CN114671994A - 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 PDF

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CN114671994A
CN114671994A CN202210317672.XA CN202210317672A CN114671994A CN 114671994 A CN114671994 A CN 114671994A CN 202210317672 A CN202210317672 A CN 202210317672A CN 114671994 A CN114671994 A CN 114671994A
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polyurethane elastomer
diisocyanate
elastomer material
polyester type
organic silicon
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CN114671994B (en
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杨靖
张耀明
王廷梅
王齐华
陈守兵
张新瑞
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes

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 adding 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

Organic silicon modified thermosetting polyester type polyurethane elastomer material and preparation method and application thereof
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 performances 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 the 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 the 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 number average molecular weight of the polycarbonate diol is 500-3000; 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 part of the diisocyanate is 60-100 parts; 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 part of the cross-linking agent is 15-25 parts; 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 (the 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 rate is low after the gear is soaked in 320% of oil for a long time.
Drawings
FIG. 1 shows the results of water-lubricated friction coefficient tests of polyurethane elastomer materials prepared in examples 1-3 and comparative example 1 under different test conditions;
FIG. 2 shows the results of mechanical property measurements of the silicone modified polyester type polyurethane elastomer material prepared in example 3 after high temperature hydrolysis;
FIG. 3 shows the results of mechanical property measurements 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 rate test of the silicone modified polyester type polyurethane elastomer material prepared in example 3 after being soaked in 320 kinds of 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 preparation raw material of the organic silicon modified thermosetting polyester type polyurethane elastomer material comprises, by mass, 140-180 parts of polycarbonate diol (PCDL), preferably 150-170 parts, and more preferably 155-165 parts. In the invention, the number average molecular weight of the polycarbonate diol is preferably 500-3000, more preferably 1000-2000, and further preferably a mixture of polycarbonate diol with a number average molecular weight of 1000 and polycarbonate diol with a number average molecular weight of 2000, and the mass ratio of the polycarbonate diol with a number average molecular weight of 1000 to the polycarbonate diol with a number average molecular weight of 2000 in the mixture is preferably 2: 0.9-1.1.
The preparation raw material of the organic silicon modified thermosetting polyester type polyurethane elastomer material comprises 40-100 parts of diisocyanate by mass based on the mass part of polycarbonate diol. In the present invention, the diisocyanate preferably includes one or more of 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate, and more preferably 2, 4-toluene diisocyanate. In the present invention, when the diisocyanate is 2, 4-toluene diisocyanate, the mass part of the diisocyanate is preferably 40 to 70 parts, and 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 part of the diisocyanate is preferably 50-90 parts, and preferably 60-70 parts.
The preparation raw materials of 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 mechanical strength and the tribological performance of the material are adjusted.
The preparation raw material of the organic silicon modified thermosetting polyester type polyurethane elastomer material comprises 10-25 parts of a cross-linking agent by mass based on polycarbonate dihydric alcohol. In the present invention, the crosslinking agent preferably includes one or both of Trimethylolpropane (TMP) and glycerol; when the cross-linking agent is trimethylolpropane, the mass portion of the cross-linking agent is preferably 15-25 parts, preferably 18-22 parts, and more preferably 20 parts; when the cross-linking agent is glycerol, the mass part of the cross-linking agent is preferably 10-18 parts, and preferably 12-15 parts.
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 organic silicon 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 organic silicon is, the higher the elongation at break of the polyurethane elastomer material is, 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 0.1cm3/1.61km。
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 2 h; the prepolymerization reaction is preferably carried out under a protective atmosphere, which 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 0.5 h. 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 0.5 h.
In the invention, the curing temperature is preferably 80-120 ℃, more preferably 80-100 ℃, 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 has no special requirements for the specific method of application, and the application method known to the skilled person can be adopted. The organic silicon modified thermosetting polyester type polyurethane elastomer material provided by the invention has good tribological property, 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the polycarbonate diol used was a mixture of polycarbonate diol having a number average molecular weight of 1000 and polycarbonate diol having a number average molecular weight of 2000 in a mass ratio of 2: 1; the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane used in the following examples is 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 Sanyou reagent works, Shanghai.
Example 1
Prepolymer synthesis: weighed polycarbonate diol160g of the mixture was placed in a three-necked flask, 1.6g of hydroxyl-terminated polydimethylsiloxane was weighed into the three-necked flask, the molar ratio of-NCO to-OH (total molar amount of hydroxyl groups in the polycarbonate diol and the hydroxyl-terminated polydimethylsiloxane) was controlled at 1:3, 55g of 2, 4-tolylene diisocyanate was added, the reaction temperature was raised to 75 ℃ under N2And reacting for 2 hours 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, the molar ratio of-NCO to-OH (the total molar amount of hydroxyl groups in the polycarbonate diol and the hydroxyl-terminated polydimethylsiloxane) was controlled to 1:3, 58g of 2, 4-tolylene diisocyanate was added, the reaction temperature was raised to 75 ℃ and N was added2And reacting for 2 hours 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: weighing 170g of polycarbonate diol, adding the polycarbonate diol into a 250mL three-neck flask, weighing 6.8g of hydroxyl-terminated polydimethylsiloxane into the three-neck flask, adding 60g of 2, 4-toluene diisocyanate by controlling the molar ratio of-NCO to-OH (the total molar weight of hydroxyl in the polycarbonate diol and the hydroxyl-terminated polydimethylsiloxane) to be 1:3, raising the reaction temperature to 75 ℃, and adding N2And reacting for 2h under protection.
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
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 1:3, adding 52g of 2, 4-toluene diisocyanate, raising the reaction temperature to 75 ℃, and carrying out N reaction at the temperature of N2And reacting for 2 hours under protection.
And (3) 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 testing
1. Test for Friction Properties
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.
According to the figure 1, the organic silicon 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 the examples 1-3 is obviously lower than that of the comparison document 1, and according to the figure 1, the control of the tribological performance of the material can be realized by controlling the content of the organic silicon resin.
2. Mechanical Property test
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 of 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 testing values of all 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. 2-4, fig. 2 is a 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 a 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 figures 2-3, the organic silicon modified polyester type polyurethane elastomer material provided by the invention has good high-temperature hydrolysis resistance and oil resistance, and the mechanical property of the material is 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 embodiments 1-2, and the results show that the mechanical properties of the organosilicon modified polyester type polyurethane elastomer materials prepared in the embodiments 1-2 are not obviously reduced after high temperature hydrolysis and oil degradation, the swelling rate change 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 (10)

1. An organic silicon modified thermosetting polyester type polyurethane elastomer material is characterized by comprising 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.
2. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 1, wherein 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.
3. The material according to claim 1, wherein the diisocyanate comprises one or more of 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and isophorone diisocyanate.
4. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 3, 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; when the diisocyanate is isophorone diisocyanate, the mass part of the diisocyanate is 50-90 parts.
5. 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.
6. The silicone-modified thermosetting polyester type polyurethane elastomer material according to claim 5, 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.
7. The preparation method of the organic silicon modified thermosetting polyester type polyurethane elastomer material as claimed in any one of claims 1 to 6, characterized by comprising 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.
8. The preparation method according to claim 7, 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.
9. The method according to claim 7, wherein the method further comprises degassing the prepolymer after the prepolymer is obtained; after the prepolymer and the cross-linking agent are mixed, degassing the obtained mixture; the curing temperature is 80-120 ℃.
10. Use of the silicone-modified thermosetting polyester type polyurethane elastomer material according to any one of claims 1 to 6 or the silicone-modified thermosetting polyester type polyurethane elastomer material prepared by the preparation method according to any one of claims 7 to 9 in a lubricating material.
CN202210317672.XA 2022-03-29 2022-03-29 Organic silicon modified thermosetting polyester type polyurethane elastomer material and preparation method and application thereof Active CN114671994B (en)

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