CN111607054A - Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof - Google Patents
Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111607054A CN111607054A CN202010576000.1A CN202010576000A CN111607054A CN 111607054 A CN111607054 A CN 111607054A CN 202010576000 A CN202010576000 A CN 202010576000A CN 111607054 A CN111607054 A CN 111607054A
- Authority
- CN
- China
- Prior art keywords
- rubber powder
- composite material
- polyurethane composite
- tire rubber
- amino modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/10—Footwear characterised by the material made of rubber
- A43B1/12—Footwear characterised by the material made of rubber of rubber waste
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Tires In General (AREA)
Abstract
The invention discloses an amino modified tire rubber powder/polyurethane composite material and a preparation method and application thereof.A swelling agent is used for fully swelling tire rubber under the action of ultrasonic waves and expanding a cross-linked network in the tire rubber, so that the surface activity of the rubber powder is improved, the surfaces of rubber particles and the interior of the rubber particles are endowed with rich pore channel structures, the specific surface area of the rubber powder is improved, the compatibility of the rubber powder is improved, and the bonding force of an interface can be improved when the rubber powder is mixed with a matrix material; the amino silane coupling agent is used for grafting amination on the surface of the rubber powder, so that the use of toxic and harmful solvents is avoided, the environment is good, and the reaction condition is mild; the aminated rubber powder with a porous structure is used as a ball, and reacts with the hydroxyl-terminated polyurethane prepolymer and the diisocyanate dimer to form a modified rubber powder-polyurethane cross-linked network structure, so that the physical and mechanical properties of the composite material are improved.
Description
Technical Field
The invention relates to the technical field of tire rubber recycling, in particular to an amino modified tire rubber powder/polyurethane composite material and a preparation method and application thereof.
Background
In recent years, based on the consideration of environmental protection, the recycling approach of waste rubber (vulcanized rubber) gradually turns to the development and application of vulcanized rubber powder products from the traditional preparation and application of regenerated rubber. At present, the vulcanized rubber powder application technology mainly focuses on the following aspects:
1) non-surface modified rubber powder product. The method is characterized in that vulcanized rubber is prepared into powder materials as fine as possible through equipment improvement or process adjustment. However, there is a rule in the powder material processing industry that no matter how the equipment and process are improved, the high energy consumption and high cost cannot be overcome for obtaining ultrafine powder material, and the situation of vulcanized rubber powder is also the same.
2) Surface mechano-chemical modification
Under the participation of a regenerative activator or a peptizer, the vulcanized rubber powder is placed in a rubber mixing mill or a double-screw extruder for repeated mechanical shearing, so that S-S bonds and S-C bonds are broken on the surface part of the vulcanized rubber powder, and the rubber powder modifier with local desulfurization is obtained. The method is characterized in that the rubber powder is subjected to repeated mechanical shearing or rolling, a large amount of mechanical equipment is required, and the mechanical energy consumption is very high.
3) Chemical modification of rubber powder surface
The surface of vulcanized rubber powder is connected with a plurality of active groups, so that the rubber powder has an opportunity to be combined with a main substance in a rubber system through a chemical reaction under the vulcanization condition, and relatively good product performance is generated. Chinese patents 95105209.8 and 03146994.9 disclose methods in which a polyene monomer is mixed with rubber powder and then added to a rubber formulation system. The essence of the method is that more than two double bonds in polyene monomer molecules are utilized to respectively combine the rubber powder surface and the rubber main body together through graft reaction under the vulcanization condition.
However, the monomers for such grafting reaction are generally volatile organic liquids which are irritating or toxic to human body, and some reactions are carried out in toxic organic solvents such as aromatic hydrocarbons or chlorinated hydrocarbons. Therefore, the modification process of the rubber powder has higher operation difficulty, and has small potential safety hazard and environmental pollution.
Disclosure of Invention
The invention aims to provide a preparation method of an amino modified tire rubber powder/polyurethane composite material, which has mild reaction conditions and good environment, improves the interface bonding force when rubber powder is mixed with a matrix material, forms a modified rubber powder-polyurethane cross-linked network structure and improves the mechanical property of the composite material.
The invention is realized by adopting the following technical scheme:
a preparation method of an amino modified tire rubber powder/polyurethane composite material comprises the following specific steps:
(1) crushing waste tire rubber powder into particles with the size of 20-30 meshes, adding a swelling agent to activate for 24-72h at room temperature, further swelling and activating for 5-12h under the action of ultrasound, filtering after activation, and evaporating to recover the swelling agent to obtain swollen porous rubber powder;
wherein the mass ratio of the waste rubber particles to the swelling agent is 1: (3-8);
(2) crushing the swollen rubber powder according to the particle size of the swollen rubber powder, controlling the particle size of the rubber powder to be below 30 meshes, then adding concentrated sulfuric acid into the rubber powder, and rapidly and mechanically stirring for 5-30min at room temperature to obtain the rubber powder treated by concentrated sulfuric acid;
(3) dispersing the rubber powder obtained in the step (2) into 2-6 times of deionized water, adding the mixture into a reactor with a stirrer and a thermometer, adding an aminosilane coupling agent, mechanically stirring the mixture for reaction for 10-24 hours at the temperature of 25-80 ℃, cooling and discharging the mixture, and filtering and drying the mixture to obtain the aminated modified rubber powder;
(4) blending the rubber powder with the surface amination modification, the hydroxyl-terminated polyurethane prepolymer and the toluene diisocyanate dimer, and performing hot press molding at the temperature of 130-170 ℃ to obtain the modified rubber powder/polyurethane composite material with the cross-linked structure.
Further, in the step (2), the mass ratio of the concentrated sulfuric acid to the rubber powder is (0.01-0.05): 1.
Further, in the step (3), the mass ratio of the aminosilane coupling agent to the rubber powder is (0.03-0.12): 1.
Further, the aminosilane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane, N-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane and N-aminoethyl-gamma-aminopropylmethyldiethoxysilane.
Further, the mass ratio of the modified rubber powder to the hydroxyl-terminated polyurethane prepolymer in the step (4) is 1: (0.5-1.0).
Further, the toluene diisocyanate dimer is used in the step (4) in an amount of 6 to 10% by weight.
Further, in the step (4), 40-55 parts of rubber powder with aminated surface, 6-12 parts of toluene diisocyanate dimer and 20-40 parts of hydroxyl-terminated polyurethane prepolymer are uniformly mixed by a high-speed stirrer at the temperature of 45-65 ℃, and are subjected to hot pressing by a flat vulcanizing machine at the temperature of 140-160 ℃ and the pressure of 10-15MPa for 30-50min for reaction and molding.
Further, preparation of the hydroxyl-terminated polyurethane prepolymer:
feeding the diisocyanate and the polymer polyol according to the molar ratio of 1: 1.05-1.20, adding the polymer polyol with the molecular weight of 2000-3000 into a reactor with a stirrer, a thermometer and a vacuum system, dehydrating for 1.0-2.0h at the temperature of 80-100 ℃ and the vacuum degree of 0.08-0.09MPa, slowly adding the diisocyanate at the temperature of 100-140 ℃ and within 0.5-1.0h, and stirring for reacting for 1.0-3.5h to obtain the light yellow viscous hydroxyl-terminated polyurethane prepolymer.
The invention also provides the amino modified tire rubber powder/polyurethane composite material prepared by the preparation method.
The amino modified tire rubber powder/polyurethane composite material is used as a raw material for preparing cables, tires, sealing elements, shoes or medical appliances.
Compared with the prior art, the invention has the following advantages:
1. under the action of ultrasound, the tire rubber is fully swelled by using a swelling agent, and a cross-linked network in the tire rubber is expanded, so that the surface activity of rubber powder is improved, the surface of rubber particles and the interior of the rubber particles are endowed with rich pore channel structures, the specific surface area of the rubber powder is improved, the compatibility of the rubber powder is improved, and the bonding force of an interface can be improved when the rubber powder is mixed with a matrix material;
2. the rich pore structure on the surface of the rubber powder is utilized, the rubber powder is treated by concentrated sulfuric acid, so that the active groups on the surface of the rubber powder are increased, and then the surface of the rubber powder is grafted and aminated by an aminosilane coupling agent, so that no toxic or harmful solvent is used in the modification process, the environment is good, and the reaction condition is mild;
3. the aminated rubber powder with a porous structure is used as a ball and reacts with the hydroxyl-terminated polyurethane prepolymer and diisocyanate dimer, the toluene diisocyanate dimer is depolymerized, the dissociated isocyanate reacts with the hydroxyl-terminated polyurethane prepolymer to form a polyurethane high polymer, the isocyanate reacts with the amino on the surface of the rubber powder to generate ureido bridge bonds, and the amino on the surface of the rubber powder can also react with the hydroxyl-terminated polyurethane prepolymer to form a modified rubber powder-polyurethane cross-linked network structure, so that the physical and mechanical properties of the composite material are improved.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
The following detailed description of embodiments of the present patent is, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
A preparation method of an amino modified tire rubber powder/polyurethane composite material comprises the following specific steps:
(1) crushing waste tire rubber powder into particles with the size of 20-30 meshes, adding a swelling agent to activate for 36h at room temperature, further swelling and activating for 8h under the action of ultrasound, filtering after activation, and evaporating to recover the swelling agent to obtain swollen porous rubber powder;
wherein the swelling agent is n-heptane, n-octane, toluene, xylene or cyclohexane, and in this embodiment, the swelling agent is xylene; the mass ratio of the waste rubber particles to the swelling agent is 1: 3;
(2) crushing the swollen rubber powder according to the particle size of the swollen rubber powder, controlling the particle size of the rubber powder to be below 30 meshes, adding concentrated sulfuric acid into the rubber powder according to the mass ratio of the concentrated sulfuric acid to the rubber powder of 0.02:1, and quickly and mechanically stirring for 15min at room temperature to obtain the rubber powder treated by concentrated sulfuric acid;
(3) dispersing the rubber powder obtained in the step (2) in 3 times of deionized water, adding the mixture into a reactor with a stirrer and a thermometer, adding gamma-aminopropyltrimethoxysilane as a coupling agent according to the mass ratio of 0.08:1 of aminosilane coupling agent to the rubber powder, mechanically stirring the mixture for reacting for 18 hours at the temperature of 80 ℃, cooling and discharging, and filtering and drying the mixture to obtain the aminated modified rubber powder;
(4) preparation of hydroxyl-terminated polyurethane prepolymer:
according to a ratio of diisocyanate to polymer polyol of 1: feeding polyester polyol 2000 into a reactor with a stirrer, a thermometer and a vacuum system according to a molar ratio of 1.1, dehydrating for 1.5h at the temperature of 90 ℃ and the vacuum degree of 0.09MPa, slowly adding diisocyanate at the temperature of 120 ℃ within 0.5h, and stirring for reacting for 3h to obtain a light yellow viscous hydroxyl-terminated polyurethane prepolymer;
(5) 50 parts of rubber powder with aminated surface, 8 parts of 2, 4-toluene diisocyanate dimer and 30 parts of hydroxyl-terminated polyurethane prepolymer are uniformly mixed by a high-speed stirrer at the temperature of 60 ℃, and are subjected to hot pressing and 45min reaction forming by a flat vulcanizing machine at the temperature of 145 ℃ and under the pressure of 10MPa to obtain the modified rubber powder/polyurethane composite material with the cross-linked structure.
Example 2
A preparation method of an amino modified tire rubber powder/polyurethane composite material comprises the following specific steps:
(1) crushing waste tire rubber powder into particles with the size of 20-30 meshes, adding a swelling agent to activate for 36h at room temperature, further swelling and activating for 8h under the action of ultrasound, filtering after activation, and evaporating to recover the swelling agent to obtain swollen porous rubber powder;
wherein the swelling agent is toluene; the mass ratio of the waste rubber particles to the swelling agent is 1: 3;
(2) crushing the swollen rubber powder according to the particle size of the swollen rubber powder, controlling the particle size of the rubber powder to be below 30 meshes, adding concentrated sulfuric acid into the rubber powder according to the mass ratio of the concentrated sulfuric acid to the rubber powder of 0.01:1, and quickly and mechanically stirring for 25min at room temperature to obtain the rubber powder treated by concentrated sulfuric acid;
(3) dispersing the rubber powder obtained in the step (2) in 3 times of deionized water, adding the mixture into a reactor with a stirrer and a thermometer, adding gamma-aminopropyltrimethoxysilane as a coupling agent according to the mass ratio of 0.07:1 of an aminosilane coupling agent to the rubber powder, mechanically stirring the mixture for reaction for 20 hours at the temperature of 80 ℃, cooling the mixture, discharging the material, and filtering and drying the material to obtain the aminated modified rubber powder;
(4) preparation of hydroxyl-terminated polyurethane prepolymer:
according to a ratio of diisocyanate to polymer polyol of 1: feeding polyester polyol 2000 into a reactor with a stirrer, a thermometer and a vacuum system according to a molar ratio of 1.1, dehydrating for 1.5h at the temperature of 90 ℃ and the vacuum degree of 0.09MPa, slowly adding diisocyanate at the temperature of 120 ℃ within 0.5h, and stirring for reacting for 3h to obtain a light yellow viscous hydroxyl-terminated polyurethane prepolymer;
(5) 50 parts of rubber powder with aminated surface, 8 parts of 2, 4-toluene diisocyanate dimer and 30 parts of hydroxyl-terminated polyurethane prepolymer are uniformly mixed by a high-speed stirrer at the temperature of 60 ℃, and are subjected to hot pressing and 45min reaction forming by a flat vulcanizing machine at the temperature of 145 ℃ and under the pressure of 10MPa to obtain the modified rubber powder/polyurethane composite material with the cross-linked structure.
Example 3
A preparation method of an amino modified tire rubber powder/polyurethane composite material comprises the following specific steps:
(1) crushing waste tire rubber powder into particles with the size of 20-30 meshes, adding a swelling agent to activate for 36h at room temperature, further swelling and activating for 8h under the action of ultrasound, filtering after activation, and evaporating to recover the swelling agent to obtain swollen porous rubber powder;
wherein the swelling agent is toluene; the mass ratio of the waste rubber particles to the swelling agent is 1: 3;
(2) crushing the swollen rubber powder according to the particle size of the swollen rubber powder, controlling the particle size of the rubber powder to be below 30 meshes, then adding concentrated sulfuric acid into the rubber powder according to the mass ratio of the concentrated sulfuric acid to the rubber powder of 0.03:1, and quickly and mechanically stirring for 10min at room temperature to obtain the rubber powder treated by concentrated sulfuric acid;
(3) dispersing the rubber powder obtained in the step (2) in 3 times of deionized water, adding the mixture into a reactor with a stirrer and a thermometer, adding gamma-aminopropyltrimethoxysilane serving as a coupling agent according to the mass ratio of 0.09:1 of aminosilane coupling agent to the rubber powder, mechanically stirring the mixture for reaction for 16 hours at the temperature of 60 ℃, cooling the mixture, discharging the material, filtering and drying the material to obtain the aminated modified rubber powder;
(4) preparation of hydroxyl-terminated polyurethane prepolymer:
according to a ratio of diisocyanate to polymer polyol of 1: feeding polyester polyol 2000 into a reactor with a stirrer, a thermometer and a vacuum system according to a molar ratio of 1.1, dehydrating for 1.5h at the temperature of 90 ℃ and the vacuum degree of 0.09MPa, slowly adding diisocyanate at the temperature of 120 ℃ within 0.5h, and stirring for reacting for 3h to obtain a light yellow viscous hydroxyl-terminated polyurethane prepolymer;
(5) 50 parts of rubber powder with aminated surface, 8 parts of 2, 4-toluene diisocyanate dimer and 30 parts of hydroxyl-terminated polyurethane prepolymer are uniformly mixed by a high-speed stirrer at the temperature of 60 ℃, and are subjected to hot pressing and 45min reaction forming by a flat vulcanizing machine at the temperature of 145 ℃ and under the pressure of 10MPa to obtain the modified rubber powder/polyurethane composite material with the cross-linked structure.
Example 4
Crushing unmodified tire rubber powder to below 30 meshes, uniformly mixing 50 parts of rubber powder, 8 parts of 2, 4-toluene diisocyanate dimer and 30 parts of hydroxyl-terminated polyurethane prepolymer at the temperature of 60 ℃ by a high-speed mixer, and carrying out hot pressing for 45min by a flat vulcanizing machine at the temperature of 145 ℃ and under the pressure of 10MPa for reaction forming to obtain an unmodified rubber powder/polyurethane composite material serving as a comparative example.
The modified rubber powder/polyurethane composite materials prepared in examples 1 to 3 and the unmodified rubber powder/polyurethane composite material prepared in example 4 were prepared into test pieces and tested, and the results of the physical and mechanical properties are shown in table 1.
TABLE 1 test results of physical and mechanical Properties
From the test results of examples 1 to 3 and comparative example (example 4), it is shown that the aminated modified rubber powder/polyurethane composite material obtained according to the invention has better physical and mechanical properties than the unmodified rubber powder/polyurethane composite material under the same conditions.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (10)
1. A preparation method of an amino modified tire rubber powder/polyurethane composite material is characterized by comprising the following specific steps:
(1) crushing waste tire rubber powder into particles with the size of 20-30 meshes, adding a swelling agent to activate for 24-72h at room temperature, further swelling and activating for 5-12h under the action of ultrasound, filtering after activation, and evaporating to recover the swelling agent to obtain swollen porous rubber powder;
wherein the mass ratio of the waste rubber particles to the swelling agent is 1: (3-8);
(2) crushing the swollen rubber powder according to the particle size of the swollen rubber powder, controlling the particle size of the rubber powder to be below 30 meshes, then adding concentrated sulfuric acid into the rubber powder, and rapidly and mechanically stirring for 5-30min at room temperature to obtain the rubber powder treated by concentrated sulfuric acid;
(3) dispersing the rubber powder obtained in the step (2) into 2-6 times of deionized water, adding the mixture into a reactor with a stirrer and a thermometer, adding an aminosilane coupling agent, mechanically stirring the mixture for reaction for 10-24 hours at the temperature of 25-80 ℃, cooling and discharging the mixture, and filtering and drying the mixture to obtain the aminated modified rubber powder;
(4) blending the rubber powder with the surface amination modification, the hydroxyl-terminated polyurethane prepolymer and the toluene diisocyanate dimer, and performing hot press molding at the temperature of 130-170 ℃ to obtain the modified rubber powder/polyurethane composite material with the cross-linked structure.
2. The preparation method of the amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein in the step (2), the mass ratio of the concentrated sulfuric acid to the rubber powder is (0.01-0.05): 1.
3. The preparation method of the amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein in the step (3), the mass ratio of the amino silane coupling agent to the rubber powder is (0.03-0.12) to 1.
4. The method for preparing amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein the aminosilane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane, N-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane, and N-aminoethyl-gamma-aminopropylmethyldiethoxysilane.
5. The preparation method of the amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein the mass ratio of the modified rubber powder to the hydroxyl-terminated polyurethane prepolymer in the step (4) is 1: (0.5-1.0).
6. The method for preparing amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein the toluene diisocyanate dimer in step (4) is used in an amount of 6-10 wt%.
7. The method for preparing amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein in the step (4), 40-55 parts of rubber powder with aminated surface, 6-12 parts of toluene diisocyanate dimer and 20-40 parts of hydroxyl-terminated polyurethane prepolymer are uniformly mixed by a high-speed mixer at 45-65 ℃, and are subjected to hot pressing by a flat vulcanizing machine at 140-160 ℃ and 10-15MPa for 30-50min for reaction and molding.
8. The method for preparing the amino modified tire rubber powder/polyurethane composite material as claimed in claim 1, wherein the hydroxyl-terminated polyurethane prepolymer is prepared by the following steps:
according to a ratio of diisocyanate to polymer polyol of 1: feeding the materials according to the molar ratio of 1.05-1.20, adding polymer polyol with the molecular weight of 2000-3000 into a reactor with a stirrer, a thermometer and a vacuum system, dehydrating for 1.0-2.0h at the temperature of 80-100 ℃ and the vacuum degree of 0.08-0.09MPa, then slowly adding diisocyanate at the temperature of 100-140 ℃ and within 0.5-1.0h, and stirring and reacting for 1.0-3.5h to obtain the light yellow viscous hydroxyl-terminated polyurethane prepolymer.
9. An amino modified tire rubber powder/polyurethane composite material prepared by the preparation method of any one of claims 1 to 8.
10. The amino-modified tire rubber powder/polyurethane composite material as claimed in claim 9, characterized by the use as a raw material for the production of cables, tires, seals, footwear or medical appliances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576000.1A CN111607054A (en) | 2020-06-22 | 2020-06-22 | Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576000.1A CN111607054A (en) | 2020-06-22 | 2020-06-22 | Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111607054A true CN111607054A (en) | 2020-09-01 |
Family
ID=72205018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010576000.1A Pending CN111607054A (en) | 2020-06-22 | 2020-06-22 | Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111607054A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127693A (en) * | 1995-01-27 | 1996-07-31 | 刘扬生 | Method for preparing super fine rubber powder from used rubber |
| CN1325917A (en) * | 2000-05-29 | 2001-12-12 | 刘扬生 | Process for regenerating waste or used rubber |
| CN103525077A (en) * | 2013-09-26 | 2014-01-22 | 四川大学 | Surface oxidation modified vulcanized rubber powder/polyurethane composite material and preparation method thereof |
| CN105037865A (en) * | 2015-08-20 | 2015-11-11 | 华南理工大学 | Modified scrap rubber powder as well as preparation method and application thereof |
-
2020
- 2020-06-22 CN CN202010576000.1A patent/CN111607054A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127693A (en) * | 1995-01-27 | 1996-07-31 | 刘扬生 | Method for preparing super fine rubber powder from used rubber |
| CN1325917A (en) * | 2000-05-29 | 2001-12-12 | 刘扬生 | Process for regenerating waste or used rubber |
| CN103525077A (en) * | 2013-09-26 | 2014-01-22 | 四川大学 | Surface oxidation modified vulcanized rubber powder/polyurethane composite material and preparation method thereof |
| CN105037865A (en) * | 2015-08-20 | 2015-11-11 | 华南理工大学 | Modified scrap rubber powder as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 中国化工学会橡胶专业委员会: "《橡胶助剂手册》", 30 April 2000, 化学工业出版社 * |
| 韩宝平主编: "《固体废物处理与利用》", 30 June 2010, 华中科技大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60306089T2 (en) | Devulcanization of cross-linked rubber | |
| CN103865028B (en) | A kind of method of package waste PET bottle synthesis aqueous polyurethane emulsion | |
| CN103408715A (en) | Internal crosslinking polypropylene carbonate waterborne polyurethane emulsion and preparation method and application thereof | |
| CN111909529A (en) | Desulfurized waste tire rubber powder crosslinked modified asphalt and preparation method thereof | |
| CN113402886A (en) | Reclaimed material silicone rubber and preparation method thereof | |
| CN1252156C (en) | Process for regeneration of rubber from scrap | |
| EP1674501A1 (en) | Microgel-containing thermosetting composition | |
| US3954681A (en) | Method of reclaiming cured polyurethane elastomers | |
| CN103525077B (en) | Surface oxidation modified vulcanized rubber powder/polyurethane composite material and preparation method thereof | |
| CN111607054A (en) | Amino modified tire rubber powder/polyurethane composite material and preparation method and application thereof | |
| CN112375308A (en) | High-strength self-healing rubber material and preparation method thereof | |
| CN113185664B (en) | Improved polyurethane foam and preparation method thereof | |
| CN112552546B (en) | Environment-friendly EVA (ethylene-vinyl acetate) foaming material and preparation method thereof | |
| CN113583428B (en) | Carbon dioxide-based polyurethane composite material and preparation method thereof | |
| CN110607000A (en) | Graphene natural rubber oil-resistant mixed foam material and preparation method thereof | |
| CN112029200B (en) | Low-density thermoplastic dynamic vulcanized rubber material and preparation method and application thereof | |
| CN114621472B (en) | Preparation method and recycling method of interfacial cross-linked rubber | |
| DE4132282C2 (en) | Process for recycling plastics | |
| CN114539633B (en) | Thermoplastic starch masterbatch with high starch content and preparation method thereof | |
| US5648431A (en) | Process for the utilization of plastics | |
| US5958988A (en) | Cross-linked polyurethane resin powder and process for producing the same | |
| CN113429500A (en) | High-performance functionalized elastomer material and preparation method of elastomer composite material | |
| CN113698566B (en) | A kind of soft polyurethane foam for car seat and its preparation method and application | |
| CN113563612B (en) | A high elastic rubber liquid phase production process | |
| CN115322435B (en) | Environment-friendly recycling method for waste rubber and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200901 |