CN113004682A - High-resilience polyurethane/organic silicon thermoplastic elastomer and preparation method thereof - Google Patents
High-resilience polyurethane/organic silicon thermoplastic elastomer and preparation method thereof Download PDFInfo
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- C08J3/246—Intercrosslinking of at least two polymers
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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Abstract
The invention relates to the technical field of dynamic vulcanization thermoplastic elastomers, and discloses a high-resilience polyurethane/organosilicon thermoplastic elastomer and a preparation method thereof, wherein thermoplastic polyurethane, vinyl silicone rubber, a compatilizer and a reinforcing filler are blended and placed in an internal mixer for premixing, and a cross-linking agent is added for continuously mixing to obtain a rubber-plastic blend; adding the rubber-plastic blend into a double-screw extruder, adding a pre-polymerization catalyst for pre-vulcanization, and performing shearing dispersion treatment; when the pre-vulcanized cross-linked substance passes through the middle section of a screw in a double-screw extruder, adding a dynamic vulcanization catalyst, and performing shearing dispersion treatment to obtain a polyurethane/organic silicon thermoplastic elastomer; the pre-polymerization catalyst and the dynamic vulcanization catalyst are both mixed rubber formed by mixing the catalyst and vinyl silicone rubber. According to the preparation method, the catalysts are added in batches, so that the silicon rubber can be favorably dispersed in the polyurethane, and the vulcanization rate can be reduced; the catalyst masterbatch can ensure uniform particle size of the silicone rubber, so that the prepared TPSiV has smooth handfeel.
Description
Technical Field
The invention belongs to the technical field of dynamically vulcanized thermoplastic elastomers, and particularly relates to a high-resilience polyurethane/organosilicon thermoplastic elastomer and a preparation method thereof.
Background
The dynamic vulcanization is to melt and blend a vulcanizable rubber phase, a thermoplastic resin or an elastomer and a vulcanizing agent at a high temperature, simultaneously carry out synchronous crosslinking reaction on the rubber phase, and shear the crosslinked rubber phase into micron-sized particles to be dispersed in the resin under the action of high shear. The dynamic thermoplastic vulcanizate (TPV) has the physical and mechanical properties of thermosetting rubber, the flow processability of thermoplastic plastics, the advantages of repeated processing and recycling, and is widely applied to the fields of automobile industry, building materials, medical health, wearable equipment and the like at present.
The elastomer material (TPSiV) prepared by dynamically vulcanizing polyurethane/silicone rubber has the advantages of wear resistance, toughness, repeatable processability of TPU, softness, ultraviolet resistance, chemical stability and the like of silicone rubber, has silky touch, good colorability and color fastness, and has wide application in intelligent wearable and electronic and electrical products.
The high elasticity of TPV is one of the most important properties of TPV, which determines that TPV can be used as an elastic material, while a high degree of crosslinking of the rubber phase is a necessary requirement for the high elasticity of TPV. The crosslinking and the shearing dispersion of the silicon rubber are synchronously carried out in the dynamic vulcanization process of TPSiV, and the crosslinking density, the crosslinking degree, the microscopic size and the dispersion state of the crosslinked silicon rubber particles determine the elasticity and the silky touch of the product.
Research shows that the initial vulcanization rate of the dynamic vulcanization reaction is very high, and the shear strength of equipment is very high. For a vulcanization system of vinyl silicone rubber-hydrogen-containing silicone oil-platinum catalyst, when the platinum catalyst is dripped into the vulcanization system, the cross-linking agent rapidly reacts with the silicone rubber, and the vulcanization reaction is rapidly finished (preparation and performance research of Liangliang polyurethane/silicone rubber dynamic vulcanization thermoplastic elastomer [ D ] Guangdong university of industry, 2011.), and the shearing requirement of the process on equipment is very high. In patent CN 108587123, chloroplatinic acid-vinyl tetramethylsiloxane complex solution and chloroplatinic acid-isopropanol mixture are used as catalysts and are dripped into a double-screw vulcanizing body from a side feeding port, so that the vulcanizing rate is high, and the vulcanizing reaction is difficult to control. Patents CN 109517367 and CN 109608867 use dow corning RD7 liquid platinum catalyst, and the catalyst is mixed into the premix in advance, the sulfidation rate is also fast, the sulfidation reaction is completed quickly, and the requirement for shear strength of twin screw is high.
In addition, the viscosity difference between the silicone rubber and the thermoplastic polyurethane elastomer material is huge, and meanwhile, the compatibility between the nonpolar silicone rubber and the polar polyurethane is poor, so that the silicone rubber is not easy to shear and break to form uniform and tiny dispersed phase particles in the dynamic vulcanization process, and finally, the microscopic morphology of the silicone rubber polyurethane thermoplastic vulcanized rubber is not fine enough, and the mechanical property and the elasticity are also poor.
At present, domestic research focuses on adopting different compatilizers to improve the compatibility between the silicone rubber and the polyurethane, and the solution to the viscosity difference between the silicone rubber and the polyurethane still mostly stays in the use of the filler. For example, in patent CN 104650591, white carbon black is used as a reinforcing filler, and the white carbon black is added into raw methyl vinyl silicone rubber, and is mixed with polyurethane to prepare a rubber compound with good mechanical properties. However, the rubber prepared by the method is a rubber compound, and the rubber crosslinked with the rubber compound cannot be repeatedly processed and utilized. The patent CN 105924972 discloses that carboxyl modified carbon nanotubes are added into silicone rubber to increase the viscosity of the silicone rubber, so as to improve the compatibility between the silicone rubber and polyurethane and the viscosity ratio between the silicone rubber and polyurethane. However, the carbon nano tube is difficult to prepare, expensive and not suitable for wide industrial popularization. Patent CN 109553982 improves the viscosity ratio of silicone rubber to polyurethane by pre-crosslinking, patent CN 108587123 increases the viscosity of silicone rubber by pre-chain extension; however, in both methods, a cross-linking agent (chain extender) must be added into the silicone rubber for high-temperature pre-crosslinking, and the method increases preparation steps and equipment, and is not favorable for continuous industrial production.
Disclosure of Invention
< problems to be solved by the present invention >
The current polyurethane/organic silicon thermoplastic elastomer has high vulcanization rate in the initial stage of dynamic vulcanization reaction in a dynamic vulcanization system, and has higher requirement on the shearing strength of equipment; in the dynamic vulcanization process, due to the poor compatibility of the silicone rubber and the polyurethane, the silicone rubber is not easy to shear, and the problem of poor mechanical property of the formed polyurethane/organic silicon thermoplastic vulcanized rubber is caused.
< technical solution adopted in the present invention >
In view of the above technical problems, a first object of the present invention is to provide a method for preparing a high resilience polyurethane/silicone thermoplastic elastomer.
The second purpose of the invention is to provide a high resilience polyurethane/silicone thermoplastic elastomer.
The specific contents are as follows:
the invention provides a preparation method of a high-resilience polyurethane/silicone thermoplastic elastomer, which comprises the following steps:
s1 rubber-plastic blend
Thermoplastic polyurethane, vinyl silicone rubber, a compatilizer and a reinforcing filler are mixed, placed in an internal mixer for premixing, cooled after being mixed uniformly, added with a cross-linking agent and continuously mixed uniformly to obtain a rubber-plastic mixture;
s2 Pre-crosslinking
Adding the rubber-plastic blend in the S1 into a double-screw extruder, adding a pre-polymerization catalyst into the front section of a screw of the double-screw extruder for pre-vulcanization, and performing shearing dispersion treatment to obtain a pre-vulcanized cross-linked substance;
s3 dynamic vulcanization
When the pre-vulcanized cross-linked product in the S2 passes through the middle section of a screw in a double-screw extruder, adding a dynamic vulcanization catalyst, performing shearing dispersion treatment, and then performing granulation to obtain a polyurethane/organic silicon thermoplastic elastomer;
wherein the pre-polymerization catalyst and the dynamic vulcanization catalyst are both mixed rubber formed by mixing the catalyst and vinyl silicone rubber.
The technical mechanism of the application is as follows:
(1) the catalyst is added in a fractional manner, so that firstly, the partially crosslinked silicon rubber can be obtained to improve the viscosity of the silicon rubber, so that the viscosity ratio of polyurethane/silicon rubber melt is closer, the fusion of the silicon rubber is reduced, and the silicon rubber is easier to disperse in the polyurethane; secondly, the problems of excessive vulcanization of the silicon rubber and over-high vulcanization reaction rate caused by adding the catalyst at one time can be avoided. Namely, different catalysts are added in different sections of the double-screw extruder, and a prepolymer with low crosslinking degree is obtained at the front section of the screw, so that the dispersion of the silicon rubber is facilitated; and the dynamic vulcanization reaction is continued in the middle and the rear section of the screw rod so as to improve the crosslinking degree and the crosslinking density of the polyurethane/silicon rubber.
(2) The preparation method is used for preparing the elastomer with high resilience, and therefore the silicon rubber with high ethylene content and the cross-linking agent with high hydrogen content are selected for cross-linking, but the vinyl content and the silicon hydrogen content are higher, the cross-linking speed is higher, and agglomeration is easy to cause. Namely, the traditional liquid catalyst is replaced by the catalyst masterbatch (the rubber compound prepared by mixing the catalyst and the rubber) so as to reduce the vulcanization rate and prolong the vulcanization time moderately, so that the vulcanization reaction is more stable, and the crosslinking degree of the silicon rubber is more controllable.
Secondly, the invention provides a high-resilience polyurethane/silicone thermoplastic elastomer obtained by the preparation method.
< advantageous effects achieved by the present invention >
(1) After the components are subjected to dynamic vulcanization reaction, the cross-linking density of silicon rubber particles is high, and the rebound resilience is good;
(2) the catalyst is added in batches, so that the silicon rubber can be favorably dispersed in the polyurethane, and the vulcanization rate can be reduced;
(3) adopt catalyst masterbatch to replace liquid catalyst, in the dynamic vulcanization system of this application, can effectively avoid because of the too fast, partial silicon rubber that screw shear strength is not enough leads to of catalysis rate excessively cross-linking, the unable problem of effectively shearing of granule to guaranteed the silicon rubber particle diameter homogeneous, dispersed evenly, makeed the TPSiV that the preparation obtained feel silky.
Drawings
FIG. 1 is a graph of rotor torque values (Nm) versus time(s) for example 1, comparative example 1, and comparative example 3;
FIG. 2 is a scanning electron micrograph of a cross-section of TPSIV of comparative example 5;
FIG. 3 is a scanning electron micrograph of TPSIV of comparative example 5 diluted to a silicone rubber concentration of 10%;
FIG. 4 is a scanning electron micrograph of a TPSIV section of example 5;
FIG. 5 is a scanning electron micrograph of TPSIV of example 5 diluted to a silicone rubber concentration of 10%.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of a high-resilience polyurethane/silicone thermoplastic elastomer, which comprises the following steps:
s1 rubber-plastic blend
Thermoplastic polyurethane, vinyl silicone rubber, a compatilizer and a reinforcing filler are mixed, placed in an internal mixer for premixing, cooled after being mixed uniformly, added with a cross-linking agent and continuously mixed uniformly to obtain a rubber-plastic mixture;
s2 Pre-crosslinking
Adding the rubber-plastic blend in the S1 into a double-screw extruder, adding a pre-polymerization catalyst into the front section of a screw of the double-screw extruder for pre-vulcanization, and performing shearing dispersion treatment to obtain a pre-vulcanized cross-linked substance;
s3 dynamic vulcanization
When the pre-vulcanized cross-linked product in the S2 passes through the middle section of a screw in a double-screw extruder, adding a dynamic vulcanization catalyst, performing shearing dispersion treatment, and then performing granulation to obtain a polyurethane/organic silicon thermoplastic elastomer;
wherein the pre-polymerization catalyst and the dynamic vulcanization catalyst are both mixed rubber formed by mixing the catalyst and vinyl silicone rubber.
According to the invention, the polyurethane/organic silicon thermoplastic elastomer comprises, by weight, 100 parts of thermoplastic polyurethane, 80-120 parts of vinyl silicone rubber, 5-15 parts of a compatilizer, 10-25 parts of a reinforcing filler, 2-8 parts of a cross-linking agent, 0.5-1 part of a pre-polymerization catalyst and 1.5-3.5 parts of a dynamic vulcanization catalyst.
In the invention, the vinyl silicone rubber is methyl vinyl silicone rubber.
In the invention, the screw part of the double-screw extruder is connected with two double-cone rubber extruders, wherein one double-cone rubber extruder is arranged at the front part of the screw, and the other double-cone rubber extruder is arranged at the middle and rear part of the screw. That is, the catalyst masterbatch (a collective term for the prepolymerized catalyst and the dynamically vulcanized catalyst) was fed through a double-cone rubber extruder. Specifically, both catalysts were added via side feed. The presulfided catalyst is added in the front 2-4 area of the screw, and the dynamic sulfided catalyst is added in the middle 6-9 area of the screw. Too much addition of prepolymerized catalyst results in too high melt viscosity, resulting in inefficient dispersion of the subsequent dynamic vulcanization catalyst into the silicone rubber/polyurethane melt, resulting in inadequate and non-uniform vulcanization. If the amount of the prepolymerization catalyst is too small, the effect of improving the viscosity ratio of polyurethane to silicone rubber cannot be achieved; therefore, the ratio of the prepolymerized catalyst must be strictly controlled to the ratio of vinyl groups in the melt: the molar mass ratio of platinum is 300-1000: 1, preferably 500-700: 1. If the dynamic vulcanization catalyst is added too little, the vulcanization rate is low, the vulcanization time is long, and incomplete vulcanization is easily caused. Thus, the proportion of dynamically sulfided catalyst should be controlled in such a way that the vinyl: the molar mass ratio of platinum is 80-250: 1, preferably 150-200: 1.
In order to make the catalyst masterbatch more easily dispersed in the silicone rubber/TPU melt, the viscosity of the catalyst masterbatch is preferably close to that of the silicone rubber/TPU melt, and therefore, different methyl vinyl silicone rubbers are selected for the pre-polymerization catalyst and the dynamic vulcanization catalyst. Wherein the prepolymerization catalyst is methyl vinyl silicone rubber crude rubber with the molecular weight of 45-60 ten thousand; the dynamic vulcanization catalyst is methyl vinyl silicone rubber compound with Shore hardness of 30-40A and white carbon black mass fraction of 5-15%.
In the present invention, the catalyst active ingredient is a compound or complex of Pt, Pd, Rh, Ru, Ni, and Co, preferably a Pt-based complex, and most preferably a complex of chloroplatinic acid and an olefin-based compound. In particular to a chloroplatinic acid-vinyl tetramethylsiloxane complex.
The specific preparation method of the catalyst masterbatch comprises the following steps: the selected methyl vinyl silicone rubber is refined in an open mill or an internal mixer for 5min at normal temperature, and a catalyst is added for blending to obtain the catalyst masterbatch. The catalyst is chloroplatinic acid-vinyl tetramethylsiloxane complex solution (the concentration is 2000-4000 ppm, calculated by platinum content), the concentration of the catalyst in the prepared prepolymerization catalyst is 100-500 ppm, and the concentration of the catalyst in the prepared dynamic vulcanization catalyst is 300-700 ppm.
In the present invention, the thermoplastic polyurethane includes any one of polyester type thermoplastic polyurethane and polyether type thermoplastic polyurethane.
In the S1, the molecular weight of the vinyl silicone rubber is 45-80 ten thousand, and the mole fraction of vinyl is 0.2-0.8 wt.%.
In the invention, the cross-linking agent is polyhydro silicone oil, the hydrogen content of the polyhydro silicone oil is 0.36-3.5 wt.%, and the molar mass ratio of hydrogen to vinyl is 2-7: 1. Preferably, the hydrogen content of the polyhydrosilicone oil is 0.36-0.45 wt.%.
In the invention, the compatilizer is a reactive compatilizer, wherein the compatilizer is unsaturated polyester, specifically polyester resin with a vinyl group in a main chain or a side chain, a vinyl group part can be crosslinked with silicon rubber to form a chemical bond effect, and the polyester part is combined with polyurethane through a hydrogen bond effect, so that a strong two-phase contact force is generated between the polyurethane and organic silicon, and the silicon rubber is prevented from sliding when an elastomer is deformed, thereby achieving the purpose of high resilience.
In the invention, the reinforcing filler is white carbon black treated by hydroxyl silicone oil by a gas phase method or a precipitation method.
In addition to the above components, processing aids including, but not limited to, antioxidants, stabilizers, flame retardants, ultraviolet light stabilizers, colorants, and the like, as well as polymeric processing aids and auxiliary fillers well known in the art, may also be added in suitable amounts.
In the invention, in S1, the temperature of premixing is 160-200 ℃, and after uniform mixing, the temperature is reduced to below 120 ℃.
In the invention, in S2, the mixture is sheared and dispersed for 20-40S at 170-180 ℃.
In the invention, in S3, the shear dispersion is carried out for 40-90S at 180-220 ℃.
In the invention, the length-diameter ratio of the double-screw extruder is not less than 36, and the number of spiral heating zones is not less than 12, so that the purpose of ensuring enough shearing strength and vulcanization time is realized.
Secondly, the invention provides a high-resilience polyurethane/silicone thermoplastic elastomer obtained by the preparation method.
< brief description >
(1) The following examples and comparative examples all used parts of raw materials in parts by weight.
(3) The following examples and comparative examples used the following starting materials, respectively:
TPU 1: huafeng HF-1085A, polyester type, with a Shore hardness of 85A;
TPU 2: huafeng HF-4095A, polyether type, with a Shore hardness of 95A;
methyl vinyl silicone rubber 1: 110-4S has a molecular weight of 50 ten thousand and a vinyl content of 0.30%;
methyl vinyl silicone rubber 2: 110-5S has molecular weight of 60 ten thousand and vinyl content of 0.50 percent;
methyl vinyl silicone rubber 3: 110-2S has a molecular weight of 60 ten thousand and a vinyl content of 0.16 percent;
reinforcing filler 1: 15% hydroxy silicone oil treated fumed silica;
reinforcing filler 2: 15% hydroxy silicone oil treated precipitated silica;
reactive compatibilizer 1: 3200# vinyl ester resin;
reactive compatibilizer 2: 6688# unsaturated polyester resin;
reactive compatibilizer 3: 191# unsaturated polyester resin;
general compatibilizer 1: polyurethane modified silicone resin, GM-6026, chemical technology ltd, worship in shanghai;
crosslinking agent 1: a methyl terminated hydrogen containing silicone oil having a hydrogen content of 0.72 wt.%;
crosslinking agent 2: a methyl terminated hydrogen containing silicone oil having a hydrogen content of 1.44 wt.%;
crosslinking agent 3: a methyl terminated hydrogen containing silicone oil having a hydrogen content of 0.36 wt.%;
prepolymerization catalyst 1: chloroplatinic acid-vinyltetramethylsiloxane complex with a methylvinylsiloxane rubber compound having a molecular weight of 45 ten thousand (concentration 150ppm, in terms of platinum content);
prepolymerized catalyst 2: chloroplatinic acid-vinyltetramethylsiloxane complex with a methylvinylsiloxane rubber compound having a molecular weight of 55 ten thousand (concentration 350ppm, based on the platinum content);
dynamic vulcanization catalyst 1: chloroplatinic acid-vinyl tetramethylsiloxane complex and methyl vinyl silicone rubber gross rubber with Shore hardness of 30A and white carbon black mass fraction of 10% (concentration is 350ppm, calculated by platinum content);
dynamic vulcanization catalyst 2: chloroplatinic acid-vinyl tetramethylsiloxane complex and methyl vinyl silicone rubber compound with Shore hardness of 40A and white carbon black mass fraction of 15% (concentration 550ppm, calculated by platinum content);
dynamic vulcanization catalyst 3: chloroplatinic acid-vinyltetramethylsiloxane complex solution (concentration 350ppm in terms of platinum content);
dynamic vulcanization catalyst 4: chloroplatinic acid-vinyltetramethylsiloxane complex solution (concentration 550ppm, in terms of platinum content);
dynamic vulcanization catalyst 5: chloroplatinic acid-vinyltetramethylsiloxane complex was mixed with a methyl vinyl silicone rubber compound having a Shore hardness of 70A and a white carbon black content of 35% by mass (concentration 550ppm, in terms of platinum content).
< example >
Example 1
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: after 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reactive compatilizer 1, 10 parts of reinforcing filler 1 and 3 parts of crosslinking agent 1 are uniformly mixed in a mixer of a torque rheometer at 180 ℃ and 120rpm, 0.8 part of prepolymerized catalyst 1 is firstly added, under the shearing action of a mixing device, the mixture is firstly mixed for about 1min at 180 ℃ and 120rpm, then 2.5 parts of dynamically vulcanized catalyst 1 are added, and dynamic vulcanization is continuously carried out, so that the high-resilience polyurethane/organic silicon thermoplastic elastomer is obtained.
Example 2
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 2, 15 parts of reactive compatilizer 1, 18 parts of reinforcing filler 2 and 2 parts of crosslinking agent 2 in a mixer of a torque rheometer at 190 ℃ and 100rpm, adding 0.5 part of prepolymerized catalyst 1, mixing at 180 ℃ and 120rpm for about 1min under the shearing action of a mixing device, adding 3 parts of dynamically vulcanized catalyst 1, and continuously carrying out dynamic vulcanization to obtain the high-resilience polyurethane/organosilicon thermoplastic elastomer.
Example 3
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU2, 90 parts of methyl vinyl silicone rubber 2, 15 parts of reactive compatilizer 2, 15 parts of reinforcing filler 1 and 2 parts of crosslinking agent 2 in a mixer of a torque rheometer at 180 ℃ and 120rpm, adding 1 part of prepolymerized catalyst 2, mixing for about 1min at 180 ℃ and 120rpm under the shearing action of a mixing device, adding 2 parts of dynamically vulcanized catalyst 2, and continuously carrying out dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Example 4
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU2, 110 parts of methyl vinyl silicone rubber 2, 12 parts of reactive compatilizer 3, 20 parts of reinforcing filler 1 and 3 parts of crosslinking agent 1 in a mixer of a torque rheometer at 200 ℃ and 100rpm, adding 1 part of prepolymerized catalyst 1, mixing at 180 ℃ and 120rpm for about 1min under the shearing action of a mixing device, adding 2.5 parts of dynamic vulcanization catalyst 2, and continuously carrying out dynamic vulcanization to obtain the high-resilience polyurethane/organosilicon thermoplastic elastomer.
Example 5
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reactive compatilizer 1 and 10 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 3 parts of cross-linking agent 1, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature of the first seven zones is set to be 170 ℃, 180 ℃, and 0.8 part of a pre-polymerization catalyst 1 is added in a fourth zone for pre-vulcanization; setting the temperature of the seventh zone to 180 ℃, 190 ℃, 200 ℃, 190 ℃ and adding 2.5 parts of dynamic vulcanization catalyst 2 to the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Example 6
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 2, 15 parts of reactive compatilizer 1 and 18 parts of reinforcing filler 2 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 2 parts of cross-linking agent 2, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature of the first seven zones is set to be 170 ℃, 180 ℃, and 0.5 part of a pre-polymerization catalyst 1 is added in a fourth zone for pre-vulcanization; the temperature of the seventh zone is set to 180 ℃, 190 ℃, 200 ℃, 190 ℃ and 3 parts of dynamic vulcanization catalyst 1 are added into the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Example 7
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 90 parts of methyl vinyl silicone rubber 2, 15 parts of reactive compatilizer 2 and 15 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 2 parts of cross-linking agent 2, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature of the first seven zones is set to be 170 ℃, 180 ℃, and 1 part of a pre-polymerization catalyst 2 is added in a fourth zone for pre-vulcanization; the temperature of the seventh zone is set to 180 ℃, 190 ℃, 210 ℃, 190 ℃ and 2 parts of dynamic vulcanization catalyst 2 are added into the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Example 8
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU2, 110 parts of methyl vinyl silicone rubber 2, 15 parts of reactive compatilizer 3 and 20 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 200 ℃, cooling to 100 ℃, finally adding 3 parts of cross-linking agent 1, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, heating the section to 14 sections, setting the temperature of the first seven zones to be 170 ℃, 180 ℃ and 180 ℃, and adding 0.5 part of a pre-polymerized catalyst 1 to a fourth zone for pre-vulcanization; the temperature of the seventh zone is set to 180 ℃, 190 ℃, 210 ℃, 190 ℃ and 2.5 parts of dynamic vulcanization catalyst 2 is added into the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
< comparative example >
Comparative example 1
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reaction type compatilizer 1, 10 parts of reinforcing filler 1 and 3 parts of crosslinking agent 1 in a mixer of a torque rheometer at 180 ℃ and 120rpm, adding 3.3 parts of dynamic vulcanization catalyst 1, and dynamically vulcanizing at 180 ℃ and 120rpm under the shearing action of a mixing device to obtain the high-resilience polyurethane/organosilicon thermoplastic elastomer.
Comparative example 2
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 3, 15 parts of common compatilizer 1, 18 parts of reinforcing filler 2 and 2 parts of cross-linking agent 3 in a mixer of a torque rheometer at 190 ℃ and 100rpm, adding 3.5 parts of dynamic vulcanization catalyst 2, and dynamically vulcanizing at 180 ℃ and 120rpm under the shearing action of a mixing device to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 3
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reaction type compatilizer 1, 10 parts of reinforcing filler 1 and 3 parts of cross-linking agent 1 in a mixer of a torque rheometer at 180 ℃ and 120rpm, then dropwise adding 3.3 parts of dynamic vulcanization catalyst 3, and dynamically vulcanizing at 180 ℃ and 120rpm under the shearing action of a mixing device to obtain the high-resilience polyurethane/organosilicon thermoplastic elastomer.
Comparative example 4
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: uniformly mixing 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 3, 15 parts of common compatilizer 1, 18 parts of reinforcing filler 2 and 2 parts of cross-linking agent 3 in a mixer of a torque rheometer at 190 ℃ and 100rpm, then dropwise adding 3.5 parts of dynamic vulcanization catalyst 4, and dynamically vulcanizing at 180 ℃ and 120rpm under the shearing action of a mixing device to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 5
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reactive compatilizer 1 and 10 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 3 parts of cross-linking agent 1, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature is set to be 170 ℃, 180 ℃, 190 ℃, 200 ℃ and 190 ℃, and 3.3 parts of a prepolymerization catalyst 1 is added into a fourth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 6
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reactive compatilizer 1 and 10 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 3 parts of cross-linking agent 1, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature is set to be 170 ℃, 180 ℃, 190 ℃, 200 ℃ and 190 ℃, and 3.3 parts of a dynamic vulcanization catalyst 1 is added into an eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 7
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1, 100 parts of methyl vinyl silicone rubber 1, 10 parts of reactive compatilizer 1 and 10 parts of reinforcing filler 1 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 3 parts of cross-linking agent 1, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65; 1, heating the section to 14 sections, setting the temperature of the first seven zones to be 170 ℃, 180 ℃ and 180 ℃, and adding 0.8 part of a pre-polymerized catalyst 1 to a fourth zone for pre-vulcanization; setting the temperature of the seventh zone to 180 ℃, 190 ℃, 200 ℃, 190 ℃ and adding 2.5 parts of dynamic vulcanization catalyst 5 into the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 8
A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer comprises the following steps: adding 100 parts of dried TPU1 and 100 parts of methyl vinyl silicone rubber 3, 15 parts of common compatilizer 1 and 18 parts of reinforcing filler 2 into an internal mixer, uniformly premixing at 180 ℃, cooling to 100 ℃, finally adding 2 parts of cross-linking agent 3, and uniformly mixing to obtain the rubber-plastic blend. Adding the rubber-plastic blend into a double-screw extruder in a first zone, wherein the length-diameter ratio of the double-screw extruder is 65:1, the heating zone is 14 sections in total, the temperature of the first seven zones is set to be 170 ℃, 180 ℃, and 0.5 part of a pre-polymerization catalyst 1 is added in a fourth zone for pre-vulcanization; the temperature of the seventh zone is set to 180 ℃, 190 ℃, 200 ℃, 190 ℃ and 3 parts of dynamic vulcanization catalyst 1 are added into the eighth zone for dynamic vulcanization to obtain the high-resilience polyurethane/organic silicon thermoplastic elastomer.
Comparative example 9
The market Dow Corning TPSIV has the trade mark of 4000-60A, and the product of the trade mark is mainly used as wearable equipment.
< test example >
(1) Torque measurements were made during sample preparation using example 1, comparative example 1, and comparative example 3 as samples, and the results are shown in fig. 1.
(2) The results of the scanning electron microscope analyses using example 5 and comparative example 5 as samples are shown in fig. 2 to 5.
(3) The silicone thermoplastic elastomers obtained in examples 1 to 8 and comparative examples 1 to 9 were measured for Shore hardness, melt flow rate, tensile properties, compression set, tear strength, and rebound resilience, respectively, and the results are shown in tables 1 and 2.
Wherein the content of the first and second substances,
shore hardness is measured according to ISO-868 standard:
the melt flow rate (MFI) is measured according to the ISO-1133 standard;
tensile properties were measured according to ISO-37;
the compression set is tested according to the ISO-815 standard;
the tear strength is measured according to ISO-34.
200% elongation test method: marking a 25mm mark length on the sample, placing the sample on a universal testing machine, enabling the graduated scale to be parallel to the sample, stopping when the sample extends to 75mm, timing for 3min, unloading the sample, stretching for 1min, and measuring the mark length. The calculation formula of the rebound resilience is as follows,
the rebound resilience (%) - (L1-L2)/(L1-L0) × 100%
Wherein, L0 is the length mm of the original standard line, L1 is the length mm of the 200% fixed extension standard line, and L2 is the length mm of the stretched standard line.
1. Torque measurement analysis
FIG. 1 is a graph of rotor torque (Nm) over time(s) in a mixer experiment, where the torque reflects the viscosity of the melt (or the melt strength), and the torque before and after vulcanization indirectly reflects the vulcanization rate and the degree of vulcanization.
The three formulations of the example 1, the comparative example 1 and the comparative example 3 are the same, and the difference is only that the adding mode of the catalyst is different, specifically, the step-by-step adding of the catalyst gel is adopted in the example 1, the one-time adding of the catalyst gel is adopted in the comparative example 1, and the one-time dripping of the catalyst liquid is adopted in the comparative example 3.
As can be seen from FIG. 1, when the catalyst liquid is added dropwise in comparative example 3, the torque value rises sharply, which indicates that the vulcanization rate is very fast, and the gradual drop after the torque value is caused by the gradual crushing of the vulcanized silicone rubber by rotor shearing, and the melt fluidity is enhanced; the catalyst glue is added in the comparative example 1, so that the activity of the catalyst can be properly reduced, the slow release effect is achieved, the torque rises quickly and slowly during dynamic vulcanization, and the catalyst glue is mild compared with the liquid activity of the catalyst; in example 1, the catalyst gum is added step by step, so that the dynamic vulcanization is more gradual, and the vulcanization rate is more easily matched with the shear strength. The torque gradually rises with time, and the final torque value is not different from the catalyst once-adding.
2. Scanning electron microscope analysis of organosilicon thermoplastic elastomer
Wherein the content of the first and second substances,
FIG. 2 is a scanning electron micrograph of a TPSIV cross section of comparative example 5. The sample preparation method comprises the following steps: the TPSIV sample obtained in comparative example 5 was extruded into a bar (190 ℃ C., 10kg) on a melt index apparatus, the extruded bar was put into liquid nitrogen to be cooled and brittle-broken, and the cross section was analyzed by a scanning electron microscope.
FIG. 3 is a scanning electron micrograph of TPSIV of comparative example 5 diluted to a silicone rubber concentration of 10%, the sample preparation method comprises: the TPSIV sample obtained in comparative example 5 and TPU were mixed uniformly (190 ℃, 120rpm) in a mixer in a mass ratio of 2:8, the obtained sample was extruded into a bar (190 ℃, 10kg) on a melt index apparatus, the extruded bar was put into liquid nitrogen for cooling and brittle fracture, and the cross section was analyzed by a scanning electron microscope.
FIG. 4 is a scanning electron micrograph of a TPSIV cross section of example 5. The sample preparation method comprises the following steps: the TPSIV sample obtained in example 5 was extruded into a melt index apparatus (190 ℃ C., 10kg), the extruded sample was cooled and brittle-broken in liquid nitrogen, and the cross section was analyzed by scanning electron microscopy.
FIG. 5 is a scanning electron micrograph of TPSIV of example 5 diluted to a silicone rubber concentration of 10%, the sampling method comprises: the TPSIV sample obtained in example 5 and TPU were mixed uniformly in a mass ratio of 2:8 (190 ℃, 120rpm) on a mixer, the obtained sample was extruded into a melt index apparatus (190 ℃, 10kg), the extruded sample was placed in liquid nitrogen for cooling and brittle fracture, and the section was analyzed by scanning electron microscopy.
As shown in fig. 2 to 5, comparative example 5 is an elastomer product obtained by adding a catalyst once, and as seen from a scanning electron microscope image, the particle size of the silicone rubber is between 5 and 20um, the particle size distribution is wide, and a large amount of silicone rubber with large particle size is dispersed in a TPU carrier; and example 5 is an elastomer product obtained by adding the catalyst step by step, wherein the particle size of the silicone rubber is between 1 and 5um, the particle size distribution of the silicone rubber is narrow, and the silicone rubber is uniformly dispersed in the TPU carrier. The comparison of a scanning electron microscope shows that the particle size of the silicon rubber obtained by adding the catalyst step by step is obviously smaller, the particle size distribution is obviously narrower, and the compatibility of the silicon rubber and the TPU carrier is obviously better.
3. Analysis of mechanical property results of organic silicon thermoplastic elastomer
TABLE 1 mechanical Property results for various groups of samples of silicone thermoplastic elastomer (example is represented by E)
| Measurement index | E1 | E2 | E3 | E4 | E5 | E6 | E7 | E8 |
| Shore hardness/A | 66.6 | 66.5 | 73.7 | 73.6 | 66.6 | 66.8 | 66.7 | 74.5 |
| MFI g/10min 190℃、10kg | 26.2 | 28.4 | 25.6 | 27.9 | 27.3 | 28.1 | 24.4 | 30.4 |
| Tensile strength/Mpa | 12.47 | 13.52 | 15.24 | 14.96 | 15.63 | 14.41 | 13.68 | 14.31 |
| Elongation at break/% | 552.6 | 561.8 | 532.2 | 545.6 | 572.4 | 576.3 | 523.4 | 523.4 |
| Compression set/%) | 20.3 | 21.7 | 20.6 | 19.3 | 20.4 | 20.7 | 20.5 | 21.1 |
| Tear Strength/KN/m | 37.6 | 38.1 | 35.4 | 33.4 | 36.1 | 35.6 | 37.9 | 37.9 |
| 200% definite elongation rebound Rate% | 87 | 85 | 88 | 89 | 86 | 87 | 85 | 89 |
| Surface of | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable | Smooth and comfortable |
TABLE 2 comparative examples the results of mechanical Properties of the silicone thermoplastic elastomer for the respective groups of samples (comparative example is represented by C)
Compared with the mode of adding the catalyst in batches in the embodiment 1 and the embodiment 2, the mode of adding the catalyst in one time in the comparative example 1 and the comparative example 2 can obtain the sample with rough surface and obviously reduced mechanical property.
The liquid catalysts used in comparative examples 3 and 4 also showed a small decrease in mechanical properties of the resulting test samples as compared to the catalyst masterbatches used in comparative examples 1 and 2. The torque chart shows that the vulcanization speed is the highest in the catalyst dropping mode, but the shearing requirement on equipment is the highest, so that local over-vulcanization is easily caused, the material vulcanization is not uniform, and the mechanical property and the hand feeling are seriously influenced.
The comparative examples 5 and 6 are that the catalyst is added in one step, and the mechanical property and the hand feeling of the obtained test sample can not meet the use requirements. The scanning electron microscope images can be combined to obtain: by adopting the mode of adding the catalyst step by step, the partial over-vulcanization in the initial stage after the catalyst is added can be effectively avoided, the vulcanization reaction is more stable, the silicon rubber has smaller particle size and narrower particle size distribution, and the obtained sample has smooth handfeel and excellent mechanical property.
Compared with example 5, the dynamic vulcanization catalyst of comparative example 7 is changed into the compound of 70A, the viscosity is higher, and the mechanical property of the obtained TPSIV is poorer, because the viscosity of the catalyst adhesive is higher than the melt viscosity of polyurethane/silicon rubber, so that the catalyst adhesive is difficult to disperse, and the dynamic vulcanization of the silicon rubber is influenced.
Comparative example 8 used low vinyl content silicone rubber and low hydrogen content silicone oil as cross-linking agents, and simultaneously it used non-reactive compatilizers, its compression deformation is significantly greater than comparative example 7, 200% constant elongation rebound is significantly smaller than comparative example 7, indicating that TPSIV has poor resilience in the presence of low cross-link density and non-reactive compatilizers.
Comparative example 9 is a typical TPSIV product commercially available, used in large quantities in wearable devices. The TPSIV prepared in the embodiment has mechanical strength and resilience which are comprehensively superior to those of the TPSIV prepared in the comparative example 9, and can meet the requirements of wearable equipment on the strength and resilience of an elastomer.
In summary, (1) the present invention prepares a silicon-based elastomer with a high crosslinking degree and a high crosslinking density by using a silicone rubber with a high vinyl content as a dispersed phase and a silicone oil with a high hydrogen content as a crosslinking agent. By adding unsaturated polyester containing vinyl as a reaction type compatilizer, unsaturated bonds in the polyester and vinyl silicone rubber are crosslinked during dynamic vulcanization, so that the interfacial bonding force between the silicone rubber and polyurethane is further improved, and the polyurethane/silicone rubber thermoplastic elastomer has high resilience. (2) According to the invention, the catalyst masterbatch is adopted to replace the traditional liquid catalyst, so that the vulcanization speed can be reduced, the vulcanization time can be prolonged moderately, the vulcanization reaction is more stable, and the crosslinking of the silicone rubber is easier to control. (3) The invention adopts a method of adding catalysts step by step, a prepolymer with lower crosslinking degree is obtained at the front section of a screw of a double-screw extruder, the viscosity ratio of polyurethane to silicon rubber is improved, the dispersibility of the silicon rubber is improved, and the prepolymer is continuously subjected to dynamic vulcanization reaction at the middle and rear sections of the screw, so that the crosslinking degree and the crosslinking density are improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of high-resilience polyurethane/organic silicon thermoplastic elastomer is characterized by comprising the following steps:
s1 rubber-plastic blend
Thermoplastic polyurethane, vinyl silicone rubber, a compatilizer and a reinforcing filler are mixed, placed in an internal mixer for premixing, cooled after being mixed uniformly, added with a cross-linking agent and continuously mixed uniformly to obtain a rubber-plastic mixture;
s2 Pre-crosslinking
Adding the rubber-plastic blend in the S1 into a double-screw extruder, adding a pre-polymerization catalyst into the front section of a screw of the double-screw extruder for pre-vulcanization, and performing shearing dispersion treatment to obtain a pre-vulcanized cross-linked substance;
s3 dynamic vulcanization
When the pre-vulcanized cross-linked product in the S2 passes through the middle section of a screw in a double-screw extruder, adding a dynamic vulcanization catalyst, performing shearing dispersion treatment, and then performing granulation to obtain a polyurethane/organic silicon thermoplastic elastomer;
wherein the pre-polymerization catalyst and the dynamic vulcanization catalyst are both mixed rubber formed by mixing the catalyst and vinyl silicone rubber.
2. The preparation method of the high resilience polyurethane/silicone thermoplastic elastomer according to claim 1, wherein the polyurethane/silicone thermoplastic elastomer comprises, by weight, 100 parts of thermoplastic polyurethane, 80-120 parts of vinyl silicone rubber, 5-15 parts of a compatibilizer, 10-25 parts of a reinforcing filler, 2-8 parts of a crosslinking agent, 0.5-1 part of a prepolymerization catalyst, and 1.5-3.5 parts of a dynamic vulcanization catalyst.
3. The method for preparing a high resilience polyurethane/silicone thermoplastic elastomer according to claim 1, wherein the catalyst is a compound or complex of a metal element, the metal element including Pt, Pd, Rh, Ru, Ni, or Co;
in the prepolymerization catalyst, the molar mass ratio of vinyl to metal elements is 300-1000: 1;
in the dynamic vulcanization catalyst, the molar mass ratio of the vinyl group to the metal element is 80-250: 1.
4. The preparation method of the high resilience polyurethane/silicone thermoplastic elastomer as claimed in claim 1 or 3, wherein in the prepolymerization catalyst, vinyl silicone rubber with a molecular weight of 45-60 ten thousand is selected.
5. The preparation method of the high resilience polyurethane/organosilicon thermoplastic elastomer as claimed in claim 1 or 3, wherein the dynamic vulcanization catalyst is a methyl vinyl silicone rubber compound with Shore hardness of 30-40A and white carbon black mass fraction of 5-15%.
6. The method for preparing the high resilience polyurethane/silicone thermoplastic elastomer according to claim 1, wherein the compatibilizer is unsaturated polyester, and the unsaturated polyester is polyester resin containing vinyl in a main chain or a side chain.
7. The preparation method of the high resilience polyurethane/silicone thermoplastic elastomer according to claim 3, wherein the preparation method of the pre-polymerization catalyst or the dynamic vulcanization catalyst comprises the steps of placing vinyl silicone rubber in an open mill or an internal mixer for internal mixing for a period of time at normal temperature, and after the internal mixing is finished, adding the catalyst for mixing;
the catalyst is a metal element complex, and the concentration of the catalyst is 2000-4000 ppm; the concentration of the catalyst in the prepolymerized catalyst is 100 to 500ppm, and the concentration of the catalyst in the dynamically vulcanized catalyst is 300 to 700 ppm.
8. The preparation method of the high resilience polyurethane/silicone thermoplastic elastomer according to claim 1, wherein in S1, the molecular weight of the vinyl silicone rubber is 45-80 ten thousand, and the mole fraction of vinyl groups is 0.2-0.8 wt.%.
9. The preparation method of the high resilience polyurethane/silicone thermoplastic elastomer according to claim 1, wherein the cross-linking agent is polyhydrosilicone oil, the hydrogen content of the polyhydrosilicone oil is 0.36-3.5 wt.%, and the molar mass ratio of hydrogen to vinyl is 2-7: 1.
10. A high resilience polyurethane/silicone thermoplastic elastomer, characterized by being obtained by the production method of any one of claims 1 to 9.
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| CN115637037A (en) * | 2022-09-28 | 2023-01-24 | 北京化工大学 | Organic silicon thermoplastic vulcanized rubber and preparation method thereof |
| CN115806738A (en) * | 2023-02-02 | 2023-03-17 | 成都思立可科技有限公司 | Low-temperature noise reduction auxiliary agent, PC/ABS alloy containing low-temperature noise reduction auxiliary agent and preparation method of PC/ABS alloy |
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