CN111205426B - Preparation method of low-temperature-resistant polyurethane elastomer - Google Patents
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Abstract
The invention discloses a preparation method of a low-temperature-resistant polyurethane elastomer, which comprises the following steps: mixing polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether, and performing vacuum dehydration; mixing diisocyanate and nano titanium oxide modified by ferric hydroxide under ultrasonic waves, and adding macromolecular diol to react to obtain a prepolymer; and adding micromolecular dihydric alcohol, a catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mould, and curing to obtain the low-temperature-resistant polyurethane elastomer. According to the invention, two kinds of macromolecular dihydric alcohol are mixed to be used as a soft segment, and the surface of the nano titanium dioxide is coated by ferric hydroxide, so that the reactivity of the titanium dioxide and polyurethane can be enhanced, and the finally obtained polyurethane elastomer has excellent mechanical property and low-temperature resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a low-temperature-resistant polyurethane elastomer.
Background
Polyurethane (polyurethane) refers to a polymer containing a repeating urethane bond structural unit (-NH-COO-) in the main chain of the polymer, and urethane is generally obtained by reacting a di-or polyvalent isocyanate with a di-or polyvalent alcohol. The main chain of the thermoplastic polyurethane elastomer (TPU) is a block polymer consisting of flexible soft segments and rigid hard segments which are alternately arranged, the soft segments consist of polyol, the hard segments consist of isocyanate and a chain extender, wherein the soft segments are in a rubber state and provide elasticity and toughness, and the hard segments are in a glass state or a semi-crystalline state and provide hardness, modulus and high-temperature performance. A large number of hydrogen bonds can be formed between the soft segment and the hard segment of the TPU, and the chain segments are orderly arranged to generate crystallization, so that microphase separation is easily generated in the chain segments, and the polyurethane material has good wear resistance, low temperature resistance and mechanical property. Due to the excellent mechanical property and good processing property, the TPU has wide application in national economy.
The soft segment in the TPU accounts for 50-90 percent, and has more obvious influence on the low temperature resistance and the mechanical property of products, so that the control of the relationship between the soft segment structure and the product property is very important for the development and the application of the TPU. The traditional polyurethane takes hydroxyl-terminated polyester and hydroxyl-terminated polyether as soft segments. Generally, polyester molecules contain ester groups with higher polarity, so that hydrogen bonds are easily formed between soft and hard segments to increase the compatibility of the two phases, and thus the polyester TPU has higher strength, wear resistance and oil resistance, but the hydrolysis resistance and low temperature resistance of the polyester TPU are relatively poor, and the physical properties of the polyester TPU are rapidly reduced in a low-temperature environment; however, polyether TPUs have better flexibility because they contain relatively easily rotating ether bonds, but their mechanical properties are poor, especially at low temperatures. Therefore, at present, no preparation method can simultaneously improve the flexibility and the mechanical property of the thermoplastic polyurethane at low temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a low-temperature-resistant polyurethane elastomer.
A preparation method of a low-temperature-resistant polyurethane elastomer comprises the following steps:
1) vacuum dehydrating the macromolecular diol mixture at 90-100 ℃ to form a component A, wherein the macromolecular polyol mixture is prepared by mixing polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 1:5-5: 1;
2) uniformly mixing diisocyanate and nano titanium oxide modified by ferric hydroxide under ultrasonic treatment, heating to 50-60 ℃, adding the component A, slowly heating to 80-90 ℃, and carrying out heat preservation reaction for 1-2 hours to obtain a prepolymer;
3) and adding micromolecular dihydric alcohol, a catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mould, and curing at 40-60 ℃ to obtain the low-temperature-resistant polyurethane elastomer.
Preferably, the weight ratio of the polycaprolactone glycol to the hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether in the step 1) is 1:1-3: 1.
Preferably, the average molecular weight of the macromolecular polyol mixture of step 1) is 5000-10000 g/moL.
Preferably, the molecular weight of the polycaprolactone diol of step 1) is 1500-2500 g/moL.
Preferably, the molar ratio of the A component to the isocyanate in step 2) is 0.5:1 to 1: 1.
Preferably, the method for modifying the nano titanium oxide by the ferric hydroxide in the step 2) comprises the following steps: preparing the nano titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 8-9, dropwise adding a ferric chloride solution, after the reaction is finished, centrifugally separating, washing with water, washing with alcohol, and drying to obtain the modified nano titanium dioxide.
Preferably, the mass ratio of the ferric hydroxide modified nano titanium oxide to the component A in the step 2) is 1-2: 100.
Preferably, the molecular weight of the small molecular diol obtained in the step 3) is 70-150 g/moL.
Preferably, the small molecule diol in step 3) is diethylene glycol, dipropylene glycol or diethylene glycol.
Preferably, the glass transition temperature of the low temperature resistant polyurethane elastomer in the step 3) is-60 to-30 ℃.
Preferably, the synthesis method of the hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether comprises the following steps: stirring and mixing polytetramethylene glycol with the number average molecular weight of 2000, dichloromethane and boron trifluoride diethyl etherate serving as a catalyst at room temperature, slowly dropwise adding monomer allyl glycidyl ether at 0 ℃, wherein the molar ratio of the polytetramethylene glycol to the allyl glycidyl ether is 1:8, continuing to react for 20-24h after dropwise adding, terminating the reaction by using a sodium carbonate solution with the mass fraction of 2%, separating an organic phase, washing with water to be neutral, and removing the solvent under reduced pressure to obtain a triblock copolyether product.
Preferably, the diisocyanate is Toluene Diisocyanate (TDI) or isophorone diisocyanate (IPDI).
At present, polyester or polyether polyol is usually used as a soft segment of a polyurethane elastomer, and because polyester molecules contain ester groups with larger polarity, hydrogen bonds are easily formed between the soft segment and a hard segment, so that the compatibility of the two phases is increased, and thus, the polyester TPU has higher strength, wear resistance and oil resistance, but the hydrolysis resistance and low temperature resistance of the polyester TPU are relatively poor, and the physical properties of the polyester TPU are sharply reduced in a low-temperature environment; however, polyether TPUs have better flexibility because they contain relatively easily rotating ether bonds, but their mechanical properties are poor, especially at low temperatures. Therefore, at present, no preparation method can simultaneously improve the flexibility and the mechanical property of the thermoplastic polyurethane at low temperature.
The inventor discovers through research that hydroxyl-terminated poly allyl glycidyl ether-poly butanediol-poly allyl glycidyl ether triblock copolyether is synthesized by taking poly butanediol and allyl glycidyl ether as raw materials and used as a soft segment of a polyurethane elastomer, allyl is used as a side chain block and distributed at two ends of the poly butanediol, the controllability of a reaction point and the molecular weight between curing and crosslinking points are improved, so that the mechanical property of the polyurethane elastomer is improved, the poly butanediol is in the middle position in the block copolymer, the poly allyl glycidyl ether is at two ends, the glass transition temperature Tg of the finally obtained discontinuous copolymer with the structure is-80 ℃, and is close to the glass transition temperature of the poly butanediol, and the triblock copolyether has good low-temperature mechanical property.
The invention takes the mixture of polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether as a soft segment, wherein the triblock copolyether contains more ether bonds, can rotate freely, has good flexibility of a molecular chain, has a regular structure, can weaken the crystallization tendency of the polycaprolactone diol by mixing the polycaprolactone diol with the copolyether, has good flexibility at room temperature, starts to crystallize only when being stretched, can enhance the mechanical property when external stress occurs, and finally obtains polyurethane with excellent mechanical property and low-temperature resistance.
In the polyurethane industry, nano powder has become a very important auxiliary agent in polyurethane formulations due to its unique action mechanism and versatile applicability. Especially, the antibacterial characteristics of the nano titanium dioxide are always in wide attention. And has several advantages in the using process: is safe and nontoxic to human bodies and has no irritation to skin; the antibacterial ability is strong, and the antibacterial range is wide; no odor, strange odor and small smell; the product is water-fast and has long storage period; the thermal stability is good, and the color is not changed, decomposed, volatilized and deteriorated at high temperature; the nano titanium dioxide is an antibacterial agent for permanently maintaining the antibacterial effect; has good safety, can be used as food additive, etc., and has no adverse effect when in contact with skin. Therefore, nano titanium dioxide has been widely used in the urethane industry. In the research and development of the inorganic particle modified polyurethane material at present, people generally adopt the prepared nanoparticles as the raw material of the polyurethane additive after the pretreatment, the main modification methods include silane coupling agent modification and inorganic or organic coating modification, but the basic principle of the modification is to reduce the surface tension and prevent the agglomeration, and the modification method is not applicable in the invention.
Because the titanium dioxide and the polyurethane have different surface properties, the titanium dioxide and the polyurethane have poor compatibility and weak interface bonding, the addition of the nano titanium dioxide has no reinforcing and toughening effects, but weakens the mechanical property of the polyurethane. Therefore, the surface of the nano titanium dioxide is coated with the ferric hydroxide, so that the reactivity of the titanium dioxide and polyurethane can be enhanced, the compatibility of the titanium dioxide and the polyurethane is better, the interface bonding force is stronger, the effect of the titanium dioxide can be fully exerted, the residual iron ions can be used as a catalyst for the reaction of isocyanate and hydroxyl, the reaction is more sufficient, and the finally obtained polyurethane elastomer has excellent performance. In addition, the isocyanate and the modified nano titanium dioxide are mixed by adopting an ultrasonic dispersion method, and the nano particles can move violently under the action of ultrasonic waves and are dispersed into smaller polymers, so that the isocyanate can fully surround the surface of the titanium dioxide, the agglomeration among the nano particles is reduced, and the mechanical property of the polyurethane composite material is improved.
The invention has the beneficial effects that: 1. according to the invention, polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether are mixed to serve as a soft segment, the flexibility at room temperature is good, and finally obtained polyurethane has excellent mechanical properties and low temperature resistance.
2. The method has the advantages of simple and easily obtained raw materials, low production cost, simple whole preparation process, low reaction temperature, short reaction time and low energy consumption, and is suitable for industrial production.
3. According to the invention, the surface of the nano titanium dioxide is coated with ferric hydroxide, so that the reactivity of the titanium dioxide and polyurethane can be enhanced, the effect of the titanium dioxide is fully exerted, the residual iron ions serve as a catalyst, the reaction is more sufficient, and the finally obtained polyurethane elastomer has excellent performance.
4. The polyurethane elastomer prepared by the invention has lower glass transition temperature which is between 60 ℃ below zero and 30 ℃ below zero, good low temperature resistance and excellent mechanical property.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below.
Example 1
Stirring and mixing polytetramethylene glycol with the number average molecular weight of 2000, dichloromethane and a catalyst boron trifluoride ether complex at room temperature, slowly dropwise adding monomer allyl glycidyl ether at 0 ℃, wherein the molar ratio of the polytetramethylene glycol to the allyl glycidyl ether is 1:8, continuing to react for 24 hours after dropwise adding, terminating the reaction by using a sodium carbonate solution with the mass fraction of 2%, separating an organic phase, washing with water to be neutral, and removing the solvent under reduced pressure to obtain a hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether product.
A preparation method of a low-temperature-resistant polyurethane elastomer comprises the following steps:
1) 1000g of macromolecular diol mixture is subjected to vacuum dehydration at 100 ℃ to form a component A, wherein the macromolecular polyol mixture is formed by mixing polycaprolactone diol with the molecular weight of 2000g/moL and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 1:1, and the average molecular weight of the macromolecular polyol mixture is 10000 g/moL;
2) mixing TDI and 16g of nano titanium oxide modified by ferric hydroxide uniformly under ultrasonic treatment, heating to 50-60 ℃, adding the component A, slowly heating to 85 ℃, keeping the molar ratio of the component A to isocyanate at 1:1, and reacting for 1h to obtain a prepolymer; the method for modifying the nano titanium oxide by the ferric hydroxide comprises the following steps: preparing nano-titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 8, dropwise adding a ferric chloride solution with the mass fraction of 10%, wherein the molar ratio of iron element to titanium element is 1:10, and after the reaction is finished, performing centrifugal separation, water washing, alcohol washing and drying to obtain modified nano-titanium dioxide;
3) and adding diethylene glycol, an organic tin catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mold, and curing at 50 ℃ to obtain the low-temperature-resistant polyurethane elastomer with the glass transition temperature of-50 ℃.
Example 2
1) Vacuum dehydrating 1000g of a macromolecular diol mixture at 90 ℃ to form a component A, wherein the macromolecular polyol mixture is formed by mixing polycaprolactone diol with the molecular weight of 2500g/moL and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 3:1, and the average molecular weight of the macromolecular polyol mixture is 5000 g/moL;
2) uniformly mixing IPDI and 20g of nano titanium oxide modified by ferric hydroxide under ultrasonic treatment, heating to 50-60 ℃, adding the component A, slowly heating to 80 ℃, keeping the molar ratio of the component A to isocyanate at 0.5:1, and reacting for 2 hours to obtain a prepolymer; the method for modifying the nano titanium oxide by the ferric hydroxide comprises the following steps: preparing nano titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 8, dropwise adding a ferric chloride solution with the mass fraction of 10%, wherein the molar ratio of iron element to titanium element is 1:15, and after the reaction is finished, performing centrifugal separation, water washing, alcohol washing and drying to obtain modified nano titanium dioxide;
3) adding dipropylene glycol, an organic tin catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mold, and curing at 40 ℃ to obtain the low-temperature-resistant polyurethane elastomer with the glass transition temperature of-40 ℃.
Example 3
1) Vacuum dehydrating 1000g of a macromolecular diol mixture at 90 ℃ to form a component A, wherein the macromolecular polyol mixture is formed by mixing polycaprolactone diol with the molecular weight of 1500g/moL and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 1:5, and the average molecular weight of the macromolecular polyol mixture is 10000 g/moL;
2) uniformly mixing IPDI and 10g of nano titanium oxide modified by ferric hydroxide under ultrasonic treatment, heating to 50-60 ℃, adding the component A, slowly heating to 90 ℃, keeping the molar ratio of the component A to isocyanate at 0.8:1, and reacting for 2 hours to obtain a prepolymer; the method for modifying the nano titanium oxide by the ferric hydroxide comprises the following steps: preparing nano-titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 9, dropwise adding a ferric chloride solution with the mass fraction of 10%, wherein the molar ratio of iron element to titanium element is 1:20, and after the reaction is finished, performing centrifugal separation, water washing, alcohol washing and drying to obtain modified nano-titanium dioxide;
3) adding diethylene glycol, an organic tin catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mold, and curing at 60 ℃ to obtain the low-temperature-resistant polyurethane elastomer with the glass transition temperature of-60 ℃.
Comparative example 1
1) 1000g polycaprolactone diol with molecular weight of 1500g/moL is dehydrated in vacuum at 90 ℃;
2) uniformly mixing IPDI and 10g of nano titanium oxide modified by ferric hydroxide under ultrasonic treatment, heating to 50-60 ℃, adding polycaprolactone diol, slowly heating to 90 ℃, keeping the molar ratio of the polycaprolactone diol to isocyanate at 0.8:1, and reacting for 2 hours to obtain a prepolymer; the method for modifying the nano titanium oxide by the ferric hydroxide comprises the following steps: preparing nano-titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 9, dropwise adding a ferric chloride solution with the mass fraction of 10%, wherein the molar ratio of iron element to titanium element is 1:20, and after the reaction is finished, performing centrifugal separation, water washing, alcohol washing and drying to obtain modified nano-titanium dioxide;
3) adding diethylene glycol, an organic tin catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mold, and curing at 60 ℃ to obtain the low-temperature-resistant polyurethane elastomer with the glass transition temperature of 30 ℃.
Comparative example 2
1) Vacuum dehydrating 1000g of a macromolecular diol mixture at 90 ℃ to form a component A, wherein the macromolecular polyol mixture is formed by mixing polycaprolactone diol with the molecular weight of 1500g/moL and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 1:5, and the average molecular weight of the macromolecular polyol mixture is 10000 g/moL;
2) uniformly stirring and mixing IPDI and 10g of nano titanium oxide modified by a coupling agent KH550, heating to 50-60 ℃, adding the component A, slowly heating to 90 ℃, keeping the molar ratio of the component A to isocyanate at 0.8:1, and reacting for 2 hours to obtain a prepolymer;
3) adding diethylene glycol, an organic tin catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mold, and curing at 60 ℃ to obtain the low-temperature-resistant polyurethane elastomer with the glass transition temperature of-60 ℃.
The mechanical properties of the polyurethane elastomers obtained in examples 1-3 and comparative examples 1-2 were determined, and the mechanical properties were tested according to the national standard GB/T528-2009. The cured film was cut into strips, the dimensions of the samples were measured with a vernier caliper, and the test was carried out with an XLD-1B type electronic tensile tester. The results are shown in Table 1.
TABLE 1 mechanical Properties of polyurethane Elastomers
As can be seen from the data in the table above, the polyurethane elastomer obtained by the preparation method of the present application has excellent mechanical properties, the tensile strength far exceeds that of comparative example 2, but the elongation at break is not much different from that of the comparative example, which indicates that the present invention mixes polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether as a soft segment, coats the surface of nano titanium dioxide with ferric hydroxide to enhance the reactivity of the titanium dioxide and polyurethane, and finally the obtained polyurethane has excellent mechanical properties, and the Tg reaches-60 ℃ to-30 ℃, and the low temperature resistance is excellent.
Although the tensile strength of the polyurethane elastomer obtained in the comparative example 1 is high, the elongation at break of the polyurethane elastomer is only 111.57%, the Tg of the polyurethane elastomer is 30 ℃, and the polyurethane elastomer is not resistant to low temperature, which indicates that the comprehensive performance of the polyurethane elastomer obtained by singly using polycaprolactone diol as a soft segment is not good.
Claims (9)
1. A preparation method of a low-temperature-resistant polyurethane elastomer is characterized by comprising the following steps:
1) vacuum dehydrating the macromolecular polyol mixture at 90-100 ℃ to form a component A, wherein the macromolecular polyol mixture is prepared by mixing polycaprolactone diol and hydroxyl-terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether according to the weight ratio of 1:5-5: 1;
2) uniformly mixing diisocyanate and nano titanium oxide modified by ferric hydroxide under ultrasonic treatment, heating to 50-60 ℃, adding the component A, slowly heating to 80-90 ℃, and carrying out heat preservation reaction for 1-2 hours to obtain a prepolymer;
3) adding micromolecular dihydric alcohol, a catalyst and an additive into the prepolymer, uniformly mixing, pouring into a mould, and curing at 40-60 ℃ to obtain a low-temperature-resistant polyurethane elastomer;
the method for modifying the nano titanium oxide by the ferric hydroxide comprises the following steps: preparing the nano titanium dioxide into a suspension with the volume fraction of 0.3%, then adding sodium hydroxide to control the pH of the suspension to be 8-9, dropwise adding an iron chloride solution, after the reaction is finished, centrifugally separating, washing with water, washing with alcohol, and drying to obtain the iron hydroxide modified nano titanium oxide.
2. The method for preparing low temperature resistant polyurethane elastomer according to claim 1, wherein the weight ratio of polycaprolactone diol to hydroxyl terminated polyallyl glycidyl ether-polytetramethylene glycol-polyallyl glycidyl ether triblock copolyether in step 1) is 1:1-3: 1.
3. The method for preparing the low temperature resistant polyurethane elastomer as claimed in claim 2, wherein the average molecular weight of the macromolecular polyol mixture of step 1) is 5000-10000 g/moL.
4. The method for preparing the low temperature resistant polyurethane elastomer as claimed in claim 1, wherein the molecular weight of the polycaprolactone diol of step 1) is 1500-.
5. The method for preparing the low temperature resistant polyurethane elastomer according to claim 1, wherein the molar ratio of the A component to the isocyanate in the step 2) is 0.5:1 to 1: 1.
6. The method for producing a low temperature-resistant polyurethane elastomer according to any one of claims 1 to 5, wherein the mass ratio of the iron hydroxide-modified nano titanium oxide to the A component in step 2) is 1 to 2: 100.
7. The method for preparing a low temperature resistant polyurethane elastomer according to any one of claims 1 to 5, wherein the molecular weight of the small molecule diol of step 3) is 70 to 150 g/moL.
8. The method for preparing the low temperature resistant polyurethane elastomer according to any one of claims 1 to 5, wherein the small molecule diol of step 3) is dipropylene glycol or diethylene glycol.
9. The method for preparing the low temperature resistant polyurethane elastomer according to any one of claims 1 to 5, wherein the glass transition temperature of the low temperature resistant polyurethane elastomer is-60 ℃ to-30 ℃.
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