Interface regulator, dynamically vulcanized elastomer material and preparation method thereof

Abstract

The present invention provides an interface regulator, a dynamically vulcanized elastomer material and a preparation method thereof. The interface regulator comprises a compound formed by chemically bonding a polysiloxane molecule and an isocyanate molecule, and the molecular weight ratio of the isocyanate molecule to the polysiloxane molecule is 1.5-10:1, and the chemical bond is -O-CO-NH- and / or -NH-CO-NH-. The interface regulator of the present invention uses a polysiloxane molecule and an isocyanate molecule as raw materials, which can be combined by forming chemical bonds of -O-CO-NH- and / or -NH-CO-NH-, and both the raw material molecules and TPU and silicone rubber have better compatibility, so it can be used as an interface regulator. By controlling the molecular weight ratio of the isocyanate molecule to the polysiloxane molecule to be 1.5-10:1, a better phase interface regulation effect can be achieved, and thus through dynamic vulcanization, TPSiV with a controllable particle size and a sea-island structure can be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material processing aids, in particular to regulators, and more particularly to an interfacial regulator, a dynamically vulcanized elastomer material and a preparation method thereof. Background Art

[0002] Natural leather has excellent touch, wear resistance and breathability, and is mostly used in high-end places. However, it also has problems of heavy pollution and high price in the preparation process. Polyurethane, as the main component of synthetic leather, can be comparable to natural leather in many aspects of performance. However, polyurethane synthetic leather has deficiencies in low-temperature flexibility, anti-sticking property and surface feel.

[0003] The polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) combines the characteristics of polysiloxane with polyurethane synthetic leather, significantly improving the low-temperature flexibility and anti-sticking property of TPU. More importantly, silicone rubber endows polyurethane with excellent properties such as silky touch, non-sticky ash, no precipitation, non-sticky, and easy demolding. It has a relatively wide range of applications in the fields of smart wearables, artificial leather, electronic appliances, medical and health, cable packaging materials, etc.

[0004] Dynamic vulcanization is to carry out high-temperature melt blending of a vulcanizable rubber phase, a thermoplastic resin or elastomer, and a vulcanizing agent. At the same time, the rubber phase undergoes a synchronous cross-linking reaction. Under the action of high shear, the cross-linked rubber phase is sheared into micron-sized particles and dispersed in the resin. During the dynamic vulcanization process of TPSiV, the cross-linking and shear dispersion of silicone rubber proceed simultaneously. The cross-linking density, microscopic size and dispersion state of silicone rubber particles determine the elasticity and silky touch of the product.

[0005] The interfacial regulator is a key additive used to reduce the interfacial tension between TPU and silicone rubber and promote the formation of micron-sized silicone rubber particles during the dynamic vulcanization process. Its molecular structure is characterized by having a polar end with good compatibility with TPU and a non-polar end with good compatibility with silicone rubber. The master's thesis of Hainan University, "Research on the Preparation, Structure and Properties of High-Somatosensory Compatibility Organosilicon Thermoplastic Vulcanizates", used self-made PDMS-PU and ethylene methyl acrylate EMA with a methyl acrylate (MA) content of 30% as interfacial regulators, and found that both had a compatibilizing effect, and the former had a better effect than the latter. However, the author did not disclose the molecular structures of the two. CN112920409B published a star-shaped polyester-modified siloxane copolymer and its preparation method for modifying TPU. The polysiloxane is connected to three polyester chain segments through a siloxy carbonyl group to improve the performance of synthetic leather. However, the siloxy carbonyl group is prone to hydrolysis. When the polysiloxane chain is exposed on the surface of polyurethane synthetic leather, hydrolysis is likely to occur, resulting in the detachment of the polysiloxane chain segment from the leather surface and causing failure. Summary of the Invention

[0006] Based on the above problems, the object of the present invention is to provide an interface regulator, which can effectively reduce the interfacial tension between TPU and silicone rubber, and promote the formation of polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) during the dynamic vulcanization process. Moreover, when using this interface regulator during the dynamic vulcanization process, it is possible to achieve the encapsulation of silicone rubber by TPU to form an island structure with uniform distribution of silicone rubber, thereby effectively improving the touch and mechanical properties of TPSiV.

[0007] To achieve the above object, in the first aspect of the present invention, an interface regulator is provided, which comprises a compound formed by chemically bonding polysiloxane molecules and isocyanate molecules. The molecular weight ratio of the isocyanate molecules to the polysiloxane molecules is 1.5 - 10:1, and the chemical bond is -O-CO-NH- and / or -NH-CO-NH-.

[0008] The interface regulator of the present invention uses polysiloxane molecules and isocyanate molecules as raw materials, which can be combined by forming chemical bonds of -O-CO-NH- and / or -NH-CO-NH-. Moreover, the raw material molecules have good compatibility with both TPU and silicone rubber, so it can be used as an interface regulator. More importantly, by controlling the molecular weight ratio of isocyanate molecules to polysiloxane molecules to be 1.5 - 10:1, it can ensure that the component of isocyanate molecules in the interface regulator molecule is greater than that of polysiloxane molecules, forming an interfacial curvature at the adsorption interface on the nano - micron scale, that is, the outer side of the curved surface is isocyanate molecules and the inner side is polysiloxane molecules, which is conducive to the formation of nano - micron scale particles of TPU encapsulating silicone rubber. That is, a better phase interface regulation effect can be achieved, and through dynamic vulcanization, TPSiV with a controllable particle size and having an island structure can be obtained.

[0009] As a technical solution of the present invention, the molar ratio of -NCO in the isocyanate molecules to -OH in the polysiloxane molecules is 1.05 - 1.25:1.

[0010] As a technical solution of the present invention, the polysiloxane molecules include at least one of Chemical Formulas I to VI. Among them, R1 is (CH2) p CH3; R2 is (CH2) q ; R3 is (CH2) r ; R4 is (CH 2)s OH or (CH2)3(CH2CH2O) t (CH2CHCH3O) u OH; R5 is (CH 2)v OH or (CH2)3(CH2CH2O) w (CH2CHCH3

[0011] O) xOH; p ranges from 0 to 7, q ranges from 1 to 6, r ranges from 1 to 6, s ranges from 1 to 6, t ranges from 5 to 10, u ranges from 0 to 5, v ranges from 1 to 6, w ranges from 5 to 10, x ranges from 0 to 5, m1, m2, m3, m4, m5 and m6 are each independently from 5 to 300, n1 ranges from 1 to 10, and n2 ranges from 4 to 50.

[0012] As a technical solution of the present invention, The isocyanate molecule is an isocyanate group-terminated oligomeric diol obtained by reacting a diisocyanate with an oligomeric diol.

[0013] As a technical solution of the present invention, the diisocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, and xylylene diisocyanate.

[0014] As a technical solution of the present invention, the oligomeric diol includes at least one of polyester diol, poly(ε-caprolactone) diol, polycarbonate diol, aromatic polyether diol, and aliphatic polyether diol.

[0015] The second aspect of the present invention provides a dynamically vulcanized elastomeric material, the preparation raw materials of which include a rubber compound, a regulator, TPU, hydrogen-containing silicone oil, an inhibitor, and a catalyst. The rubber compound is a silicone rubber containing a -Si-CH=CH2 bond, and the regulator is the aforementioned interfacial regulator.

[0016] The preparation raw materials of the dynamically vulcanized elastomeric material of the present invention select a special interfacial regulator, which is beneficial to TPU encapsulating the silicone rubber during the vulcanization process to form an island structure with uniform distribution of the silicone rubber, thereby effectively improving the touch and mechanical properties of TPSiV.

[0017] As a technical solution of the present invention, the hydrogen content of the hydrogen-containing silicone oil is 0.05 to 1.6%, and the molar amount of the -Si-H bond in the hydrogen-containing silicone oil is 1.1 to 2.5 times the molar amount of the -Si-CH=CH2 bond in the rubber compound.

[0018] As a technical solution of the present invention, the inhibitor includes at least one of alkynol compounds, polyvinyl polysiloxanes, amide compounds, and maleate compounds.

[0019] As a technical solution of the present invention, the mass of the inhibitor is 50 to 500 ppm of the mass of the rubber compound.

[0020] As a technical solution of the present invention, the catalyst includes at least one of a platinum-vinylsiloxane complex and its modified products, an alcohol-modified chloroplatinic acid catalyst, and a platinum-alkynyl complex.

[0021] As a technical solution of the present invention, the mass of platinum in the catalyst is 3-200 ppm of the mass of the mixed rubber.

[0022] As a technical solution of the present invention, the preparation method of the mixed rubber includes blending raw rubber, silica, and a structure control agent, and placing them in a mixer for mixing to obtain.

[0023] As a technical solution of the present invention, the mixture can be pre-mixed, slowly heated to 120 °C within 30-120 min, then evacuated, and then slowly heated to 145-165 °C within 90-120 min, and kept warm for 30-60 min.

[0024] The third aspect of the present invention provides a preparation method of a dynamically vulcanized elastomer material, including the steps:

[0025] (1) Mixing the mixed rubber, the regulator, and the TPU in a mixer to obtain a rubber-plastic melt;

[0026] (2) After adding the rubber-plastic melt into a torque rheometer for blending, adding the hydrogen-containing silicone oil and the inhibitor for blending, and then adding a catalyst for reaction.

[0027] As a technical solution of the present invention, the reaction conditions in the torque rheometer are 110-150 °C and 30-100 rpm.

[0028] As a technical solution of the present invention, the time of each blending step in step (2) is independently 3-10 min.

[0029] As a technical solution of the present invention, after adding the catalyst in step (2), the reaction is carried out for 7-20 min. Specific embodiments

[0030] The interfacial regulator of the present invention can be used as an auxiliary agent for the reaction between various polymers with poor compatibility to improve the interfacial phase and thus promote the reaction, and is particularly suitable for the preparation of polyurethane / silicone rubber dynamically vulcanized elastomer materials (TPSiV).

[0031] The raw materials for the preparation of polyurethane / silicone rubber dynamically vulcanized elastomer materials (TPSiV) usually include mixed rubber, regulator, TPU, hydrogen-containing silicone oil, inhibitor, and catalyst. The mixed rubber is a silicone rubber containing -Si-CH=CH2 bonds. The mass parts of the mixed rubber, regulator, and TPU are 20-40 parts, 1-10 parts, and 60-80 parts respectively.

[0032] Among them, the hydrogen content of the hydrogen-containing silicone oil is 0.05 - 1.6%, preferably 0.1 - 1.5%, more preferably 0.5 - 1.0%, or 0.75 - 1.0%. The molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.1 - 2.5 times, preferably 1.4 - 2 times, more preferably 1.5 - 1.8 times the molar amount of -Si-CH=CH2 bonds in the blended rubber.

[0033] The inhibitor includes at least one of alkynol compounds, polyvinyl polysiloxanes, amide compounds, and maleate compounds. The mass of the inhibitor is 50 - 500 ppm, preferably 50 - 300 ppm, more preferably 100 - 200 ppm of the mass of the blended rubber.

[0034] The catalyst includes at least one of platinum-vinylsiloxane complexes and their modified products, alcohol-modified chloroplatinic acid catalysts, and platinum-alkyne complexes. The mass of platinum in the catalyst is 3 - 200 ppm, preferably 5 - 150 ppm, more preferably 20 - 100 ppm of the mass of the blended rubber.

[0035] The preparation method of the blended rubber includes blending raw rubber, fumed silica, and a structure control agent, and placing them in an internal mixer for mixing. Premixing can be carried out in the mixture, slowly heating to 120°C within 30 - 120 min, then evacuating, and then slowly heating to 145 - 165°C within 90 - 120 min, and holding for 30 - 60 min. The structure control agent can be a conventional organosilicon compound structure control agent, such as hydroxyl-containing silane, alkoxysilane, silazane, and boron-containing siloxane.

[0036] The preparation method of the polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) includes the steps:

[0037] (1) Mix the blended rubber, regulator, and TPU in an internal mixer to obtain a rubber-plastic melt;

[0038] (2) After adding the rubber-plastic melt into a torque rheometer for blending, add the hydrogen-containing silicone oil and the inhibitor for blending, and then add the catalyst for reaction.

[0039] Among them, in step (2), the reaction conditions in the torque rheometer are 110 - 150°C and 30 - 100 rpm. Of course, in actual operation, the reaction conditions are not limited to this and can be adjusted according to the preparation raw materials and the external environment, etc.

[0040] The time of each blending step is independently not limited to 3 - 10 min. The reaction time after adding the catalyst is not limited to 7 - 20 min.

[0041] The regulator used in the preparation of polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) may include a compound formed by chemically bonding polysiloxane molecules and isocyanate molecules. The molecular weight ratio of isocyanate molecules to polysiloxane molecules is 1.5 to 10:1, preferably 3 to 9:1, more preferably 3 to 6:1, or 3 to 5:1. The chemical bond is -O-CO-NH- and / or -NH-CO-NH-.

[0042] Furthermore, the molar ratio of -NCO in isocyanate molecules to -OH in polysiloxane molecules is 1.05 to 1.25:1, preferably the molar ratio is 1.05 to 1.15:1, more preferably 1.05 to 1.20:1. Selecting this molar ratio ensures that the formed compound is -NCO terminated.

[0043] Furthermore, the polysiloxane molecule includes at least one of Chemical Formulas I to VI, wherein, R1 is (CH2) p CH3; R2 is (CH2) q ; R3 is (CH2) r ; R4 is (CH 2)s OH or (CH2)3(CH2CH2O) t (CH2CH

[0044] CH3O) u OH; R5 is (CH 2)v OH or (CH2)3(CH2CH2O) w (CH2CHCH3O) x OH; p is 0 to 7, q is 1 to 6, r is 1 to 6, s is 1 to 6, t is 5 to 10, u is 0 to 5, v is 1 to 6, w is 5 to 10, x is 0 to 5, m1, m2, m3, m4, m5 and m6 are each independently 5 to 300, n1 is 1 to 10, n2 is 4 to 50.

[0045] Furthermore, the isocyanate molecule is an isocyanate group-terminated oligomeric diol obtained by reacting a diisocyanate with an oligomeric diol. The structural formula of the isocyanate group-terminated oligomeric diol is: OCN-R6-NH-CO-O-R7-O-CO-NH-R6-NCO, wherein, R6 is the non-isocyanate functional group part of the diisocyanate, and R7 is the hydroxyl functional group part of the oligomeric diol.

[0046] To better illustrate the purpose, technical solution and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the methods described in the following embodiments are further explanatory descriptions of the present invention and should not be regarded as limitations on the present invention.

[0047] Example 1

[0048] This example is a kind of dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0049] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain a mixed rubber;

[0050] Add 30 parts of the mixed rubber, 70 parts of TPU (model BASF Elastollan 1170A), and 5 parts of an interfacial modifier to the Banbury mixer for mixing to obtain a rubber-plastic melt.

[0051] (2) Add the rubber-plastic melt to a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the mixed rubber) and 100 ppm of an alkyne alcohol compound (accounting for the mass of the mixed rubber) and blend for 5 min. Finally, add 70 ppm of a platinum-vinyl silicone complex (platinum accounts for the mass of the mixed rubber), and the TPSiV material can be prepared after reacting for 7 min.

[0052] The structural formula of the interfacial modifier is as shown in Formula 1.

[0053]

[0054] Formula 1

[0055] Example 2

[0056] This example is a kind of dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0057] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain a mixed rubber;

[0058] Add 30 parts of the mixed rubber, 70 parts of TPU (model BASF Elastollan 1170A), and 5 parts of an interfacial modifier to the Banbury mixer for mixing to obtain a rubber-plastic melt.

[0059] (2) Add the rubber-plastic melt into a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 100 ppm of alkynol compound (accounting for the mass of the blended rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounts for the mass of the blended rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0060] The structural formula of the interfacial regulator is as shown in Formula II below.

[0061]

[0062] Formula II

[0063] Example 3

[0064] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0065] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxyl silicone oil, and place them in a mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain the blended rubber;

[0066] Add 30 parts of the blended rubber, 70 parts of TPU (model BASF Elastollan 1170A), and 5 parts of the interfacial regulator into a mixer and mix to obtain the rubber-plastic melt.

[0067] (2) Add the rubber-plastic melt into a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 100 ppm of alkynol compound (accounting for the mass of the blended rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounts for the mass of the blended rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0068] The structural formula of the interfacial regulator is as shown in Formula III.

[0069] Formula III

[0070] Example 4

[0071] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0072] (1) Blend 100 parts of raw rubber of type 110 - 3, 55 parts of fumed silica, and 10 parts of hydroxyl silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120°C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165°C within 90 min. Keep the temperature for 30 min, discharge and open mill to obtain the mixed rubber.

[0073] Add 30 parts of the mixed rubber, 70 parts of TPU (model: BASF Elastollan 1170A), and 5 parts of the interfacial regulator to the Banbury mixer for mixing to obtain the rubber - plastic melt.

[0074] (2) Add the rubber - plastic melt to a torque rheometer at 140°C and 50 rpm, blend for 5 min, then add hydrogen - containing silicone oil (the hydrogen content of the hydrogen - containing silicone oil is 0.05%, and the molar amount of - Si - H bonds in the hydrogen - containing silicone oil is 1.4 times the molar amount of - Si - CH=CH2 bonds in the mixed rubber) and 100 ppm of alkynol compound (accounting for the mass of the mixed rubber) and blend for 5 min. Finally, add 70 ppm of platinum - vinylsiloxane complex (platinum accounting for the mass of the mixed rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0075] The structural formula of the interfacial regulator is as shown in Formula 4.

[0076]

[0077] Formula 4

[0078] Example 5

[0079] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0080] (1) Blend 100 parts of raw rubber of type 110 - 3, 55 parts of fumed silica, and 10 parts of hydroxyl silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120°C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165°C within 90 min. Keep the temperature for 30 min, discharge and open mill to obtain the mixed rubber.

[0081] Add 30 parts of the mixed rubber, 70 parts of TPU (model: BASF Elastollan 1170A), and 5 parts of the interfacial regulator to the Banbury mixer for mixing to obtain the rubber - plastic melt.

[0082] (2) Add the rubber-plastic melt into a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 100 ppm of alkynol compounds (accounting for the mass of the blended rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounting for the mass of the blended rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0083] The structural formula of the interfacial regulator is as shown in Formula 5.

[0084]

[0085] Formula 5

[0086] Example 6

[0087] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0088] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxyl silicone oil, and place them in a mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain the blended rubber;

[0089] Add 30 parts of the blended rubber, 70 parts of TPU (model BASF Elastollan 1170A), and 5 parts of the interfacial regulator into a mixer and mix to obtain the rubber-plastic melt.

[0090] (2) Add the rubber-plastic melt into a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 100 ppm of alkynol compounds (accounting for the mass of the blended rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounting for the mass of the blended rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0091] The structural formula of the interfacial regulator is as shown in Formula 6.

[0092]

[0093] Formula 6

[0094] Example 7

[0095] This embodiment is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0096] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120 °C within 30 minutes, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 minutes, keep the temperature for 30 minutes, discharge and open mill to obtain the mixed rubber.

[0097] Add 30 parts of the mixed rubber, 70 parts of TPU (model BASF Elastollan 1170A), and 5 parts of the interfacial regulator to the Banbury mixer for mixing to obtain the rubber-plastic melt.

[0098] (2) Add the rubber-plastic melt to a torque rheometer at 140 °C and 50 rpm, blend for 5 minutes, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the mixed rubber) and 100 ppm of alkynol compound (accounting for the mass of the mixed rubber) and blend for 5 minutes. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounts for the mass of the mixed rubber), and the TPSiV material can be prepared after reacting for 7 minutes.

[0099] The structural formula of the interfacial regulator is as shown in Formula 7.

[0100] Formula 7

[0101] Example 8

[0102] This embodiment is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0103] (1) Blend 100 parts of 110-3 type raw rubber, 60 parts of fumed silica, and 12 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 130 °C within 25 minutes, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 160 °C within 100 minutes, keep the temperature for 40 minutes, discharge and open mill to obtain the mixed rubber.

[0104] Add 40 parts of the mixed rubber, 75 parts of TPU, and 8 parts of the interfacial regulator (the interfacial regulator is the same as that in Example 1) to the Banbury mixer for mixing to obtain the rubber-plastic melt.

[0105] (2) Add the rubber-plastic melt into a torque rheometer at 145 °C and 50 rpm, blend for 8 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.8%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 2.0 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 120 ppm of alkynol compounds (accounting for the mass of the blended rubber) and blend for 8 min. Finally, add 100 ppm of platinum-vinylsiloxane complex (platinum accounting for the mass of the blended rubber), and after reacting for 9 min, the TPSiV material can be prepared.

[0106] For Comparative Examples 1 to 3, commercially available dynamically vulcanized elastomer materials were selected. Among them, Comparative Example 1 was BASF Elastollan 1170A type elastic rubber, Comparative Example 2 was Zhengan Organosilicon GA-9061 platinum rubber, and Comparative Example 3 was Dupont TPSiV 4000-60A type elastic rubber.

[0107] Comparative Example 4

[0108] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0109] (1) Blend 100 parts of 110-3 type raw rubber, 55 parts of fumed silica, and 10 parts of hydroxyl silicone oil, and place them in a mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain the blended rubber; Add 30 parts of the blended rubber and 70 parts of TPU (model BASF Elastollan 1170A) into the mixer for mixing to obtain the rubber-plastic melt.

[0110] (2) Add the rubber-plastic melt into a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the blended rubber) and 100 ppm of alkynol compounds (accounting for the mass of the blended rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounting for the mass of the blended rubber), and after reacting for 7 min, the TPSiV material can be prepared.

[0111] Comparative Example 5

[0112] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0113] (1) Blend 100 parts of raw rubber of type 110-3, 55 parts of fumed silica, and 10 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain the mixed rubber;

[0114] Add 30 parts of the mixed rubber, 70 parts of TPU (model: BASF Elastollan 1170A), and 5 parts of the interface regulator to the Banbury mixer for mixing to obtain the rubber-plastic melt.

[0115] (2) Add the rubber-plastic melt to a torque rheometer at 140 °C and 50 rpm, blend for 5 min, then add hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 0.05%, and the molar amount of -Si-H bonds in the hydrogen-containing silicone oil is 1.4 times the molar amount of -Si-CH=CH2 bonds in the mixed rubber) and 100 ppm of alkynol compound (accounting for the mass of the mixed rubber) and blend for 5 min. Finally, add 70 ppm of platinum-vinylsiloxane complex (platinum accounts for the mass of the mixed rubber) and react for 7 min to prepare the TPSiV material.

[0116] The structural formula of the interface regulator is as in Example 1. Among them, the ratio of the molecular weight of the isocyanate molecule to the molecular weight of the polysiloxane molecule in the interface regulator is 1:1.

[0117] Comparative Example 6

[0118] This example is a dynamically vulcanized elastomer material, and its preparation method includes the following steps.

[0119] (1) Blend 100 parts of raw rubber of type 110-3, 55 parts of fumed silica, and 10 parts of hydroxy silicone oil, and place them in a Banbury mixer for premixing. Slowly heat up to 120 °C within 30 min, then evacuate (vacuum degree 0.06 MPa), and then slowly heat up to 165 °C within 90 min, keep warm for 30 min, discharge and open mill to obtain the mixed rubber;

[0120] Add 30 parts of the mixed rubber, 70 parts of TPU (model: BASF Elastollan 1170A), and 5 parts of the interface regulator to the Banbury mixer for mixing to obtain the rubber-plastic melt.

[0121] (2) The rubber-plastic melt was added to a torque rheometer at 140 °C and 50 rpm and blended for 5 min. Subsequently, hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil was 0.05%, and the molar amount of the -Si-H bond in the hydrogen-containing silicone oil was 1.4 times the molar amount of the -Si-CH=CH2 bond in the blended rubber) and 100 ppm of an alkynol compound (accounting for the mass of the blended rubber) were added and blended for 5 min. Finally, 70 ppm of a platinum-vinylsiloxane complex (platinum accounting for the mass of the blended rubber) was added, and after reacting for 7 min, the TPSiV material could be prepared.

[0122] The structural formula of the interfacial regulator was as in Example 1. Among them, the ratio of the molecular weight of the isocyanate molecule to the molecular weight of the polysiloxane molecule in the interfacial regulator was 15:1.

[0123] The TPSiV materials of Examples 1 to 8 and Comparative Examples 1 to 6 were subjected to product performance tests, and the test results are shown in Table 1.

[0124] Among them, the Shore hardness of each TPSiV material was tested according to the standard of "GB / T 531.1-2008 Test Method for Indentation Hardness of Vulcanized Rubber or Thermoplastic Rubber". The tear strength of each TPSiV material was tested according to the standard of "Standard Test Method for Tear Properties - Resistance to Tear of Conventional Vulcanized Rubber and Thermoplastic Elastomers ASTM D624-00(2020)". The tensile strength and elongation at break of each TPSiV material were tested according to the standard of "SMTC 3 261005-2011 Test Specification for Tensile Properties of Elastomeric Materials". The average particle size was observed and statistically obtained by using an atomic force microscope (AFM).

[0125] Handfeel standard: A handfeel that is smooth without a blocking feeling is rated 9-10, a handfeel that is relatively smooth with a slight blocking feeling is rated 7-8 points, a handfeel with astringency and an obvious blocking feeling is rated 4-6 points, the handfeel of TPU is rated 3 points, and the handfeel of the blended rubber after vulcanization is rated 0 points.

[0126] Table 1 Performance of TPSiV materials in each example

[0127]

[0128] It can be seen from the results in Table 1 that compared with Comparative Examples 1 to 6, the polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) of the present invention not only has better mechanical properties, but also has a smaller average particle size, a more uniform particle size distribution, and a better handfeel.

[0129] In Comparative Example 1, no interfacial regulator was used, so the performance of the prepared polyurethane / silicone rubber dynamically vulcanized elastomer material (TPSiV) was poor. In the interfacial regulator of Comparative Example 2, the ratio of the molecular weight of the isocyanate molecule to the molecular weight of the polysiloxane molecule was 1:1, and in the interfacial regulator of Comparative Example 3, the ratio of the molecular weight of the isocyanate molecule to the molecular weight of the polysiloxane molecule was 15:1. The former ratio was too low and the latter ratio was too high, resulting in limited phase interface regulation effect of the interfacial regulator. Therefore, the silicone rubber could not be evenly wrapped in the TPU, and thus the particle size performance was poor.

[0130] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it is not limited to only those listed in the embodiments. Those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An interface regulator, characterized in that, Comprising a compound formed by chemically bonding polysiloxane molecules and isocyanate molecules, the molecular weight ratio of the isocyanate molecules to the polysiloxane molecules being 1.5 to 10:1, the chemical bond being -O-CO-NH- and / or -NH-CO-NH-, the isocyanate molecules being isocyanate group-terminated oligomer diols obtained by reacting toluene diisocyanate with polyester diols, the polysiloxane molecules including at least one of Chemical Formulas I, II, and IV, wherein, R1 is (CH2) p CH3, R2 is (CH2) q , R3 is (CH2) r , p is 0 to 7, q is 1 to 6, r is 1 to 6, m1, m2, and m4 are each independently 5 to 300, 。 2. The interface regulator according to claim 1, wherein The molar ratio of the amount of -NCO in the isocyanate molecule to the amount of -OH in the polysiloxane molecule is 1.05 to 1.25:

1.

3. A dynamically vulcanized elastomeric material, characterized in that, The preparation raw materials include a kneaded rubber, a regulator, TPU, a hydrogen-containing silicone oil, an inhibitor, and a catalyst. The kneaded rubber is a silicone rubber containing a -Si-CH=CH2 bond, and the regulator is the interface regulator described in any one of claims 1 to 2.

4. The dynamically vulcanized elastomeric material according to claim 3, characterized in that The hydrogen content of the hydrogen-containing silicone oil is 0.05 to 1.6%, and the molar amount of the -Si-H bond in the hydrogen-containing silicone oil is 1.1 to 2.5 times the molar amount of the -Si-CH=CH2 bond in the kneaded rubber.

5. The dynamically vulcanized elastomeric material according to claim 3, wherein The preparation method of the kneaded rubber includes blending raw rubber, silica, and a structure control agent, and kneading them in a mixer to obtain it.

6. The preparation method of the dynamically vulcanized elastomer material according to any one of claims 3 to 5, characterized in that, It includes the steps: (1) Mix the kneaded rubber, the regulator, and the TPU in a mixer to obtain a rubber-plastic melt; (2) After adding the rubber-plastic melt to a torque rheometer for blending, add the hydrogen-containing silicone oil and the inhibitor for blending, and then add a catalyst for reaction.

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