CN105968395A - Preparation method of modified polyurethane and composite material prepared by preparation method of modified polyurethane - Google Patents
Preparation method of modified polyurethane and composite material prepared by preparation method of modified polyurethane Download PDFInfo
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- CN105968395A CN105968395A CN201610321933.XA CN201610321933A CN105968395A CN 105968395 A CN105968395 A CN 105968395A CN 201610321933 A CN201610321933 A CN 201610321933A CN 105968395 A CN105968395 A CN 105968395A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- 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
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- 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
- C08G18/6688—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 C08G18/3271
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention provides a preparation method of modified polyurethane and a composite material prepared by the preparation method of the modified polyurethane. Polyether polyol, a cross-linking agent, a stabilizing agent, a foaming agent and nano particles are agitated and mixed uniformly, and are mixed, foamed and reacted with polyisocyanate according to a certain conveying proportion; a layer of mold release agent containing a wear-resistant nano material in a mixing manner is spray-coated on an inner cavity of a mold, so as to obtain polyurethane enriched in the wear-resistant nano material on a surface layer. The modified polyurethane obtained through the preparation method has more excellent mechanical properties and impact resistance, can be widely applied to various fields of impact resistance; the preparation method is simple.
Description
[technical field]
The present invention relates to a kind of elastomer macromolecule material field, particularly to a kind of modified polyurethanes
Preparation method and composite.
[background technology]
Polyurethanes (polyurethane；Hereinafter referred to as PU) it is a kind of emerging organic polymer material
Material, is described as " the fifth-largest plastics ", is widely used in the numerous neck of national economy because of the performance of its brilliance
Territory, uses the product applications prepared of polyurethanes to relate to light industry, chemical industry, electronics, weave, cure
Treatment, building, building materials, automobile, national defence, space flight, aviation etc..
With PU industrial development and lower bound time stamp, it is as new in selected that modern foam product has developed multiple technologies
Foaming agent, exploitation soften/stabilize auxiliary agent, force foaming cooling technology, varying pressure in foaming technology, carbon dioxide
System and isophorone diisocyanate (isophorone diisocyanate, hereinafter referred to as IPDI) are PU
Foamed materials and technique.Current research center of gravity more they tend to environmental protection (selection of halogen-free material), non-xanthochromia,
And high-quality.
Its shortcoming of PU foamed materials being widely used in each field is that weather resisteant is the best, easily high humility,
Hydrolysis, thermal cracking, thermo-oxidative pyrolysis and ultraviolet light cracking is produced under the conditions of high temperature, intensive ultraviolet etc..
The easy xanthochromia of PU foamed materials, reason is broadly divided into four kinds: (1) additive is divided a word with a hyphen at the end of a line: the little molecule of additive
It is scattered in foamed materials macromolecule, gradually can be travelled to surface by foam interior.(2) ultraviolet shines
Penetrate: the ultraviolet of sunlight and part light causes foamed materials variable color.(3) nitrogen oxide (NOx) gas exposes
Dew: automobile exhaust gas contains a large amount of nitrogen oxide gas, causes foamed materials variable color.(4) it is heated.
Though using the aliphatic isocyanates such as IPDI can avoid xanthochromia, but it being reactive less than containing aromatic
Such as isocyanates such as MDI or TDI.According to prepolymer (prepolymer) as foamed materials precursor,
The reactivity of the isocyanates at two ends can further reduce.Therefore, it is difficult to by aliphatic isocyanates
Prepolymer makes PU foamed materials.
European Patent No. EP 0423621, HDI is added Aethoxy Sklerol in mixing by Bridgestone company
Solvent such as diformazan benzene/methylbenzene/cellulose ether alcohol (15/25/60) reacts, and repastes and is distributed on dress material.Due to instead
Answer speed slow, porous type PU foamed materials need to be formed after 220 DEG C of high temperature dryings.
U.S. Patent No. 5147897, Nisshin company is by the polyhydric alcohol manufacture of HDI and two functional groups
Become prepolymer post-foaming.Owing to the most clearly disclosing the kind of cross-linking agent and needing longer hardening time, and because of anti-
Answering property deficiency is difficult to qualitative, the easy atrophy of foamed materials of formation.
[summary of the invention]
It is desirable to provide the modified polyurethanes that a kind of mechanical performance is excellent, shock-absorbing capacity is good
Preparation method and composite thereof.
For achieving the above object, the present invention is by the following technical solutions:
On the one hand, it is provided that the preparation method of a kind of modified polyurethanes, comprise the steps:
Step S110: under conditions of stirring, adds cross-linking agent, stabilizer, foaming agent and environment-friendly type
Agent joins in polyether polyol；
Step S120: after continuing stirring 10～30min, add nanoparticle under continuous agitation,
Obtaining nanoparticle mixture, described nanoparticle is nano-graphene granule；
Step S130: by described nanoparticle mixture and polyisocyanates by delivery ratio be 2:1 to 5:1 it
Between mix；
Step S140: the inner chamber at mould sprays the one layer of mixing releasing agent containing nanometer antiwear material；
Step S150: the mixed liquor described in step S130 is expressed in the mould described in step S140 one-tenth
Type, the rich surface of the formation a kind of modified polyurethanes containing nanometer antiwear material.
Specifically, in step S110, also include being joined by pigment in described polyether polyol, described face
Material is at least one in phthalein viridescent, iron oxide red, cadmium yellow, titanium dioxide, colour carbon black.
Specifically, in step S110, described polyether polyol also includes polymer polyatomic alcohol, described poly-
Compound polyhydric alcohol is at least in polyesters or polyether alcohol, butanediol, trimethylolpropane
Kind.
Specifically, in step S110, described cross-linking agent be selected from dibutyl tin laurate, stannous octoate,
At least one in triethanolamine, phosphoric acid.
Specifically, in step S110, described stabilizer is selected from antioxidant 264, antioxidant 1010, resists
Oxygen agent 1076 and hydrolysis stabilizer list carbodiimides, at least one in many carbodiimides.
Specifically, in step S110, described foaming agent is selected from water, pentane, Pentamethylene., HFC-
At least one in 245fa, HFC-365mfc.
Specifically, in step S120, the mass fraction adding described nano-graphene granule is 0.1%～3.6%,
Described nano-graphene granule is the graphene oxide granule after being processed by thermal expansion.
Specifically, described cross-linking agent, stabilizer, foaming agent, environment protection additive and polyether polyol are placed in
Stirring in batching kettle, described batching kettle includes that agitating device, described agitating device are the stirring paddle of helical-ribbon type.
Specifically, described environment protection additive comprise at least one choosing freely reclaim macromolecular material, Plant fiber,
The material of the group that mineral and metal dust are constituted.
Specifically, also include described nanoparticle mixture is carried out supersound process after completing step S120
Step.
Specifically, in step S130, described polyisocyanates is selected from MDI, TDI, HDI, IPDI
In at least one.
Specifically, in step S140, described is stannic oxide/graphene nano material containing nanometer antiwear material
Or silica nano material.
Specifically, in step S140, the described mixing mass fraction containing nanometer antiwear material is poly-ammonia
The 1%～2% of carbamate, preferential for the graphene nano powder body of this component and releasing agent mix homogeneously, institute
Stating polyurethanes when foaming in mould, the nanometer antiwear material of dies cavity is formed at described uniformly
The surface of polyurethane material.
It addition, the composite obtained by preparation method of a kind of modified polyurethanes, described modification gathers
Carbamate surface is provided with graphene film.
Use technique scheme, the beneficial effects of the present invention is:
The preparation method of the modified polyurethanes that the present invention provides and composite thereof, by polyether polyols
Alcohol, cross-linking agent, stabilizer, foaming agent and nanoparticle are stirred mix homogeneously, and by certain conveying
Ratio is reacted with polyisocyanates mixed foaming, and sprays one layer of mixing containing nanometer antiwear at the inner chamber of mould
The releasing agent of material, obtains the surface layer polyurethanes rich in nanometer antiwear material, by above-mentioned preparation
The modified polyurethanes that way obtains, has more excellent mechanical performance and shock resistance, Ke Yiguang
General being applied to various shock resistance field, above-mentioned preparation method is simple.
[accompanying drawing explanation]
The flow chart of steps of the preparation method of the modified polyurethanes that Fig. 1 provides for the present invention.
[detailed description of the invention]
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and reality
Execute example, the present invention is further elaborated.Only should be appreciated that specific embodiment described herein
Only in order to explain the present invention, it is not intended to limit the present invention.
As long as additionally, technical characteristic involved in each embodiment of invention described below is each other
Between do not constitute conflict just can be mutually combined.
Referring to Fig. 1, the preparation method of a kind of modified polyurethanes that the present invention provides, including following
Step:
Step S110: under conditions of stirring, adds cross-linking agent, stabilizer, foaming agent and environment-friendly type
Agent joins in polyether polyol；
In above-mentioned steps S110, also including being joined by pigment in described polyether polyol, described pigment is
At least one in phthalein viridescent, iron oxide red, cadmium yellow, titanium dioxide, colour carbon black；Described polyethers is many
Unit's alcohol also includes that polymer polyatomic alcohol, described polymer polyatomic alcohol are selected from PEPA or polyether polyols
At least one in alcohol, butanediol, trimethylolpropane；Described cross-linking agent is selected from di lauric dibutyl
At least one in stannum, stannous octoate, triethanolamine, phosphoric acid；Described stabilizer be selected from antioxidant 264,
Antioxidant 1010, antioxidant 1076 and hydrolysis stabilizer list carbodiimides, in many carbodiimides extremely
Few one；Described foaming agent is selected from water, pentane, Pentamethylene., HFC-245fa, HFC-365mfc
In at least one；Described environment protection additive comprises at least one choosing and freely reclaims macromolecular material, plant fibre
The material of the group that dimension, mineral and metal dust are constituted, wherein, reclaims macromolecular material and comprises at least one
Select free polyethylene, polrvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate, nylon
Group's material that material, fluorine plastic cement, polyimides, Merlon are constituted；Plant fiber is derived from comprising
At least one is constituted selected from cork, bamboo charcoal, wood powder, bagasse, coffee grounds, tealeaf residue and mixture thereof
Group's material；Mineral comprise at least one selection zeolite, clay, kieselguhr, graphite and limestone and are constituted
Group's material；And this environment protection additive account for polyether polyol overall 0.1～50 percentage by weight.
In better embodiment of the present invention, environment protection additive non-limiting regenerant matter, further include one
The additive friendly to environment.
In better embodiment of the present invention, described cross-linking agent, stabilizer, foaming agent, environment protection additive
And polyether polyol is placed in batching kettle stirring, described batching kettle includes that agitating device, described agitating device are
The stirring paddle of helical-ribbon type, can make material roll up and down inside batching kettle under the effect of stirring paddle, strengthens
The mixing effect of material.
Specifically, a certain amount of polyether polyol or polymer polyatomic alcohol are injected in batching kettle (A), opens
Dynamic stirring, and a certain amount of cross-linking agent, stabilizer, foaming agent, pigment crude are added batching kettle (A),
Mixing and stirring.
Step S120: after continuing stirring 10～30min, add nanoparticle under continuous agitation,
Obtain nanoparticle mixture；
In above-mentioned steps S120, described nanoparticle is nano-graphene granule, described nano-graphene
Grain is spherical, and particle diameter is 200-1000nm.Nanoparticle is a kind of important functional material, nano-silica
The STF that SiClx particle and specific liquid prepare is a kind of new function material, in the world
Claim STF liquid.Under high speed impact, there is huge change in this liquid apparent viscosity, even rapidly by
Liquid phase becomes solid phase, can present the shock resistance of solid；After impulsive force eliminates, again rapidly from solid
Phase in version becomes liquid phase.This shear thickening effect is a kind of non-Newtonian fluid behavior, and its change is reversible.
This characteristic, can be applied to shock resistance field, such as bullet resistant material or other protection aspects, simultaneously this
Plant material also to have broad application prospects in fields such as dampings.In this patent use nano-particle material with
This same type that can be used for preparing the particle of STF.
As in the present invention preferably embodiment, the mass fraction adding described nano-graphene granule is
0.1%～3.6%, above-mentioned nano-graphene granule the most also carries out the graphene oxide after thermal expansion process
Granule.
Preferably, the mass fraction adding described nano-graphene granule is 0.6%.
In better embodiment of the present invention, mixing time is 20-30min.
In better embodiment of the present invention, also included above-mentioned nanoparticle before carrying out step S120
Carry out the step of ball milling dispersion process.
In better embodiment of the present invention, also include described nanoparticle is mixed after completing step S120
Compound carries out the step of supersound process.It is appreciated that the most again by, after ultrasonic disperse, making nanoparticle
Son is preferably scattered in liquid, thus avoids nanoparticle and there is also slight agglomeration, improves
The uniformity of product.
Specifically, mixture step S110 obtained, after stirring 10-30min, a certain amount of process
The nanoparticle that grinding distribution processes adds batching kettle (A), continues dispersed with stirring 30-60min, is received
Rice corpuscles mixture.
Step S130: be that 3:1 injection mixes by delivery ratio by described nanoparticle mixture and polyisocyanates；
In above-mentioned steps S130, polyisocyanates is selected from methyl diphenylene diisocyanate
(MDI；Diphenyl-methane-diisocyanate), toluene di-isocyanate(TDI) (TDI
Toluene-2,4-diisocyanate), at least one in isophorone diisocyanate (IPDI).
Specifically, a certain amount of polyisocyanates is injected batching kettle (B), start batching kettle (A), join
The bottom precision metering pump of material still (B) still, by nanoparticle mixture and the batching kettle of batching kettle (A)
(B) polyisocyanates is ejected into van-type according to the conveying ratio of XX by jet gun and seals in grinding tool and send out
Bubble reaction.
Step S140: the inner chamber at mould sprays the one layer of mixing releasing agent containing nanometer antiwear material；
Step S150: the mixed liquor described in step S130 is expressed in the mould described in step S140 one-tenth
Type, the rich surface of the formation a kind of modified polyurethanes containing nanometer antiwear material.
In this specific embodiment, it is stannic oxide/graphene nano material or titanium dioxide containing nanometer antiwear material
Silicon nano material.Mixing contains mass fraction is polyurethanes 1%～the 2% of nanometer antiwear material,
Preferential for the graphene nano powder body of this component and releasing agent mix homogeneously, polyurethanes is sent out in mould
During bubble, the nanometer antiwear material of dies cavity is formed at the surface of described polyurethane material uniformly.
It addition, present invention also offers the composite of a kind of modified polyurethanes, modified poly-amino first
Acid esters surface is provided with graphene film.Specifically comprises the processes of: upper cover and the base plate of described mould have vac sorb
It is equipped with the equally distributed aperture of 0.1-0.5mm, by applying in function, and the upper cover of mould and base plate
The pull of vacuum of-0.002 to-0.01mpa, adsorbs graphene film on upper cover and base plate, then root respectively
Preparing according to above-mentioned preparation method, the material prepared is the defense of resistance to impact material that surface recombination has graphene film
Material, the graphene film that this material is high owing to being compounded with intensity, so except the excellent anti-impact originally possessed
Hitting outside performance, there are extraordinary intensity and wearability in the surface also imparting material.
The preparation method of the modified polyurethanes that the present invention provides and composite thereof, by polyether polyols
Alcohol, cross-linking agent, stabilizer, foaming agent and nanoparticle are stirred mix homogeneously, and by certain conveying
Ratio is reacted with polyisocyanates mixed foaming, and sprays one layer of mixing containing nanometer antiwear at the inner chamber of mould
The releasing agent of material, obtains the surface layer polyurethanes rich in nanometer antiwear material, by above-mentioned preparation
The modified polyurethanes that way obtains, has more excellent mechanical performance and shock resistance, Ke Yiguang
General being applied to various shock resistance field, above-mentioned preparation method is simple.
Embodiment 1
The polyether polyol of 60 parts (GEP-330N) and polymer polyatomic alcohol (GPOP-36/28G) 40
Part add in batching kettle (A), start stirring, be separately added into 1 part of alcamines polyol crosslink agent, 0.6
Part low molecular polyether triol cross-linking agent, 0.7 part of foam stabiliser L5309, add matter after stirring 30min
Amount mark is the nano-graphene granule of 0.1%；
98TDI80/20 is added in batching kettle (B), starts and be arranged at batching kettle (A), batching kettle (B)
The precision metering pump of bottom, the material in the material in batching kettle (A) and batching kettle (B) according to 1.2:1
Conveying ratio be sprayed onto an inner chamber to be sprayed with mass fraction by jet gun be 1% silica nano material
The van-type of releasing agent seals foamable reaction in grinding tool, after 12min, opens the lid of mould, obtains modification
Polyurethane sheet material.
Testing result shows: the rich surface carbamate sheet material containing silica nano material improves wear-resisting
Property.
Embodiment 2
The polyether polyol of 60 parts (GEP-330N) and polymer polyatomic alcohol (GPOP-36/28G) 40
Part add batching kettle (A), start stirring, be separately added into 1 part of alcamines polyol crosslink agent, 0.6 part low
Molecular weight polyether triol cross-linking agent, 0.7 part of foam stabiliser L5309, stirring mixing 10min, it is subsequently adding
The ground mass fraction of 8 parts be 0.6% nano-graphene granule (particle diameter is 620nm, ball milling 20min,
Start ultrasonic disperse, disperse 30min).
98TDI 80/20 is added in batching kettle (B), starts and be arranged at batching kettle (A), batching kettle (B)
The precision metering pump of bottom, the material in the material in batching kettle (A) and batching kettle (B) according to 1.2:1
Conveying ratio be sprayed onto an inner chamber to be sprayed with mass fraction by jet gun be 1.5% graphene nano material
The van-type of releasing agent seals in grinding tool and foams, and after 12min, opens the lid of grinding tool, obtains the poly-ammonia of modification
Carbamate sheet material.
Testing result shows: the carbamate sheet material of surfaces rich in graphene nano material improves resistance to
Mill property.
Embodiment 3
The polyether polyol of 60 parts (GEP-330N) and polymer polyatomic alcohol (GPOP-36/28G) 40
Part add batching kettle (A), start stirring, be separately added into 1 part of alcamines polyol crosslink agent, 0.6 part low
Molecular weight polyether triol cross-linking agent, 0.7 part of foam stabiliser L5309, stirring mixing 10min, it is subsequently adding
The ground mass fraction of 8 parts be 3.6% nano-graphene granule (particle diameter is 620nm, ball milling 20min,
Start ultrasonic disperse, disperse 30min).
98TDI 80/20 is added in batching kettle (B), starts and be arranged at batching kettle (A), batching kettle (B)
The precision metering pump of bottom, the material in the material in batching kettle (A) and batching kettle (B) according to 1.2:1
Conveying ratio be sprayed onto van-type by jet gun and seal in grinding tool and foam, after 12min, open grinding tool
Lid, obtains the polyurethane sheet material of modification.
Testing result shows: the rich surface carbamate sheet material containing silica nano material improves wear-resisting
Property.
Embodiment 4
The polyether polyol of 60 parts (GEP-330N) and polymer polyatomic alcohol (GPOP-36/28G) 40
Part add batching kettle (A), start stirring, be separately added into 1 part of alcamines polyol crosslink agent, 0.6 part low
Molecular weight polyether triol cross-linking agent, 0.7 part of foam stabiliser L5309, stirring mixing 10min, it is subsequently adding
The ground mass fraction of 8 parts be 0.6% graphene oxide granule (particle diameter is 620nm, ball milling 20min,
Start ultrasonic disperse, disperse 30min).
98TDI 80/20 is added in batching kettle (B), starts and be arranged at batching kettle (A), batching kettle (B)
The precision metering pump of bottom, the material in the material in batching kettle (A) and batching kettle (B) according to 1.2:1
Conveying ratio be sprayed onto van-type by jet gun and seal in grinding tool and foam, after 12min, open grinding tool
Lid, obtains the polyurethane sheet material of modification.
Testing result shows: the rich surface carbamate sheet material containing silica nano material improves wear-resisting
Property.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (14)
1. the preparation method of a modified polyurethanes, it is characterised in that comprise the steps:
Step S110: under conditions of stirring, adds cross-linking agent, stabilizer, foaming agent and environment-friendly type
Agent joins in polyether polyol；
Step S120: after continuing stirring 10～30min, add nanoparticle under continuous agitation,
Obtaining nanoparticle mixture, described nanoparticle is nano-graphene granule；
Step S130: by described nanoparticle mixture and polyisocyanates by delivery ratio be 2:1 to 5:1 it
Between mix；
Step S140: the inner chamber at mould sprays the one layer of mixing releasing agent containing nanometer antiwear material；
Step S150: the mixed liquor described in step S130 is expressed in the mould described in step S140 one-tenth
Type, the rich surface of the formation a kind of modified polyurethanes containing nanometer antiwear material.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S110, also including being joined by pigment in described polyether polyol, described pigment is blue or green selected from phthalein
At least one in green, iron oxide red, cadmium yellow, titanium dioxide, colour carbon black.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S110, also including polymer polyatomic alcohol in described polyether polyol, described polymer polyatomic alcohol is
At least one in polyesters or polyether alcohol, butanediol, trimethylolpropane.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S110, described cross-linking agent be selected from dibutyl tin laurate, stannous octoate, triethanolamine,
At least one in phosphoric acid.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S110, described stabilizer is selected from antioxidant 264, antioxidant 1010, antioxidant 1076 and water
Solve stabilizer list carbodiimides, at least one in many carbodiimides.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S110, described foaming agent is selected from water, pentane, Pentamethylene., HFC-245fa, HFC-
At least one in 365mfc.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
In step S120, the mass fraction adding described nano-graphene granule is 0.1%～3.6%, described nanometer
Graphene granule is the graphene oxide granule after being processed by thermal expansion.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
Described cross-linking agent, stabilizer, foaming agent, environment protection additive and polyether polyol are placed in batching kettle stirring,
Described batching kettle includes that agitating device, described agitating device are the stirring paddle of helical-ribbon type.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
Described environment protection additive comprises at least one choosing and freely reclaims macromolecular material, Plant fiber, mineral and metal
The material of the group that powder is constituted.
The preparation method of modified polyurethanes the most according to claim 1, it is characterised in that
The step that described nanoparticle mixture is carried out supersound process is also included after completing step S120.
The preparation method of 11. modified polyurethanes according to claim 1, it is characterised in that
In step S130, described polyisocyanates is at least one in MDI, TDI, HDI, IPDI.
The preparation method of 12. modified polyurethanes according to claim 1, it is characterised in that
In step S140, described is stannic oxide/graphene nano material or silicon dioxide containing nanometer antiwear material
Nano material.
The preparation method of 13. modified polyurethanes according to claim 1, it is characterised in that
In step S140, the described mixing mass fraction containing nanometer antiwear material is polyurethanes
1%～2%, preferential for the graphene nano powder body of this component and releasing agent mix homogeneously, described polyurethane
When ester foams in mould, the nanometer antiwear material of dies cavity is formed at described polyurethanes uniformly
The surface of material.
14. 1 kinds according to claim 1～13 arbitrary as described in the preparation method of modified polyurethanes
Obtained composite, it is characterised in that described modified polyurethanes surface is provided with graphene film.
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| CN106832189A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene compound polyurethane material |
| CN108395560A (en) * | 2018-03-28 | 2018-08-14 | 株洲九方因赛德技术有限公司 | A kind of method and its SMC products for improving SMC product surface performances |
| CN108690179A (en) * | 2018-06-07 | 2018-10-23 | 浙江高裕家居科技有限公司 | A kind of compound polyurethane material and preparation method thereof |
| CN109548394A (en) * | 2018-11-27 | 2019-03-29 | 湖南国盛石墨科技有限公司 | A kind of flexibility PU graphene electromagnetic shielding material and preparation method thereof |
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