CN113278127A - Elastic material based on polyurethane modification and preparation method thereof - Google Patents
Elastic material based on polyurethane modification and preparation method thereof Download PDFInfo
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- CN113278127A CN113278127A CN202110661654.9A CN202110661654A CN113278127A CN 113278127 A CN113278127 A CN 113278127A CN 202110661654 A CN202110661654 A CN 202110661654A CN 113278127 A CN113278127 A CN 113278127A
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Abstract
The invention relates to an elastic material based on polyurethane modification and a preparation method thereof, wherein high molecular polyester diol and an adhesion agent are melted and vacuum-dehydrated, acrylonitrile is added for capacity sharing, in the stirring process, the high molecular polyester diol and the acrylonitrile form a tightly interwoven structure under the action of the adhesion agent, the high molecular polyester diol and diisocyanate are mixed to be prepolymerized under the catalysis of tert-butyl peroxy 3,5, 5-trimethyl hexyl ester to obtain a mixture in which a prepolymer and the acrylonitrile are tightly embedded, low molecular diol, polybutadiene rubber and styrene are added into the mixture, the prepolymer is further subjected to chain extension reaction, the acrylonitrile, the polybutadiene rubber and the styrene are polymerized under the catalysis of the tert-butyl peroxy 3,5, 5-trimethyl hexyl ester to obtain a copolymer, and the prepolymer and the copolymer are compounded on a micro scale to obtain the elastic material based on polyurethane modification, the material overcomes the defects of easy fracture and uneven modification of the traditional two plastics by direct mixing modification, and effectively improves the performance of the elastic material.
Description
Technical Field
The invention relates to the field of elastic material manufacturing, in particular to a preparation method of an elastic material based on polyurethane modification.
Background
Polyurethane (TPU) is a thermoplastic polyurethane elastomer, is a high polymer material between rubber and plastic, has excellent characteristics of high tension, high tensile force, toughness and aging resistance, and is a mature environment-friendly material. At present, polyurethane is widely applied to the aspects of medical sanitation, electronic appliances, industry, sports and the like, has the characteristics of high strength, good toughness, wear resistance, cold resistance, oil resistance, water resistance, aging resistance, weather resistance and the like which are incomparable with other plastic materials, and simultaneously has a plurality of excellent functions of high waterproofness, moisture permeability, wind resistance, cold resistance, antibiosis, mildew resistance, warm keeping, ultraviolet resistance, energy release and the like. However, when the material is applied to daily necessities, sports goods, toys and decorative materials, the grade rigidity and the strength of the material are not enough, and plastic modification is often needed.
In order to make the elastic material have the elasticity of polyurethane and the rigidity of ABS resin, it is a conventional practice to directly mix and melt TPU and ABS. The modified polyurethane material for the special-shaped harbour sheet disclosed in patent publication No. CN105295355B is prepared by mixing and stirring 20-90 parts of polyurethane powder, 10-50 parts of engineering plastic, 0-20 parts of soft modified material and 0-10 parts of filler, wherein the polyurethane powder and the engineering plastic are prepared firstly and then the polyurethane powder is mixed with the rest components during preparation, the preparation process is complicated, and the phenomenon of uneven mixing is easy to occur when the polyurethane powder is mixed in a powder form, so that the modified material obtained at the later stage has uneven performance and is easy to break, and the soft modified material and the filler are added to ensure that the modified material has good elasticity and stiffness.
Disclosure of Invention
The invention provides an elastic material based on polyurethane modification and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
an elastic material based on polyurethane modification is prepared by the following components in percentage by weight:
the elastic material based on polyurethane modification has the advantages of good strength, good wear resistance and good elasticity, makes up the rigidity defect of polyurethane, enhances the toughness and the rigidity, has excellent hardness, good performance stability and good comprehensive performance, and can be widely applied to the fields of daily necessities, sports goods, toys, decorative materials, machinery, electricity, vehicles and the like.
Preferably, the molecular weight of the high molecular polyester glycol is 1800g/mol, preferably 1300 g/mol and 1500g/mol, and one or at least two of polyethylene glycol, polylactone glycol, succinic acid polyester glycol, tetraphenyl ethylene glycol, polycarbonate glycol, polyethylene adipate glycol, polyether glycol, polytetramethylene ether glycol and polypropylene glycol can be selected for use. The high molecular polyester diol can be prepared by dehydration polycondensation of polybasic acid and polybasic ester, and can also be obtained by purchasing ready-made products on the market.
Preferably, the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, polyhexamethylene diisocyanate and isophorone diisocyanate, and can be used for prepolymerization reaction with high-molecular polyester diol. The diphenylmethane diisocyanate can be at least one isomer selected from 4, 4-diphenylmethane diisocyanate, 2-diphenylmethane diisocyanate and the like; the toluene diisocyanate can be at least one of 2, 4-toluene diisocyanate (2,4-TDI) and 2, 6-toluene diisocyanate (2,6-TDI), and preferably 2,4-TDI and 2,6-TDI are used in a ratio of 65% to 80%: 20 to 35 percent of the composition.
Preferably, the low molecular weight diol is one or more of 1, 4-butanediol, ethylene glycol, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 2-propanediol, and 1, 5-pentanediol. The low molecular diol is used as a chain extender and a dispersing auxiliary agent, so that the reaction is stable during the polymerization chemical reaction of each component, the ordered arrangement of hard chain segments and soft chain segments is easy to form, macromolecules have larger interaction and better microphase separation degree, the crosslinking reaction can be further improved, and the elastic material with ultrahigh molecular weight can be obtained.
Preferably, the adhesive is one of diethyl butanol, polymethyl methacrylate, chlorinated polyethylene, alpha-methylstyrene-styrene-acrylonitrile copolymer, acrylate polymer and maleic anhydride grafted acrylonitrile-polybutadiene rubber-styrene terpolymer. The function of the adhesion agent in the system is to improve the compatibility among the components, improve the adhesive force of the interface, improve the impact property without influencing the properties such as tensile strength, flexural modulus and the like, and reduce the elongation at break.
A preparation method of an elastic material based on polyurethane modification comprises the following steps:
step 1: melting high-molecular polyester diol and an adhesive in a reaction tank A, heating and vacuumizing, introducing nitrogen and cooling to 30-70 ℃ when the water content is less than 0.05% by vacuum dehydration, adding acrylonitrile in the reaction tank A under the protection of the nitrogen, and stirring uniformly;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, stirring for 0.5-2h, and introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the low molecular weight diol, the polybutadiene rubber and the styrene in a C reaction tank, stirring for 0.5-1h in a vacuum atmosphere, wherein the temperature in the C reaction tank is 30-55 ℃, and dehydrating in vacuum until the water content is less than 0.05%, and taking nitrogen as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 0.5-1h, transferring the components in the reaction tank C to the casting head, stirring uniformly at a high speed, inputting the mixture into a double-screw reaction extruder for mixing and polymerization chemical reaction, mixing for 3-30min, extruding, cooling and granulating to obtain the elastic material.
Preferably, through the vacuum dehydration treatment in the steps 1 to 3, the water content of the components in the reaction tank A, the reaction tank B and the reaction tank C is lower than 0.05 percent, the diisocyanate can be uniformly connected to both ends of the high molecular polyester diol, the movement space of the oligomer chain segment can be reduced, and the free diisocyanate can be prevented from reacting with the low molecular diol when the low molecular diol is subjected to chain extension, so that the viscosity at the initial stage of the reaction is sharply increased, and the processability of the elastic material is poor.
Preferably, in the step 1, the initial temperature-raising rate of the reaction tank A is 10 ℃/min, when the temperature reaches 80-90 ℃, the temperature is maintained for 0.5-1h, then the temperature is raised at 2 ℃/min, when the temperature reaches 112-160 ℃, the temperature is maintained for 1-2h, the vacuum degree is 150Pa, and the stirring rate is 100-300 r/min.
Preferably, in the step 2, the initial heating rate of the B reaction tank is 10 ℃/min, when the temperature reaches 60-70 ℃, the temperature is kept for 0.5-1h, the vacuum degree is 150Pa, and the stirring rate is 300 r/min.
Preferably, in the step 1, the mass ratio of the high molecular polyester glycol to the acrylonitrile is 12-8: 2-6.
Preferably, in the step 3, the mass ratio of the low molecular diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 15-7: 2-20; the mass ratio of polybutadiene rubber to styrene is 1-3: 3-7.
Preferably, in the step 4, the high-speed stirring rate is 300-500 r/min.
Preferably, in the step 4, the initial mixing temperature of the mixture fed into the twin-screw reaction extruder is 50-80 ℃, the mixture is heated to 170-180 ℃ at a speed of 15 ℃/min after 3-10min of mixing, and the mixing time is 5-27 min.
The preparation method of the invention is simple and fast to collect, firstly the high molecular polyester diol and the adhesion agent are melted and vacuum dehydrated, acrylonitrile is added for compatibility, in the stirring process, the high molecular polyester diol and the acrylonitrile form a tightly interweaving structure under the action of the adhesion agent, the high molecular polyester diol and the diisocyanate are mixed to be prepolymerized under the catalysis of tert-butyl peroxy 3,5, 5-trimethyl hexyl ester to obtain a mixture in which a prepolymer and the acrylonitrile are tightly embedded, low molecular diol, polybutadiene rubber and styrene are added into the mixture, the prepolymer is further subjected to chain extension reaction, the acrylonitrile, the polybutadiene rubber and the styrene are polymerized under the catalysis of the tert-butyl peroxy 3,5, 5-trimethyl hexyl ester to obtain a copolymer, the prepolymer and the copolymer are compounded on a microscopic scale, and the defects of easy fracture and uneven modification of the traditional two plastics by direct mixing modification are overcome, effectively improves the performance of the elastic material.
The invention has the beneficial effects that:
the polyurethane modified elastic material and the preparation method thereof provided by the invention are superior to other currently used polyurethane and ABS modified materials in impact strength and comprehensive performance, and have wide application prospects and low production cost in the fields of daily necessities, sports goods, toys, decorative materials, machinery, electricity, vehicles and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The raw materials and methods used in the examples of the present invention are those conventionally available in the art and those conventionally used, and the equipment used is equipment conventional in the art, and the specific types are not further limited, unless otherwise specified.
Example 1
An elastic material based on polyurethane modification is prepared by the following components in percentage by weight:
wherein the high-molecular polyester diol is prepared by mixing polyethylene glycol adipate and polyether diol in a mass ratio of 3: 2; the adhesion agent is diethyl butoxide; the diisocyanate is formed by mixing 4, 4-diphenylmethane diisocyanate, 2, 4-diphenylmethane diisocyanate and 2, 2-diphenylmethane diisocyanate in a mass ratio of 1:1: 1; the low molecular weight diol is 1,4 butanediol.
A preparation method of an elastic material based on polyurethane modification comprises the following steps:
step 1: melting high-molecular polyester glycol and an adhesion agent in a reaction tank A, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 80 ℃, keeping the temperature for 1h, then heating at 2 ℃/min, when the temperature reaches 135 ℃, keeping the temperature for 1.2h, the vacuum degree is 150Pa, dehydrating in vacuum until the water content is less than 0.05%, introducing nitrogen and cooling to 50 ℃, adding acrylonitrile into the reaction tank A under the protection of the nitrogen, and stirring uniformly at the stirring rate of 120 r/min;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 65 ℃, preserving the heat for 0.6h, the vacuum degree is 150Pa, the stirring rate is 100r/min, and when vacuum dehydration is carried out until the water content is less than 0.05%, introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the materials in a C reaction tank, stirring the materials for 0.8h in a vacuum atmosphere, controlling the temperature in the C reaction tank to be 40 ℃, dehydrating the materials in the vacuum atmosphere until the water content is less than 0.05 percent, and using nitrogen as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 0.8h, transferring the components in the reaction tank C to the casting head, uniformly stirring at a high speed of 500r/min, inputting the components into a double-screw reaction extruder, carrying out mixing and polymerization chemical reaction, inputting the components into the double-screw reaction extruder, carrying out mixing at an initial mixing temperature of 65 ℃ for 5min, heating to 175 ℃ at a speed of 15 ℃/min, mixing for 15min, cooling, and granulating to obtain the elastic material.
Wherein in the step 1, the mass ratio of the high molecular polyester glycol to the acrylonitrile is 8: 2; in the step 3, the mass ratio of the low molecular weight diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 13: 9; the mass ratio of polybutadiene rubber to styrene is 3: 6.
example 2
An elastic material based on polyurethane modification is prepared by the following components in percentage by weight:
wherein the high molecular polyester diol is prepared by mixing polycarbonate diol, poly epsilon-caprolactone diol and tetraphenyl ethylene glycol in a mass ratio of 1:2: 1; the adhesion agent is maleic anhydride grafted acrylonitrile-polybutadiene rubber-styrene terpolymer; the diisocyanate is formed by mixing isophorone diisocyanate and 2, 4-diphenylmethane diisocyanate in a mass ratio of 1: 1.5; the low molecular diol is formed by mixing neopentyl glycol and 1, 2-propylene glycol according to the mass ratio of 1: 3.
A preparation method of an elastic material based on polyurethane modification comprises the following steps:
step 1: melting high-molecular polyester glycol and an adhesion agent in a reaction tank A, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 85 ℃, keeping the temperature for 1h, then heating at 2 ℃/min, when the temperature reaches 121 ℃, keeping the temperature for 1h, the vacuum degree is 150Pa, dehydrating in vacuum until the water content is less than 0.05%, introducing nitrogen, cooling to 40 ℃, adding acrylonitrile into the reaction tank A under the protection of the nitrogen, and stirring uniformly at the stirring rate of 110 r/min;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 70 ℃, preserving the heat for 0.8h, the vacuum degree is 150Pa, the stirring rate is 100r/min, and when vacuum dehydration is carried out until the water content is less than 0.05%, introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the low molecular weight diol, the polybutadiene rubber and the styrene in a C reaction tank, stirring for 1h in a vacuum atmosphere, keeping the temperature in the C reaction tank at 45 ℃, and dehydrating in vacuum until the water content is less than 0.05 percent, wherein nitrogen is used as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 0.6h, transferring the components in the reaction tank C to the casting head, uniformly stirring at a high speed of 450r/min, inputting the components into a double-screw reaction extruder, carrying out mixing and polymerization chemical reaction, inputting the components into the double-screw reaction extruder, carrying out mixing at an initial mixing temperature of 80 ℃, carrying out mixing for 4min, heating to 180 ℃ at a speed of 15 ℃/min, mixing for 20min, cooling, and granulating to obtain the elastic material.
In the step 1, the mass ratio of the high-molecular polyester glycol to the acrylonitrile is 12: 2; in the step 3, the mass ratio of the low molecular weight diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 14: 7; the mass ratio of polybutadiene rubber to styrene is 2: 5.
example 3
An elastic material based on polyurethane modification is prepared by the following components in percentage by weight:
wherein the high molecular polyester glycol is prepared by mixing polytetramethylene ether glycol and polypropylene glycol in a ratio of 3: 2: the adhesive is prepared by mixing polymethyl methacrylate, chlorinated polyethylene and acrylate polymers in a ratio of 2:1: 1; diisocyanate was prepared as a mixture of 2,4-TDI and 2,6-TDI in 65%: 35 percent of the components are compounded; the low molecular weight diol is 1,3 propanediol, 1,2 butanediol and 1,3 butanediol, and the mass ratio of 1:2: 2.
A preparation method of an elastic material based on polyurethane modification comprises the following steps:
step 1: melting high-molecular polyester glycol and an adhesion agent in a reaction tank A, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 81 ℃, keeping the temperature for 1h, then heating at 2 ℃/min, when the temperature reaches 130 ℃, keeping the temperature for 1h, the vacuum degree is 150Pa, when vacuum dehydration is carried out until the water content is less than 0.05 percent, introducing nitrogen and cooling to 50 ℃, under the protection of the nitrogen, adding acrylonitrile into the reaction tank A, and stirring uniformly, wherein the stirring rate is 100 r/min;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 60 ℃, preserving the heat for 1h, the vacuum degree is 150Pa, the stirring rate is 100r/min, and when vacuum dehydration is carried out until the water content is less than 0.05%, introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the low molecular weight diol, the polybutadiene rubber and the styrene in a C reaction tank, stirring for 1h in a vacuum atmosphere, keeping the temperature in the C reaction tank at 45 ℃, and dehydrating in vacuum until the water content is less than 0.05 percent, wherein nitrogen is used as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 1h, transferring the components in the reaction tank C to the casting head, uniformly stirring at a high speed of 480r/min, inputting the components into a double-screw reaction extruder, carrying out mixing and polymerization chemical reaction, inputting the components into the double-screw reaction extruder, carrying out mixing at an initial mixing temperature of 70 ℃, after mixing for 8min, heating to 172 ℃ at a speed of 15 ℃/min, mixing for 22min, cooling, and granulating to obtain the elastic material.
In the step 1, the mass ratio of the high-molecular polyester glycol to the acrylonitrile is 12: 6; in the step 3, the mass ratio of the low molecular weight diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 15: 15; the mass ratio of polybutadiene rubber to styrene is 3: 6.
example 4
An elastic material based on polyurethane modification is prepared by the following components in percentage by weight:
wherein the high molecular polyester glycol is prepared by mixing polyether glycol and polypropylene glycol in a ratio of 1: the adhesion agent is formed by mixing diethyl butanol and alpha-methylstyrene-styrene-acrylonitrile copolymer in a ratio of 2:1: 1; the diisocyanate is polyhexamethylene diisocyanate; the low molecular diol is formed by mixing 1,4 butanediol and 1,5 pentanediol according to the mass ratio of 3: 2.
A preparation method of an elastic material based on polyurethane modification comprises the following steps:
step 1: melting high-molecular polyester glycol and an adhesion agent in a reaction tank A, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 83 ℃, keeping the temperature for 1h, then heating at 2 ℃/min, when the temperature reaches 141 ℃, keeping the temperature for 1h, the vacuum degree is 150Pa, when vacuum dehydration is carried out until the water content is less than 0.05%, introducing nitrogen and cooling to 50 ℃, under the protection of the nitrogen, adding acrylonitrile into the reaction tank A, and stirring uniformly, wherein the stirring rate is 100 r/min;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, wherein the initial heating rate is 10 ℃/min, when the temperature reaches 60 ℃, preserving the heat for 1h, the vacuum degree is 150Pa, the stirring rate is 100r/min, and when vacuum dehydration is carried out until the water content is less than 0.05%, introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the low molecular weight diol, the polybutadiene rubber and the styrene in a C reaction tank, stirring for 1h in a vacuum atmosphere, keeping the temperature in the C reaction tank at 45 ℃, and dehydrating in vacuum until the water content is less than 0.05 percent, wherein nitrogen is used as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 1h, transferring the components in the reaction tank C to the casting head, uniformly stirring at a high speed of 480r/min, inputting the components into a double-screw reaction extruder, carrying out mixing and polymerization chemical reaction, inputting the components into the double-screw reaction extruder, carrying out mixing at an initial mixing temperature of 70 ℃, after mixing for 6min, heating to 180 ℃ at a speed of 15 ℃/min, mixing for 20min, cooling, and granulating to obtain the elastic material.
Wherein in the step 1, the mass ratio of the high molecular polyester glycol to the acrylonitrile is 8: 3; in the step 3, the mass ratio of the low molecular weight diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 12: 14; the mass ratio of polybutadiene rubber to styrene is 2: 12.
comparative example 1
A polyurethane modified material is composed of the following raw materials in parts by weight:
70 parts of polyurethane powder, 20 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of soft modified material and 5 parts of filler; wherein the soft modified material is a mixture of ethylene-vinyl acetate copolymer, polyvinyl chloride and polyethylene-butylene copolymer in a weight ratio of 1:0.5: 1.5; the filler is a mixture of calcium carbonate, titanium dioxide and zinc stearate in a weight ratio of 0.5:1.8: 1.
The preparation method comprises the following steps:
(1) grinding polyurethane powder to a particle size of 30 meshes, and respectively grinding the engineering plastic and the soft modified material to a particle size of 30 meshes for later use;
(2) weighing the filler, the ground polyurethane powder, the engineering plastic and the soft modified material according to the parts by weight, mixing and stirring uniformly.
Comparative example 2
A thermoplastic polyurethane composition is composed of the following raw materials in parts by weight:
65 parts of thermoplastic polyurethane, 5 parts of polysiloxane, 5 parts of polyformaldehyde polymer and 25 parts of acrylonitrile-butadiene-styrene copolymer.
The preparation method comprises the following steps:
thermoplastic Polyurethane (TPU), polysiloxane, polyoxymethylene polymer, and acrylonitrile-butadiene-styrene (ABS) copolymer are added to a vessel and heated to form a mixture.
Performance testing
The impact resistance test method, shear strength test, tensile property test and elastic modulus test were carried out using the samples obtained from comparative examples 1 and 2 as a control group and the samples obtained from examples 1 to 4 as a test group.
The test method comprises the following steps:
(1) impact resistance test method: measuring the notch impact strength of the GB T1043.1-2008 plastic simply supported beam;
(2) shear strength test: HG/T3839-2006 Plastic shear Strength test method;
(3) tensile property test: GB1040 plastic tensile test method;
(4) elastic modulus test: GB9341 Plastic bending property test method.
And (3) test results: as shown in table 1.
Table 1 shows the results of the tests on the properties of the elastic materials obtained in comparative example 1, comparative example 2 and examples 1 to 4
| Group of | Impact strength (J/m) | Shear strength (MPa) | StretchingStrength (MPa) | Flexural Strength (MPa) |
| Example 1 | 432.2 | 6.248 | 56 | 116 |
| Example 2 | 418.6 | 5.894 | 53 | 123 |
| Example 3 | 468.7 | 7.139 | 58 | 109 |
| Example 4 | 444.9 | 6.827 | 55 | 112 |
| Comparative example 1 | 269.4 | 2.316 | 43 | 79 |
| Comparative example 2 | 280.1 | 3.141 | 49 | 86 |
As a result of the performance test, the impact resistance, shear resistance, tensile property and bending strength of the materials prepared in examples 1-4 are obviously superior to those of the materials prepared in comparative examples 1 and 2, so that the elastic material of the present application is superior to other polyurethane and ABS modified materials in impact resistance and comprehensive performance.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. An elastic material based on polyurethane modification, which is characterized in that: the catalyst is prepared by reacting the following components in percentage by weight:
2. the polyurethane modified elastic material as claimed in claim 1, wherein: the high molecular polyester diol is one or more of polyethylene glycol, polylactone diol, succinic acid polyester diol, tetraphenyl ethylene glycol, polycarbonate diol, polyethylene adipate diol, polyether diol, polytetramethylene ether glycol and polypropylene glycol; the low molecular diol is one or more than one of 1,4 butanediol, ethylene glycol, 2-methyl-1, 3 propanediol, 1,2 butanediol, 1,3 butanediol, neopentyl glycol, 1,2 propanediol and 1,5 pentanediol; the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, polyhexamethylene diisocyanate and isophorone diisocyanate.
3. The polyurethane modified elastic material as claimed in claim 1, wherein: the adhesion agent is one of diethyl butanol, polymethyl methacrylate, chlorinated polyethylene, alpha-methylstyrene-styrene-acrylonitrile copolymer, acrylate polymer and maleic anhydride grafted acrylonitrile-polybutadiene rubber-styrene terpolymer.
4. A process for the preparation of an elastomeric material based on polyurethane modification according to any of claims 1 to 3, characterized in that: the method comprises the following steps:
step 1: melting high-molecular polyester diol and an adhesive in a reaction tank A, heating and vacuumizing, introducing nitrogen and cooling to 30-70 ℃ when the water content is less than 0.05% by vacuum dehydration, adding acrylonitrile in the reaction tank A under the protection of the nitrogen, and stirring uniformly;
step 2: melting diisocyanate in a reaction tank B, heating and vacuumizing, stirring for 0.5-2h, and introducing nitrogen as a protective atmosphere;
and step 3: accurately weighing low molecular weight diol, polybutadiene rubber and styrene according to a formula, melting the low molecular weight diol, the polybutadiene rubber and the styrene in a C reaction tank, stirring for 0.5-1h in a vacuum atmosphere, wherein the temperature in the C reaction tank is 30-55 ℃, and dehydrating in vacuum until the water content is less than 0.05%, and taking nitrogen as a protective atmosphere;
and 4, step 4: transferring the components in the reaction tank A and the reaction tank B to a casting head according to the formula proportion, dripping tert-butyl peroxy 3,5, 5-trimethyl hexyl ester into the casting head, stirring for 0.5-1h, transferring the components in the reaction tank C to the casting head, stirring uniformly at a high speed, inputting the mixture into a double-screw reaction extruder for mixing and polymerization chemical reaction, mixing for 3-30min, extruding, cooling and granulating to obtain the elastic material.
5. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 1, the initial heating rate of the reaction tank A is 10 ℃/min, when the temperature reaches 80-90 ℃, the temperature is kept for 0.5-1h, then the temperature is raised at 2 ℃/min, when the temperature reaches 112-160 ℃, the temperature is kept for 1-2h, the vacuum degree is 150Pa, and the stirring rate is 300 r/min.
6. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 2, the initial heating rate of the reaction tank B is 10 ℃/min, when the temperature reaches 60-70 ℃, the temperature is kept for 0.5-1h, the vacuum degree is 150Pa, and the stirring rate is 300 r/min.
7. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 1, the mass ratio of the high molecular polyester glycol to the acrylonitrile is 12-8: 2-6.
8. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 3, the mass ratio of the low molecular weight diol to the sum of the mass of the polybutadiene rubber and the mass of the styrene is 15-7: 2-20; the mass ratio of polybutadiene rubber to styrene is 1-3: 3-7.
9. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 4, the high-speed stirring speed is 300-500 r/min.
10. A method for preparing an elastic material based on polyurethane modification according to claim 4, wherein: in the step 4, the initial mixing temperature of the mixture input into the double-screw reaction extruder is 50-80 ℃, the mixture is heated to 170-180 ℃ at the speed of 15 ℃/min after being mixed for 3-10min, and the mixture is mixed for 5-27 min.
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