CN104974370A - Preparation method of thermoplastic polyurethane beads and bead molding technology - Google Patents
Preparation method of thermoplastic polyurethane beads and bead molding technology Download PDFInfo
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Abstract
The present invention discloses a preparation method of thermoplastic polyurethane beads and a bead molding technology. High foaming thermoplastic polyurethanes (TPU) beads are obtained through: melting and granulating TPU, melt viscosity modifiers, fillers and age resisters to prepare TPU co-blending granules; using clean, cheap, environmentally-friendly CO2 and/or N2 as foaming agents; and performing medium-temperature and high-pressure soakage, dissolution equilibrium, pressure relief and pre-foaming, saturated steam secondary foaming and other techniques. The obtained high foaming TPU beads are small in shrinkage ratio and smooth in surface. The invention further discloses the bead molding technology which uses a water vapor assisted mould pressing technology to prepare molded bodies of the TPU foaming beads, the prepared molded bodies of the TPU foaming beads are low in density, small in shrinkage ratio and uniform in surface texture, and also have an unique property of TPU resin. The TPU beads can be widely applied in the fields of vibration-absorptive materials, packaging materials, toys for children, sporting goods, aviation models, heat insulating materials, automotive interior materials, etc.
Description
Technical field
The present invention relates to a kind of high-foaming thermoplastic polyurethane bead (TPU) utilizing eco-friendly pneumatogen and low pressure steam to prepare any surface finish, epidermis not fold, and assist die press technology for forming to obtain expanded bead formed body by water vapour, particularly a kind of preparation method of thermoplastic polyurethane bead and this bead moulding process.
Background technology
In prior art, most of foam material is all be matrix with plastics, by adding physics or chemical foaming agent makes plastic substrate inside obtain a large amount of bubbles.Foam material due to its light specific gravity, and has heat insulation, the characteristic such as damping and sound-absorbing, is therefore obtained in fields such as daily necessities, packaging and automobiles and applies widely.
In daily necessities industry, ethylene-vinyl acetate copolymer (EVA) foam material is applied to sneaker sole material because it has light, good elasticity more, but because EVA shoe base compression tension set is large, after for some time worn by shoes, sole can become very thin and lose elasticity.In addition, EVA resin is low due to melt strength, must carry out certain chemically crosslinked while foaming, and this just loses melting after causing EVA resin to foam and reclaims ability.EVA foaming all adopts chemical foaming, and chemical foaming agent release toxic gas, causes certain harm to environment and operator on the one hand, and also have residual chemical foaming agent in the EVA material on the other hand after foaming, this can cause the unstable properties of material.
Polystyrene (PS) and Low Density Polyethylene (LDPE) foam material are used for packaging industry, but due to PS foam material be difficult to degraded, easily produce white pollution, united nations environment was organized and is determined to stop using PS foam material in recent years.LDPE foam material resistance to elevated temperatures is poor, and can not use under high-temperature field, these all seriously limit their development.
Urethane (PU) is soft is applied to automobile engine lid and inner decoration material with hard foam more, but easy residual isocyanate in the process of PU foaming, this can know from experience generation harm to people, PU foam material creates chemically crosslinked in addition, and this just result in it and can not melting reclaim.
Thermoplastic polyurethane (TPU) can be divided into polyester and polyether-type substantially, its durometer level very broad (50HA-80HD), and has the advantages such as excellent wear-resisting, high physical strength, good water-fast, oil resistant and melting recycling.TPU foam material not only remains the excellent properties of protocorm material, but also the good rebound resilience of tool, low density and can using in the temperature range of broadness, based on above advantage, TPU foam material has good application prospect in fields such as damping, packaging, toy for children, sports goods, model airplane, heat insulating and automotive trims.
Up to now, a lot of researcher all adopts different foaming methods to be that matrix prepares foam material with TPU, comprises and adopts suspension foaming, extrusion molding, low temperature dipping method etc.For foam material, avoid the contraction of foam material particularly important, blowing temperature is generally be in matrix semi-melting state, and the contraction of product size is mainly by the motor capacity of resin segment under the viscosity of resin, degree of crystallinity and blowing temperature.
Chinese invention patent application CN103408922A and CN102276785A discloses TPU foam material preparation technology, take TPU as matrix, TPU foam material is obtained by adding the auxiliary agents such as chemical foaming agent, linking agent and additional crosslinker, foam process and EVA foaming kind are seemingly, also exist and need crosslinked and feature of environmental protection problem, in addition, adopt chemical foaming agent can make foam structure heterogeneity, the chemical foaming agent of incomplete decomposing has harm to human body and material property.
WO2010136398A1 is with CO in world inventions patent application
2, N
2be whipping agent Deng rare gas element, adopt suspesion process to obtain low density TPU expanded bead.Also there is obvious deficiency in this patent of invention, be mainly manifested in the following aspects, suspesion process take water as medium, as everyone knows, the difference that TPU hydrolysis all compares, the especially TPU of polyester type, suspension method needs to boil 2 hours in 100-140 DEG C of hot water, the long poach of this high temperature easily makes TPU degrade, thus causes the TPU degradation after foaming; On the other hand, all contain small-molecule substance in TPU particle after blended, such as: pigment, anti-aging agent, filler etc., these small-molecule substances boil for a long time through superheated water, easily separate out in particle or move to surface, thus causing TPU expanded particle to occur a series of problem.Also there is above similar problem in Chinese invention patent application CN103642200A and CN104130439A.
Chinese invention patent application CN101370861A and CN103804889A openly employs C
4-C
10aliphatic alkane, as pneumatogen, comprises the isomer of butane, pentane, hexane and octane, and employing is extruded continuously or batch tank foam process has prepared TPU expanded particle.Although extrusion foaming output is large, is difficult to the structure of control TPU abscess, makes expanded particle abscess heterogeneity, and easily obtain the TPU expanded particle of opening, subsequent forming TPU expanded particle shrinking percentage can be made so high.In addition, use aliphatic hydrocarbon to there is potential safety hazard as whipping agent in large quantities, easily produce the danger of blast.
Chinese invention patent application CN103951965A discloses and adopts high pressure fluid (CO
2or N
2) low temperature dipping TPU particle, then short period of time heating, obtains TPU expanded particle.On the one hand, under low temperature, TPU molecular chain free volume is little, and chain mobility is lower, and CO
2and N
2spread coefficient is little, and this can cause dipping time long, and production efficiency is low; In addition on the one hand, the TPU particle flooded need carry out foamable at once, because the TPU particle flooded can As time goes on, and the CO of its inside
2and N
2can toward external diffusion, this can cause TPU particle expansion ratio diminish or lose foaming power.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and this bead moulding process of thermoplastic polyurethane bead, to solve the problem proposed in above-mentioned background technology.
In order to overcome above-mentioned the deficiencies in the prior art, the invention discloses a kind of preparation method and this bead moulding process of thermoplastic polyurethane bead, mainly solve that prior art exists TPU expanded bead abscess heterogeneity, foaming process produces environmental pollution, TPU expanded particle easily shrinks under high magnification, TPU foam material cannot again recycle and suspension process makes TPU foaming material performance reduce and the problem such as lower-molecular substance migration.
The present invention selects clean, cheap, eco-friendly CO
2and/or N
2high pressure fluid is as whipping agent, and by techniques such as middle temperature high-pressure impregnation, dissolution equilibrium, pressure release pre-frothing, saturated vapo(u)r second time of foaming, having prepared density is 0.02-0.3g/cm
3, any surface finish, shrinking percentage be little, abscess-size is the TPU closed-cell foam particle of 150 μm.Water vapour is adopted to assist compression molding technology, by water vapour as thermal source and pneumatogen, make to produce between expanded particle bond and reexpand, obtain TPU expanded bead formed body, it has that density is low, cohesiveness is strong, resilience and wear resistance good, the fields such as cushioning material, wrapping material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material can be widely used in.
The technical solution adopted in the present invention is:
The preparation method of thermoplastic polyurethane bead and this bead moulding process, comprise the steps:
1) by TPU particle on the market and melt viscosity modifiers, filler, anti-aging agent premix; again by the particle after premix through forcing machine melt blending; granulation underwater or tank pelletizing obtain the blended particle of thermoplasticity TPU; in addition purposes that can be different according to bead molding; add different auxiliary agents; such as: formed body needs certain flame retardant effect, fire retardant can be added.
2) the blended particle of TPU that step 1) is obtained is put into autoclave, open and stir, pass into high pressure CO
2and/or N
2fluid, and be heated to particle softening temperature, make high pressure fluid and TPU particle reach dissolution equilibrium;
3) by step 2) the blended particle of TPU that reaches dissolution equilibrium carries out progressively pressure release, obtains pre-frothing TPU bead;
4) pre-frothing TPU bead step 3) obtained puts into autoclave, and passes into saturated steam and high-pressure air in still, pre-frothing TPU bead is reexpanded and obtains the higher TPU bead of expansion ratio;
5) high-foaming TPU bead step 4) obtained injects water vapour and assists in compression molding forming machine mould, matched moulds, then the steam of certain pressure is passed into from the ventilating pit mould, bead is made to reexpand also clinkering for overall, now stop passing into steam and shedding mold pressing, foaming product is just expanded to further and is full of whole mold cavity, through cold water cooling, and obtained TPU expanded bead formed body after the demoulding.
In described step 1), TPU particle is the mixing of a kind of in polyester type TPU, polyether-type TPU or two kinds, and wherein TPU density is 1-1.2g/cm
3, hardness is shore A60-90, the weight added is 100 parts; Melt viscosity modifiers is the mixing of one or more in ethylene-vinyl acetate copolymer (EVA), Low Density Polyethylene (LDPE) or acrylonitrile-butadiene-styrene copolymer (ABS), and the weight added is 1-20 part; Filler is the mixture of one or more in calcium carbonate, talcum powder, clay, and the weight added is 0-20 part; The weight that anti-aging agent adds is 0.1-2 part; Wherein the add-on of melt viscosity modifiers, auxiliary agent and filler is with TPU particle weight for benchmark, and the blended particle of TPU of extruding pelletization gained is circular, oval, particle length at 1-4mm, length-to-diameter ratio 1-2.
Described step 2) in, whipping agent is CO
2, N
2in a kind of or mixture of two kinds, the pressure of its high pressure fluid is 6-30MPa, is preferably 7-26MPa; The temperature of autoclave is 70-190 DEG C, is preferably 90-180 DEG C; The high pressure fluid dipping TPU blended particle time is 0.5-6h, is preferably 1-5h.
In described step 3), pressure release implements progressively pressure release under middle temperature, and venting duration is 1-30s, is preferably 5-20s.
In described step 4), the pressure of saturated steam is 0.2-1 MPa, and heat-up time is 60-300 s, is preferably 0.3-0.8 MPa, 140-250 s; The pressure of described high-pressure air is 0.2-0.8MPa, and temperature is room temperature, is preferably 0.4-0.8 MPa; The described secondary steam TPU particle density obtained that foams is 0.02-0.3g/cm
3, expansion ratio is 5-60 times.
In described step 5), the mold pressure of mould is 0.5-8MPa, and the temperature of saturated steam is 100-160 DEG C, and heat-up time is 50-300s; Described obtained TPU expanded bead formed body density is 0.04-0.7g/cm
3, hardness is shore C 30-60, and obtained formed body can be widely used in the fields such as cushioning material, wrapping material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material.
Compared with prior art beneficial effect of the present invention is as follows:
1) clean, cheap high pressure CO is adopted
2and/or N
2fluid, the blended particle of middle temperature dipping TPU, not only can shorten the time that high pressure fluid and the blended particle of TPU flood, enhance productivity, but also effectively can solve the chemical foaming agent and aliphatic alkane whipping agent pollution on the environment that other patents use.
2) the present invention can solve the variety of problems that existing patent adopts suspension method to produce effectively, and such as in aqeous suspension, small-molecule substance easily moves out and the easy hydrolysising aging of TPU particle from TPU particle.
3) melt viscosity modifiers is adopted, improve TPU Melt processing temperatures on the one hand, avoid TPU melt viscosity too high, on the other hand in blowing temperature and molded temperature, TPU is in semi-molten state, melt viscosity modifiers add the motor capacity that can increase segment, avoid the hard section of TPU to produce tear consumingly or larger strain when foaming, thus avoid contraction and the fold of expanded bead and goods.
4) adopt the technique means such as high pressure fluid pre-frothing and steam second time of foaming, efficiently solve a series of shortcomings such as foam structure heterogeneity, shrinkage crack and rate of expansion that other patented technologies produce are low.
5) moulding process of the present invention adopts water vapour to assist mould pressing technology to prepare TPU expanded bead formed body, the formed body prepared has that density is low, shrinking percentage is little, surface texturisation is even, also there is the distinctive performance of TPU resin simultaneously, such as: wear-resisting with resilience is very excellent, permanent compression set is little and chemical stability is strong, the fields such as cushioning material, wrapping material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material are particularly suitable for.
Accompanying drawing illustrates:
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.
Fig. 1 is embodiment 1 thermoplastic polyurethane elastomer blended particle DSC curve
Fig. 2 is embodiment 1 thermoplastic polyurethane elastomer blended particle FT-IR curve
Fig. 3 is the high-foaming Polyurethane Thermoplastic Elastomer expanded bead digital photograph that embodiment 1 obtains
Fig. 4 is the high-foaming Polyurethane Thermoplastic Elastomer expanded bead scanning electron microscope (SEM) photograph that embodiment 1 obtains.
Embodiment
In order to explain technical scheme of the present invention further, with specific embodiment, the present invention is described further below, but protection scope of the present invention is not limited thereto.
In each embodiment, the add-on of Polyurethane Thermoplastic Elastomer and each component is as shown in table 1:
Table 1
Note: 1, the add-on of melt viscosity modifiers, filler and anti-aging agent is all with TPU weight percent.
2, Polyurethane Thermoplastic Elastomer A: Bayer 786E; Polyurethane Thermoplastic Elastomer B: BASF 1190A; Polyurethane Thermoplastic Elastomer C: BASF 1180A; Polyurethane Thermoplastic Elastomer D: the magnificent WHT-1185 in Yantai ten thousand; Polyurethane Thermoplastic Elastomer E: BASF 60A.
3, anti-aging agent is purchased from Shanghai Ren Fu Chemical Co., Ltd..
Embodiment 1
By 100kg TPU particle, 15Kg EVA melt viscosity modifiers, 10kg calcium carbonate and 1.2kg anti-aging agent premix in homogenizer in table 1, make through forcing machine melt blending granulation underwater the blended particle G1 of oval TPU that length is 1.3 mm, length-to-diameter ratio is 1.2.Thermoplastic polyurethane elastomer blended particle DSC curve as shown in Figure 1, this curve is secondary temperature elevation curve, to eliminate thermal history, be-37.39 DEG C by the known TPU second-order transition temperature of curve, melting range is 111.5-176.4 DEG C, this TPU optimal foaming temperature can be inferred, generally melting range peak is decided to be optimal foaming temperature.Thermoplastic polyurethane elastomer blended particle infrared spectrum as shown in Figure 2,3327cm
-1for imino-infrared absorption peak in carbamate, 2956 and 2861cm
-1for methyl and methylene radical infrared absorption peak, strong 1724cm
-1infrared absorption peak is carbonyl peak in ester bond, 1724cm
-1infrared absorption peak polyester type (DSC and FT-IR curve, following examples just do not illustrate one by one) more eager to excel in whatever one does than polyether-type TPU absorption peak.
Take the blended particle G1 of 10 kgTPU and put into autoclave, autoclave is warming up to 155 DEG C, passes into high pressure CO
2fluid makes autoclave pressure reach 18MPa, and flood to make the blended particle G1 of TPU and be heated more even, autoclave is opened low rate and stirred, and dipping time is 2 h.Treat high pressure CO
2fluid reaches dissolution equilibrium in TPU resin, carries out progressively pressure release, and venting duration is 20s, obtains pre-frothing TPU particle Y1.Above-mentioned pre-expanded beads Y1 is moved into second time of foaming autoclave, pass into 0.4 MPa saturated vapo(u)r, saturated vapo(u)r heat-up time is 200 s, close saturated vapo(u)r intake valve, open the vent valve that autoclave covers end the steam in autoclave is discharged rapidly simultaneously, pass into 0.6MPa high-pressure air and progressively cool to normal temperature, driving still, to obtain density be 0.038 g/cm
3, expansion ratio be 30 high-foaming spheroid shape TPU bead F1.As shown in figures 3 and 4, F1 high-foaming surface of beads is bright and clean, bead size is evenly full, expanded bead inner cell even compact, and abscess belongs to unicellular structure, cell diameter is 150 μm (thermoplastic polyurethane foam's bead profile that following examples obtain and cross section Electronic Speculum figure and accompanying drawings 3,4 similar, so do not provide one by one).
Above-mentioned high-foaming TPU bead F1 is filled into water vapour to be assisted in compression molding captain 260mm × wide 125mm × thick 10mm mould, matched moulds makes mold pressure reach 8MPa, 160 DEG C of water vapour are passed into from mould ventilating pit, water vapour s heat-up time 120, shed mold pressing, carry out cold water cooling to mould, namely die sinking obtains TPU expanded bead formed body M1, also can obtain different expanded bead formed bodys according to the different shapes of mould.In formed body M1, between expanded bead, bonding is better, and surface arrangement is even, and its density is 0.25g/cm
3, hardness is shore C50, wear-resisting better with resilience, can be widely used in the fields such as cushioning material, wrapping material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material.
Embodiment 2
By 100kg TPU particle, 15Kg LDPE melt viscosity modifiers, 13kg talcum powder and 1kg anti-aging agent premix in homogenizer in table 1, make through forcing machine melt blending granulation underwater the blended particle G2 of circular TPU that length is 1.5 mm, length-to-diameter ratio is 1.
Take the blended particle G2 of 15kgTPU and put into autoclave, autoclave is warming up to 180 DEG C, passes into high pressure CO
2and N
2fluid makes autoclave pressure reach 20MPa, and flood to make the blended particle G2 of TPU and be heated more even, autoclave is opened low rate and stirred, and dipping time is 1 h.Treat that high pressure fluid reaches dissolution equilibrium in TPU resin, carry out progressively pressure release, venting duration is 10s, obtains pre-frothing TPU particle Y2.Above-mentioned pre-expanded beads Y2 is moved into second time of foaming autoclave, pass into 0.6 MPa saturated vapo(u)r, saturated vapo(u)r heat-up time is 180s, close saturated vapo(u)r intake valve, open the vent valve that autoclave covers end the steam in autoclave is discharged rapidly simultaneously, pass into 0.5MPa high-pressure air and progressively cool to normal temperature, driving still, to obtain density be 0.045 g/cm
3, expansion ratio be 25 high-foaming spheroid shape TPU bead F2.
Above-mentioned high-foaming TPU bead F2 is filled into water vapour to be assisted in compression molding captain 260mm × wide 125mm × thick 10mm mould, matched moulds makes mold pressure reach 5MPa, 150 DEG C of water vapour are passed into from mould ventilating pit, water vapour 200s heat-up time, shed mold pressing, carry out cold water cooling to mould, namely die sinking obtains TPU expanded bead formed body M2.Bond better between expanded bead through detecting in formed body M2, and surface arrangement is even, its density is 0.5g/cm
3, hardness is shore C60, wear-resisting better with resilience.
Embodiment 3
By 100kg TPU particle, 12Kg ABS melt viscosity modifiers, 12kg clay and 2kg anti-aging agent premix in homogenizer in table 1, make through forcing machine melt blending granulation underwater the blended particle G3 of oval TPU that length is 3 mm, length-to-diameter ratio is 1.7.
Take the blended particle G3 of 14kgTPU and put into autoclave, autoclave is warming up to 130 DEG C, passes into high pressure CO
2and N
2fluid makes autoclave pressure reach 19 MPa, and flood to make the blended particle G3 of TPU and be heated more even, autoclave is opened low rate and stirred, and dipping time is 1.5 h.Treat that high pressure fluid reaches dissolution equilibrium in TPU resin, carry out progressively pressure release, venting duration is 13s, obtains pre-frothing TPU particle Y3.Above-mentioned pre-expanded beads Y3 is moved into second time of foaming autoclave, pass into 0.4 MPa saturated vapo(u)r, saturated vapo(u)r heat-up time is 170s, close saturated vapo(u)r intake valve, open the vent valve that autoclave covers end the steam in autoclave is discharged rapidly simultaneously, pass into 0.7MPa high-pressure air and progressively cool to normal temperature, driving still, to obtain density be 0.05 g/cm
3, expansion ratio be 22 high-foaming spheroid shape TPU bead F3.
Above-mentioned high-foaming TPU particle F3 is filled into water vapour to be assisted in compression molding captain 260mm × wide 125mm × thick 10mm mould, matched moulds makes mold pressure reach 2.5MPa, 135 DEG C of water vapour are passed into from mould ventilating pit, water vapour 150s heat-up time, shed mold pressing, carry out cold water cooling to mould, namely die sinking obtains TPU expanded bead formed body M3.Bond better between expanded bead through detecting in formed body M3, and surface arrangement is even, its density is 0.4g/cm
3, hardness is shore C55, wear-resisting better with resilience.
Embodiment 4
By 100kg TPU particle, 14Kg EVA+LDPE melt viscosity modifiers, 15kg calcium carbonate and clay, 0.8kg anti-aging agent premix in homogenizer in table 1, make through forcing machine melt blending granulation underwater the blended particle G4 of oval TPU that length is 1.6 mm, length-to-diameter ratio is 1.5.
Take the blended particle G4 of 20kgTPU and put into autoclave, autoclave is warming up to 120 DEG C, passes into high pressure N
2fluid makes autoclave pressure reach 18 MPa, and flood to make the blended particle G4 of TPU and be heated more even, autoclave is opened low rate and stirred, and dipping time is 1.8 h.Treat that high pressure fluid reaches dissolution equilibrium in TPU resin, carry out progressively pressure release, venting duration is 12s, obtains pre-frothing TPU particle Y4.Above-mentioned pre-expanded beads Y4 is moved into second time of foaming autoclave, pass into 0.5 MPa saturated vapo(u)r, saturated vapo(u)r heat-up time is 190s, close saturated vapo(u)r intake valve, open the vent valve that autoclave covers end the steam in autoclave is discharged rapidly simultaneously, pass into 0.5MPa high-pressure air and progressively cool to normal temperature, driving still, to obtain density be 0.06 g/cm
3, expansion ratio be 20 high-foaming spheroid shape TPU bead F4.
Above-mentioned high-foaming TPU bead F4 is filled into water vapour to be assisted in compression molding captain 260mm × wide 125mm × thick 10mm mould, matched moulds makes mold pressure reach 3MPa, 130 DEG C of water vapour are passed into from mould ventilating pit, water vapour 180s heat-up time, shed mold pressing, carry out cold water cooling to mould, namely die sinking obtains TPU expanded bead formed body M4.Bond better between expanded bead through detecting in formed body M4, and surface arrangement is even, its density is 0.3g/cm
3, hardness is shore C47, wear-resisting better with resilience.
Embodiment 5
By 100kg TPU particle, 15Kg EVA+ABS melt viscosity modifiers, 15kg talcum powder and clay, 1.5kg anti-aging agent premix in homogenizer in table 1, make through forcing machine melt blending granulation underwater the blended particle G5 of oval TPU that length is 1.3 mm, length-to-diameter ratio is 2.
Take the blended particle G5 of 18kgTPU and put into autoclave, autoclave is warming up to 110 DEG C, passes into high pressure N
2fluid makes autoclave pressure reach 16 MPa, and flood to make the blended particle G5 of TPU and be heated more even, autoclave is opened low rate and stirred, and dipping time is 2.4 h.Treat that high pressure fluid reaches dissolution equilibrium in TPU resin, carry out progressively pressure release, venting duration is 15s, obtains pre-frothing TPU particle Y5.Above-mentioned pre-expanded beads Y5 is moved into second time of foaming autoclave, pass into 0.35MPa saturated vapo(u)r, saturated vapo(u)r heat-up time is 140s, close saturated vapo(u)r intake valve, open the vent valve that autoclave covers end the steam in autoclave is discharged rapidly simultaneously, pass into 0.7MPa high-pressure air and progressively cool to normal temperature, driving still, to obtain density be 0.03 g/cm
3, expansion ratio be 40 high-foaming spheroid shape TPU bead F5.
Above-mentioned high-foaming TPU particle F5 is filled into water vapour to be assisted in compression molding captain 260mm × wide 125mm × thick 10mm mould, matched moulds makes mold pressure reach 2MPa, 120 DEG C of water vapour are passed into from mould ventilating pit, water vapour 100s heat-up time, shed mold pressing, carry out cold water cooling to mould, namely die sinking obtains TPU expanded bead formed body M5.Bond better between expanded bead through detecting in formed body M5, and surface arrangement is even, its density is 0.07g/cm
3, hardness is shore C40, wear-resisting better with resilience.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. a preparation method for thermoplastic polyurethane bead, its preparation method adopts following steps:
The first step: by Polyurethane Thermoplastic Elastomer, melt viscosity modifiers, filler and anti-aging agent premix in high-speed mixer, mixes melting mixing in rear input forcing machine, and underwater cutpellet or tank pelletizing obtain the blended particle of thermoplastic polyurethane;
Second step: the blended particle of thermoplastic polyurethane above-mentioned steps obtained adds in autoclave, stir, pass into high pressure fluid and be warming up to polyurethane comixing particle and soften, high pressure fluid and polyurethane comixing particle is made to reach dissolution equilibrium by middle temperature high-pressure impregnation 0.5-6h, then under middle temperature, progressively pressure release is implemented, obtain pre-frothing thermoplastic polyurethane bead, then in still, pass into saturated steam and high-pressure air, pre-frothing thermoplastic polyurethane bead is reexpanded and obtains high-foaming thermoplastic polyurethane bead.
2. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, is characterized in that, described Polyurethane Thermoplastic Elastomer is polyester type and/or polyether-type, and its density is 1-1.2g/cm
3, hardness is shore A60-90, weight is 100 parts.
3. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, it is characterized in that, described melt viscosity modifiers is the mixing of one or more in Low Density Polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and the weight added is 1-20 part.
4. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, is characterized in that, described filler is the mixture of one or more in calcium carbonate, talcum powder, clay, and the weight added is 0-20 part.
5. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, is characterized in that, described high pressure fluid is CO
2and/or N
2, described middle temperature high pressure, its temperature is 70-190 DEG C, and pressure is 6-30MPa.
6. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, is characterized in that, described saturated steam and the pressure of high-pressure air are respectively 0.2-1MPa, 0.2-0.8MPa.
7. the preparation method of a kind of thermoplastic polyurethane bead as claimed in claim 1, is characterized in that, described high-foaming thermoplastic polyurethane bead density is 0.02-0.3g/cm
3, expansion ratio is 5-60 times.
8. a thermoplastic polyurethane bead, is characterized in that, this bead is obtained by claim 1-7 any means.
9. the moulding process of a kind of thermoplastic polyurethane bead as claimed in claim 8, adopt with the following method:
High-foaming thermoplastic polyurethane bead is injected water vapour assists in the mould of moulding press, matched moulds, then the steam of certain pressure is passed into from the ventilating pit mould, bead is made to reexpand also clinkering for overall, now stop passing into steam and shedding mold pressing, foaming product is just expanded to further and is full of whole mold cavity, through cold water cooling, just obtains high-foaming thermoplastic polyurethane bead molding after the demoulding.
10. the moulding process of a kind of thermoplastic polyurethane bead as claimed in claim 9, it is characterized in that, described mold pressure is 0.5-8MPa, the temperature of described saturated steam is 100-160 DEG C, heat-up time is 50-300s, and described high-foaming thermoplastic polyurethane bead molding density is 0.04-0.7g/cm
3, hardness is shore C 30-60.
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