CN114539761B - Polymer composite material and preparation method and application thereof - Google Patents

Polymer composite material and preparation method and application thereof Download PDF

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CN114539761B
CN114539761B CN202011344460.8A CN202011344460A CN114539761B CN 114539761 B CN114539761 B CN 114539761B CN 202011344460 A CN202011344460 A CN 202011344460A CN 114539761 B CN114539761 B CN 114539761B
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polytetrafluoroethylene
composite material
polyurethane
polyaryletherketone
polymer composite
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CN114539761A (en
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周光远
姜敏
王志鹏
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
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    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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    • 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
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    • C08G18/44—Polycarbonates
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    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • 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
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    • 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
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
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    • 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
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract

The application discloses a polymer composite material and a preparation method and application thereof. The polymer composite material is formed by cross-linking polymerization of double bonds in polyurethane and thermal oxygen in polyaryletherketone by oxygen free radicals, and grafting with polytetrafluoroethylene to form a staggered polymer chain in a net-shaped form. The polymer composite material has the advantages of low thermal expansion coefficient, high dimensional stability (medium such as water, lubricating oil, and the like), acid and alkali resistance and other conventional solvents, high and low temperature resistance, irradiation resistance and the like, and can be conveniently manufactured into products such as polymer composite material bearings, plates and the like according to actual needs. The application prospect in the fields of high polymer material bearings such as ships, hydropower, wind power, nuclear power and the like is very wide.

Description

Polymer composite material and preparation method and application thereof
Technical Field
The application relates to a polymer composite material, and belongs to the technical field of advanced composite materials.
Background
The high polymer material has comprehensive outstanding advantages in mechanical performance, friction self-lubrication, processing, transportation, maintenance, cost and the like, and is widely installed in various mechanical devices requiring sliding friction, such as hydropower, wind power, nuclear power, ships and the like, and is a core key component. At present, commercial polymer bearing materials mainly comprise rubber, polyurethane, nylon, ultra-high molecular weight polyethylene, polytetrafluoroethylene, polyester, phenolic aldehyde, epoxy, polyether ether ketone, polyether sulfone and the like, and are usually processed into shapes such as battens, cylinders, half tiles, split and the like in modes of mould pressing, casting, injection molding, fiber dipping irradiation and the like for different working conditions. The various macromolecular materials have obvious advantages and disadvantages, for example, the rubber material has the characteristics of sediment-resistant working condition and best shock absorption and noise reduction performance, but has limited bearing capacity, relatively large required size, high production, processing and installation precision requirements, high maintenance cost, poor dry friction resistance, and most serious abrasion and noise problems in the water-break starting stage; the polyurethane material can balance flexibility and hardness, and can be designed and provided with corresponding model products according to different working conditions, and has the main technical advantages of excellent dry-grinding resistance, simple production process, high yield, moderate material hardness and easy processing of a lathe, but has the defects of poor hot water resistance and easy hydrolysis at high temperature; in addition, nylon, polyester, phenolic aldehyde, epoxy, polyether-ether-ketone and polyether-sulfone materials can be classified into the same type, the hardness and the strength are the highest, the high-temperature resistance and the high-temperature resistance are excellent, the dry abrasion resistance and the wet abrasion resistance are both very good, the defects are that the hardness of the material is too high, the elasticity is too poor, the abrasion of a shaft is serious particularly under a sediment working condition, and meanwhile, the central axis is easy to deviate in the running process, and polarization type rapid abrasion is generated; the ultra-high molecular weight polyethylene and polytetrafluoroethylene have the best self-lubricating performance, but have poor dimensional stability, and particularly the thermal deformation caused by friction heat generation is easy to cause safety accidents.
Although there are several patents and literature reports how to consider the performances of materials in various aspects by means of formulation, process and the like, for example, the prior art discloses a phenolic-polyurethane composite system, and the process of dipping polyurethane fiber filaments is used for solving the problems of material bearing and toughness, the polyurethane fiber and phenolic resin in the material have regional differences and are not homogeneous materials due to a dipping hot-pressing method, and the material has cracking risk in the using process and poor safety; the prior art discloses a method for modifying polyether sulfone, which is toughened by introducing thermoplastic polyurethane, and the miscibility between two polymers can be increased by banburying, extrusion granulation and injection molding processes, so that the overall uniformity of the material is obviously improved, but the materials are subjected to simple physical blending and gradually migrate phase separation along with time, so that the performance is changed, and the friction stability is not high; the prior art provides the thinking of bilayer structure's polyurethane, low hardness polyurethane is as the frictional layer, high hardness polyurethane is outer the support, adjust bearing capacity through adjusting the thickness of frictional layer, and the outer layer also can be traded any stereoplasm polymer, balanced bearing and toughness with another thinking, but still can only be applied to those to polyurethane medium influence not big operating mode, it is very little to require frictional layer material thickness when high bearing demand moreover, in case wearing and tearing will not ensure subsequent fail safe and reliable, risk coefficient is bigger.
Disclosure of Invention
In order to solve the problem that the bearing performance of the high polymer material in the prior art cannot be taken into consideration in the comprehensive aspects of bearing, toughness, medium resistance, dimensional stability and the like, the high-bearing high-toughness super-wear-resistant self-lubricating high polymer composite material and the preparation method thereof are provided, and the bearing can be manufactured according to the required form.
According to a first aspect of the present application, a polymeric composite is provided. The polymer composite material has the advantages of low thermal expansion coefficient, high dimensional stability (medium such as water, lubricating oil, and the like), acid and alkali resistance and other conventional solvents, high and low temperature resistance, radiation resistance, and the like. And can be conveniently manufactured into the form of a bearing and the like according to the actual required form.
A polymer composite material is prepared from double bonds in polyurethane and thermal oxygen in polyaryletherketone through cross-linking polymerization of oxygen free radicals, and grafting with polytetrafluoroethylene to form interlaced macromolecular chains in a net shape.
Optionally, the mass ratio of the polyurethane to the polyaryletherketone to the polytetrafluoroethylene is as follows:
5～30：50～100：0.5～10。
optionally, the mass ratio of the polyurethane to the polyaryletherketone to the polytetrafluoroethylene is as follows:
4～25：50～60：3～6。
optionally, the polyurethane is a functional polyurethane; the polytetrafluoroethylene is from polytetrafluoroethylene material modified by electron beam irradiation.
Optionally, the elongation at break of the polymer composite is 60-110%.
Optionally, the dry friction coefficient of the polymer composite material is 0.13-0.18.
Optionally, the water lubrication friction coefficient of the polymer composite material is 0.01-0.025.
According to a second aspect of the present application, a method of preparing a polymeric composite is provided.
The preparation method of the polymer composite material comprises the following steps: and (3) obtaining three-phase composite powder containing polyurethane, polyaryletherketone and polytetrafluoroethylene, and performing compression molding to obtain the polymer composite material.
Optionally, polyurethane solution, polyaryletherketone solution and polytetrafluoroethylene powder are respectively obtained, and three-phase composite powder containing polyurethane, polyaryletherketone and polytetrafluoroethylene is formed after atomization and drying.
Optionally, obtaining the polyurethane solution comprises the steps of: and (3) reacting the mixture containing the polymer polyol, the diisocyanate and the inert solvent I in an inactive atmosphere, adding the small molecule chain extender containing double bonds, continuing the reaction, and cooling to obtain the polyurethane solution.
Optionally, the mass ratio of the polymer polyol, the inert solvent I, the diisocyanate and the small molecule chain extender containing double bonds is 100:80-250:10-50:4-25.
Optionally, the mass ratio of the polymer polyol, the inert solvent I, the diisocyanate and the small molecule chain extender containing double bonds is 100-200:200-400:35-200:30-60.
Optionally, the polymer polyol has a number average molecular weight of 500 to 5000;
the polymer polyol is at least one selected from polyester diol of a poly adipic acid series, polycaprolactone diol, polycarbonate diol, polytetrahydrofuran ether diol, polypropylene oxide ether diol and hydroxyl-terminated polybutadiene.
Optionally, the poly (adipic acid) series polyester diol is at least one selected from poly (ethylene adipate) diol, poly (butylene adipate) diol, poly (ethylene adipate) butanediol copolydiol and poly (1, 3-propylene adipate) diol.
Optionally, the inert solvent I is at least one selected from toluene, acetone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
Optionally, the diisocyanate is selected from at least one of toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate and 1, 5-naphthalene diisocyanate.
Alternatively, the conditions of the reaction under an inert atmosphere are: the temperature is 50-80 ℃ and the time is 1-3 h.
Optionally, the inactive atmosphere is at least one selected from nitrogen and argon.
Optionally, obtaining the polyaryletherketone solution comprises the steps of: and dissolving the polyaryletherketone in the inert solvent II to obtain a polyaryletherketone solution.
Optionally, the solid content of the polyaryletherketone solution is 10% -65%.
Optionally, the solid content of the polyaryletherketone solution is 10% -60%.
Optionally, the solid content of the polyaryletherketone solution is 40% -63%.
Alternatively, the solids content of the polyaryletherketone solution is independently selected from any of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range of values between any two.
In the present application, the solid content refers to the mass percentage of the residual substances in the total amount after the system is dried.
In this application, the polyaryletherketone is derived from the prior art, such as the polyaryletherketone of various structures mentioned in patents CN201610796153.0, CN201610796206.9, CN201610796300.4, CN 2015110182341. X, CN201310440166.0, CN201310440208.0, CN201210407687.1, CN201210382679.6, CN201210086808.7, CN 201210041298.1.
Optionally, the inert solvent II is selected from at least one of sulfolane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and sulfolane.
Optionally, the polytetrafluoroethylene powder is modified by electron beam irradiation. Under the aerobic condition, after polytetrafluoroethylene is irradiated, a large number of stable oxygen-containing free radicals are arranged on the main chain.
Optionally, the polytetrafluoroethylene powder has a particle size of 1-10 microns.
Optionally, the dose of the electron beam is 300-1500 KGy.
Optionally, the dose of the electron beam is 1000-1200 KGy.
Optionally, the electron beam irradiation modification time is 5 to 150 days.
According to the dose of the electron beam and the irradiation modification time, the irradiation dose of each day can be calculated, for example, the irradiation dose of the electron beam is 1000KGy for modification treatment, the treatment time is 100 days, and the dose of each day is 10KGy.
Optionally, the conditions of the atomization drying are: the drying chamber temperature was 100 ℃. The specific application is that the common vacuum spray drying setting is adopted.
Optionally, in the three-phase composite powder, the mass ratio of polyurethane to poly (arylene ether ketone) to polytetrafluoroethylene is as follows:
5～30：50～100：0.5～10。
optionally, in the three-phase composite powder, the mass ratio of polyurethane to poly (arylene ether ketone) to polytetrafluoroethylene is as follows:
4～25：50～60：3～6。
optionally, the particle size of the three-phase composite powder is 10-50 microns.
Optionally, the conditions of the compression molding are: carrying out gradient heating and heat preservation on the three-phase composite powder for a certain period of time for compression molding, wherein the compression molding pressure is 5-25 MPa;
the gradient heating and heat preservation period is 100-150 ℃ for 10-30 min, 150-200 ℃ for 10-30 min, 200-250 ℃ for 10-30 min and 250-300 ℃ for 10-30 min.
As a specific embodiment, the preparation method comprises the following steps:
step one, preparing functional Polyurethane (PU) solution
Vacuum dehydrating polymer polyol, cooling, adding the dehydrated polymer polyol into a reaction device filled with an inert solvent and diisocyanate, reacting for 1-3 hours at 50-80 ℃ under nitrogen atmosphere, adding a small molecular chain extender containing double bonds, continuously reacting for 1 hour, and cooling to room temperature to obtain functional PU emulsion;
the polymer polyol is one or more of poly (adipic acid) series polyester diol, polycaprolactone diol, polycarbonate diol, polytetrahydrofuran ether glycol, polypropylene oxide ether diol and hydroxyl-terminated polybutadiene with the number average molecular weight of 500-5000;
the inert solvent is one or more of toluene, acetone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate and 1, 5-naphthalene diisocyanate;
the small molecule chain extender containing double bonds is one or more of 1, 4-butylene glycol, 1, 5-hexadiene-3, 4-diol and 2, 4-hexadiene-1, 6-diol;
the mass ratio of the polymer polyol to the inert solvent to the diisocyanate to the small molecular chain extender containing double bonds is (100-200): 200-400): 35-200): 30-60;
step two, preparing Polyaryletherketone (PAEK) solution
Based on various structures PAEKs mentioned in patents CN201610796153.0, CN201610796206.9, CN201610796300.4, CN 2015110182341. X, CN201310440166.0, CN201310440208.0, CN201210407687.1, CN201210382679.6, CN201210086808.7 and CN201210041298.1, dissolving PAEK solution configured to a certain solid content with an inert solvent;
the inert solvent is one or more of sulfolane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the solid content is 10% -60%;
step three, irradiation modified polytetrafluoroethylene micro powder
The purchased commercial polytetrafluoroethylene micro powder is irradiated by electron beam to carry out irradiation with a certain dosage, and the surface of the polytetrafluoroethylene micro powder is modified
The commercialized polytetrafluoroethylene micro powder is superfine micro powder with the particle size range of 1-10 microns, for example, one or more of polytetrafluoroethylene micro powder special for coating, polytetrafluoroethylene micro powder special for printing ink, polytetrafluoroethylene micro powder special for lubricating grease and the like of Shenyang Seamount of science and technology Co., ltd;
the certain dosage is 300-1500 KGy;
step four, adding the PU solution, the PAEK solution and the polytetrafluoroethylene micro powder subjected to irradiation modification into a spray blast drying chamber from different feed inlets respectively according to a certain mass ratio, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK-PTFE three-phase composite micro powder with uniform particle size distribution;
the certain mass ratio is that the mass ratio of the fixed components in the three phases after drying is PU, PAEK and PTFE are (5-30): (50-100): (0.5-10);
the particle size distribution is uniform, and the particle size distribution interval of the three-phase composite micro powder is 10-50 microns;
step five, carrying out compression molding on the obtained three-phase composite micro powder for a certain period of time through gradient heating and heat preservation according to the required form of the bearing, so as to obtain the high-bearing high-toughness super wear-resistant self-lubricating polymer composite material;
the gradient heating and heat preservation is carried out for a certain period of time at 100-150 ℃, 10-30 min, 150-200 ℃, 10-30 min, 200-250 ℃, 10-30 min, 250-300 ℃ and 10-30 min;
the mould pressing pressure is 5-25 MPa.
According to a third aspect of the application, the application of the polymer composite material in bearings and plates is provided.
Optionally, the polymer composite material bearing comprises three-phase composite powder of polyurethane, polyaryletherketone and polytetrafluoroethylene, and is obtained by compression molding according to the required form of the bearing.
The application solves the problem that the existing polymer bearing material cannot be well-cured between performances such as bearing property, toughness, dimensional stability and friction and abrasion for a long time. The method comprises the steps of respectively preparing a functional Polyurethane (PU) solution and a Polyaryletherketone (PAEK) solution, then synchronously combining the functional Polyurethane (PU) solution and the Polyaryletherketone (PAEK) solution with polytetrafluoroethylene Powder (PTFE) subjected to radiation modification treatment in a high-temperature drying process to form PU-PAEK-PTFE three-phase composite micro powder, gradually heating and compression molding the obtained composite micro powder within a certain temperature range, and naturally cooling to room temperature to obtain the high-load high-toughness super-wear-resistant self-lubricating polymer composite bearing material.
In this application, unless otherwise indicated, the data ranges given are selected from any of the values in the ranges and include the endpoints of the ranges.
In this application, PU refers to polyurethane.
In the present application PAEK refers to polyaryletherketone.
In this application, PTFE refers to polytetrafluoroethylene.
The beneficial effects that this application can produce include:
1) The polymer composite material provided by the application has excellent friction performance, has the excellent characteristics of high-bearing high-toughness super-wear-resistant self-lubrication, creatively introduces functional PU, directly combines the PU, PAEK and PTFE modified by irradiation together by a synchronous spray drying method to form three-phase micro powder with uniform particle size distribution, adopts gradient heating mould pressing, enables double bonds in the functional PU to generate oxygen free radical crosslinking polymerization with thermal oxygen in the PAEK under high temperature and high pressure, grafts with PTFE modified by irradiation to form complex and staggered firm macromolecular chains similar to a reticular form, can achieve the flexibility of the PU, the high bearing performance of the PAEK and the self-lubrication performance of the PTFE on the basis of ensuring the uniformity of the material, and effectively prevents the problem of poor dimensional stability of the material caused by the movement of the molecular chains such as sliding, stretching and the like, and improves the performance of the material in terms of medium resistance. The polymer composite material can be conveniently manufactured into products such as polymer composite material bearings, plates and the like according to actual needs.
2) According to the preparation method of the polymer composite material, the composition and the particle size of the three-phase composite micro powder obtained through spray drying can be regulated and controlled through the solubility of the PU solution, the solid content of the PAEK solution, the particle size of the PTFE micro powder, the mass ratio among the three and the temperature of a spraying chamber, and finally the composite material with different moduli, toughness and friction performance can be obtained.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples. Unless otherwise specified, the test methods all use conventional methods, and the instrument settings all use manufacturer recommended settings.
Wherein, the polyaryletherketone is prepared by adopting a method disclosed in patent CN201310440208.0, the specific preparation method adopts the polyaryletherketone with an I-a structure, which is obtained by adopting a toluene azeotropic water outlet method, by adopting benzimidazolone and difluorobenzophenone of the embodiment 1 and taking sulfolane as a solvent under the catalysis of a catalyst potassium carbonate.
Comparative example 1
Because PU and modified PTEF are not contained in the poly (arylene ether ketone) powder, the poly (arylene ether ketone) powder is directly subjected to die pressing under the pressure of 10MPa according to the temperature-raising procedures of heat preservation at 150 ℃ for 10min, 220 ℃ for 10min and 280 ℃ for 30min, and finally pressure is released and the die is opened after pressure is reduced to room temperature, so that the small plate with the length, width and height of 50 multiplied by 5mm is prepared.
Comparative example 2 (PU-PAEK composite)
Step 1, preparing functional PU emulsion
Vacuum dehydrating 100g of polycaprolactone diol with the molecular weight of 2000, cooling, adding into a reaction device filled with 200g of toluene and 17.5g of toluene diisocyanate, reacting for 2 hours at 65 ℃ under nitrogen atmosphere, adding 4.4g of 1, 4-butylene glycol, continuing to react for 1 hour, and cooling to room temperature to obtain functional PU emulsion;
step 2, preparing PAEK solution
Dissolving 100g of polyaryletherketone in 100g of N, N-dimethylacetamide, and fully stirring to prepare a uniform solution with 50% of solid content;
step 3, preparing PU-PAEK two-phase composite micro powder
Adding 20g of PU solution and 100g of PAEK solution into a spray blasting drying chamber from different feed inlets, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK two-phase composite micro powder with the particle size distribution area of 20-30 microns, wherein the mass ratio PU to PAEK is 1.5:10;
step 4, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of 10min at 100 ℃,10 min at 150 ℃,10 min at 220 and 20min at 280 ℃, wherein the pressure is 10MPa, and finally, after the pressure is reduced to room temperature, releasing pressure and opening the mould to prepare the small plate with the length and width height of 50 multiplied by 5 mm.
Comparative example 3 (PAEK-PTFE composite)
Step 1, preparing PAEK solution
Dissolving 100g of polyaryletherketone in 100g of N, N-dimethylacetamide, and fully stirring to prepare a uniform solution with 50% of solid content;
step 2, preparing irradiation modified PTFE particles
The special polytetrafluoroethylene micro powder (particle size 1-10 microns) for coating is directly modified by using electron beam irradiation dose of 1200KGy for 120 days, wherein the daily dose is 10KGy;
step 3, preparing PAEK-PTFE two-phase composite micro powder
100g of PAEK solution and 5g of PTFE micropowder are respectively added into a spray blasting drying chamber from different feed inlets, the temperature of the drying chamber is controlled to be 100 ℃, and PAEK-PTFE two-phase composite micropowder with the particle size distribution area of 20-30 microns is obtained by collecting, wherein the mass ratio of the PAEK to the PTFE is 10:1;
step 4, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of 10min at 100 ℃,10 min at 150 ℃,10 min at 220 and 20min at 280 ℃, wherein the pressure is 10MPa, and finally, after the pressure is reduced to room temperature, releasing pressure and opening the mould to prepare the small plate with the length and width height of 50 multiplied by 5 mm.
Example 1
Step 1, preparing functional PU emulsion
Vacuum dehydrating 100g of polycaprolactone diol with the molecular weight of 2000, cooling, adding into a reaction device filled with 200g of toluene and 17.5g of toluene diisocyanate, reacting for 2 hours at 65 ℃ under nitrogen atmosphere, adding 4.4g of 1, 4-butylene glycol, continuing to react for 1 hour, and cooling to room temperature to obtain functional PU emulsion;
step 2, preparing PAEK solution
Dissolving 100g of polyaryletherketone in 100g of N, N-dimethylacetamide, and fully stirring to prepare a uniform solution with 50% of solid content;
step 3, preparing irradiation modified PTFE particles
The special polytetrafluoroethylene micro powder (particle size 1-10 microns) for coating is directly modified by using electron beam irradiation dose of 1200KGy for 120 days, wherein the daily dose is 10KGy;
step 4, preparing the PU-PAEK-PTFE three-phase composite micro powder
Respectively adding 20g of PU solution, 100g of PAEK solution and 5g of PTFE micro powder into a spray blasting drying chamber from different feed inlets, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK-PTFE three-phase composite micro powder with the particle size distribution area of 20-30 microns, wherein the mass ratio of the PU to the PAEK to the PTFE is 7.5:50:5;
step 5, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of 10min at 100 ℃,10 min at 150 ℃,10 min at 220 and 20min at 280 ℃, wherein the pressure is 10MPa, and finally, after the pressure is reduced to room temperature, releasing pressure and opening the mould to prepare the small plate with the length and width height of 50 multiplied by 5 mm.
Example 2
Step 1, preparing functional PU emulsion
Vacuum dehydrating 100g of polytetrahydrofuran ether glycol with molecular weight of 1000, cooling, adding into a reaction device filled with 250g of acetone and 50g of diphenylmethane diisocyanate, reacting for 2 hours at 60 ℃ under nitrogen atmosphere, adding 22.8g of 1, 5-hexadiene-3, 4-diol, continuing to react for 1 hour, and cooling to room temperature to obtain functional PU emulsion;
step 2, preparing PAEK solution
100g of polyaryletherketone is dissolved in 60g of sulfolane, and the mixture is fully stirred and dissolved to prepare a uniform solution with the solid content of 62.5 percent;
step 3, preparing irradiation modified PTFE particles
The special polytetrafluoroethylene micro powder for printing ink is directly modified by electron beam irradiation dose of 1200KGy for 120 days, wherein the daily dose is 10KGy;
step 4, preparing the PU-PAEK-PTFE three-phase composite micro powder
Adding 30g of PU solution, 80g of PAEK solution and 6g of PTFE micropowder into a spray blasting drying chamber from different feed inlets, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK-PTFE three-phase composite micropowder with the particle size distribution area of 30-40 microns, wherein the mass ratio of PU to PAEK to PTFE is 12.2:50:6;
step 5, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of heat preservation at 120 ℃ for 20min, 160 ℃ for 15min, 240 for 10min and 280 ℃ for 15min, wherein the pressure is 10MPa, and finally, pressure relief and mould opening are carried out after the pressure is reduced to room temperature, so as to prepare the small plate with the length and width of 50 multiplied by 5 mm.
Example 3
Step 1, preparing functional PU emulsion
Vacuum dehydrating 100g of polyethylene glycol adipate glycol with molecular weight of 3000, cooling, adding into a reaction device filled with 80g of dimethyl sulfoxide and 10.68g of terephthalyl diisocyanate, reacting for 1.5 hours at 70 ℃ under nitrogen atmosphere, adding 7.6g of 2, 4-hexadiene-1, 6-diol, continuing to react for 1.5 hours, and cooling to room temperature to obtain functional PU emulsion;
step 2, preparing PAEK solution
100g of polyaryletherketone is dissolved in 150g of dimethyl sulfoxide, and the mixture is fully stirred and dissolved to prepare a uniform solution with the solid content of 40%;
step 3, preparing irradiation modified PTFE particles
The special polytetrafluoroethylene micro powder for lubricating grease is directly modified by using electron beam irradiation dose of 1000KGy for 100 days, wherein the dose per day is 10KGy;
step 4, preparing the PU-PAEK-PTFE three-phase composite micro powder
Adding 40g of PU solution, 150g of PAEK solution and 3g of PTFE micropowder into a spray blasting drying chamber from different feed inlets, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK-PTFE three-phase composite micropowder with the particle size distribution area of 30-40 microns, wherein the mass ratio of PU to PAEK to PTFE is 23.8:60:3;
step 5, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of heat preservation at 140 ℃ for 30min, 180 ℃ for 20min, 240 for 20min and 290 ℃ for 10min, wherein the pressure is 10MPa, and finally, pressure relief and mould opening are carried out after pressure reduction is carried out at room temperature, so as to prepare the small plate with the length and width of 50 multiplied by 5 mm.
Example 4
Step 1, preparing functional PU emulsion
Vacuum dehydrating 100g of polycarbonate diol with molecular weight of 1000, cooling, adding into a reaction device filled with 150g of N, N-dimethylformamide and 42g of 1, 5-naphthalene diisocyanate, reacting for 1h at 80 ℃ under nitrogen atmosphere, adding 8.8g of 1, 4-butylene glycol, continuing to react for 1h, and cooling to room temperature to obtain functional PU emulsion;
step 2, preparing PAEK solution
Dissolving 100g of polyaryletherketone in 100g of N, N-dimethylformamide, and fully stirring to dissolve to prepare a uniform solution with 50% of solid content;
step 3, preparing irradiation modified PTFE particles
The special polytetrafluoroethylene micro powder for lubricating grease is directly modified by using electron beam irradiation dose of 1000KGy for 100 days, wherein the dose per day is 10KGy;
step 4, preparing the PU-PAEK-PTFE three-phase composite micro powder
Adding 8g of PU solution, 100g of PAEK solution and 5g of PTFE micropowder into a spray blasting drying chamber from different feed inlets, controlling the temperature of the drying chamber to be 100 ℃, and collecting to obtain PU-PAEK-PTFE three-phase composite micropowder with the particle size distribution area of 15-20 microns, wherein the mass ratio of PU to PAEK to PTFE is 4:50:5;
step 5, die pressing to obtain the composite material plate
And (3) carrying out mould pressing according to a heating program of heat preservation at 120 ℃ for 10min, 160 ℃ for 10min, 220 ℃ for 10min and 260 ℃ for 10min, wherein the pressure is 10MPa, and finally, pressure relief and mould opening are carried out after the pressure is reduced to room temperature, so that the small plate with the length and width height of 50 multiplied by 5mm is prepared.
Example 5
The small plate samples obtained in comparative examples 1 to 3 and examples 1 to 4 were compared with commercial ultra-high molecular weight polyethylene plate samples (manufactured by Tadalton rubber and plastic Co., ltd., ningjin county, molecular weight: 570 ten thousand) under the same conditions according to the test standards of Table 1, and the properties such as hardness, tensile strength, elongation at break, notched impact strength, friction coefficient and dimensional stability in water and oil were measured and shown in Table 1:
TABLE 1 comparison of the properties of comparative examples 1 to 3, examples 1 to 4 and ultra high molecular weight polyethylene sheets
Figure BDA0002799427380000131
As can be seen from Table 1, compared with the pure polyaryletherketone resin material before modification, the composite material obtained by the invention has obviously improved key performance indexes, especially both bearing and toughness are simultaneously considered, and in addition, the composite material has excellent self-lubricating performance, especially dimensional stability, and extremely low water absorption and oil absorption expansion rate, and can be widely applied to sliding friction parts with extremely severe bearing clearance requirements.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (24)

1. A polymer composite material is characterized in that double bonds in polyurethane and thermal oxygen in polyaryletherketone generate oxygen free radical crosslinking polymerization, and are grafted with polytetrafluoroethylene to form interlaced macromolecular chains in a net shape.
2. The polymer composite material according to claim 1, wherein the mass ratio of polyurethane, polyaryletherketone and polytetrafluoroethylene is:
5～30：50～100：0.5～10。
3. the polymer composite material according to claim 1, wherein the polyurethane is functional polyurethane, and is obtained by reacting a mixture containing polymer polyol and diisocyanate in an inert atmosphere, adding a small molecular chain extender containing double bonds, and continuing the reaction; the polytetrafluoroethylene is from polytetrafluoroethylene material modified by electron beam irradiation.
4. A method for producing the polymer composite material according to any one of claims 1 to 3, comprising the steps of: and (3) obtaining three-phase composite powder containing polyurethane, polyaryletherketone and polytetrafluoroethylene, and performing compression molding to obtain the polymer composite material.
5. The preparation method according to claim 4, wherein polyurethane solution, polyaryletherketone solution and polytetrafluoroethylene powder are obtained respectively, and three-phase composite powder containing polyurethane, polyaryletherketone and polytetrafluoroethylene is formed after atomization and drying.
6. The method of preparing as claimed in claim 5, wherein obtaining the polyurethane solution comprises the steps of: and (3) reacting the mixture containing the polymer polyol, the diisocyanate and the inert solvent I in an inactive atmosphere, adding the small molecule chain extender containing double bonds, continuing the reaction, and cooling to obtain the polyurethane solution.
7. The method according to claim 6, wherein,
the mass ratio of the polymer polyol to the inert solvent I to the diisocyanate to the small molecule chain extender containing double bonds is 100:80-250:10-50:4-25.
8. The method according to claim 6, wherein,
the number average molecular weight of the polymer polyol is 500-5000;
the polymer polyol is at least one selected from polyester diol of a poly adipic acid series, polycaprolactone diol, polycarbonate diol, polytetrahydrofuran ether diol, polypropylene oxide ether diol and hydroxyl-terminated polybutadiene.
9. The method according to claim 8, wherein,
the poly (adipic acid) series polyester diol is at least one selected from poly (ethylene adipate) diol, poly (butylene adipate) diol, poly (ethylene adipate) butanediol copolydiol and poly (1, 3-propylene adipate) diol.
10. The method according to claim 6, wherein,
the inert solvent I is at least one selected from toluene, acetone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
11. The method according to claim 6, wherein,
the diisocyanate is at least one selected from toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate and 1, 5-naphthalene diisocyanate.
12. The method according to claim 6, wherein,
the reaction conditions under the inactive atmosphere are: the temperature is 50-80 ℃ and the time is 1-3 h.
13. The method of claim 5, wherein obtaining a polyaryletherketone solution comprises the steps of: and dissolving the polyaryletherketone in the inert solvent II to obtain a polyaryletherketone solution.
14. The method according to claim 5, wherein,
the solid content of the polyaryletherketone solution is 10-65%.
15. The method of claim 13, wherein the process comprises,
the inert solvent II is selected from at least one of sulfolane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and sulfolane.
16. The method according to claim 5, wherein the polytetrafluoroethylene powder is a polytetrafluoroethylene powder modified by electron beam irradiation.
17. The method of claim 16, wherein the process comprises,
the particle size of the polytetrafluoroethylene powder is 1-10 microns.
18. The method of claim 16, wherein the process comprises,
the dose of the electron beam is 300-1500 KGy.
19. The method of claim 16, wherein the process comprises,
the electron beam irradiation modification time is 5-150 days.
20. The method according to claim 5, wherein the conditions for the atomization drying are: the drying chamber temperature was 100 ℃.
21. The method according to claim 5, wherein,
in the three-phase composite powder, the mass ratio of polyurethane to poly (arylene ether ketone) to polytetrafluoroethylene is as follows:
5～30：50～100：0.5～10。
22. the method according to claim 5, wherein,
the particle size of the three-phase composite powder is 10-50 microns.
23. The method according to claim 4, wherein,
the conditions of the compression molding are as follows: carrying out gradient heating and heat preservation on the three-phase composite powder for a certain period of time for compression molding, wherein the compression molding pressure is 5-25 MPa;
the gradient heating and heat preservation period is 100-150 ℃ for 10-30 min, 150-200 ℃ for 10-30 min, 200-250 ℃ for 10-30 min and 250-300 ℃ for 10-30 min.
24. Use of at least one of the polymer composite material according to any one of claims 1 to 3 and the polymer composite material prepared by the preparation method according to any one of claims 4 to 23 in bearings and plates.
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Publication number Priority date Publication date Assignee Title
CN105255189A (en) * 2015-11-30 2016-01-20 长春安旨科技有限公司 Polyether sulfone composite material and preparation method and application thereof
CN106046663A (en) * 2016-05-26 2016-10-26 长春安旨科技有限公司 Macromolecular composite bearing and preparation method therefor
CN107725601A (en) * 2017-07-10 2018-02-23 北华大学 A kind of preparation method of double-decker polyurethane composite bearing
CN110181886A (en) * 2019-05-29 2019-08-30 明阳科技（苏州）股份有限公司 A kind of thin-walled bonding self-lubricating plate material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105255189A (en) * 2015-11-30 2016-01-20 长春安旨科技有限公司 Polyether sulfone composite material and preparation method and application thereof
CN106046663A (en) * 2016-05-26 2016-10-26 长春安旨科技有限公司 Macromolecular composite bearing and preparation method therefor
CN107725601A (en) * 2017-07-10 2018-02-23 北华大学 A kind of preparation method of double-decker polyurethane composite bearing
CN110181886A (en) * 2019-05-29 2019-08-30 明阳科技（苏州）股份有限公司 A kind of thin-walled bonding self-lubricating plate material

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