Polyurethane-polyamide copolymerized elastomer composition as well as preparation method and application thereof

Abstract

The invention provides a polyurethane-polyamide copolymerized elastomer composition as well as a preparation method and application thereof, and the polyurethane-polyamide copolymerized elastomer composition is prepared from the following raw material components in percentage by mass: A) 5-50 wt% of diisocyanate, B) 30-80 wt% of a polyhydroxy compound containing reactive hydrogen, C) 5-25 wt% of a chain extender, and D) 1-30 wt% of a cyclic lactam prepolymer. The polyurethane prepolymer, the cyclic lactam prepolymer and the chain extender are mixed and granulated, so that the compatibility problem of TPU and PEBA can be solved, and the performance of the polyurethane-polyamide copolymerized elastomer is improved.

Description

Technical Field

[0001] The invention belongs to the field of thermoplastic materials, and in particular relates to a polyurethane-polyamide copolymer elastomer composition, a preparation method and application thereof. Background Art

[0002] Both thermoplastic polyurethane elastomer (TPU) and nylon elastomer (PEBA) are microphase-separated elastomers, and their microstructures contain hard segments and soft segments. They have similarities in structure and many common application areas, such as foaming applications.

[0003] Patent CN108250734B discloses a PEBA / TPU physical blended foaming material, which is granulated after PEBA and TPU are blended, and a physical foaming agent is introduced into a high-pressure reactor, and the temperature and pressure are increased to reach a supercritical state, and then the pressure is quickly released to obtain microporous foaming beads. It adopts a physical blending method to prepare the blended material, and then further foams to prepare the foaming material. However, there are problems with the compatibility of TPU and PEBA, and they cannot achieve good compatibility at the microscopic molecular scale, nor can they maximize the material characteristics and advantages of the two.

[0004] Therefore, it is necessary to develop a polyurethane-polyamide copolymer elastomer material that can maximize the advantages of both. Summary of the invention

[0005] In view of this, one of the objects of the present invention is to provide a polyurethane-polyamide copolymer elastomer composition and a preparation method. By mixing and granulating a polyurethane prepolymer and a cyclic lactam prepolymer with a chain extender, the compatibility problem between TPU and PEBA can be solved and the performance of the polyurethane-polyamide copolymer elastomer can be improved.

[0006] The present invention also aims to provide the use of the polyurethane-polyamide copolymer elastomer composition, which can be used to prepare foaming materials and has the advantages of high resilience, high delamination tearing, low compression deformation, etc.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a polyurethane-polyamide copolymer elastomer composition, which is prepared from raw material components comprising the following weight percentages:

[0009] A) diisocyanate, 5-50wt%, including but not limited to 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt% or a range consisting of any two thereof, preferably 5-35wt%;

[0010] B) 30-80wt% of a polyhydroxy compound containing active hydrogen, including but not limited to 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or a range consisting of any two thereof, preferably 40-75wt%;

[0011] C) chain extender, 5-25wt%, including but not limited to 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt% or a range consisting of any two thereof, preferably 5-20wt%;

[0012] D) cyclic lactam prepolymer, 1-30wt%, including but not limited to 1wt%, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt% or a range consisting of any two thereof, preferably 3-25wt%.

[0013] In one embodiment, the polycyclic lactam prepolymer described in component D) is prepared by reacting a cyclic lactam with an organic dibasic acid;

[0014] The cyclic lactam is selected from one or more of caprolactam, undecanoic acid lactam and laurolactam, preferably one or more of undecanoic acid lactam and laurolactam.

[0015] The organic dibasic acid is selected from one or more of aliphatic dibasic acids and aromatic dibasic acids, preferably one or more of aliphatic dibasic acids, more preferably one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, etc., further preferably one or more of succinic acid, adipic acid, and sebacic acid.

[0016] In a specific example, the molecular weight of the polycyclic lactam prepolymer is 200-2000, including but not limited to 200, 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000 or a range consisting of any two thereof.

[0017] The method for preparing a polycyclic lactam prepolymer by reacting a cyclic lactam with an organic dibasic acid as described above in the present invention is a known process in the prior art. The relevant operations and process conditions in the preparation method of the present invention, and the devices used therein, can be carried out by using the corresponding conventional selections in the art, and there is no particular limitation thereto. The technicians can optimize the known processes in the prior art according to actual needs. Specifically, for example, the conditions listed in the following embodiments of the present invention can be used:

[0018] The mass ratio of the cyclic lactam to the organic dibasic acid is 1:0.5-2, including but not limited to 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2 or a range consisting of any two thereof;

[0019] The reaction has a temperature of 200 to 270° C., a pressure of 20 to 30 bar, and a time of 4 to 10 hours. Specifically, the temperature may be 200° C., 210° C., 220° C., 230° C., 240° C., 250° C., 260° C., 270° C., or a range between any two thereof; the pressure may be 20 bar, 22 bar, 24 bar, 26 bar, 28 bar, 30 bar, or a range between any two thereof; and the time may be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or a range between any two thereof;

[0020] The reaction is carried out in the presence of water, wherein the amount of water is 3-25wt% of the total mass of the cyclic lactam and the organic dibasic acid, including but not limited to 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt% or a range consisting of any two thereof, preferably 10-15%;

[0021] The reaction is carried out under protective gas conditions, such as nitrogen environment;

[0022] The reaction preferably uses a reactor, which is a jacketed stirred reactor with a heat medium jacket on the outside; the stirring paddle of the reactor is preferably a three-blade, four-blade or five-blade inclined paddle with an aspect ratio of 1.5-2.5, including but not limited to 1.5, 1.7, 1.9, 2.0, 2.2, 2.4, 2.5 or a range consisting of any two of them.

[0023] In one embodiment, the diisocyanate described in component A) is selected from one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), pentamethylene diisocyanate (PDI), naphthalene diisocyanate (NDI), tetramethylene meta-xylylene diisocyanate (TMXDI), para-phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI) and dimethyl diphenyl diisocyanate (TODI), preferably one or more of TDI, MDI, HMDI, HDI and IPDI.

[0024] In one embodiment, the polyhydroxy compound containing active hydrogen described in component B) is a polyol with a functionality of 2 or more, preferably a polyol with a functionality of 2, selected from one or more of ester-containing polyols, ether-containing polyols, silicon-containing polyols, fluorine-containing polyols, olefin-containing polyols, and urea-containing polyols, preferably polyoxypropylene polyols, polyurea polyols, polytetramethylene glycol polyols, copolyether polyols, aromatic polyether polyols, polyacrylate polyols, polyolefin polyols, alkyd polyester polyols, polycaprolactone polyols, polycarbonate polyols, hydroxyl-terminated polydimethylsiloxanes, hydroxyl-terminated polyether-modified silicone oils, hydroxyl-terminated fluorine-containing polyether polyols, etc., more preferably one or more of polytetramethylene glycol polyols, alkyd polyester polyols, polycaprolactone polyols, and polycarbonate polyols;

[0025] The hydroxyl value of the polyhydroxy compound containing active hydrogen is 26 to 224 mgKOH / g, including but not limited to 26 mgKOH / g, 50 mgKOH / g, 75 mgKOH / g, 100 mgKOH / g, 125 mgKOH / g, 150 mgKOH / g, 175 mgKOH / g, 200 mgKOH / g, 224 mgKOH / g or a range consisting of any two thereof, preferably 30 to 220 mgKOH / g;

[0026] The acid value of the polyhydroxy compound containing active hydrogen is less than 1.5 mgKOH / g, for example, 1.5 mgKOH / g, 1.3 mgKOH / g, 1.1 mgKOH / g, 1.0 mgKOH / g, 0.8 mgKOH / g, 0.5 mgKOH / g, 0.3 mgKOH / g, 0.1 mgKOH / g, and preferably less than 1.0 mgKOH / g.

[0027] In one embodiment, the chain extender described in component C) is selected from one or more of aliphatic diols, aromatic diols, alcohol amine diols, aliphatic diamines, aromatic diamines, etc., preferably one or more of aliphatic diols, aromatic diols, aliphatic diamines, more preferably one or more of aliphatic diols, further preferably ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, methyl propanediol, 1,6-hexanediol, One or more of 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, butyl ethyl propylene glycol, diethyl pentanediol, trimethyl pentanediol, 1,3-butanediol, 1,2-butanediol, dodecanediol, spiro glycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexane, etc., most preferably one or more of ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, methyl propanediol, 1,6-hexanediol, 1,3-propylene glycol.

[0028] In a second aspect, the present invention provides a method for preparing the polyurethane-polyamide copolymer elastomer composition, comprising the steps of:

[0029] S1: mixing a polyhydroxy compound containing active hydrogen with diisocyanate to carry out a prepolymerization reaction to obtain an isocyanate prepolymer;

[0030] S2: mixing the isocyanate prepolymer, the cyclic lactam prepolymer and the chain extender, and granulating the mixture through a twin-screw extruder to obtain polyurethane-polyamide copolymer elastomer composition particles.

[0031] In one embodiment, the prepolymerization reaction in step S1 is carried out at a temperature of 50 to 200° C. and for a time of 10 to 240 s. Specifically, the temperature may be 50° C., 70° C., 90° C., 100° C., 120° C., 140° C., 160° C., 180° C., 200° C. or a range consisting of any two thereof, and the time may be 10 s, 20 s, 40 s, 60 s, 80 s, 100 s, 120 s, 140 s, 160 s, 180 s, 200 s, 220 s, 240 s or a range consisting of any two thereof;

[0032] In a specific example, the diisocyanate and the polyol containing active hydrogen are respectively metered by metering pumps and enter the mixer, the feed temperature is controlled by a temperature control device, and then enter the reactor (such as a tubular reactor) through a booster pump, which are all conventional operations in the field. Preferably, the feed temperature of the diisocyanate is controlled by a temperature control device to be 30-70°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, etc., preferably 30-60°C; the feed temperature of the polyol containing active hydrogen is controlled by a temperature control device to be 50-150°C, for example, 50°C, 70°C, 100°C, 120°C, 150°C, etc., preferably 80-130°C.

[0033] In one embodiment, the prepolymerization reaction in step S1 may be carried out in a conventional reactor; in a specific example, a tubular reactor is preferably used;

[0034] The tubular reactor has a length of 10 to 200 cm, preferably 20 to 150 cm, and a diameter of 40 to 100 mm, preferably 50 to 80 mm. Specifically, the length may be 10 cm, 30 cm, 50 cm, 80 cm, 100 cm, 120 cm, 140 cm, 160 cm, 180 cm, 200 cm, or a range between any two thereof, and the diameter may be 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, or a range between any two thereof;

[0035] The tubular reactor has internal components to promote mixing and an external jacket for temperature control;

[0036] Preferably, in the prepolymerization reaction of step S1, the reaction residence time of the raw materials in the tubular reactor is 20 to 180 s, including but not limited to 20 s, 40 s, 60 s, 80 s, 100 s, 120 s, 140 s, 160 s, 180 s or a range consisting of any two thereof;

[0037] In one embodiment, the isocyanate prepolymer in step S1 has a viscosity of 1000 to 20000 cp at 100°C, preferably a viscosity of 1500 to 15000 cp at 100°C.

[0038] In a specific example, the isocyanate prepolymer described in step S2 is mixed with the cyclic lactam prepolymer and the chain extender by a high-speed mixer, and then enters the starting feed port of the twin-screw extruder zone 1, and then is extruded and granulated into product particles through the extruder reaction; wherein, the chain extender is metered by a metering pump, and the feed temperature is controlled by a temperature controller, which are conventional operations in the field. Preferably, the chain extender is controlled by a temperature control device to have a feed temperature of 30 to 80°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc., preferably 30 to 70°C.

[0039] According to the method of the present invention, in actual application, when the isocyanate prepolymer described in step S1 and the cyclic lactam prepolymer described above are prepared, a nitrogen purge port is usually provided at the outlet of the metering pump, and nitrogen is used to discharge the liquid in the pipeline and the tubular reactor to the extruder for extrusion after the production is completed.

[0040] In one embodiment, the twin-screw extruder in step S2, the extruder temperature is controlled to be 100-280°C, preferably 150-250°C; the extruder speed is controlled to be 100-300rpm, preferably 150-250rpm; specifically, the temperature can be 100°C, 120°C, 150°C, 170°C, 200°C, 220°C, 250°C, 280°C or a range consisting of any two thereof, and the speed can be 100rpm, 150rpm, 200rpm, 250rpm, 300rpm or a range consisting of any two thereof;

[0041] The twin-screw extruder has an aspect ratio of 40 to 120, including but not limited to 40, 60, 80, 100, 120 or a range between any two thereof, preferably 45 to 95.

[0042] In a specific example, a catalyst is further added to the raw material in step S2, and the catalyst is added at a high-speed mixer, mixed with the isocyanate prepolymer, the cyclic lactam prepolymer, and the chain extender through the high-speed mixer at the same time, and then enters the twin-screw extruder;

[0043] The catalyst is one or more of an organic tin catalyst, an organic bismuth catalyst, a titanate catalyst, and a zirconate catalyst, preferably one or more of stannous octoate, dibutyltin dilaurate, bismuth isooctanoate, bismuth neodecanoate, zirconium n-propoxide, zirconium n-butoxide, tetrabutyl zirconate, tetraethyl titanate, and tetrabutyl titanate;

[0044] Preferably, the catalyst addition amount is 10 to 2000 ppm, based on the total mass of the raw materials in step S2.

[0045] In a third aspect, the present invention provides applications of the polyurethane-polyamide copolymer elastomer composition.

[0046] The polyurethane-polyamide copolymer elastomer composition can be used in consumer goods, industrial products and other industries, and is particularly suitable for preparing foamed material products.

[0047] Specifically, the composition can be foamed in various conventional forms in the field, for example:

[0048] The composition is subjected to injection molding, extrusion, blow molding, casting, calendering and other processes to obtain a composition product of a certain state and shape. The composition product is saturated in a supercritical physical foaming agent, and then the pressure is reduced or the temperature is increased to obtain a foamed product of the composition;

[0049] The composition is blended and granulated by an extruder, a kneader and the like, and then saturated with a supercritical physical foaming agent in a foaming kettle, and then the foamed beads of the composition are obtained by reducing the pressure or increasing the temperature;

[0050] The composition is passed through an extrusion device, the composition is mixed with a supercritical physical foaming agent in the extrusion device, and is continuously extruded to obtain foamed beads of the composition.

[0051] The supercritical physical foaming agent is one or more of carbon dioxide, nitrogen, and alkanes in a supercritical state, preferably one or more of carbon dioxide and nitrogen in a supercritical state.

[0052] The composition foamed products and foamed beads prepared from the above-mentioned polyurethane-polyamide copolymer elastomer composition can be widely used in shoe midsoles, insoles, yoga mats, helmet shockproofs, bicycle seats, tires, decorations, toys, shock-absorbing, noise-reducing and high-rebound products, etc.

[0053] By adopting the above technical solution, the present invention has the following beneficial effects:

[0054] The foaming material prepared by the polyurethane-polyamide copolymer elastomer composition provided by the present invention can solve the compatibility problem between TPU and PEBA, and improve the performance of the polyurethane-polyamide copolymer elastomer, wherein the ball rebound is ≥77%, the layered tear strength is ≥2.5N / cm, the shrinkage is ≤0.8%, and the compression permanent deformation is ≤20%. DETAILED DESCRIPTION

[0055] The following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the rights claimed by the present invention.

[0056] In the embodiments and comparative examples of the present invention, the sources of the main raw materials used are shown in Table 1 below. Other raw materials and reagents, unless otherwise specified, were purchased from commercial sources:

[0057] Table 1 Main raw material information

[0058]

[0059]

[0060] In each embodiment and comparative example of the present invention, the main equipment information used is shown in Table 2 below:

[0061] Table 2 Equipment manufacturers and models

[0062] serial number Equipment Type Equipment manufacturer and model Evaluation and use 1 Extruder Nanjing Ruiya Extruder Manufacturing Co., Ltd. Extrusion 2 Tensile testing machine SHIMADZU AGX-X Delamination tear strength 3 Falling ball rebound tester GOTECH GT-7042-RE Ball Rebound 4 Compression Deformation Tester GOTECH GT-7049 Compression set 5 Acid value Chengyang glass burette Acid value 6 Hydroxyl value analyzer Thermo Fisher Antarisll Hydroxyl

[0063] The specific preparation process of the polyurethane-polyamide copolymer elastomer composition that can be used for foaming in the following examples is as follows:

[0064] In a nitrogen environment, cyclic lactam, deionized water and organic dibasic acid are added to a reactor, and stirred for reaction for 4 to 10 hours at a reaction temperature of 200 to 270° C. and a pressure of 20 to 30 bar. After vacuuming to remove the water in the reactor, nitrogen is then filled to restore the reactor to normal pressure to obtain a polycyclic lactam prepolymer. The molecular weight of the polycyclic lactam prepolymer is 200 to 2000.

[0065] The polyhydroxy compound containing active hydrogen and the diisocyanate are respectively metered by metering pumps and enter a mixer. After the temperature is controlled by a temperature control device, they enter a tubular reactor through a booster pump. The temperature is controlled at 50-200° C. for prepolymerization reaction. The residence time is controlled at 20-180 seconds to prepare an isocyanate prepolymer.

[0066] The chain extender is mixed with the isocyanate prepolymer, the polycyclic lactam prepolymer and the catalyst through a high-speed mixer, and then enters the starting feed port of the twin-screw extruder zone 1, and then is extruded and granulated into product particles through the extruder reaction.

[0067] The chain extender is metered by a metering pump and the temperature is controlled by a temperature controller. The metering pumps for isocyanate prepolymer and polylactam prepolymer are equipped with a nitrogen purge port at the outlet. After the production is completed, nitrogen is used to discharge the liquid in the pipeline and tubular reactor to the extruder for extrusion.

[0068] The feed temperature of diisocyanate is controlled at 30-60°C; the feed temperature of polyhydroxy compound containing active hydrogen is controlled at 80-130°C; and the feed temperature of chain extender is controlled at 30-70°C.

[0069] The tubular reactor has a length of 10 to 200 cm and a diameter of 40 to 100 mm, is provided with internal components to promote mixing, and is equipped with a jacket for temperature control.

[0070] The reactor is a jacketed stirred reactor with a heat medium jacket on the outside, and the stirring propeller is a four-blade inclined propeller with a length-to-diameter ratio of 2.5.

[0071] The length-to-diameter ratio of the twin-screw extruder is 75; the temperature of the extruder is controlled at 100-280° C.; and the speed of the extruder is controlled at 100-300 rpm.

[0072] Preparation Example 1

[0073] Polylactam prepolymer sample 1-sample 3

[0074] Preparation of sample 1: Under a nitrogen environment, 1000 g of lauryl lactam, 200 g of deionized water, and 1000 g of adipic acid were added into a reactor, and the mixture was stirred for 4 hours at a reaction temperature of 270°C and a pressure of 30 bar to obtain a polycyclic lactam prepolymer with a molecular weight of 2000, which was numbered as sample 1.

[0075] Preparation of sample 2: Under a nitrogen environment, 1000 g of lauryl lactam, 220 g of deionized water, and 500 g of sebacic acid were added to a reactor, and the mixture was stirred and reacted for 8 hours at a reaction temperature of 240°C and a pressure of 25 bar to obtain a polycyclic lactam prepolymer with a molecular weight of 1000, numbered as sample 2.

[0076] Preparation of sample 3: Under a nitrogen environment, 1000 g of lauryl lactam, 100 g of deionized water, and 2000 g of succinic acid were added to a reactor, and the mixture was stirred for 10 hours at a reaction temperature of 200°C and a pressure of 20 bar to obtain a polycyclic lactam prepolymer with a molecular weight of 200, numbered as sample 3.

[0077] Example 1

[0078] A polyurethane-polyamide copolymer elastomer composition is prepared by the production process of the above embodiment and according to the raw material selection and dosage of Example 1 in Table 3 to obtain a corresponding composition. The specific operating conditions are as follows:

[0079] The bifunctional compound containing active hydrogen and diisocyanate enter into a tubular reactor with a length of 150 cm, a diameter of 80 mm, a temperature control of 160° C., and a reaction residence time of 180 s to obtain an isocyanate prepolymer.

[0080] The chain extender, isocyanate prepolymer and polycyclic lactam prepolymer are mixed in a high-speed mixer, and 2000ppm of zirconium n-butoxide catalyst is added at the same time. The mixture is then extruded and granulated through a twin-screw extruder. The feed inlet temperature of zone 1 of the extruder is 150°C, the extrusion temperature of zones 2 to 14 is controlled at 200-240°C, and the screw speed of the extruder is 250rpm.

[0081] Example 2

[0082] A polyurethane-polyamide copolymer elastomer composition is prepared by the production process of the above embodiment and according to the raw material selection and dosage of Example 2 in Table 3 to obtain a corresponding composition. The specific operating conditions are as follows:

[0083] The bifunctional compound containing active hydrogen and diisocyanate enter into a tubular reactor with a length of 100 cm and a diameter of 70 mm. The temperature is controlled at 130° C. and the reaction residence time is 100 s to obtain an isocyanate prepolymer.

[0084] The chain extender, isocyanate prepolymer and polycyclic lactam prepolymer are mixed in a high-speed mixer, and 800 ppm of bismuth neodecanoate as a catalyst is added. The mixture is then extruded and granulated through a twin-screw extruder. The feed inlet temperature of zone 1 of the extruder is 140° C., the extrusion temperature of zones 2 to 14 is controlled at 190 to 240° C., and the screw speed of the extruder is 200 rpm.

[0085] Example 3

[0086] A polyurethane-polyamide copolymer elastomer composition is prepared by the production process of the above embodiment and according to the raw material selection and dosage of Example 3 in Table 3 to obtain a corresponding composition. The specific operating conditions are as follows:

[0087] The bifunctional compound containing active hydrogen and diisocyanate enter into a tubular reactor with a length of 20 cm and a diameter of 50 mm. The temperature is controlled at 80° C. and the reaction residence time is 20 s to obtain an isocyanate prepolymer.

[0088] The chain extender, isocyanate prepolymer and polycyclic lactam prepolymer are mixed in a high-speed mixer, and 10 ppm of stannous octoate catalyst is added at the same time. The mixture is then extruded and granulated through a twin-screw extruder. The feed inlet temperature of zone 1 of the extruder is 120°C, the extrusion temperature of zones 2 to 14 is controlled at 190 to 230°C, and the screw speed of the extruder is 200 rpm.

[0089] Examples 4-8

[0090] The polyurethane-polyamide copolymer elastomer composition is prepared by the production process of the above embodiment, specifically using the same operating conditions as Example 1 and according to the raw material composition of Examples 4-8 in Table 3 to obtain the corresponding composition.

[0091] Comparative Examples 1-6

[0092] The polyurethane-polyamide copolymer elastomer composition is prepared by the production process of the above embodiment, specifically using the same operating conditions as Example 1, and according to the raw material compositions of Comparative Examples 1-6 in Table 3 to obtain the corresponding composition.

[0093] Comparative Example 7

[0094] The polyurethane-polyamide copolymer elastomer composition is produced by the production process of the above embodiment, specifically using the same operating conditions and raw material composition as Example 1, with the only difference being that the component D cyclic lactam prepolymer sample 1 is replaced with lauryl lactam for comparison to prepare the corresponding composition.

[0095] Table 3 Raw material composition formula ratio of the polyurethane-polyamide copolymer elastomer composition of the embodiment and the comparative example (mass ratio wt%)

[0096]

[0097] The polyurethane-polyamide copolymer elastomer composition prepared in the embodiment and the comparative example was extruded and granulated by an extruder, and then placed in a foaming kettle (140-150° C.) and saturated with supercritical physical foaming agents carbon dioxide and nitrogen (pressure 20-35 MPa, gas ratio 1:3) for a certain period of time (6-8 hours), and then the pressure was reduced to normal pressure to obtain foamed beads of the composition. Foamed products and samples were prepared by steam molding and tested. The results are shown in Table 5.

[0098] Table 4 Performance evaluation

[0099]

[0100]

[0101] Note: Compression set GB / T 6669-2008C method 50℃, compression 50%, 6h, recovery 24h.

Claims

1. A polyurethane-polyamide copolymer elastomer composition, characterized in that: Prepared from raw material components including the following mass percentages: A) diisocyanate, 5 to 50 wt%, preferably 5 to 35 wt%; B) a polyhydroxy compound containing active hydrogen, 30 to 80 wt%, preferably 40 to 75 wt%; C) chain extender, 5 to 25 wt%, preferably 5 to 20 wt%; D) Cyclic lactam prepolymer, 1 to 30 wt%, preferably 3 to 25 wt%.

2. The polyurethane-polyamide copolymer elastomer composition according to claim 1, characterized in that: The polycyclic lactam prepolymer described in component D) is prepared by reacting a cyclic lactam with an organic dibasic acid; Preferably, the cyclic lactam is selected from one or more of caprolactam, undecanoic acid lactam and laurolactam, preferably one or more of undecanoic acid lactam and laurolactam; Preferably, the organic dibasic acid is selected from one or more of aliphatic dibasic acids and aromatic dibasic acids, preferably one or more of aliphatic dibasic acids, more preferably one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, further preferably one or more of succinic acid, adipic acid, and sebacic acid; Preferably, the mass ratio of the cyclic lactam to the organic dibasic acid is 1:0.5-2; Preferably, the reaction is carried out at a temperature of 200 to 270°C, a pressure of 20 to 30 bar, and a time of 4 to 10 hours; Preferably, the reaction is carried out in the presence of water, and the amount of water used is 3-25% of the total mass of the cyclic lactam and the organic dibasic acid, preferably 10-15%; Preferably, the reaction is carried out under protective gas conditions, and the protective gas is preferably nitrogen; Preferably, the reaction is carried out in a reactor, which is a jacketed stirred reactor; the stirring paddle of the reactor is preferably a three-blade, four-blade or five-blade pitched paddle with a length-to-diameter ratio of 1.5-2.5; and / or The polycyclic lactam prepolymer described in component D) has a molecular weight of 200 to 2000.

3. The polyurethane-polyamide copolymer elastomer composition according to claim 1, characterized in that: The diisocyanate described in component A) is selected from one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), pentamethylene diisocyanate (PDI), naphthalene diisocyanate (NDI), tetramethylene meta-xylylene diisocyanate (TMXDI), p-phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI) and dimethyl diphenyl diisocyanate (TODI), preferably one or more of TDI, MDI, HMDI, HDI and IPDI.

4. The polyurethane-polyamide copolymer elastomer composition according to claim 1, characterized in that: The polyhydroxy compound containing active hydrogen described in component B) has a functionality of 2 or more, preferably a polyol with a functionality of 2, selected from one or more of ester-containing polyols, ether-containing polyols, silicon-containing polyols, fluorine-containing polyols, olefin-containing polyols, and urea-containing polyols, preferably one or more of polyoxypropylene polyols, polyurea polyols, polytetrahydrofuran polyols, copolyether polyols, aromatic polyether polyols, polyacrylate polyols, polyolefin polyols, alkyd polyester polyols, polycaprolactone polyols, polycarbonate polyols, hydroxyl-terminated polydimethylsiloxanes, hydroxyl-terminated polyether-modified silicone oils, hydroxyl-terminated fluorine-containing polyether polyols, etc., more preferably one or more of polytetrahydrofuran polyols, alkyd polyester polyols, polycaprolactone polyols, and polycarbonate polyols; and / or The polyhydroxy compound containing active hydrogen has a hydroxyl value of 26 to 224 mgKOH / g, preferably 30 to 220 mgKOH / g; and / or The acid value of the polyhydroxy compound containing active hydrogen is less than 1.5 mgKOH / g, preferably less than 1.0 mgKOH / g.

5. The polyurethane-polyamide copolymer elastomer composition according to claim 1, characterized in that: The chain extender described in component C) is selected from one or more of aliphatic diols, aromatic diols, alcohol amine diols, aliphatic diamines, aromatic diamines, etc., preferably one or more of aliphatic diols, aromatic diols, aliphatic diamines, more preferably one or more of aliphatic diols, further preferably ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, methyl propanediol, 1,6-hexanediol, 1,3- One or more of propylene glycol, dipropylene glycol, tripropylene glycol, butyl ethyl propylene glycol, diethyl pentanediol, trimethyl pentanediol, 1,3-butanediol, 1,2-butanediol, dodecanediol, spiro glycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexane, and most preferably one or more of ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, methyl propanediol, 1,6-hexanediol, and 1,3-propanediol.

6. A method for preparing the polyurethane-polyamide copolymer elastomer composition according to any one of claims 1 to 5, characterized in that the steps include: S1: mixing a polyhydroxy compound containing active hydrogen with diisocyanate to carry out a prepolymerization reaction to obtain an isocyanate prepolymer; S2: mixing the isocyanate prepolymer, the cyclic lactam prepolymer and the chain extender, and granulating the mixture through a twin-screw extruder to obtain polyurethane-polyamide copolymer elastomer composition particles.

7. The preparation method according to claim 6, characterized in that: The prepolymerization reaction in step S1 is carried out at a temperature of 50 to 200° C. and a time of 10 to 240 seconds; Preferably, the feed temperature of the diisocyanate is controlled to be 30-70°C, preferably 30-60°C; the feed temperature of the polyhydroxy compound containing active hydrogen is controlled to be 50-150°C, preferably 80-130°C; and / or The prepolymerization reaction in step S1 adopts a tubular reactor; Preferably, the tubular reactor has a length of 10 to 200 cm, preferably 20 to 150 cm, and a diameter of 40 to 100 mm, preferably 50 to 80 mm; Preferably, the tubular reactor has internal components to promote mixing and an external jacket for temperature control; Preferably, in the prepolymerization reaction described in step S1, the reaction residence time of the raw materials in the tubular reactor is 20 to 180 seconds.

8. The preparation method according to claim 6, characterized in that: The chain extender in step S2 controls the feed temperature to be 30-80°C, preferably 30-70°C; and / or The twin-screw extruder in step S2, the extruder temperature is controlled to be 100-280°C, preferably 150-250°C; the extruder speed is controlled to be 100-300rpm, preferably 150-250rpm; Preferably, the twin-screw extruder has an aspect ratio of 40 to 120, preferably 45 to 95.

9. The preparation method according to claim 6, characterized in that: A catalyst is also added to the raw material in step S2; Preferably, the catalyst is one or more of an organotin catalyst, an organobismuth catalyst, a titanate catalyst, and a zirconate catalyst, more preferably one or more of stannous octoate, dibutyltin dilaurate, bismuth isooctanoate, bismuth neodecanoate, zirconium n-propoxide, zirconium n-butoxide, tetrabutyl zirconate, tetraethyl titanate, and tetrabutyl titanate; Preferably, the catalyst addition amount is 10 to 2000 ppm, based on the total mass of the raw materials in step S2.

10. Use of the polyurethane-polyamide copolymer elastomer composition according to any one of claims 1 to 5 or the polyurethane-polyamide copolymer elastomer composition prepared by the method according to any one of claims 6 to 9 in the fields of consumer goods and industrial products, especially for preparing foamed material products.

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