame retardant, transferring the mixture into an internal mixer for mixing for 6min, pouring the internal mixer into a mold at the working temperature of 117 ℃, vulcanizing the mixture for 1.2h at the temperature of 102 ℃ by using a vulcanizing machine, and putting the mixture into a 100 ℃ oven for vulcanizing the mixture for 25h after molding to obtain the montmorillonite-modified polyurethane elastomer.
Wherein: the ultraviolet light stabilizer is 2- (2' -hydroxy-3 ',5' -di-tert-amyl phenyl) benzotriazole;
the flame retardant is obtained by compounding ammonium polyphosphate and boric acid, wherein the mass ratio of the ammonium polyphosphate to the boric acid is 5: 1;
the isocyanated composite montmorillonite accounts for 0.22 percent of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer;
the preparation of the isocyanated composite montmorillonite comprises the following steps:
1) mixing 4g of montmorillonite with 40mL of saturated sodium chloride solution, stirring for 23h at 68 ℃, centrifuging, and drying to obtain sodium-based montmorillonite;
2) dissolving 40mg of ammonium molybdate and 50mg of thiourea in distilled water, stirring for 1.5h, adding sodium-based montmorillonite, continuing stirring for 1.5h, transferring to an autoclave with a polytetrafluoroethylene lining, preserving heat at 195 ℃ for 23h, centrifuging, washing and drying to obtain composite montmorillonite;
3) mixing 100mg of composite montmorillonite and 25mLN, N-dimethylformamide, and then ultrasonically stirring to obtain montmorillonite suspension; mixing and stirring 8g of 4,4' -diphenylmethane diisocyanate and 15mLN, N-dimethylformamide, heating to 55 ℃, adding a montmorillonite suspension, then adding 3 drops of dibutyltin dilaurate, keeping the temperature for 9 hours, centrifuging, washing and drying to obtain the isocyanated composite montmorillonite.
Example 3
A method for modifying polyurethane elastomer by using montmorillonite comprises the following steps:
s1: heating 80g of polytetrahydrofuran ether glycol to 105 ℃, vacuumizing to remove water for 1h, cooling to 85 ℃, adding 0.14g of isocyanated composite montmorillonite, keeping the temperature for 1h, cooling to 50 ℃, adding 22g of toluene-2, 4-diisocyanate, heating to 80 ℃, keeping the temperature for 2h, vacuumizing to remove bubbles, and obtaining a polyurethane prepolymer;
s2: mixing the polyurethane prepolymer, 10g of dimethyl-sulfur-based toluene diamine, 1g of ultraviolet light stabilizer and 1g of flame retardant, transferring the mixture into an internal mixer for mixing for 8min, controlling the working temperature of the internal mixer to be 120 ℃, pouring the mixture into a mold, vulcanizing the mixture for 1h at 105 ℃ by using a vulcanizing machine, and putting the mixture into a 100 ℃ oven for vulcanizing the mixture for 26h after molding to obtain the montmorillonite-modified polyurethane elastomer.
Wherein: the ultraviolet light stabilizer is 2- (2' -hydroxy-3 ',5' -di-tert-amyl phenyl) benzotriazole;
the flame retardant is obtained by compounding ammonium polyphosphate and boric acid, wherein the mass ratio of the ammonium polyphosphate to the boric acid is 6: 1;
the isocyanated composite montmorillonite accounts for 0.12 percent of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer;
the preparation of the isocyanated composite montmorillonite comprises the following steps:
1) mixing 4g of montmorillonite with 40mL of saturated sodium chloride solution, stirring for 22h at 70 ℃, centrifuging, and drying to obtain sodium-based montmorillonite;
2) dissolving 40mg of ammonium molybdate and 50mg of thiourea in distilled water, stirring for 2h, adding sodium-based montmorillonite, continuing stirring for 2h, transferring to an autoclave with a polytetrafluoroethylene lining, preserving heat for 22h at 200 ℃, centrifuging, washing and drying to obtain composite montmorillonite;
3) mixing 100mg of composite montmorillonite and 25mLN, N-dimethylformamide, and then ultrasonically stirring to obtain montmorillonite suspension; mixing and stirring 8g of 4,4' -diphenylmethane diisocyanate and 15mLN, N-dimethylformamide, heating to 55 ℃, adding a montmorillonite suspension, then adding 4 drops of dibutyltin dilaurate, keeping the temperature for 10 hours, centrifuging, washing and drying to obtain the isocyanated composite montmorillonite.
Comparative example 1
This comparative example differs from example 2 in that isocyanated composite montmorillonite was replaced with the same mass of composite montmorillonite.
Comparative example 2
This comparative example differs from example 2 in that the isocyanated composite montmorillonite was replaced with montmorillonite of the same mass.
Comparative example 3
This comparative example differs from example 2 in that the flame retardant is ammonium polyphosphate.
Comparative example 4
This comparative example differs from example 2 in that the flame retardant is boric acid.
Comparative example 5
The difference between the comparative example and the example 2 is that the dosage of the isocyanated composite montmorillonite is 0.11g, which accounts for 0.1 percent of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer.
Comparative example 6
The difference between the comparative example and the example 2 is that the dosage of the isocyanated composite montmorillonite is 0.27g, which accounts for 0.25 percent of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer, and other procedures are normal.
The polyurethane elastomers prepared in examples 1-3 and comparative examples 1-6 were tested for mechanical properties and flammability, and the samples were 26mm long, 2mm wide and 4mm thick; the test results are shown in table 1;
and (3) testing tensile property: an electronic universal tester needs to be dried and kept stand for 24 hours before testing, the testing temperature is 25 ℃, and the stretching speed is 2 mm/min; taking 10 samples in each group, and taking the average value of the test results;
and (3) oxygen index test: referring to IOS4589-2, the oxygen-nitrogen mixture gas at a temperature of 23 ℃ was removed every 5s, and the minimum oxygen concentration just required to maintain combustion was the oxygen index.
TABLE 1
Compared with the embodiment 2, the oxygen index and the tensile property of the comparative example 1 are both reduced, which shows that in the preparation of the isocyanated composite montmorillonite, the sodium-based montmorillonite is prepared by a cation filling method, and then the flower-shaped molybdenum disulfide grows in situ on the surface of the sodium-based montmorillonite by a hydrothermal method to obtain the composite montmorillonite, so that the active sites of the composite montmorillonite are greatly improved, the polyurethane is modified, and the synergistic flame retardant effect is achieved;
compared with the comparative example 1 and the comparative example 2, the embodiment 2 shows that the composite montmorillonite is subjected to covalent grafting modification by adopting 4,4' -diphenylmethane diisocyanate to prepare the composite montmorillonite with high activity and high dispersibility and isocyanate characteristics, and the technical problem of agglomeration of the montmorillonite in a polyurethane matrix is better solved; isocyanate composite montmorillonite and toluene-2, 4-diisocyanate are taken as hybrid reactants to prepare a grafted polyurethane elastomer, and the mechanical property and the flame retardant property of polyurethane are obviously improved by adding the isocyanate composite montmorillonite;
compared with comparative examples 3 and 4, the oxygen index of the polyurethane elastomer obtained in example 2 is significantly higher, which shows that the polyurethane elastomer obtained by compounding ammonium polyphosphate and boric acid as a flame retardant has better flame retardant property.
The tensile property and the oxygen index of the polyurethane elastomer obtained in the example 2 are higher than those of the polyurethane elastomer obtained in the comparative examples 5 and 6, which shows that the self structure of the composite montmorillonite is not damaged in the process of generating the-NCO-terminated composite montmorillonite; with the increase of the content of the isocyanated composite montmorillonite, the tensile strength of the polyurethane elastomer shows a trend of increasing first and then decreasing; when the mass fraction of the isocyanated composite montmorillonite is 0.22%, the tensile strength of the polyurethane reaches an extreme value; because a proper amount of isocyanated composite montmorillonite well plays a nanometer effect in a matrix, the tensile strength of the polyurethane elastomer is improved, and then the tensile strength is reduced as the isocyanated composite montmorillonite is increased to cause stress concentration. And because of the increase of the isocyanated composite montmorillonite, the crosslinking degree between the composite montmorillonite and the polyurethane matrix is increased, the complexity of a crosslinking network is increased, and the thermal conductivity and the thermal stability of the obtained polyurethane are improved.
In conclusion, the montmorillonite modified polyurethane elastomer prepared by the invention has excellent mechanical property, good flame retardance and good application prospect.
The above detailed description is only for explaining the present application and not for limiting the present application, and those skilled in the art can make modifications to the present embodiment without inventive contribution as required after reading the present specification, but all of them are protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. A method for modifying a polyurethane elastomer by using montmorillonite is characterized by comprising the following steps: the method comprises the following steps:
s1, adding isocyanated composite montmorillonite into polytetrahydrofuran ether glycol, then adding toluene-2, 4-diisocyanate, preserving heat for 1-2h at 80-90 ℃, and removing bubbles to obtain a polyurethane prepolymer;
s2, mixing the polyurethane prepolymer, dimethyl-sulfur-based toluene diamine, ultraviolet light stabilizer and flame retardant, mixing and stirring at 110-120 ℃ for 5-8min, and vulcanizing to obtain the montmorillonite-modified polyurethane elastomer.
2. The method of claim 1, wherein the polyurethane elastomer is modified by montmorillonite: the preparation method of the isocyanated composite montmorillonite comprises the following steps:
1) mixing montmorillonite and saturated sodium chloride solution, stirring at 65-70 deg.C for 22-24 hr, centrifuging, and drying to obtain sodium-based montmorillonite;
2) dissolving ammonium molybdate and thiourea in distilled water, stirring for 1-2h, adding sodium-based montmorillonite, continuing stirring for 1-2h, then keeping the temperature at 190-;
3): adding the composite montmorillonite into the solvent, and ultrasonically stirring to obtain montmorillonite suspension; adding 4,4' -diphenylmethane diisocyanate into a solvent, stirring and mixing, heating to 55 ℃, adding the montmorillonite suspension and a catalyst, keeping the temperature for 8-10h, washing and drying to obtain the isocyanated composite montmorillonite.
3. The method of claim 2, wherein the polyurethane elastomer is modified by montmorillonite: the mass ratio of montmorillonite to ammonium molybdate to thiourea is 4: 0.04: 0.05.
4. the method of claim 2, wherein the montmorillonite is used to modify the polyurethane elastomer, and the method comprises the following steps: the mass ratio of the composite montmorillonite to the 4,4' -diphenylmethane diisocyanate is 0.1: 8.
5. the method of claim 2, wherein the polyurethane elastomer is modified by montmorillonite: the solvent is N, N-dimethylformamide, and the catalyst is dibutyltin dilaurate.
6. The method for modifying polyurethane elastomer by montmorillonite as claimed in claim 1, wherein: the flame retardant is obtained by compounding ammonium polyphosphate and boric acid, and the mass ratio of the ammonium polyphosphate to the boric acid is (4-6): 1.
7. the method of claim 1, wherein the polyurethane elastomer is modified by montmorillonite: the raw materials for preparing the montmorillonite modified polyurethane elastomer comprise the following components in parts by weight: 70-80 parts of polytetrahydrofuran ether glycol, 0.1-0.3 part of isocyanated composite montmorillonite, 20-22 parts of toluene-2, 4-diisocyanate, 8-10 parts of dimethyl-thio-toluene diamine, 0.5-1 part of ultraviolet light stabilizer and 0.5-1 part of flame retardant.
8. The method of claim 7, wherein the polyurethane elastomer is modified with montmorillonite: the isocyanated composite montmorillonite accounts for 0.12-0.24% of the total mass of the raw materials for preparing the montmorillonite modified polyurethane elastomer.
9. The method of claim 1, wherein the polyurethane elastomer is modified by montmorillonite: the specific conditions of vulcanization are: firstly, a vulcanizing machine is used for vulcanizing at the temperature of 100-105 ℃ for 1-1.5h, and the molded product is placed into an oven at the temperature of 100-105 ℃ for vulcanizing for 24-26 h.
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| CN116333444A (en) * | 2023-04-04 | 2023-06-27 | 盛鼎高新材料有限公司 | Fiber-reinforced polyurethane elastomer composite material and preparation method thereof |
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