CN102501422A - Nano-wear-resistant polyurethane heel lift composite material and preparation method - Google Patents
Nano-wear-resistant polyurethane heel lift composite material and preparation method Download PDFInfo
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- CN102501422A CN102501422A CN2011102870208A CN201110287020A CN102501422A CN 102501422 A CN102501422 A CN 102501422A CN 2011102870208 A CN2011102870208 A CN 2011102870208A CN 201110287020 A CN201110287020 A CN 201110287020A CN 102501422 A CN102501422 A CN 102501422A
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Abstract
The invention relates to a nano-wear-resistant polyurethane heel lift composite material and a preparation method. By means of nano composite technology, a polyurethane heel lift is modified, and the mechanical strength and the comprehensive performance of the materials are improved. Materials on an upper material layer A and materials on a lower material layer B are successively filled into a mould by a filling machine according to a certain time interval, are extruded by a flat vulcanizing machine at a certain pressure and a certain pressure, and are solidified into a whole to obtain the nano-wear-resistant polyurethane composite heel lift, the wear resistance and flexibility of the lower material layer B of the heel lift are improved, the upper material layer A has good hardness and strength and is stably engaged with a pinned top piece, the hydrolysis resistance, the impact strength and the like of the heel lift are further improved, the service life of the heel lift is effectively prolonged, noise generated by knocking the ground with the heel lift in use is lower, and quality in use of women's leather shoes is improved.
Description
Technical field
The present invention relates to high-heeled shoes wear-resistant pad field, specifically is a kind of nano wearproof polyurethane sky veneer composite material and preparation method.
Background technology
Ladies leather shoe is enormous amount not only, and style is various, has increased great delight of life to the women.Ladies leather shoe is different from most of in men's style leather shoes, is the heel that has differing heights, to adapt to different occupation occasion and all ages and classes women demand.The women of high-heeled shoes, it is taller and more straight not only can to let the figure show, but also can inspire enthusiasm.Usually, the bottom of woman style high-heeled shoes heel be equipped with usually one can mobile assembled and disassembled replacing the sky cortex, be worn when preventing that the shoes heel from using, day cortex is installed in the installing hole that high-heeled shoes heel bottom is provided with in advance through pinned top-piece usually.The sky skin great majority of most of Women's Leather Shoes heel adopt polyvinyl chloride (PVC) and TPU material.The drawbacks limit that thermal stability of polyethylene is bad its scope of application and development space.Though TPU has general wearability, hardness is too high, and the sound of walking is bigger, particularly in quiet environment and wood floors, is easy to generate the sound that knocks ground, brings inconvenience.How to develop that a kind of high abrasion, pliability are moderate, novel day skin of easy processing, become the problem that present industry is concerned about.
At present, developed one type of new polyurethane (PUR) day skin product.Polyurethane product has excellent abrasive, high tensile and high elongation rate usually.At hydrolysis, acidproof, aqueous slkali corrosion aspect, polyether-type PUR is superior to polyester-type PUR.Polyurethane products have intensity height, thermal insulation, sound insulation, fire-retardant, cold-resistant, anticorrosion, do not absorb water, excellent characteristics such as easy construction is quick, become the new selection of day leathercraft.Because the special environment for use of day skin product; Need many factor affecting such as underwriter's body weight, ground friction, temperature, rainwater, sunlight; Therefore quickened its service life, characteristics such as, acid and alkali-resistance moderate except pliability, wearability is an important techniques index.
Research shows; Inorganic nano material shows small-size effect, skin effect and macro quanta tunnel effect etc.; Make material have many function that are different from conventional material; Its adding can be given nano composite material and had special nature at aspects such as mechanics, optics, electricity and magnetics, and this has opened up new direction for the quality-improving of polyurethane sky skin.But inorganic nano material has very high surface-active, and specific area is big, is in non-Thermodynamically stable state between particle, very easily reunites.In addition, its surface or interfacial property with the organic polymer matrix is different, and compatibility is relatively poor, thereby is difficult in matrix, evenly disperse, and direct or too much filling often causes some mechanical property of material to reduce.Therefore, be necessary the inorganic nano-particle sub-surface is carried out chemical modification, can with the surface that reduces particle; Change the surface polarity of particle; Reduce the mutual reunion between the nano material, improve the dispersion of nano material in macromolecular material, improve the mechanical strength and the combination property of material.
Summary of the invention
The objective of the invention is through nanometer composite technology; Optimize polyurethane sky skin technology, produce a kind of more wear-resistingly, it is littler to knock the ground noise; Greatly prolong the service life of day skin, improved the nano wearproof polyurethane sky veneer composite material and the preparation method of the using character of Women's Leather Shoes.
Technical scheme of the present invention is achieved in that
A kind of nano wearproof polyurethane sky veneer composite material; Its structure comprises the last A bed of material and the following B bed of material that thermosol connects; Wherein, The said component that goes up the A bed of material comprises PTMG and toluene di-isocyanate(TDI), and said PTMG and the toluene di-isocyanate(TDI) weight portion in the last A bed of material is respectively:
PTMG is 50%-75%;
Toluene di-isocyanate(TDI) is 25%-50%;
The said component of the B bed of material down comprises dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and composite coupler, and said dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and the composite coupler weight portion in the following B bed of material is respectively:
The dichloro-diphenyl methane diamines is 40%-60%;
PPOX ether glycol is 35%-55%;
Nano material is 0.5%-5%;
Coupling agent is 0.025%-0.25%;
Catalyst is 0.1%-0.3%.
The present invention is scheme preferably:
Said PTMG and the toluene di-isocyanate(TDI) weight portion in the last A bed of material is respectively:
PTMG is 62%;
Toluene di-isocyanate(TDI) is 38%;
Said dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and the composite coupler weight portion in the following B bed of material is respectively:
The dichloro-diphenyl methane diamines is 51.86%;
PPOX ether glycol is 44.9%;
Nano material is 2.0%;
Coupling agent is 0.04%;
Catalyst is 0.2%.
The said height of the B bed of material down is the 3/10-7/10 of compound day skin height of whole nano wearproof polyurethane.In order to obtain higher anti-wear performance and toughness preferably, guarantee also that simultaneously the A bed of material is to the intensity of pinned top-piece interlock on day skin, the height of the following B bed of material is 3/5 of a compound day skin height of whole nano wearproof polyurethane.
Nano material of the present invention comprises nano imvite MMT, nano silicon SiO
2, nano titanium oxide TiO
2, many walls of nanometer carbon pipe MWNTs, nano aluminium oxide Al
2O
3, nano magnesia MgO, nano-calcium carbonate CaCO
3, nano zine oxide ZnO, nano-silicon nitride Si
3N
4, nanometer silicon carbide SiC wherein one or more compound uses.
Coupling agent of the present invention is for there being silane coupler; Said two-[γ-(triethoxysilicane) propyl group] tetrasulfide (si-69) that has silane coupler to comprise, two-[g-(triethoxysilicane) propyl group]-disulphide (si-75), gamma-aminopropyl-triethoxy-silane (KH-550), HMDS (HMDS), VTES (KH-151), vinyltrimethoxy silane (KH-171), γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570).
Said coupling agent also can be titanate coupling agent, and titanate coupling agent comprises monoalkoxytitanates coupling agent (JTW-101), monoalkoxy phosphate titanate coupling agent (JTW-102), two (dioctyl phosphate) titanate esters (JTW-311) of fluoroacetic acid ester, aluminium titanium composite coupler (JTW-1618).
The preparation method of a kind of nano wearproof polyurethane of the present invention sky veneer composite material, its preparation technology's flow process is following:
1). the technological process of the A bed of material is following in the preparation:
1.1). adopt a certain amount of normal temperature PTMG, be heated to 100-110 ℃ of vacuum dehydration, through 40-60 ℃ of water quench, add toluene di-isocyanate(TDI) more in batches, freely be warming up to 80 ℃; 80 ℃ of insulations 2-3 hour;
1.2). inspection by sampling, if defective, adjustment back insulation inspection by sampling again in 2-3 hour; If qualified, continue next step; Promptly to NCO assay in the semi-prepolymer, its assay method is following in inspection by sampling in this step:
Accurately take by weighing 0.2 gram sample in dry triangular flask by glass bar, add 10 milliliters of di-n-butylamine-toluene solutions, shake and make it and dissolve (shake down too slowly suitably like dissolving and heat) fully with pipette; Room temperature was placed 5 minutes, added 40 milliliters of AR level isopropanols then, dripped 5 bromocresol green indicator; With the HCL titration of the 0.1mol/L for preparing, when solution by the proper flavescence look of indigo plant and keep 15S not become terminal point, two of each minimum samplings; Do blank assay simultaneously, NCO cubage formula is following:
NCO％＝{[(V
0-V
S)×C×42]/1000M}×100％
Wherein, the mass percent of NCO%: NCO;
V
0: blank titration consumes HCL volume, ml;
V
S: the sample titration consumes HCL volume, ml;
C:HCL concentration, mol/L;
M: sample quality, gram;
The molal weight of 42:NCO, g/mol;
Wherein, the compound method of above-mentioned di-n-butylamine-toluene solution: take by weighing the anhydrous di-n-butylamine of 25.8 gram AR levels, be diluted to 1L, shake up and store in the brown reagent bottle with dry toluene.
Above-mentioned bromocresol green indicator preparation (0.1%): 0.1 gram bromocresol green adds 100 milliliters of AR level isopropanols or absolute ethyl alcohol and grinds molten in 100 ml beakers.
Above-mentioned 0.1MOL/LHCL solution preparation and demarcation: the dense HCL adding distil water of 9ml is diluted to 1L, mixes, and places demarcation in several hours.
Accurately take by weighing the anhydrous benchmark sodium carbonate of 0.1 gram and add an amount of dissolved in distilled water, add 5 0.1% bromocresol green indicator, use the 0.1MOL/L HCL solution titration of being disposed; When just becoming yellow by blueness; Nondiscolouring is a terminal point in the 15S, repeats 3-5 time, and computing formula is following:
C＝{M/[(106/2)×V
HCL]}×1000；
Wherein, C:HCL solution concentration;
M: sodium carbonate quality, gram;
106: the molal weight of sodium carbonate, g/mol;
V
HCL: titration consumes HCL volume, ml.
1.3). be cooled to 40-60 ℃, discharging, inflated with nitrogen seals after the extracting vacuum, processes the last A bed of material materials of semi-prepolymer;
2). the technological process of the B bed of material is following down in preparation:
2.1). prepare polyurethane sky skin raw material B material earlier; Specifically be that load weighted PPOX ether glycol is warming up to 80-100 ℃; Stir, add load weighted dichloro-diphenyl methane diamines again, treat to add load weighted catalyst again after dichloro-diphenyl methane two amine solvents finish; Stir, process polyurethane sky skin raw material B material.
2.2). nano material is carried out modification, and nano-material modified technological process has following two kinds of methods:
2.2.1). the polyurethane sky skin raw material B material of weighing certain mass; One or more composite nano materials that add its mass fraction 0.5%-5%; One or more composite couplers that add the 0.5%-5% of nano material mass fraction are again heated to 25 ℃-100 ℃, mix material; Reaction time 1-3h obtains the component material of the nano-material modified following B bed of material;
2.2.2.). first weighing certain amount of nano material and certain amount of organic solvent, organic solvent comprises toluene, ethyl acetate, ethanol, oxolane, benzinum, adds one or more composite couplers of nano material mass fraction 0.5%-5%; Heat to 25 ℃-80 ℃; Mix material, reaction time 1-3h, decompression distillation goes out organic solvent; The oven dry of nano material after the modification is ground, obtain one or more composite modified nano materials of organic modification; Follow the polyurethane sky skin raw material of weighing certain mass again, and add one or more composite modified nano materials of its mass fraction 0.5%-5%, heat, mix material 1-3h, obtain the component material of the nano-material modified following B bed of material to 25-100 ℃.
3). to nano-polyurethane sky skin form; Specifically be last A bed of material materials and the following B bed of material materials that contain nano material,, adopt through computer numerical controlled bottler placer according to certain ratio with the semi-prepolymer that configures; Successively be filled into last A bed of material materials and following B bed of material materials in day skin mould; Under certain temperature and pressure condition, utilize the vulcanizing press moulding again, obtain compound day skin of nano wearproof polyurethane.
The present invention adopts novel nanometer composite technology, utilizes the nano effect of nano material, modified polyurethane sky skin product; Earlier the inorganic nano-particle sub-surface is carried out chemical modification; Reduce the surface ability of particle, changed the surface polarity of particle, reduced the mutual reunion between the nano material; Improve the dispersion of nano material in macromolecular material, improve the mechanical strength and the combination property of material.The last A bed of material of the present invention material is pressed certain hour at interval with following B bed of material material, successively is poured in the mould through bottler placer, then under uniform temperature and pressure condition; Utilize the vulcanizing press extrusion modling; A bed of material material is connected with the following B bed of material is solidified as one, obtain compound day skin of nano wearproof polyurethane, owing to contain nano composite material in the B bed of material down through modification; Thereby improved the wearability of day subcutaneous B bed of material and pliable and tough; And go up the performance that the A bed of material has better hardness and intensity, and can guarantee the stable occlusion pinned top-piece, prevent in use to come off.The produced sky of the present invention skin product is except the antiwear characteristic of further lifting polyurethane sky skin product; The hydrolysis, impact strength of day skin product etc. have also been improved; Prolonged service life effectively, to knock the ground noise littler for the sky skin during use, improved the using character of Women's Leather Shoes.
Below in conjunction with accompanying drawing the present invention is further described.
Description of drawings
Fig. 1 is the sketch map of the synthesis technique operating process of the A bed of material on the semi-prepolymer of the present invention.
The specific embodiment
One, make the A bed of material on the semi-prepolymer earlier, the synthesis technique operating process of the A bed of material is as shown in Figure 1 on the semi-prepolymer, and details are as follows to make semi-prepolymer technique:
(1), to adopt specification be PTMEG1000 to PTMG, its treatment process is following:
1, opens the agitated reactor charging aperture, add behind accurate measurement PTMG PTMEG1000, to start and stir and the conduction oil circulating pump.
2, when temperature rises to 100 ℃, start vavuum pump, and remain on 100-110 ℃, vacuum-0.1Mpa handles 1-1.5h down, and purpose is to eliminate PTMG PTMEG1000 moisture content.
3, the dewater back that finishes lowers the temperature and vacuum breaker at once, and temperature drops to 60 ℃.Vacuum breaker concrete operations mode is: close the vacuum suction valve earlier, close vavuum pump again.After the nitrogen tube alignment interface, open air intake valve earlier, open the nitrogen pressure-reducing valve again, control nitrogen slowly sucks in the still, up to gauge hand return during normal pressure 0.
(2), toluene di-isocyanate(TDI) TDI100 adds:
When temperature was reduced to 60 ℃, look its concrete condition can be once or add through the accurate toluene di-isocyanate(TDI) TDI100 of timing in batches.Once or batch processing look different toluene di-isocyanate(TDI) TDI100 and decide.Purpose is that to prevent once to add high activity toluene di-isocyanate(TDI) TDI100 too many in batches, and causing freely heats up surpasses 80 ℃ even the higher possibility that might cause gel to scrap.Add the fashionable 1/3 toluene di-isocyanate(TDI) TDI100 that generally adds first, visual response temperature rise degree treats that temperature rise adds remaining amount after constant more according to circumstances in batches.Adding behind the toluene di-isocyanate(TDI) TDI100 temperature in the kettle a kind of falling earlier can occur and afterwards rise phenomenon; And finally understand and freely be warming up to 60-80 ℃; Do not reach 80 ℃ as freely heating up; Then must make it reach 80-85 ℃ through slow heating, as surpassing 90 ℃, must lower the temperature with cooling water makes it finally be stabilized in 80-85 ℃ at once.
(3), reaction insulation:
After adding toluene di-isocyanate(TDI) TDI100, temperature is raised to 80 ℃ and promptly reaches the reaction holding stage, and this phase temperature should maintain under 80-85 ℃ the optimum temperature fully reacts, up to reacting completely.This must notice that temperature never can surpass more than 90 ℃ even 100 ℃ in stage, otherwise has gel to scrap danger.
(4), detect adjustment:
Later stage get final product sample analysis in insulation, probe in the agitated reactor that stops to stir with a dry cleansing glass bar or wooden stick during sampling, dip in and get 10-20g and get final product, splash in the disposal plastic cup, horse back send the laboratory detection.As detect defectively, and must add toluene di-isocyanate(TDI) TDI100, the general back 20-30min sample analysis once more that adds, as adding PTMG PTMEG1000, the detection of just can taking a sample after generally must 40-90min.
(5), cooling discharge:
As detect qualifiedly, and different material is looked in the cooling that then will begin in a minute, and general temperature drops to 40-70 ℃ and gets final product discharging.Must be filled in the specified containers with funnel during discharging, must dry exclusion and any objectionable impurities in the container.Discharging finish must once more agitated reactor be evacuated down to-0.1MPa after, charge into nitrogen and behind 0MPa, seal, guarantee in the agitated reactor that under off working state residual glue is under nitrogen protects, and prevents its gel cementing.
(6), finished product is sealed sign up for safekeeping:
After specified output is gone into container, must drive air in the container with nitrogen before sealing, guarantee to make finished product to be under the drying nitrogen protection, harden in case contact the glue gel with air.Seal the back and stick Product labelling, note model, lot number etc. at the container assigned address.
A kind of nano wearproof polyurethane of the present invention sky veneer composite material; Comprise the last A bed of material and the following B bed of material that thermosol connects; Wherein, The said component that goes up the A bed of material comprises PTMG (PTMEG1000) and toluene di-isocyanate(TDI) (TDI100), and said PTMG (PTMEG1000) and the weight portion of toluene di-isocyanate(TDI) (TDI100) in the last A bed of material are respectively:
PTMG (PTMEG1000) is 50%-75%;
Toluene di-isocyanate(TDI) (TDI100) is 25%-50%;
The said component of the B bed of material down comprises dichloro-diphenyl methane diamines (MOCA), PPOX ether glycol (DL1000), nano material and composite coupler, and said dichloro-diphenyl methane diamines (MOCA), PPOX ether glycol (DL1000), nano material and the composite coupler weight portion in the following B bed of material is respectively:
Dichloro-diphenyl methane diamines (MOCA) is 40%-60%;
PPOX ether glycol (DL1000) is 35%-55%;
Nano material is 0.5%-5%;
Coupling agent is 0.025%-0.25%;
Catalyst is 0.1%-0.3%.
The present invention embodiment preferably adopts following prescription:
Said PTMG (PTMEG1000) and the weight portion of toluene di-isocyanate(TDI) (TDI100) in the last A bed of material are respectively:
PTMG (PTMEG1000) is 62%;
Toluene di-isocyanate(TDI) (TDI100) is 38%;
Said dichloro-diphenyl methane diamines (MOCA), PPOX ether glycol (DL1000), nano material and the composite coupler weight portion in the following B bed of material is respectively:
Dichloro-diphenyl methane diamines (MOCA) is 51.86%;
PPOX ether glycol (DL1000) is 44.9%;
Nano material is 2.0%;
Coupling agent is 0.04%;
Catalyst is 0.2%.
Embodiment one: a) weigh is the polyurethane sky skin raw material B component material of 10kg; Add 20g nano silicon and 180g nano calcium carbonate composite material, add silane resin acceptor kh-550 4g again, heat to 65 ℃; Mix material; Reaction time 2h is cooled to normal temperature, obtains nano-material modified B component material.
B) weigh is the nano aluminium oxide of 1kg and the ethyl acetate of 5kg, adds silane resin acceptor kh-550 20g, heats to 65 ℃; Mix material, reaction time 2h, decompression distillation goes out organic solvent; The oven dry of nano material after the modification is ground, obtain the nano aluminium oxide of organic modification.Weigh is the polyurethane sky skin raw material B component of 10kg again, and adds the nano aluminium oxide 200g after the modification, heats to 65 ℃, mixes material 2h, obtains nano-material modified B component material.
C) A bed of material 100kg and the B component material 60kg that contains nano material on the metering semi-prepolymer adopt computer numerical controlled bottler placer to be filled in day skin mould.The temperature of vulcanizing press moulding is made as 80 ℃, pressure 30MPa, in 30 minutes reaction time, obtains nano-polyurethane sky skin.
During making, the height of the following B bed of material is the 3/10-7/10 of compound day skin height of whole nano wearproof polyurethane.Its aspect ratio can select 3/10; Also can select 7/10; In order to obtain anti-wear performance preferably; Guarantee also that simultaneously the A bed of material is to the intensity of pinned top-piece interlock on day skin, most preferred embodiment of the present invention is that the height of the B bed of material down is 3/5 of a compound day skin height of whole nano wearproof polyurethane, and just descending the height of the B bed of material and the height ratio in the last A bed of material is 3: 2.
In order to prove the wear-resisting effect of nano-polyurethane of the present invention sky skin; Respectively nano-polyurethane sky skin, TUP material sky skin and conventional polyurethanes sky skin are done 3 tests, experimental condition: 10 millimeters of day skin external diameters, day skin thickness: 5.5 millimeters; Load 1 kilogram; Cloth sand paper 80#, the reciprocating friction distance: 120 millimeters, reciprocating friction: 720 times; The time of each test: 20 minutes, test data such as following table:
Test data to sum up, the prepared nano-polyurethane sky leatherware of the present invention have excellent abrasive can, substantially exceed TUP material and common polyurethane sky skin product.
The foregoing description is the specific embodiment of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. nano wearproof polyurethane sky veneer composite material is characterized in that: comprise the last A bed of material and the following B bed of material that thermosol connects, wherein,
The said component that goes up the A bed of material comprises PTMG and toluene di-isocyanate(TDI), and said PTMG and the toluene di-isocyanate(TDI) weight portion in the last A bed of material is respectively:
PTMG is 50%-75%;
Toluene di-isocyanate(TDI) is 25%-50%;
The said component of the B bed of material down comprises dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and composite coupler, and said dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and the composite coupler weight portion in the following B bed of material is respectively:
The dichloro-diphenyl methane diamines is 40%-60%;
PPOX ether glycol is 35%-55%;
Nano material is 0.5%-5%;
Coupling agent is 0.025%-0.25%;
Catalyst is 0.1%-0.3%.
2. polyurethane according to claim 1 sky veneer composite material is characterized in that:
Said PTMG and the toluene di-isocyanate(TDI) weight portion in the last A bed of material is respectively:
PTMG is 62%;
Toluene di-isocyanate(TDI) is 38%;
Said dichloro-diphenyl methane diamines, PPOX ether glycol, nano material and the composite coupler weight portion in the following B bed of material is respectively:
The dichloro-diphenyl methane diamines is 51.86%;
PPOX ether glycol is 44.9%;
Nano material is 2.0%;
Coupling agent is 0.04%;
Catalyst is 0.2%.
3. polyurethane according to claim 1 and 2 sky veneer composite material is characterized in that: said nano material comprises nano imvite MMT, nano silicon SiO
2, nano titanium oxide TiO
2, many walls of nanometer carbon pipe MWNTs, nano aluminium oxide Al
2O
3, nano magnesia MgO, nano-calcium carbonate CaCO
3, nano zine oxide ZnO, nano-silicon nitride Si
3N
4, nanometer silicon carbide SiC wherein one or more compound uses.
4. polyurethane according to claim 3 sky veneer composite material; It is characterized in that: said coupling agent is for there being silane coupler; Said two-[γ-(triethoxysilicane) propyl group] tetrasulfide (si-69) that has silane coupler to comprise, two-[g-(triethoxysilicane) propyl group]-disulphide (si-75), gamma-aminopropyl-triethoxy-silane (KH-550), HMDS (HMDS), VTES (KH-151), vinyltrimethoxy silane (KH-171), γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570).
5. compound day skin of polyurethane according to claim 3; It is characterized in that: said coupling agent is a titanate coupling agent, and titanate coupling agent comprises monoalkoxytitanates coupling agent (JTW-101), monoalkoxy phosphate titanate coupling agent (JTW-102), two (dioctyl phosphate) titanate esters (JTW-311) of fluoroacetic acid ester, aluminium titanium composite coupler (JTW-1618).
6. polyurethane according to claim 3 sky veneer composite material is characterized in that: the said height of the B bed of material down is the 3/10-7/10 of compound day skin height of whole nano wearproof polyurethane.
7. polyurethane according to claim 4 sky veneer composite material is characterized in that: the said height of the B bed of material down is the 3/10-7/10 of compound day skin height of whole nano wearproof polyurethane.
8. polyurethane according to claim 4 sky veneer composite material is characterized in that: the said height of the B bed of material down is 3/5 of a compound day skin height of whole nano wearproof polyurethane.
9. the preparation method of a nano wearproof polyurethane sky veneer composite material, it is characterized in that: its preparation technology's flow process is following:
1). the technological process of the A bed of material is following in the preparation:
1.1). adopt a certain amount of normal temperature PTMG, be heated to 100-110 ℃ of vacuum dehydration, through 40-60 ℃ of water quench, add toluene di-isocyanate(TDI) more in batches, freely be warming up to 80 ℃; 80 ℃ of insulations 2-3 hour;
1.2). inspection by sampling, if defective, adjustment back insulation inspection by sampling again in 2-3 hour; If qualified, continue next step;
1.3). be cooled to 40-60 ℃, discharging, inflated with nitrogen seals after the extracting vacuum, processes the last A bed of material materials of semi-prepolymer;
2). the technological process of the B bed of material is following down in preparation:
2.1). prepare polyurethane sky skin raw material B material earlier; Specifically be that load weighted PPOX ether glycol is warming up to 80-100 ℃; Stir, add load weighted dichloro-diphenyl methane diamines again, treat to add load weighted catalyst again after dichloro-diphenyl methane two amine solvents finish; Stir, process polyurethane sky skin raw material B material;
2.2). nano material is carried out modification, and nano-material modified technological process has following two kinds of methods:
2.2.1). the polyurethane sky skin raw material B material of weighing certain mass; One or more composite nano materials that add its mass fraction 0.5%-5%; One or more composite couplers that add the 0.5%-5% of nano material mass fraction are again heated to 25 ℃-100 ℃, mix material; Reaction time 1-3h obtains the component material of the nano-material modified following B bed of material;
2.2.2.). first weighing certain amount of nano material and certain amount of organic solvent, organic solvent comprises toluene, ethyl acetate, ethanol, oxolane, benzinum, adds one or more composite couplers of nano material mass fraction 0.5%-5%; Heat to 25 ℃-80 ℃; Mix material, reaction time 1-3h, decompression distillation goes out organic solvent; The oven dry of nano material after the modification is ground, obtain one or more composite modified nano materials of organic modification; Follow the polyurethane sky skin raw material of weighing certain mass again, and add one or more composite modified nano materials of its mass fraction 0.5%-5%, heat, mix material 1-3h, obtain the component material of the nano-material modified following B bed of material to 25-100 ℃;
3). to nano-polyurethane sky skin form; Specifically be last A bed of material materials and the following B bed of material materials that contain nano material,, adopt through computer numerical controlled bottler placer according to certain ratio with the semi-prepolymer that configures; Successively be filled into last A bed of material materials and following B bed of material materials in day skin mould; Under certain temperature and pressure condition, utilize the vulcanizing press extrusion modling again, obtain compound day skin of nano wearproof polyurethane.
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| CN2011102870208A CN102501422A (en) | 2011-09-23 | 2011-09-23 | Nano-wear-resistant polyurethane heel lift composite material and preparation method |
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| CN2011102870208A Pending CN102501422A (en) | 2011-09-23 | 2011-09-23 | Nano-wear-resistant polyurethane heel lift composite material and preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675854A (en) * | 2011-03-14 | 2012-09-19 | 佛山星期六鞋业股份有限公司 | Abrasion-proof composite material for heel lift of shoe and preparation method for abrasion-proof composite material |
| CN102850771A (en) * | 2012-09-18 | 2013-01-02 | 广州市邦尔福鞋材有限公司 | Composite for manufacturing heel lifts and preparation method of composite |
| CN104356346A (en) * | 2014-10-22 | 2015-02-18 | 内蒙古农业大学 | Foaming material, preparation method and application |
| CN104448784A (en) * | 2013-11-15 | 2015-03-25 | 江苏吉星管业科技有限公司 | Nano composite system modified polyurethane steel plastic composite tube and preparation method thereof |
| CN107930092A (en) * | 2017-10-16 | 2018-04-20 | 江苏曜彰体育用品有限公司 | A kind of production technology for the pulley that changes colour |
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| 潘祖仁: "《高分子化学》", 31 July 2007, 化学工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675854A (en) * | 2011-03-14 | 2012-09-19 | 佛山星期六鞋业股份有限公司 | Abrasion-proof composite material for heel lift of shoe and preparation method for abrasion-proof composite material |
| CN102850771A (en) * | 2012-09-18 | 2013-01-02 | 广州市邦尔福鞋材有限公司 | Composite for manufacturing heel lifts and preparation method of composite |
| CN104448784A (en) * | 2013-11-15 | 2015-03-25 | 江苏吉星管业科技有限公司 | Nano composite system modified polyurethane steel plastic composite tube and preparation method thereof |
| CN104356346A (en) * | 2014-10-22 | 2015-02-18 | 内蒙古农业大学 | Foaming material, preparation method and application |
| CN107930092A (en) * | 2017-10-16 | 2018-04-20 | 江苏曜彰体育用品有限公司 | A kind of production technology for the pulley that changes colour |
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