CN111393582B - Method for recycling and reusing waste thermosetting polyurethane - Google Patents

Method for recycling and reusing waste thermosetting polyurethane Download PDF

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Publication number
CN111393582B
CN111393582B CN202010354785.8A CN202010354785A CN111393582B CN 111393582 B CN111393582 B CN 111393582B CN 202010354785 A CN202010354785 A CN 202010354785A CN 111393582 B CN111393582 B CN 111393582B
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thermosetting polyurethane
particles
parts
polyurethane particles
waste
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CN111393582A (en
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赵波
郝凤亮
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Sichuan Runyingda Electronic Technology Co ltd
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Sichuan Runyingda Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Abstract

The invention discloses a method for recycling and reusing waste thermosetting polyurethane, which comprises the following steps: 1) Crushing: crushing and sieving the waste thermosetting polyurethane to obtain particles with the particle size of less than 10 mm; 2) And (3) activation: irradiating the thermosetting polyurethane particles by gamma rays to obtain activated thermosetting polyurethane particles; 3) Modification: uniformly premixing the activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water, grinding by a colloid mill, drying and sieving to obtain the surface grafting modified thermosetting polyurethane particles. According to the invention, the thermosetting polyurethane particles are irradiated by high-energy rays with large dose, so that molecular chains of polymers are broken, thereby destroying the cross-linking structure of the thermosetting polyurethane, generating active free radicals, and then grafting and modifying with vinyl monomers under certain conditions, thereby obtaining the thermosetting polyurethane particles with reactive groups, and realizing the functionalization of the surfaces of the thermosetting polyurethane particles.

Description

Method for recycling and reusing waste thermosetting polyurethane
Technical Field
The invention relates to the field of recycling of waste plastics, in particular to a method for recycling waste thermosetting polyurethane.
Background
The plastic industry in China gains remarkable results from ever-present to small to large, the total yield of plastic products jumps the second place in the world, and the plastic processing technology and equipment, the types of plastic products and the application field are all advanced in the world. High polymer materials such as plastics, rubber, fibers and the like, together with steel, wood and cement, constitute four major basic materials in modern society.
Since the 21 st century, the human society has developed the economy rapidly, and the high and new technologies are in the future and the world economy is integrated to prosper, and at the same time, the human society is faced with the severe reality of dramatic population increase, resource shortage, environmental pollution and ecological metamorphosis. How to reach the human society and the harmonious development of the ecological environment is a common wish of all countries in the world. The concept of circular economy arises from the fact that it changes the past "resource-product-waste" material linear flow pattern to a "resource-product-renewable resource" material feedback process. The researchers proposed: on one hand, the reutilization rate of resources is improved, and the resources can be preferably used repeatedly, and for plastics, a method for recycling is sought, the energy is recovered by burning, and finally the residues are put into a landfill; on the other hand, when raw materials are used, the materials which are easy to recycle are selected as much as possible, and in the case of plastics, the thermoplastic type is easier to recycle than the thermosetting type. However, most of the high-performance functional composite materials currently in wide use are thermosetting composite materials such as epoxy resin, cyano resin, polyurethane and the like, and the composite materials are insoluble and infusible, i.e. cannot be dissolved in a solvent, and cannot be used for thermoplastic reprocessing. Therefore, recycling of waste thermosetting composite materials has been a major and difficult point of research in academic and engineering fields.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for recycling and reusing waste thermosetting polyurethane, which can effectively crush and functionalize the surface of thermosetting polyurethane particles, and the obtained modified thermosetting polyurethane particles can be used to improve the mechanical properties and dielectric properties of thermosetting epoxy resins.
The invention is realized by the following technical scheme:
a method for recycling waste thermosetting polyurethane is characterized by comprising the following steps: 1) Crushing: crushing and sieving the waste thermosetting polyurethane to obtain particles with the particle size of less than 10 mm; 2) And (3) activation: irradiating the thermosetting polyurethane particles by gamma rays to obtain activated thermosetting polyurethane particles; 3) Modification: uniformly premixing the activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water, grinding by a colloid mill, drying and sieving to obtain the surface grafting modified thermosetting polyurethane particles.
Because the cured thermosetting polyurethane is insoluble and infusible, can not be dissolved in a solvent and can not be subjected to secondary hot melting processing, the cured thermosetting polyurethane can only be broken into small particles by common mechanical crushing, and the surface functionalization of the cured thermosetting polyurethane is difficult to realize. According to the invention, the thermosetting polyurethane particles are irradiated by high-energy rays with large dose, so that molecular chains of polymers are broken, thereby destroying the cross-linking structure of the thermosetting polyurethane, generating active free radicals, and then grafting and modifying with vinyl monomers under certain conditions, thereby obtaining the thermosetting polyurethane particles with reactive groups, and realizing the functionalization of the surfaces of the thermosetting polyurethane particles.
Wherein, the step 1) uses a grinder to grind and sieve the thermosetting polyurethane to obtain particles with the particle size less than 10 mm; the main function is to break large thermosetting polyurethane particles into small particles, which is beneficial to the action of high-energy rays, so that the surface area contacting with rays is larger, the molecular chain of the thermosetting polyurethane is easier to destroy, active free radicals are easier to form on the surface, and the preparation in the next step is facilitated when the thermosetting polyurethane particles enter a colloid mill.
In the step 2), the thermosetting polyurethane particles are placed in a gamma ray irradiation box, and are irradiated by gamma rays to obtain activated thermosetting polyurethane particles, so that the molecular weight of a polymer cannot be damaged and active free radicals cannot be formed when the radiation is measured and radiated by rays, and the surface functionalization effect is influenced; the radiation dose is controlled to be 10 to 30KGy because the measurement is too large, the degradation of the polymer is severe, the intrinsic performance of the thermosetting polyurethane polymer cannot be maintained, and the effect of strengthening and toughening cannot be realized in the recycling process.
Step 3) placing the activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water in a high-speed stirrer for premixing, providing a grafting group and a grafting medium through the addition, providing an active catalyst to improve the grafting rate to a great extent, and grinding, drying and sieving the mixture by a colloid mill to obtain surface-graft-modified thermosetting polyurethane particles; the thermosetting polyurethane can be further crushed into functionalized particles with the particle size of less than 80 microns in a grinding mode, so that the grafting rate is further improved; the gamma ray has the functions of functionalizing the surface of thermosetting polyurethane particle and breaking some molecular chains inside the thermosetting polyurethane particle, and is favorable to grinding to form fine powder material.
The modification step 3) comprises the following components in parts by weight: 100 parts of activated thermosetting polyurethane particles, 10-20 parts of nitric acid, 5-10 parts of acrylic acid and 200 parts of deionized water, wherein preferably, the activated thermosetting polyurethane particles are prepared by the following steps: nitric acid: acrylic acid: the proportion of deionized water is 100:10:5:200 or 100:20:5:200.
the thermosetting polyurethane in the step 1) is selected from thermosetting polyurethane with the crosslinking degree of more than 50% and the hardness of more than 88D.
The concentration of nitric acid is 40%, the main purpose is to remove basic impurities in the reaction process, then neutralize the alkalinity of amido bonds, enable the amido bonds to be more easily broken and to be more easily ground, if nitric acid is not added, acrylic acid is consumed to complete the reaction processes of the basic impurities, the neutralization of the amido bonds and the catalysis of amido bond degradation, and therefore the grafting efficiency is influenced; therefore, the addition of the nitric acid can catalyze the degradation, so that the grinding is easier and the effect which is not intended is obtained, and the grafting efficiency is greatly improved.
In the step 3), activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water are mixed at normal temperature by adopting a high-speed mixer, and colloid milling is carried out at the temperature of 50-70 ℃, so that the reaction efficiency of surface active free radicals of thermosetting polyurethane and acrylic acid monomers can be increased, and the reaction efficiency is improved by increasing the collision among molecules through increasing the temperature.
In the step 2), irradiation is carried out by adopting gamma rays with the measurement of 10-30KGy under the environment of normal temperature and normal pressure.
A method for recycling waste thermosetting polyurethane utilizes thermosetting polyurethane particles with surface grafting modification to modify epoxy resin, and comprises the following specific steps: 1) Firstly, placing epoxy resin and diethylaminopropylamine in a high-speed mixer to be uniformly mixed; 2) Then adding the thermosetting polyurethane with the surface graft modification and mixing evenly; 3) And curing in an oven to obtain the thermosetting polyurethane modified epoxy resin composite material.
The invention further utilizes the thermosetting polyurethane micro powder with functionalized surface as the functional filler of the epoxy resin, so that the mechanical property and the dielectric property of the epoxy resin can be greatly improved. Specifically, the epoxy resin and the diethylaminopropylamine are placed in a high-speed mixer to be uniformly mixed, firstly, the curing agent and the epoxy resin are uniformly mixed, then, the thermosetting polyurethane particles with the surface grafted and modified are added to be mixed by the high-speed mixer, so that the functional filler can be dispersed more uniformly, the reaction between the acrylic functional group on the surface of the thermosetting polyurethane with the surface grafted and modified and the curing agent is avoided, the consumption of the curing agent is avoided, on the other hand, the surface group of the thermosetting polyurethane with the surface functionalized can react with the epoxy resin to form a cross-linking point, the mechanical property of the composite material is improved, and the thermosetting polyurethane can be used as a substitute of the curing agent, and the addition of the curing agent is reduced; finally, the epoxy resin composite material modified by the thermosetting polyurethane is obtained after the epoxy resin composite material is placed in an oven for curing.
The surface grafting modified thermosetting polyurethane particles obtained by the functionalization treatment can be chemically linked with thermosetting epoxy resin to form a cross-linked bond on an interface, so that the mechanical property and the dielectric property of the epoxy resin composite material are greatly enhanced, the effective utilization of the waste thermosetting polyurethane is realized, and waste is changed into valuable. Specifically, it is detected that: the tensile strength of the pure epoxy resin composite material is 68.5Mpa, and the impact strength is 7.4KJ/m 2 The dielectric loss is 0.44 (10 GHZ), the tensile strength of the epoxy resin composite material modified by adding the thermosetting polyurethane particles with the surface graft modification is 70.3Mpa, and the impact strength is 18.4KJ/m 2 The dielectric loss is 0.38 (10 GHZ), so that the addition of the functionalized thermosetting polyurethane particles provided by the invention can greatly improve the tensile strength and impact strength of the epoxy resin, effectively reduce the dielectric loss and provide a solid foundation for the application of the epoxy resin composite material in the field of electric appliances. Therefore, compared with the traditional polyurethane particle material obtained by simply crushing, the recycling method of the waste thermosetting polyurethane has obvious superiority.
The modification process comprises the following components in parts by weight: 100 parts of epoxy resin; 2-8 parts of diethylaminopropylamine, 10-60 parts of surface graft modified thermosetting polyurethane particles, preferably, epoxy resin: diethylaminopropylamine: the proportion of the thermosetting polyurethane particles with the surface graft modification is 100:4:10 or 100:4:20.
the temperature of the oven in the curing process is 60-70 ℃, and the curing time is 4h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention relates to a method for recycling and reusing waste thermosetting polyurethane, which comprises the steps of irradiating thermosetting polyurethane particles by utilizing gamma rays to break molecular chains of polymers, thus destroying the cross-linking structure of the thermosetting polyurethane and generating active free radicals, and then grafting and modifying the thermosetting polyurethane particles with vinyl monomers under certain conditions to obtain the thermosetting polyurethane particles with reactive groups so as to realize functionalization of the surfaces of the thermosetting polyurethane particles;
2. the invention relates to a method for recycling and reusing waste thermosetting polyurethane, wherein surface-grafted and modified thermosetting polyurethane particles obtained by functional treatment are used for modifying epoxy resin, can be chemically linked with thermosetting epoxy resin, and form cross-linking bonds at an interface, so that the mechanical property and the dielectric property of an epoxy resin composite material are greatly enhanced, and the effective utilization of the waste thermosetting polyurethane is realized;
3. according to the method for recycling and reusing the waste thermosetting polyurethane, only a small amount of nitric acid is applied in the process, other toxic and harmful solvents are not contained, and the method is beneficial to the health of operators and environmental protection;
4. the method for recycling and reusing the waste thermosetting polyurethane does not need special treatment on waste polyurethane raw materials, and has the advantages of simple preparation process, convenience in operation and control, high production efficiency, low production cost and wide industrialization and market prospects.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
A method for recycling and reusing waste thermosetting polyurethane comprises the following steps: 1) Selecting a crumbed thermosetting polyurethane waste material (the content of calcium carbonate is 30%), crushing the crumbed thermosetting polyurethane waste material by using a roller crusher at normal temperature (the rotating speed of a motor is 1000 rpm), and sieving to obtain granular thermosetting polyurethane granules with the grain size of less than 10 mm; 2) Placing the thermosetting polyurethane particles in a steel box so that the box rotates in a circle around the box 60 Irradiating Co by gamma rays, controlling the dose to be 150Gy every rotation, controlling the number of the rotation cycles and the irradiation dose to be 25Kgy, and then obtaining activated thermosetting polyurethane particles; 3) Preparing the following components in parts by weight: 100 parts of activated thermosetting polyurethane particles, 10 parts of nitric acid (the concentration is 40%), 5 parts of acrylic acid and 200 parts of deionized water; 4) Placing the activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water in a high-speed stirrer for premixing, grinding by a colloid mill (the rotating speed of a motor is 600 revolutions per minute), drying in an oven for 10 hours, and sieving by using a 80-micron sieve to obtain thermosetting polyurethane particles with surface graft modification; 5) Preparing the following components in parts by weight: 100 parts of epoxy resin, 4 parts of diethylaminopropylamine and 10 parts of thermosetting polyurethane particles with surface graft modification; 6) And (3) placing the epoxy resin and the diethylaminopropylamine in a high-speed mixer, mixing for 8 minutes, adding the dried thermosetting polyurethane with the surface graft modification, mixing for 8 minutes, and then placing in a 70 ℃ oven for curing for 4 hours to obtain the thermosetting polyurethane modified epoxy resin composite material.
Comparative example 1
The difference from the example 1 is that the epoxy resin is not modified by the thermosetting polyurethane with surface graft modification, and the specific steps are as follows: and (3) placing 100 parts of epoxy resin and 4 parts of diethylaminopropylamine in a high-speed mixer, mixing for 8 minutes, and then placing in a 70 ℃ oven for curing for 4 hours to obtain the epoxy resin composite material.
Comparative example 2
The difference from example 1 is that this comparative example does not have nitric acid added in step 3).
Example 2
The difference from the example 1 is that in the step 5), the weight parts of the components are as follows: 100 parts of epoxy resin, 2 parts of diethylaminopropylamine, 10 parts of surface graft modified thermosetting polyurethane particles, and the addition amount of the diethylaminopropylamine is reduced by half.
Comparative example 3
The difference from example 2 is that this comparative example does not add acrylic acid for graft modification in step 3).
Example 3
The difference from example 1 is that in step 3), 100 parts of activated thermosetting polyurethane particles, 20 parts of nitric acid (concentration: 40%), 5 parts of acrylic acid, 200 parts of deionized water, and the amount of nitric acid added were doubled.
Example 4
The difference from the embodiment 1 is that in the step 5), the weight parts of the components are as follows: 100 parts of epoxy resin, 4 parts of diethylaminopropylamine and 20 parts of surface graft modified thermosetting polyurethane particles, wherein the addition amount of the surface graft modified thermosetting polyurethane particles is doubled.
The epoxy resin composites prepared in examples 1 to 4 and comparative examples 1 to 3 were cut into standard sample bars using a sample cutter to perform mechanical property tests and dielectric property tests, as shown in the following table:
tensile strength (Mpa) High impact strengthDegree (KJ/m) 2 ) Dielectric loss (10 GHZ)
Example 1 70.3 18.4 0.38
Comparative example 1 68.5 7.4 0.44
Comparative example 2 65.7 7.9 0.42
Example 2 71.6 19.3 0.37
Comparative example 3 66.8 9.9 0.43
Example 3 69.4 16.7 0.39
Example 4 64.6 15.8 0.35
By combining the embodiment 1 and the comparative example 1, the embodiment shows that the surface graft modified thermosetting polyurethane particle modified epoxy resin prepared by the method of the invention can be beneficial to improving the mechanical strength of the epoxy resin composite material and reducing the dielectric loss.
Combining example 1 and comparative example 2, it can be seen that the tensile strength and impact strength of the composite material are significantly improved and the dielectric loss is reduced when nitric acid is not added in comparative example 2, but is added in example 1.
Combining example 1 and example 2, it can be seen that the addition amount of diethylaminopropylamine in example 2 is reduced by half, but the tensile strength and impact strength are slightly improved, and the dielectric loss is also slightly reduced, which indicates that the use of the thermosetting polyurethane particles modified by surface grafting of the present invention can reduce the amount of the curing agent, and can effectively improve the mechanical properties of the composite material and reduce the dielectric loss.
Combining example 2 and comparative example 3, it can be seen that comparative example 3 does not use acrylic acid for graft modification, both tensile strength and impact strength are significantly reduced, and dielectric loss is significantly increased, so that functionalization of the surface of the thermosetting polyurethane particles is beneficial to improving the mechanical strength of the epoxy resin composite material, and reducing the dielectric loss.
It can be seen from the combination of example 1 and example 3 that the amount of nitric acid added in example 3 is doubled, but the tensile strength and impact strength are both slightly reduced, and the dielectric loss is increased, so it is known that the surface graft-modified thermosetting polyurethane particles prepared by adding too much nitric acid are not beneficial to improving the mechanical properties of the epoxy resin composite material and reducing the dielectric loss.
As can be seen from the combination of examples 1 and 4, the addition amount of the thermosetting polyurethane particles surface graft-modified in example 4 is doubled, and the tensile strength and impact strength are both reduced although the dielectric loss is reduced, so that the mechanical properties are affected by too much addition amount of the thermosetting polyurethane particles surface graft-modified, which is advantageous for reducing the dielectric loss, and thus the addition amount should be properly adjusted.
The recovery method of the waste thermosetting polyurethane can greatly enhance the mechanical property and the dielectric property of the epoxy resin composite material, thereby effectively utilizing the waste thermosetting polyurethane and changing waste into valuable.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. A method for recycling waste thermosetting polyurethane is characterized by comprising the following specific steps: 1) Firstly, placing epoxy resin and diethylaminopropylamine in a high-speed mixer to be uniformly mixed; 2) Then adding the thermosetting polyurethane with the surface graft modified and mixing evenly; 3) Curing in a baking oven to obtain the thermosetting polyurethane modified epoxy resin composite material;
the paint comprises the following components in parts by weight: 100 parts of epoxy resin; 2-8 parts of diethylaminopropylamine and 10-60 parts of thermosetting polyurethane particles with surface graft modification;
the preparation method of the thermosetting polyurethane with the surface graft modification comprises the following steps: 1) Crushing: crushing and sieving the waste thermosetting polyurethane to obtain particles with the particle size of less than 10 mm; 2) And (3) activation: irradiating the thermosetting polyurethane particles by gamma rays to obtain activated thermosetting polyurethane particles; 3) Modification: uniformly premixing activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water, grinding by a colloid mill, drying and sieving to obtain surface-graft-modified thermosetting polyurethane particles;
the paint comprises the following components in parts by weight: 100 parts of activated thermosetting polyurethane particles, 10-20 parts of nitric acid, 5-10 parts of acrylic acid and 200 parts of deionized water.
2. The recycling method of waste thermosetting polyurethane as claimed in claim 1, wherein the thermosetting polyurethane in step 1) is selected from thermosetting polyurethanes having a degree of crosslinking of more than 50% and a hardness of more than 88D.
3. The recycling method of waste thermosetting polyurethane as set forth in claim 1, wherein the concentration of nitric acid is 40%.
4. The method for recycling waste thermosetting polyurethane according to claim 1, wherein in the step 3), activated thermosetting polyurethane particles, nitric acid, acrylic acid and deionized water are mixed by a high-speed mixer at normal temperature, and are subjected to colloid milling at 50-70 ℃.
5. The recycling method of waste thermosetting polyurethane as claimed in claim 1, wherein the irradiation in step 2) is performed under normal temperature and pressure environment with gamma ray of 10-30KGy.
6. The recycling method of waste thermosetting polyurethane as claimed in claim 1, wherein the temperature of the oven in the curing process is 60-70 ℃ and the curing time is 4 hours.
CN202010354785.8A 2020-04-29 2020-04-29 Method for recycling and reusing waste thermosetting polyurethane Active CN111393582B (en)

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CN106589814A (en) * 2016-12-02 2017-04-26 合肥龙多电子科技有限公司 Epoxy resin glass cloth composite printed circuit board material with good heat dispersion property and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989005316A1 (en) * 1987-12-10 1989-06-15 E.I. Du Pont De Nemours And Company Epoxy ester urethane graft acrylic water-based primer surfaces
CN1323843A (en) * 2001-06-20 2001-11-28 山东大学 Composite epoxy-modified acrylic acid-polyurethane emulsion and its prepn. process
CN1438257A (en) * 2003-03-06 2003-08-27 华南理工大学 Acrylic polyurethane copolymer emulsion, its preparation method and use
JP2005281334A (en) * 2004-03-26 2005-10-13 Toshiba Corp Method for recovering urethane resin and method for reclaiming urethane resin
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