CN114805736A - Polyurethane elastomer composite material and preparation method thereof - Google Patents

Polyurethane elastomer composite material and preparation method thereof Download PDF

Info

Publication number
CN114805736A
CN114805736A CN202210359660.3A CN202210359660A CN114805736A CN 114805736 A CN114805736 A CN 114805736A CN 202210359660 A CN202210359660 A CN 202210359660A CN 114805736 A CN114805736 A CN 114805736A
Authority
CN
China
Prior art keywords
graphite
polyurethane elastomer
stirring
prepolymer
parts
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
Application number
CN202210359660.3A
Other languages
Chinese (zh)
Inventor
王世伟
徐铁宁
孙中梁
李伟
战思琪
丁文贺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun University of Technology
Original Assignee
Changchun University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun University of Technology filed Critical Changchun University of Technology
Publication of CN114805736A publication Critical patent/CN114805736A/en
Pending legal-status Critical Current

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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C08K7/12—Asbestos
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a polyurethane elastomer material and a preparation method thereof. The material comprises the following raw materials in parts by weight: 100 parts by weight of polyol, 10-70 parts by weight of diisocyanate, 0-50 parts by weight of chain extender, 0-25 parts by weight of cross-linking agent, 10-20 parts by weight of antimony compound, 0-25 parts by weight of graphite derivative and 0-35 parts by weight of fiber, and the polyurethane elastomer material is a polyurethane elastomer material with a specific composition and structure. The invention adopts the specific antimony compound, the graphite and the fiber for matching use, thereby obviously improving the frictional wear performance of the polyurethane elastomer material. The high wear-resistant polyurethane elastomer prepared by the technology of the invention maintains the mechanical properties of high hardness, high elasticity and the like, and simultaneously further improves the wear-resistant property of the polyurethane elastomer. The technology has simple preparation process and environmental protection, and the material can be widely applied to the manufacturing production of bearing linings, shock pads, sealing elements and the like.

Description

Polyurethane elastomer composite material and preparation method thereof
The present application claims the priority of the chinese patent application entitled "a highly abrasion resistant polyurethane elastomer article and method for making the same" filed by the chinese patent office at 24.02/2022 under the application number 202210176683.0, which is incorporated herein by reference in its entirety.
Technical Field
The invention belongs to the technical field of polyurethane elastomers, relates to a polyurethane elastomer composite material and a preparation method thereof, and particularly relates to a high-wear-resistance polyurethane elastomer composite material and a preparation method thereof.
Background
Polyurethane is an important functional polymer material and has extremely wide application. The high molecular long chain of the polyurethane is substantially linear, and a partially crosslinked structure is formed by the chain extender and the crosslinking agent. The urethane group of the polyurethane can cause a plurality of physical cross-links among molecular chain lines formed by hydrogen bonds, and the physical cross-links formed by the hydrogen bonds have the characteristics of high strength, good wear resistance, chemical resistance, hydrolysis resistance and the like. And because the polyurethane elastomer has 2 soft and hard chain segments, the polyurethane elastomer can endow the material with excellent performances such as high strength, good toughness, wear resistance, oil resistance and the like through the design of the chain segments, is called as 'wear-resistant rubber', and simultaneously has the high elasticity of the rubber and the rigidity of the plastic. These good properties have led to polyurethane elastomers being widely used in many areas such as shoe materials, cables, clothing, automobiles, medical and health, pipes, films and sheets. In particular, abrasion-resistant polyurethane elastomers have excellent abrasion resistance and are widely used in industrial fields where abrasion problems are serious, and have many important applications such as mining, oil and gas industries, and the like.
In mining industry equipment, a polyurethane sieve plate and a polyurethane screen are used as working surfaces for ore screening, in the operation process, materials have the effects of sliding friction, rolling friction, impact, abrasion, corrosion and the like on the sieve plate and the screen, the working environment is severe, and the abrasion resistance of the sieve plate and the screen is an important factor influencing the service life of the sieve plate and the screen. In the prior art, corresponding high-wear-resistance polyurethane elastomers and preparation methods thereof are also disclosed, for example, in patent CN103923457A, fumed silica and an organic friction reducer are used together, and a chain extender is composed of a mixture of methyl-bis (3-chloro-2, 6-diethyl-aniline) (MCDEA) and other diamine chain extenders, so that the dispersion uniformity of organic auxiliaries in materials is improved, and the wear resistance of the materials is integrally improved. The abrasion of the obtained high-abrasion-resistance polyurethane elastomer is 24mm at the lowest 3 。
However, the modified high-wear-resistance polyurethane elastomer can cause dust pollution harm due to the use of nanoscale inorganic raw materials such as white carbon black in the preparation process, and the hardness and mechanical properties of the original material cannot be maintained after the filler is added.
Therefore, if a more appropriate preparation and production technology can be found, the problems of the modified polyurethane in the prior art are solved, the original mechanical property is fully maintained, the wear resistance of the polyurethane elastomer is further improved, and the prepared composite material has more application fields, including workpieces such as screens, bushings and seals, and the environment-friendly pollution production is realized.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a polyurethane elastomer composite material and a preparation method thereof, in particular to a polyurethane elastomer composite material with high wear resistance. The polyurethane elastomer provided by the invention further improves the wear resistance of the polyurethane elastomer while fully maintaining the original mechanical property. The method avoids the use of nano-scale micro particles, avoids environmental pollution, has simple preparation method, and is more suitable for industrial application and popularization.
The invention provides a polyurethane elastomer composite material, which comprises the following raw materials in parts by weight:
Figure BDA0003584507630000021
preferably, the polyol comprises one or more of polyether diol, polycaprolactone diol, polycarbonate diol, polyester diol and polyethylene glycol;
the diisocyanate comprises one or more of naphthalene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
Preferably, the chain extender comprises one or more of 1, 4-butanediol, ethylene glycol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, ethylenediamine, N-dihydroxy (diisopropyl) aniline, dimethylthiotoluenediamine and 3,3 '-dichloro-4, 4' -diphenylmethanediamine;
the cross-linking agent comprises one or more of trimethylolpropane, trimethylolpropane triacrylate, carbodiimide, glycerol, diethylenetriamine, hexamethylenetetramine, dicumyl peroxide, benzoyl peroxide, dicumyl peroxide, diethylene glycol and epoxy silane.
Preferably, the graphite derivative comprises one or more of crystalline flake graphite, bulk graphite, cryptocrystalline graphite, graphene oxide, expandable graphite, graphite fluoride and carbon nanotubes;
the size of the graphite fluoride is 0.05-150 mu m;
the antimony compound comprises antimony trioxide and/or antimony pentoxide;
the particle size of the antimony compound is 0.05 to 10 μm.
Preferably, the fibers comprise one or more of carbon fibers, glass fibers, polyester fibers, polyaramide fibers, and asbestos fibers;
the polyurethane elastomer is a high-wear-resistance polyurethane composite material.
The invention also provides a preparation method of the polyurethane elastomer composite material, which comprises the following steps:
1) dispersing and mixing polyol and graphite derivatives to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and diisocyanate under a protective atmosphere to obtain a graphite-doped prepolymer;
blending and stirring antimony compounds and the prepolymer uniformly, then adding fibers and stirring uniformly to obtain a composite prepolymer;
2) under the stirring condition, adding a chain extender and a cross-linking agent into the composite prepolymer obtained in the step, and stirring and mixing to obtain a mixture;
3) and pouring the mixture obtained in the step into a mold, and carrying out polymerization reaction, curing and molding to obtain the polyurethane elastomer composite material.
Preferably, the dispersing and mixing step further comprises a dehydration step;
the temperature of the prepolymerization reaction is 60-100 ℃;
the prepolymerization time is 0.5-10 h.
Preferably, the rotating speed of the stirring is 50-2000 rpm;
the chain extension coefficient for the polymerization reaction is 0.6-2.20.
Preferably, the temperature for stirring and mixing in the step (2) is 50-160 ℃;
and (3) stirring and mixing in the step (2) for 0.2-30 min.
Preferably, the temperature for curing and molding the polymerization reaction is 70-180 ℃;
the time for curing and molding the polymerization reaction is 10-90 min;
and the post-vulcanization step is also included after the curing and forming.
The invention provides a polyurethane elastomer composite material which comprises, by mass, 100 parts of polyol, 10-50 parts of diisocyanate, 10-50 parts of chain extender, 0-25 parts of cross-linking agent, 10-20 parts of antimony compound, 0-20 parts of graphite derivative and 0-35 parts of fiber. Compared with the prior art, the invention aims at the problems that the existing wear-resistant polyurethane elastomer composite material has dust pollution harm caused by inorganic raw materials and fails to maintain the mechanical property of the original material.
The invention creatively designs a polyurethane elastomer composite material with specific composition and structure, and the invention particularly adopts the matching use of fiber, antimony compound and graphite, combines a certain amount of usage and specific preparation steps, thereby obtaining the high wear-resistant polyurethane elastomer composite material. According to the high-wear-resistance polyurethane elastomer composite material and the preparation method thereof, the polyurethane elastomer can fully maintain the original mechanical property and further improve the wear resistance of the polyurethane elastomer. In addition, in the preparation process, the use of nano-scale micro particles is avoided, the environmental pollution and the injury of operators caused by process steps are reduced, and the corresponding complex post-treatment procedures are reduced.
The experimental result shows that the polyurethane elastomer material containing the fiber, the antimony compound and the graphite derivative provided by the invention keeps the original propertyThe mechanical property of 40MPa tensile strength and 60 Shore D hardness are simultaneously realized, the friction coefficient is remarkably reduced from 1.2 to 0.153, and the abrasion loss is from 30mm 3 Reduced to 16mm 3 And the friction performance of the polyurethane elastomer is greatly improved.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity which is conventional in the field of industrial purity or polyurethane production.
All noun expressions, acronyms and designations of the invention belong to the general noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expression, acronyms and designations.
The invention provides a polyurethane elastomer composite material, which comprises the following raw materials in parts by weight:
Figure BDA0003584507630000051
in the present invention, the diisocyanate is added in an amount of 10 to 50 parts by weight, preferably 15 to 45 parts by weight, more preferably 20 to 40 parts by weight, and still more preferably 25 to 35 parts by weight.
In the present invention, the addition amount of the chain extender is 0 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight, and more preferably 15 to 30 parts by weight.
In the present invention, the amount of the crosslinking agent added is 0 to 25 parts by weight, preferably 5 to 20 parts by weight, more preferably 7 to 17 parts by weight, and still more preferably 10 to 15 parts by weight.
In the present invention, the antimony compound is added in an amount of 10 to 20 parts by weight, preferably 12 to 18 parts by weight, and more preferably 14 to 16 parts by weight.
In the present invention, the amount of the graphite derivative added is 0 to 20 parts by weight, and may be 0.01 to 20 parts by weight, preferably 2 to 16 parts by weight, more preferably 4 to 12 parts by weight, and still more preferably 6 to 10 parts by weight.
In the present invention, the amount of the fiber added is 0 to 35 parts by weight, and may be 5 to 30 parts by weight, preferably 10 to 25 parts by weight, and more preferably 15 to 20 parts by weight.
In the present invention, the polyol preferably includes one or more of polyether diol, polycaprolactone diol, polycarbonate diol, polyester diol, and polyethylene glycol, and more preferably polytetrahydrofuran ether diol, polyethylene lactone diol, or polycarbonate diol.
In the present invention, the diisocyanate preferably includes one or more of Naphthalene Diisocyanate (NDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), 4 '-dicyclohexylmethane diisocyanate, and more preferably 4, 4' -dicyclohexylmethane diisocyanate, liquefied MDI, or toluene diisocyanate.
In the present invention, the chain extender preferably includes one or more of 1, 4-Butanediol (BDO), Ethylene Glycol (EG), hydroquinone dihydroxyethyl ether (HQEE), resorcinol dihydroxyethyl ether (HER), ethylenediamine (DA), N-dihydroxy (diisopropyl) aniline (HPA), dimethylthiotoluenediamine (DMTDA), and 3,3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), and more preferably 1, 4-butanediol, ethylene glycol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, ethylenediamine, N-dihydroxy (diisopropyl) aniline, dimethylthiotoluenediamine, or 3,3 '-dichloro-4, 4' -diphenylmethanediamine.
In the present invention, the antimony-based compound is preferably antimony trioxide and/or antimony pentoxide, and more preferably antimony trioxide or antimony pentoxide.
In the present invention, the graphite derivative preferably includes one or more of flake graphite, bulk graphite, cryptocrystal graphite, graphene oxide, expandable graphite, graphite fluoride, and carbon nanotubes, and more preferably flake graphite, bulk graphite, or graphene.
In the present invention, the size of the graphite is preferably 0.5 to 150 μm, more preferably 30 to 120 μm, and still more preferably 60 to 90 μm.
In the present invention, the crosslinking agent preferably includes one or more of trimethylolpropane, trimethylolpropane triacrylate, carbodiimide, glycerol, diethylenetriamine, hexamethylenetetramine, dicumyl peroxide, benzoyl peroxide, dicumyl peroxide, diethylene glycol and epoxy silane, and more preferably trimethylolpropane, trimethylolpropane triacrylate, carbodiimide, glycerol, diethylenetriamine.
In the present invention, the fibers preferably include one or more of glass fibers, carbon fibers, polyester fibers, polyaramide fibers, and asbestos fibers, and more preferably glass fibers, carbon fibers, and asbestos fibers.
In the present invention, the polyurethane elastomer is preferably an abrasion-resistant polyurethane elastomer, more preferably a highly abrasion-resistant polyurethane elastomer.
The invention provides a preparation method of a polyurethane elastomer composite material, which comprises the following steps:
1) dispersing and mixing polyol and graphite derivatives to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and diisocyanate under a protective atmosphere to obtain a graphite-doped prepolymer;
blending and stirring antimony compounds and the prepolymer uniformly, then adding fibers and stirring uniformly to obtain a composite prepolymer;
2) under the stirring condition, adding a chain extender and a cross-linking agent into the composite prepolymer, and stirring and mixing to obtain a mixture;
3) and pouring the mixture obtained in the step into a mold, and carrying out polymerization reaction, curing and molding to obtain the polyurethane elastomer composite material.
The preparation method comprises the steps of firstly dispersing and mixing the polyol and the graphite derivative to obtain the graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and diisocyanate in a protective atmosphere to obtain the graphite-doped prepolymer.
And blending and stirring the antimony compound and the prepolymer uniformly, then adding fibers and stirring uniformly to obtain the composite prepolymer.
In the present invention, it is preferable to further include a dehydration step after the dispersive mixing. Specifically, the dehydration step is a dehydration step for a polyol. That is, the polyol preferably comprises a dehydrated polyol.
In the invention, the temperature of the prepolymerization reaction is preferably 60-100 ℃, more preferably 64-86 ℃, and more preferably 68-72 ℃.
In the invention, the time of the prepolymerization reaction is preferably 0.5-10 h, more preferably 1.8-8 h, and more preferably 2.1-2.4 h.
And then adding a chain extender and a cross-linking agent into the composite prepolymer under the stirring condition, and stirring and mixing to obtain a mixture.
In the present invention, the chain extension coefficient for the polymerization reaction is preferably 0.6 to 2.20, more preferably 0.75 to 2.20, and more preferably 1.0 to 1.50.
In the present invention, the stirring is preferably high-speed stirring. The stirring speed is 50-2000 rpm, more preferably 100-1800 rpm, more preferably 300-1500 rpm, more preferably 500-1200 rpm, more preferably 700-1000 rpm.
In the invention, the stirring and mixing temperature is preferably 50-160 ℃, more preferably 60-150 ℃, more preferably 70-140 ℃, more preferably 80-130 ℃, and more preferably 90-110 ℃.
In the invention, the stirring and mixing time is preferably 0.2-30 min, more preferably 1-25 min, more preferably 3-20 min, and more preferably 5-15 min.
Finally, pouring the mixture obtained in the step into a mold, and carrying out polymerization reaction, curing and molding to obtain the polyurethane elastomer composite material.
In the present invention, the above steps are completed in a short time, so that the obtained mixture is slurry and can be poured into a mold, and the main process of polymerization and curing of the mixture is performed in the mold, so as to finally obtain the molded polyurethane elastomer composite material.
In the invention, the temperature for curing and molding the polymerization reaction is preferably 70-180 ℃, more preferably 88-146 ℃, and more preferably 108-112 ℃.
In the invention, the time for the polymerization reaction curing molding is preferably 10-90 min, more preferably 25-75 min, more preferably 30-600 min, and more preferably 35-45 min.
In the present invention, it is preferable that the curing step is further included after the curing.
The invention is a complete and refined integral preparation process, better ensures the composition and structure of the polyurethane elastomer composite material, improves the wear resistance and mechanical property of the polyurethane elastomer composite material, and the preparation method of the high wear-resistant polyurethane elastomer composite material can specifically comprise the following steps:
the preparation process of the antimony-containing polyurethane elastomer composite material doped with graphite provided by the invention can comprise the following steps of:
1) dispersing and mixing polyol and graphite derivatives to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and diisocyanate under a protective atmosphere to obtain a graphite-doped prepolymer;
blending and stirring antimony compounds and the prepolymer uniformly, then adding fibers and stirring uniformly to obtain a composite prepolymer;
2) under the condition of stirring, adding a chain extender and a cross-linking agent into the composite prepolymer, and stirring and mixing;
3) and (3) pouring the mixture obtained in the step (2) into a mold, and carrying out polymerization reaction, curing and molding to obtain the polyurethane elastomer composite material.
The performance was tested after 7 days at room temperature.
Specifically, the graphite is a graphite derivative such as crystalline flake graphite, bulk graphite, fluorinated graphene and the like. The content of the doped graphite fluoride is between 0 and 20 percent.
Specifically, the size of the graphite is 0.5-150 microns.
Specifically, the polyurethane elastomer composite material comprises the following raw materials in parts by weight:
Figure BDA0003584507630000091
specifically, the polyol comprises polyether diol, polycaprolactone diol, polycarbonate diol, polyester diol and polyethylene glycol.
Specifically, the diisocyanate includes naphthalene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, liquefied MDI, and toluene diisocyanate.
Specifically, the chain extender includes 1, 4-Butanediol (BDO), Ethylene Glycol (EG), hydroquinone dihydroxyethyl ether (HQEE), resorcinol dihydroxyethyl ether (HER), ethylenediamine (DA), N-dihydroxy (diisopropyl) aniline (HPA) dimethylthiotoluenediamine (DMTDA), and 3,3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA).
Specifically, the crosslinking agent includes trimethylolpropane, trimethylolpropane triacrylate, carbodiimide, glycerol, diethylenetriamine, hexamethylenetetramine, dicumyl peroxide, benzoyl peroxide, dicumyl peroxide, diethylene glycol, and epoxy silane.
Specifically, the antimony-based compound includes: antimony trioxide, antimony pentoxide.
The steps of the invention provide a high wear-resistant polyurethane elastomer composite material and a preparation method thereof. The invention particularly adopts the specific antimony compound and graphite to be matched for use, dopes the fiber, combines a certain dosage and specific preparation steps, and thus obtains the high-wear-resistance polyurethane elastomer composite material. According to the high-wear-resistance polyurethane elastomer composite material and the preparation method thereof, the polyurethane elastomer can fully maintain the original mechanical property and further improve the wear resistance of the polyurethane elastomer. In addition, in the preparation process, the use of nano-scale micro particles is avoided, the environmental pollution and the injury of operators caused by process steps are reduced, and the corresponding complex post-treatment procedures are reduced.
Experimental results show that the polyurethane elastomer material containing the fiber, the antimony compound and the graphite provided by the invention has the advantages that the friction coefficient is remarkably reduced from 1.2 to 0.153 and the abrasion loss is 30mm while the original mechanical property of 40MPa tensile strength and 60 Shore D hardness are maintained 3 Reduced to 16mm 3 And the friction performance of the polyurethane elastomer is greatly improved.
For further illustration of the present invention, a polyurethane elastomer composite and a preparation method thereof provided by the present invention are described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
PTMG is polytetrahydrofuran ether glycol, PCL is polycaprolactone, PCDL is polycarbonate, PPG is polypropylene glycol, MDI is diphenylmethane diisocyanate, TDI is toluene diisocyanate, NDI is naphthalene diisocyanate, HMDI is 4,4 ' -dicyclohexylmethane diisocyanate, MOCA is 3,3 dichloro ' -4,4 ' -diaminodiphenylmethane, BDO is 1, 4-butanediol, E-300 is dimethylthio toluene diamine
Comparative example 1
Carrying out prepolymerization reaction on 100g of PCL-1000 polyhydric alcohol and 40g of MDI to obtain a prepolymer;
adding 40g of BDO into the obtained prepolymer, and stirring and mixing at a high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Comparative example 2
Is an imported polyurethane elastomer product and is a CPU polyether series product.
Example 1
Dispersing and mixing 100g of PCL-1000 and 10g of graphite to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 45g of TDI at 60 ℃ for 2h in a protective atmosphere to obtain graphite-doped prepolymer;
blending 10g of antimony trioxide and the prepolymer, stirring uniformly, adding 10g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 40g of MOCA and 10g of glycerol into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and molding, and vulcanizing for 16 hours at 100 ℃ to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 2
Dispersing and mixing 100g of PCL-2000 and 7g of graphene to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 43.6g of MDI at 70 ℃ for 5h in a protective atmosphere to obtain a graphene-doped prepolymer;
blending 16g of antimony trioxide and the prepolymer, stirring uniformly, adding 20g of carbon fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, adding 32gE-300 and 3g carbodiimide rapidly into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 130 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 105 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 3
Dispersing and mixing 100g of PCDL-1000 and 6g of graphene oxide to obtain a graphene oxide doped polyol, and then carrying out prepolymerization reaction on the graphite doped polyol obtained in the step and 43.6g of MDI at 70 ℃ for 1.5 hours in a protective atmosphere to obtain a graphite doped prepolymer;
mixing 15g of antimony pentoxide and the prepolymer, stirring uniformly, adding 10g of asbestos, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 30g of BDO and 3g of carbodiimide into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 130 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 105 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 4
Dispersing and mixing 100g of PCDL-2000 and 8g of crystalline flake graphite to obtain doped/graphene/polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 43.6g of NDI at 90 ℃ for 3h in a protective atmosphere to obtain a graphite-doped prepolymer;
after 17g of antimony pentoxide and the prepolymer are blended and stirred uniformly, 20g of glass fiber is added and stirred uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 30g of MOCA and 5g of benzoyl peroxide into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 90 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 130 ℃ for 24 hours to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 5
Dispersing and mixing 100g of PCDL-1000 and 10g of carbon nano tubes to obtain carbon nano tube doped polyol, and then carrying out prepolymerization reaction on the carbon nano tube doped polyol obtained in the step and 43.6g of MDI at 60 ℃ for 3h in a protective atmosphere to obtain carbon nano tube doped prepolymer;
blending 10g of antimony pentoxide and the prepolymer, stirring uniformly, adding 20g of polyester fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 40g of MOCA and 10g of trimethylolpropane into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 140 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 140 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 6
Dispersing and mixing 100g of PTMG-2000 and 10g of graphite fluoride to obtain polyol doped with graphite fluoride, and then carrying out prepolymerization reaction on the polyol doped with the carbon nano tube obtained in the step and 39.6g of HMDI at 90 ℃ for 5 hours in a protective atmosphere to obtain a prepolymer doped with graphite fluoride;
blending 12g of antimony trioxide and the prepolymer, stirring uniformly, adding 10g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 40g of MOCA and 10g of dicumyl peroxide into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 140 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 140 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 7
Dispersing and mixing 100g of PTMG-1000 and 2g of graphite to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 40g of TDI at 60 ℃ for 3h in a protective atmosphere to obtain graphite-doped prepolymer;
blending 10g of antimony trioxide and the prepolymer, stirring uniformly, adding 20g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 45g of MOCA and 5g of glycerol into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 130 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 8
Dispersing and mixing 100g of PTMG-2000 and 10g of graphene to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 33.6g of MDI at 80 ℃ for 5h in a protective atmosphere to obtain a graphene-doped prepolymer;
blending 19g of antimony trioxide and the prepolymer, stirring uniformly, adding 10g of carbon fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 30g of E-300 and 10g of carbodiimide into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 115 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 125 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 9
Dispersing and mixing 100g of PCDL-1500 and 10g of carbon nano tubes to obtain carbon nano tube doped polyol, and then carrying out prepolymerization reaction on the carbon nano tube doped polyol obtained in the step and 43.6g of MDI at 60 ℃ for 3h under a protective atmosphere to obtain a carbon nano tube doped prepolymer;
blending and stirring 20g of antimony pentoxide and the prepolymer uniformly, adding 15g of polyester fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 30g of MOCA and 10g of trimethylolpropane into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 100 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 10
Dispersing and mixing 100g of PTMG-3000 and 5g of graphite fluoride to obtain polyol doped with graphite fluoride, and then carrying out prepolymerization reaction on the polyol doped with the carbon nano tube obtained in the step and 45.6g of HMDI at 90 ℃ for 3h in a protective atmosphere to obtain a prepolymer doped with graphite fluoride;
blending 16g of antimony trioxide and the prepolymer, stirring uniformly, adding 20g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, quickly adding 44g of MOCA and 15g of dicumyl peroxide into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 140 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 140 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 11
Dispersing and mixing 100g of PTMG-3000 and 10g of graphite fluoride to obtain polyol doped with graphite fluoride, and then carrying out prepolymerization reaction on the polyol doped with graphite fluoride obtained in the step and 45g of NDI at 60 ℃ for 2h in a protective atmosphere to obtain a prepolymer doped with graphite fluoride;
blending and stirring 17g of antimony trioxide and the prepolymer uniformly, adding 10g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, adding 42g of E-300 and 10g of hydrogen peroxide diisopropylbenzene into the composite prepolymer quickly, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 160 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 90 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 12
Dispersing and mixing 100g of PPG-1000 and 10g of blocky graphite to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 45g of HMDI at 800 ℃ for 5h in a protective atmosphere to obtain graphite-doped prepolymer;
blending 10g of antimony pentoxide and the prepolymer, stirring uniformly, adding 10g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, adding 42g of MOCA and 10g of glycerol into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 13
Dispersing and mixing 100g of PCL-2000 and 5g of graphite to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 45g of TDI at 60 ℃ for 2h in a protective atmosphere to obtain graphite-doped prepolymer;
after 17g of antimony anhydride and the prepolymer are blended and stirred uniformly, 15g of polyester fiber is added and stirred uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, adding 42g of MOCA and 10g of glycerol into the composite prepolymer, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 14
Dispersing and mixing 100g of PPG-2000 and 8g of graphite carbon nano tube to obtain carbon nano tube doped polyol, and then carrying out prepolymerization reaction on the carbon nano tube doped polyol obtained in the step and 37g of TDI at 60 ℃ for 2h in a protective atmosphere to obtain a carbon nano tube doped prepolymer;
blending and stirring 20g of antimony trioxide and the prepolymer uniformly, adding 10g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, 42g of BDO and 10g of hexamethylenetetramine are quickly added into the composite prepolymer, and the mixture is stirred and mixed at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at 100 ℃ for 16h to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
Example 15
Dispersing and mixing 100g of PTMG-1500 and 10g of graphite to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and 45g of HMDI at 60 ℃ for 1h in a protective atmosphere to obtain graphite-doped prepolymer;
blending 10g of antimony trioxide and the prepolymer, stirring uniformly, adding 25g of glass fiber, and stirring uniformly at a high speed to obtain a composite prepolymer;
under the condition of high-speed stirring, adding 42gE-300 and 10g of glycerol into the composite prepolymer quickly, and stirring and mixing at high speed;
and pouring the mixture obtained in the step into a mold with the temperature of 120 ℃ and the thickness of 2mm, carrying out polymerization reaction, curing and forming, and vulcanizing at the temperature of 130 ℃ for 24 hours to obtain the polyurethane elastomer composite material. The performance was tested after 7 days at room temperature.
The performance of the polyurethane elastomer composite materials prepared in comparative examples 1 and 2 and the high-wear-resistance polyurethane elastomer composite materials prepared in examples 1-15 of the invention was tested.
Referring to table 1, table 1 shows the performance test results of the polyurethane elastomer composite materials prepared in the comparative examples and examples 1 to 5 of the present invention.
Referring to table 2, table 2 shows the performance test results of the polyurethane elastomer composites prepared in the comparative examples and examples 6 to 10 of the present invention.
Referring to table 3, table 3 shows the performance test results of the polyurethane elastomer composites prepared in the comparative examples and examples 11 to 15 according to the present invention.
TABLE 1
Test items Comparative example 1 Comparative example 2 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5
hardness/Shore D 55 50 59 62 61 60 63
Tensile strength/MPa 40 45 46 43 42 47 49
Elongation/percent 360 420 440 430 440 420 400
Abrasion loss mm 3 55 38 25 23 20 19 16
Coefficient of friction 1.2 0.88 0.87 0.62 0.45 0.341 0.153
TABLE 2
Figure BDA0003584507630000171
Figure BDA0003584507630000181
TABLE 3
Test items Comparative example 1 Comparative example 2 EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 EXAMPLE 15
hardness/Shore D 55 50 59 62 61 60 63
Tensile strength/MPa 40 45 46 43 48 43 43.4
Elongation/percent 360 420 364 447 415 394 387
Abrasion loss mm 3 55 38 19.3 19.4 20.11 17.4 16.9
Coefficient of friction 1.2 0.88 0.35 0.72 0.59 0.51 0.43
Wherein the friction test meets the standard: GB/T3960-1983 sliding friction wear test method.
The tensile test meets the standard: GB/T528-1998 tensile stress strain performance determination method.
While the present invention has been described in detail with respect to a highly abrasion resistant polyurethane elastomer composite and a method of making the same, the principles and embodiments of the present invention are described herein using specific examples, which are set forth only to facilitate an understanding of the method and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The polyurethane elastomer composite material is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003584507620000011
2. the polyurethane elastomer composite of claim 1, wherein the polyol comprises one or more of a polyether diol, a polycaprolactone diol, a polycarbonate diol, a polyester diol, and a polyethylene glycol;
the diisocyanate comprises one or more of naphthalene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
3. The polyurethane elastomer composite of claim 1, wherein the chain extender comprises one or more of 1, 4-butanediol, ethylene glycol, hydroquinone bis hydroxyethyl ether, resorcinol bis hydroxyethyl ether, ethylenediamine, N-dihydroxy (diisopropyl) aniline, dimethylthiotoluenediamine, and 3,3 '-dichloro-4, 4' -diphenylmethanediamine;
the cross-linking agent comprises one or more of trimethylolpropane, trimethylolpropane triacrylate, carbodiimide, glycerol, diethylenetriamine, hexamethylenetetramine, dicumyl peroxide, benzoyl peroxide, dicumyl peroxide, diethylene glycol and epoxy silane.
4. The polyurethane elastomer composite of claim 1, wherein the graphite derivative comprises one or more of flake graphite, bulk graphite, cryptocrystalline graphite, graphene oxide, expandable graphite, graphite fluoride, and carbon nanotubes;
the size of the graphite fluoride is 0.05-150 mu m;
the antimony compound comprises antimony trioxide and/or antimony pentoxide;
the particle size of the antimony compound is 0.05 to 10 μm.
5. The polyurethane elastomer composite of claim 1, wherein the fibers comprise one or more of carbon fibers, glass fibers, polyester fibers, polyaramid fibers, and asbestos fibers;
the polyurethane elastomer is a high-wear-resistance polyurethane composite material.
6. A preparation method of a polyurethane elastomer composite material is characterized by comprising the following steps:
1) dispersing and mixing polyol and graphite derivatives to obtain graphite-doped polyol, and then carrying out prepolymerization reaction on the graphite-doped polyol obtained in the step and diisocyanate under a protective atmosphere to obtain a graphite-doped prepolymer;
blending and stirring antimony compounds and the prepolymer uniformly, then adding fibers and stirring uniformly to obtain a composite prepolymer;
2) under the stirring condition, adding a chain extender and a cross-linking agent into the composite prepolymer obtained in the step, and stirring and mixing to obtain a mixture;
3) and pouring the mixture obtained in the step into a mold, and carrying out polymerization reaction, curing and molding to obtain the polyurethane elastomer composite material.
7. The method of claim 6, further comprising a dehydration step after said dispersive mixing;
the temperature of the prepolymerization reaction is 60-100 ℃;
the prepolymerization time is 0.5-10 h.
8. The preparation method according to claim 6, wherein the rotation speed of the stirring is 50 to 2000 rpm;
the chain extension coefficient for the polymerization reaction is 0.6-2.20.
9. The preparation method according to claim 6, wherein the temperature of stirring and mixing in the step (2) is 50-160 ℃;
and (3) stirring and mixing in the step (2) for 0.2-30 min.
10. The preparation method of claim 6, wherein the temperature for the polymerization reaction curing molding is 70-180 ℃;
the time for curing and molding the polymerization reaction is 10-90 min;
and the post-vulcanization step is also included after the curing and forming.
CN202210359660.3A 2022-02-24 2022-04-07 Polyurethane elastomer composite material and preparation method thereof Pending CN114805736A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2022101766830 2022-02-24
CN202210176683 2022-02-24

Publications (1)

Publication Number Publication Date
CN114805736A true CN114805736A (en) 2022-07-29

Family

ID=82534792

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210359660.3A Pending CN114805736A (en) 2022-02-24 2022-04-07 Polyurethane elastomer composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114805736A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120022215A1 (en) * 2010-07-22 2012-01-26 Fuji Xerox Co., Ltd. Urethane resin, fixing member, and image forming apparatus
CN102643529A (en) * 2012-04-27 2012-08-22 中国科学院长春应用化学研究所 Polymer composite for bearing and preparation method thereof
CN106519650A (en) * 2016-11-15 2017-03-22 王世伟 Polymer composite and bearing bush made of same
CN107698963A (en) * 2017-10-13 2018-02-16 南京旭羽睿材料科技有限公司 Applied to graphene composite material for preparing textile rubber roll and preparation method thereof
CN108192315A (en) * 2018-02-09 2018-06-22 重庆邮电大学 A kind of vehicle instrument instrument housing electromagnetic shielding composite material and preparation method thereof
CN109642615A (en) * 2016-08-26 2019-04-16 日本精工株式会社 Rolling bearing and its manufacturing method
CN109679251A (en) * 2019-01-14 2019-04-26 安徽新安线缆材料有限公司 A kind of cold-resistant Stretch-resistant cable material and preparation method thereof for high-tension electricity conveying
CN111574680A (en) * 2020-06-10 2020-08-25 东莞市英捷工程塑料有限公司 Heat-conducting polyurethane with insulating and flame-retardant properties

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120022215A1 (en) * 2010-07-22 2012-01-26 Fuji Xerox Co., Ltd. Urethane resin, fixing member, and image forming apparatus
CN102643529A (en) * 2012-04-27 2012-08-22 中国科学院长春应用化学研究所 Polymer composite for bearing and preparation method thereof
CN109642615A (en) * 2016-08-26 2019-04-16 日本精工株式会社 Rolling bearing and its manufacturing method
CN106519650A (en) * 2016-11-15 2017-03-22 王世伟 Polymer composite and bearing bush made of same
CN107698963A (en) * 2017-10-13 2018-02-16 南京旭羽睿材料科技有限公司 Applied to graphene composite material for preparing textile rubber roll and preparation method thereof
CN108192315A (en) * 2018-02-09 2018-06-22 重庆邮电大学 A kind of vehicle instrument instrument housing electromagnetic shielding composite material and preparation method thereof
CN109679251A (en) * 2019-01-14 2019-04-26 安徽新安线缆材料有限公司 A kind of cold-resistant Stretch-resistant cable material and preparation method thereof for high-tension electricity conveying
CN111574680A (en) * 2020-06-10 2020-08-25 东莞市英捷工程塑料有限公司 Heat-conducting polyurethane with insulating and flame-retardant properties

Similar Documents

Publication Publication Date Title
CN111662633B (en) Anti-static wear-resistant polyurethane floor coating and preparation method thereof
CN109535375B (en) Preparation method of highly-stripped two-dimensional nanosheet-reinforced polyurethane composite material
JP5484770B2 (en) Nanocarbon dispersant and nanocarbon dispersion containing the dispersant
CN111411416B (en) Graphene spandex and preparation method thereof
Zhang et al. A novel POSS-containing polyimide: Synthesis and its composite coating with graphene-like MoS2 for outstanding tribological performance
CN104861145A (en) Polyurethane elastomer/ halloysite nanotube composite material and preparation method thereof
CN106633778A (en) High-content glass fiber reinforced antistatic PC composite material and preparation method thereof
CN114395160A (en) Graphene modified polyurethane composite material and preparation method thereof
CN106866921A (en) A kind of elastic polyurethane of utilization hydroxylating carbon nano-tube modification and its preparation method
US5043410A (en) Cross-linkable polyurethane rubbers containing polyoxyperfluoroalkylene blocks
CN111777810A (en) PU resin type wear-resistant nitrile rubber and preparation method thereof
JP4938513B2 (en) Polyurethane elastomer resin composition and process for producing the same
Yang et al. Carbon nanotubes grafted by polyurethane chains with dopamine-mediation to enhance the mechanical and damping properties of polyurethane elastomer
CN114805736A (en) Polyurethane elastomer composite material and preparation method thereof
CN110903636B (en) Polyurethane elastomer and preparation method and application thereof
CN116041663A (en) Polyurethane composition, polyurethane elastomer and preparation method thereof
CN111763417A (en) Nano titanium dioxide filled thermoplastic polyurethane/chloroprene rubber blend composite material and preparation method thereof
CN111303371A (en) Antibacterial, mildewproof, antistatic and yellowing-resistant TPU
CN113698764A (en) Organic silicon thermoplastic vulcanizate blend and preparation method thereof
CN115141348A (en) High-performance polyurethane material for sweeper and preparation method thereof
Chen et al. A comparative evaluation of mechanically reinforced and heat-resistant organic powder/polyurethane elastomer hybrid composites
CN115141355A (en) High-performance PU/CF composite material for sweeper and preparation method thereof
CN106566017A (en) Super-hydrophobic oil-resistant corrosion-resistant material for high-pressure oil pipe and preparation method thereof
CN107746567A (en) A kind of printer's roll composite material special
CN115850642A (en) Preparation method of high-performance polyurethane elastomer

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