CN114671994B - Organic silicon modified thermosetting polyester type polyurethane elastomer material and preparation method and application thereof - Google Patents
Organic silicon modified thermosetting polyester type polyurethane elastomer material and preparation method and application thereof Download PDFInfo
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The invention relates to the technical field of polyurethane elastomer materials, and provides an organic silicon modified thermosetting polyester type polyurethane elastomer material as well as a preparation method and application thereof. The raw materials for preparing the organic silicon modified thermosetting polyester type polyurethane elastomer material comprise polycarbonate dihydric alcohol, diisocyanate, hydroxyl-terminated polydimethylsiloxane and a cross-linking agent. The invention utilizes the organic silicon resin as a modifier to improve the physical and chemical properties of the polyurethane elastomer material. The end group of the organic silicon resin adopted by the invention has an active group, and can carry out copolymerization addition reaction with diisocyanate, so that the compatibility with a matrix can be improved; meanwhile, the mechanical strength and the tribological performance of the material can be adjusted by changing the addition proportion of the organic silicon resin. The results of the examples show that the organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention has good mechanical property, water lubrication friction property, high-temperature hydrolysis resistance and oil resistance.
Description
Technical Field
The invention relates to the technical field of polyurethane elastomer materials, in particular to an organic silicon modified thermosetting polyester type polyurethane elastomer material and a preparation method and application thereof.
Background
The polyurethane is named polyurethane, is a high polymer material, has various types, has excellent mechanical properties, medium resistance and self-lubricating properties, and is widely applied to the fields of sealing materials, water-lubricated bearings and the like. In the synthesis process, polyurethane elastomers with different properties can be formed according to different synthesis processes and raw material proportions, and the polyurethane can be classified into polyesters, polyethers, polyolefins, polyacrylates and the like according to the types of polyols.
Polyurethane-based materials can exhibit elastomeric characteristics over their operating temperature range, which is necessary to achieve the relevant application areas. The polyurethane material has excellent mechanical properties such as high strength, high abrasion resistance, high tensile property and the like. However, since polyurethane materials still have the characteristics of thermoplastic materials, they soften or even melt at 80 ℃, which lowers the upper limit of their working temperature. Therefore, the development of a novel thermosetting polyurethane material with high performance and medium resistance has important research significance.
Disclosure of Invention
In view of the above, the invention provides an organosilicon modified thermosetting polyester type polyurethane elastomer material, and a preparation method and an application thereof. The organic silicon modified thermosetting polyester polyurethane provided by the invention has the advantages of high heat resistance, good medium resistance, excellent mechanical property and good tribological property.
In order to achieve the above object, the present invention provides the following technical solutions:
an organic silicon modified thermosetting polyester type polyurethane elastomer material comprises the following preparation raw materials in parts by mass: 140-180 parts of polycarbonate diol, 40-100 parts of diisocyanate, 1-10 parts of hydroxyl-terminated polydimethylsiloxane and 10-25 parts of a cross-linking agent.
Preferably, the polycarbonate diol has a number average molecular weight of 500 to 3000; the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane is 3000-5000.
Preferably, the diisocyanate comprises one or more of 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate.
Preferably, when the diisocyanate is 2, 4-toluene diisocyanate, the mass part of the diisocyanate is 40-70 parts; when the diisocyanate is 4,4' -diphenylmethane diisocyanate, the mass portion of the diisocyanate is 60-100 portions; and when the diisocyanate is isophorone diisocyanate, the mass part of the diisocyanate is 50-90 parts.
Preferably, the crosslinking agent comprises one or both of trimethylolpropane and glycerol.
Preferably, when the cross-linking agent is trimethylolpropane, the mass portion of the cross-linking agent is 15-25 portions; when the cross-linking agent is glycerol, the mass portion of the cross-linking agent is 10-18.
The invention also provides a preparation method of the organic silicon modified thermosetting polyester type polyurethane elastomer material, which comprises the following steps:
mixing polycarbonate dihydric alcohol, hydroxyl-terminated polydimethylsiloxane and diisocyanate for a prepolymerization reaction to obtain a prepolymer;
and mixing the prepolymer and a cross-linking agent, and curing to obtain the organic silicon modified thermosetting polyester type polyurethane elastomer material.
Preferably, the temperature of the prepolymerization reaction is 60-80 ℃, and the time is 1.5-4 h; the molar ratio of the isocyanate group in the diisocyanate to the total amount of the hydroxyl groups in the polycarbonate diol and the hydroxyl-terminated polydimethylsiloxane is (2-5): 1.
Preferably, after the prepolymer is obtained, degassing the prepolymer; after the prepolymer and the cross-linking agent are mixed, degassing the obtained mixture; the curing temperature is 80-120 ℃.
The invention also provides an application of the organic silicon modified thermosetting polyester type polyurethane elastomer material or the organic silicon modified thermosetting polyester type polyurethane elastomer material prepared by the preparation method in the scheme in a lubricating material.
The invention provides an organic silicon modified thermosetting polyester type polyurethane elastomer material which comprises the following preparation raw materials in parts by mass: 140-180 parts of polycarbonate diol, 40-100 parts of diisocyanate, 1-10 parts of hydroxyl-terminated polydimethylsiloxane and 10-25 parts of a cross-linking agent. The organic silicon resin has good low-temperature flexibility and lower surface tension, and the organic silicon resin (hydroxyl-terminated polydimethylsiloxane) is used as a modifier, so that the heat resistance, cold resistance, hydrophobicity, solvent resistance, wear resistance and other properties of the polyurethane elastomer material can be improved. The end group of the organic silicon resin adopted by the invention has active group (hydroxyl group), so that the organic silicon resin can be subjected to copolymerization addition reaction with diisocyanate, and the compatibility with a matrix can be improved compared with single physical blending; meanwhile, the organosilicon is used as a soft segment in the polyurethane, and the proportion of the soft segment and the soft segment of the polyurethane can be adjusted by changing the adding proportion of the organosilicon resin, so that the mechanical strength and the tribological performance of the material are finally adjusted. In addition, the preparation raw materials of the polyurethane also comprise a cross-linking agent, and the obtained polyurethane elastomer material is a cross-linked polyurethane elastomer which has higher physical and chemical properties due to the increase of cross-linking density compared with the traditional thermoplastic polyurethane. In addition, the polyurethane elastomer material provided by the invention takes polycarbonate dihydric alcohol as a main raw material, and the prepared polycarbonate polyurethane has excellent wear resistance.
The invention also provides a preparation method of the organic silicon modified thermosetting polyester type polyurethane elastomer material, and the organic silicon modified thermosetting polyester type polyurethane elastomer material is prepared by a prepolymer method, so that the obtained polyurethane elastomer material not only has excellent mechanical property, but also has regular molecular chain segments, and the heat resistance of the polyurethane elastomer material can be further improved.
The results of the examples show that the organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention has good mechanical property and water lubrication friction property, and the mechanical property and the friction property can be regulated and controlled by regulating and controlling the content of the organic silicon resin; the high-temperature hydrolysis resistance and oil resistance are good, and the mechanical property of the high-temperature hydrolysis resistance and oil resistance is not obviously reduced after the high-temperature hydrolysis resistance and oil resistance are soaked in a solution for a long time; the oil-resistant gear oil has good oil resistance, and the swelling ratio is low after the gear oil is soaked for a long time.
Drawings
FIG. 1 shows the results of the water-lubricated coefficient of friction test of the polyurethane elastomer materials prepared in examples 1 to 3 and comparative example 1 under different test conditions;
FIG. 2 is a result of mechanical property test of the organosilicon modified polyester type polyurethane elastomer material prepared in example 3 after high temperature hydrolysis;
FIG. 3 shows the results of testing the mechanical properties of the silicone modified polyester type polyurethane elastomer material prepared in example 3 after being soaked in 320% gear oil;
FIG. 4 shows the results of the swelling ratio test of the silicone modified polyester type polyurethane elastomer material prepared in example 3 after being soaked in 320 gear oil.
Detailed Description
The invention provides an organic silicon modified thermosetting polyester type polyurethane elastomer material which comprises the following preparation raw materials in parts by mass: 140-180 parts of polycarbonate diol, 40-100 parts of diisocyanate, 1-10 parts of hydroxyl-terminated polydimethylsiloxane and 10-25 parts of a cross-linking agent.
Unless otherwise specified, the starting materials for the preparation used in the present invention are commercially available.
The raw materials for preparing the organic silicon modified thermosetting polyester type polyurethane elastomer material comprise, by mass, 140-180 parts of polycarbonate diol (PCDL), preferably 150-170 parts, and more preferably 155-165 parts. In the present invention, the number average molecular weight of the polycarbonate diol is preferably 500 to 3000, more preferably 1000 to 2000, and still more preferably a mixture of a polycarbonate diol having a number average molecular weight of 1000 and a polycarbonate diol having a number average molecular weight of 2000, and the mass ratio of the polycarbonate diol having a number average molecular weight of 1000 to the polycarbonate diol having a number average molecular weight of 2000 in the mixture is preferably 2.
The raw materials for preparing the organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention comprise 40-100 parts of diisocyanate by weight based on the parts by weight of polycarbonate dihydric alcohol. In the present invention, the diisocyanate preferably includes one or more of 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate, and more preferably 2, 4-tolylene diisocyanate. In the present invention, when the diisocyanate is 2, 4-tolylene diisocyanate, the mass part of the diisocyanate is preferably 40 to 70 parts, more preferably 50 to 60 parts; when the diisocyanate is 4,4' -diphenylmethane diisocyanate, the mass part of the diisocyanate is preferably 60 to 100 parts, and preferably 70 to 90 parts; when the diisocyanate is isophorone diisocyanate, the mass portion of the diisocyanate is preferably 50 to 90 parts, and preferably 60 to 70 parts.
The raw materials for preparing the organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention comprise 1-10 parts of hydroxyl-terminated Polydimethylsiloxane (PDMS), preferably 2-8 parts, and more preferably 3-6 parts by weight based on the mass part of polycarbonate diol. In the present invention, the hydroxyl-terminated polydimethylsiloxane preferably has a number average molecular weight of 3000 to 5000, more preferably 3500 to 4500, and still more preferably 4200. The hydroxyl-terminated polydimethylsiloxane is organic silicon resin, an organic silicon chain segment can be introduced into polyurethane, organic silicon serves as a soft segment in the polyurethane, the proportion of the soft segment and the soft segment of the polyurethane can be adjusted by changing the adding proportion of the organic silicon resin, and finally the adjustment of the mechanical strength and the tribological performance of the material is realized.
Based on the mass portion of the polycarbonate dihydric alcohol, the raw materials for preparing the organic silicon modified thermosetting polyester type polyurethane elastomer material comprise 10-25 portions of a cross-linking agent. In the present invention, the crosslinking agent preferably includes one or both of Trimethylolpropane (TMP) and glycerol; when the crosslinking agent is trimethylolpropane, the mass portion of the crosslinking agent is preferably 15 to 25 parts, preferably 18 to 22 parts, and more preferably 20 parts; when the cross-linking agent is glycerol, the mass portion of the cross-linking agent is preferably 10 to 18 portions, and preferably 12 to 15 portions.
In the invention, the mechanical property and the tribological property of the organic silicon modified thermosetting polyester type polyurethane elastomer material can be adjusted by the addition proportion of organic silicon.Specifically, the elongation at break of the organosilicon modified thermosetting polyester type polyurethane elastomer material is preferably not less than 140%, more preferably 140-200%, the tensile strength is preferably not less than 25MPa, more preferably 25-40 MPa, the elastic modulus is preferably 100-190 MPa, and the higher the addition proportion of the organosilicon, the higher the elongation at break of the polyurethane elastomer material is, and the lower the tensile strength and the elastic modulus are; the water lubrication friction coefficient of the organic silicon modified thermosetting polyester type polyurethane elastomer material is preferably less than or equal to 0.04, and particularly, the friction coefficient is preferably 0.03-0.04 under the conditions that the loading force is 66N and the rotating speed is 70 rad/min; under the conditions that the loading force is 132N and the rotating speed is 70rad/min, the friction coefficient is preferably 0.01-0.02; the higher the adding proportion of the organic silicon is, the lower the friction coefficient of the polyurethane elastomer material is; the Akron abrasion of the organic silicon modified thermosetting polyester type polyurethane elastomer material is less than or equal to 0.1cm 3 /1.61km。
The invention also provides a preparation method of the organic silicon modified thermosetting polyester type polyurethane elastomer material, which comprises the following steps:
mixing polycarbonate dihydric alcohol, hydroxyl-terminated polydimethylsiloxane and diisocyanate for a prepolymerization reaction to obtain a prepolymer;
and mixing the prepolymer and a cross-linking agent, and curing to obtain the organic silicon modified thermosetting polyester type polyurethane elastomer material.
Polycarbonate dihydric alcohol, hydroxyl-terminated polydimethylsiloxane and diisocyanate are mixed for a prepolymerization reaction to obtain a prepolymer. In the present invention, the molar ratio of the isocyanate group (-NCO) in the diisocyanate to the total amount of the hydroxyl group (-OH) in the polycarbonate diol and the hydroxyl terminated polydimethylsiloxane is preferably (2-5): 1, more preferably (3-4): 1; the temperature of the prepolymerization reaction is preferably 60-80 ℃, more preferably 65-75 ℃, and the time of the prepolymerization reaction is preferably 2h; the prepolymerization reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen. In the embodiment of the present invention, it is preferable to add the polycarbonate diol into the reaction vessel, then add the hydroxyl polydimethylsiloxane, then add the diisocyanate according to the above molar ratio, and then raise the temperature to the prepolymerization temperature for reaction. During the prepolymerization reaction, the polycarbonate diol, the hydroxyl-terminated polydimethylsiloxane and the diisocyanate are copolymerized. After the prepolymerization reaction is finished, no treatment is needed, and the obtained reaction product is the prepolymer.
After the prepolymer is obtained, the prepolymer and a cross-linking agent are mixed and then cured to obtain the organic silicon modified thermosetting polyester type polyurethane elastomer material. According to the invention, the prepolymer is preferably degassed and then mixed with the crosslinking agent, the degassing is preferably carried out in a vacuum drying oven, the degassing temperature is preferably 80 ℃, and the degassing time is preferably 0.5h. The invention has no special requirement on the mixing mode of the prepolymer and the cross-linking agent, can be mixed uniformly, and can adopt a stirring and mixing mode. After the prepolymer and the crosslinking agent are mixed, the mixture is preferably degassed and then cured, the mixture is degassed, preferably in a vacuum drying oven, and the mixing is carried out at a degassing temperature of preferably 80 ℃ for a time of preferably 0.5h.
In the present invention, the curing temperature is preferably 80 to 120 ℃, more preferably 80 to 100 ℃, and further preferably 80 ℃; the solidification is preferably carried out in a polytetrafluoroethylene mold, and after the solidification is finished, the cooling is carried out to room temperature, and then the demolding is carried out. In the curing process, hydroxyl in the cross-linking agent reacts with isocyanate groups to generate carbamate groups, and the cross-linking agent with three functional groups is used in the invention, so that cross-linking type thermosetting polyurethane can be obtained, and the obtained thermosetting polyurethane has high cross-linking density, more excellent physical and chemical properties, good heat resistance and difficult softening or melting at high temperature.
The invention also provides an application of the organic silicon modified thermosetting polyester type polyurethane elastomer material or the organic silicon modified thermosetting polyester type polyurethane elastomer material prepared by the preparation method in the scheme in a lubricating material. The invention does not require any special method for the application, and the application method known to those skilled in the art can be adopted. The organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention has the advantages of good tribological performance, low friction coefficient and good wear resistance, and has wide application prospect in the field of lubricating materials.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the polycarbonate diol used was a mixture of a polycarbonate diol having a number average molecular weight of 1000 and a polycarbonate diol having a number average molecular weight of 2000 in a mass ratio of 2; the hydroxyl-terminated polydimethylsiloxanes used in the following examples have number average molecular weights of 4000 to 4500; polycarbonate diol was purchased from Jining Hongming Chemicals, inc., hydroxy terminated polydimethylsiloxane, trimethylolpropane was purchased from Annaiji Chemicals, inc., and 2, 4-toluene diisocyanate was purchased from Sanyo reagent works, shanghai.
Example 1
Prepolymer synthesis: 160g of weighed polycarbonate diol was added to a three-necked flask, 1.6g of hydroxyl-terminated polydimethylsiloxane was added to the three-necked flask, the molar ratio of-NCO to-OH (total molar amount of hydroxyl groups in polycarbonate diol and hydroxyl-terminated polydimethylsiloxane) was controlled to 1 2 And reacting for 2h under protection.
And (3) polyurethane synthesis: and (2) degassing the prepolymer in a vacuum oven at 80 ℃ for 0.5h, adding 19g of trimethylolpropane, stirring uniformly, degassing in the vacuum oven at 80 ℃ for 0.5h, pouring into a polytetrafluoroethylene mold, curing at 80 ℃ for 24h, cooling, and demolding at room temperature to obtain the organic silicon modified polyester type polyurethane elastomer material.
Example 2
Prepolymer synthesis: 163g of polycarbonate diol was weighed into a 250mL three-necked flask, 3.2g of hydroxyl-terminated polydimethylsiloxane was weighed into the three-necked flask, 58g of 2, 4-toluene diisocyanate was added with the molar ratio of-NCO to-OH (total molar amount of hydroxyl groups in polycarbonate diol and hydroxyl-terminated polydimethylsiloxane) being controlled to 1 2 And reacting for 2h under protection.
And (3) polyurethane synthesis: and (2) degassing the prepolymer in a vacuum oven at 80 ℃ for 0.5h, adding 20g of trimethylolpropane, stirring uniformly, degassing in the vacuum oven at 80 ℃ for 0.5h, pouring into a polytetrafluoroethylene mold, curing at 80 ℃ for 24h, cooling, and demolding at room temperature to obtain the organic silicon modified polyester type polyurethane elastomer material.
Example 3
Prepolymer synthesis: 170g of polycarbonate diol was weighed into a 250mL three-necked flask, 6.8g of hydroxyl-terminated polydimethylsiloxane was weighed into the three-necked flask, and by controlling the molar ratio of-NCO to-OH (total molar amount of hydroxyl groups in polycarbonate diol and hydroxyl-terminated polydimethylsiloxane) to be 1:3, 60g of 2, 4-toluene diisocyanate was added, the reaction temperature was raised to 75 ℃ and the reaction temperature was increased to N 2 And reacting for 2 hours under protection.
And (3) polyurethane synthesis: degassing the prepolymer in a vacuum oven at 80 ℃ for 0.5h, adding 21g of trimethylolpropane, stirring uniformly, degassing in the vacuum oven at 80 ℃ for 0.5h, pouring into a polytetrafluoroethylene mold, curing at 80 ℃ for 24h, cooling, and demolding at room temperature to obtain the organic silicon modified polyester type polyurethane elastomer material.
Comparative example 1
And (2) prepolymer synthesis, namely weighing 150g of polycarbonate diol, adding the polycarbonate diol into a 250mL three-neck flask, controlling the molar ratio of-NCO to-OH to be 1 2 And reacting for 2h under protection.
Polyurethane synthesis: degassing the prepolymer in a vacuum oven at 80 ℃ for 0.5h, adding 18g of trimethylolpropane, uniformly stirring, degassing in the vacuum oven at 80 ℃ for 0.5h, pouring into a polytetrafluoroethylene mold, curing at 80 ℃ for 24h, cooling, and demolding at room temperature to obtain the polyurethane elastomer material.
Performance test
1. Friction Performance test
A high-speed ring block friction wear testing machine is adopted, the polyester polyurethane elastomer material and 304 steel are subjected to opposite grinding, the loading force is 66N or 132N, the rotating speed is 70r/min, the running time is 3h, and the friction coefficient is the average value of the last two hours. The test results are shown in fig. 1.
As can be seen from FIG. 1, the silicone modified polyester type polyurethane elastomer material prepared by the invention has a good water lubrication friction coefficient, the friction coefficient of the polyurethane elastomer material obtained in examples 1-3 is obviously lower than that of comparative example 1, and as can be seen from FIG. 1, the control of the tribological performance of the material can be realized by controlling the content of the silicone resin.
2. Mechanical Property measurement
The polyurethane elastomer materials prepared in examples 1 to 3 and comparative example 1 were tested for mechanical properties at room temperature using a Shimadzu AG-X (5000N) electronic universal tester, the tensile rate was 10mm/min, and the sample shape was cut into a dumbbell shape according to International Standard ISO-527-2/5B. The results are shown in Table 1.
TABLE 1 mechanical Property test results
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Elongation at Break (%) | 173.8±27.3 | 149.6±13.0 | 164.0±2.9 | 136.6±12.9 |
| Tensile Strength (MPa) | 32.8±3.0 | 29.7±3.2 | 31.8±1.5 | 33.9±2.9 |
| Modulus of elasticity (MPa) | 176.9±12.9 | 110.8±9.1 | 129.3±25.9 | 159.4±7.0 |
According to the data in the table 1, the organic silicon modified polyester type polyurethane elastomer material provided by the invention has good mechanical property, and the mechanical property can be regulated and controlled by regulating and controlling the addition amount of organic silicon.
3. Oil and high-temperature hydrolysis resistance
The oil and high temperature hydrolysis resistance of the silicone modified polyester type polyurethane elastomer material prepared in example 3 is tested, the testing steps are carried out according to national standard GBT1690-2010, the sample prepared in example 3 is cut into a dumbbell shape according to international standard ISO-527-2/5B (75 samples are prepared in total, 5 samples are tested under each condition, the average value of the test values of all the samples is taken), the mechanical properties of the sample after being soaked in 320 gear oil and 80 ℃ distilled water are tested, and the swelling rate of the sample after being soaked in 320 gear oil is tested.
The test results are shown in fig. 2 to 4, fig. 2 is the mechanical property test result of the organosilicon modified polyester type polyurethane elastomer material prepared in example 3 after high-temperature hydrolysis, and fig. 3 is the mechanical property test result of the organosilicon modified polyester type polyurethane elastomer material prepared in example 3 after being soaked in 320 gear oil; FIG. 4 shows the results of the swelling ratio test of the silicone modified polyester type polyurethane elastomer material prepared in example 3 after being soaked in 320 gear oil. As can be seen from the graphs of FIGS. 2 to 3, the organosilicon modified polyester type polyurethane elastomer material provided by the invention has good high-temperature hydrolysis resistance and oil resistance, and the mechanical properties of the organosilicon modified polyester type polyurethane elastomer material are not obviously reduced after long-time solution soaking. According to the graph in FIG. 4, the organosilicon modified polyester type polyurethane elastomer material provided by the invention has good oil resistance, and the swelling rate is low after the material is soaked in 320 gear oil for a long time.
The same oil degradation resistance and high temperature hydrolysis resistance tests are carried out on the organosilicon modified polyester type polyurethane elastomer materials prepared in the examples 1-2, and the results show that the mechanical properties of the organosilicon modified polyester type polyurethane elastomer materials prepared in the examples 1-2 are not obviously reduced after high temperature hydrolysis and oil degradation, the change of the swelling rate is small, and the organosilicon modified polyester type polyurethane elastomer materials have high oil degradation resistance and high temperature hydrolysis resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. An organic silicon modified thermosetting polyester type polyurethane elastomer material is characterized by being prepared from the following preparation raw materials in parts by mass: 140-180 parts of polycarbonate diol, 40-100 parts of diisocyanate, 1-10 parts of hydroxyl-terminated polydimethylsiloxane and 10-25 parts of a cross-linking agent; the polycarbonate diol is a mixture of polycarbonate diol with the number average molecular weight of 1000 and polycarbonate diol with the number average molecular weight of 2000, and the mass ratio of the polycarbonate diol with the number average molecular weight of 1000 to the polycarbonate diol with the number average molecular weight of 2000 in the mixture is 2.9-1.1; the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane is 3000-5000.
2. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 1, wherein the diisocyanate comprises one or more of 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate.
3. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 2, wherein when the diisocyanate is 2, 4-toluene diisocyanate, the mass part of the diisocyanate is 40 to 70 parts; when the diisocyanate is 4,4' -diphenylmethane diisocyanate, the mass part of the diisocyanate is 60-100 parts; and when the diisocyanate is isophorone diisocyanate, the mass part of the diisocyanate is 50-90 parts.
4. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 1, wherein the crosslinking agent comprises one or both of trimethylolpropane and glycerol.
5. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 4, wherein when the crosslinking agent is trimethylolpropane, the mass part of the crosslinking agent is 15 to 25 parts; when the cross-linking agent is glycerol, the mass portion of the cross-linking agent is 10-18.
6. A method for preparing the silicone-modified thermosetting polyester type polyurethane elastomer material according to any one of claims 1 to 5, comprising the steps of:
mixing polycarbonate diol, hydroxyl-terminated polydimethylsiloxane and diisocyanate to carry out prepolymerization reaction to obtain a prepolymer;
and mixing the prepolymer and a cross-linking agent, and curing to obtain the organic silicon modified thermosetting polyester type polyurethane elastomer material.
7. The preparation method according to claim 6, wherein the prepolymerization reaction is carried out at 60-80 ℃ for 1.5-4 h; the molar ratio of the isocyanate group in the diisocyanate to the total amount of the hydroxyl groups in the polycarbonate diol and the hydroxyl-terminated polydimethylsiloxane is (2-5): 1.
8. The method of claim 6, wherein after obtaining the prepolymer, degassing the prepolymer; after the prepolymer and the cross-linking agent are mixed, degassing the obtained mixture; the curing temperature is 80-120 ℃.
9. Use of the silicone-modified thermosetting polyester type polyurethane elastomer material according to any one of claims 1 to 5 or the silicone-modified thermosetting polyester type polyurethane elastomer material prepared by the preparation method according to any one of claims 6 to 8 in a lubricating material.
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