CN104974370B - A kind of preparation method of thermoplastic polyurethane bead and the bead moulding process - Google Patents
A kind of preparation method of thermoplastic polyurethane bead and the bead moulding process Download PDFInfo
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- CN104974370B CN104974370B CN201510024941.3A CN201510024941A CN104974370B CN 104974370 B CN104974370 B CN 104974370B CN 201510024941 A CN201510024941 A CN 201510024941A CN 104974370 B CN104974370 B CN 104974370B
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Abstract
The invention discloses the preparation method and the bead moulding process of a kind of thermoplastic polyurethane bead, particle is blended by the way that thermoplastic polyurethane, melt viscosity modifiers, filler, age resistor melt pelletization are made into TPU, with cleaning, cheap, environment-friendly CO2And/or N2It is foaming agent, by middle temperature high-pressure impregnation, dissolution equilibrium, pressure release prefoam, the techniques such as saturated vapor second time of foaming, obtain shrinkage factor small, the high-foaming TPU beads of any surface finish, the invention also discloses the moulding process of the bead, moulding process prepares TPU expanded bead formed bodys using vapor auxiliary mould pressing technology, the formed body prepared has density low, shrinkage factor is small, surface texturisation is uniform, also there is the distinctive performance of TPU resins simultaneously, can be widely used in vibration-absorptive material, packaging material, toy for children, sports goods, model airplane, the field such as heat preserving and insulating material and automotive interior material.
Description
Technical field
The present invention relates to a kind of any surface finish, epidermis are prepared using environment-friendly physical blowing agent and low pressure steam not
The high-foaming thermoplastic polyurethane bead of fold（TPU）, and by vapor aid in die press technology for forming obtain expanded bead into
Type body, the preparation method and the bead moulding process of more particularly to a kind of thermoplastic polyurethane bead.
Background technology
Most of expanded material is all, with plastics as matrix, to be made by adding physics or CBA in the prior art
Obtain and obtain substantial amounts of bubble inside plastic substrate.Expanded material possesses heat-insulated, damping and sound-absorbing etc. due to its light specific gravity
Characteristic, therefore be obtained for and widely apply in commodity, packaging and the field such as automobile.
In commodity industry, ethylene-vinyl acetate copolymer（EVA）Expanded material has light, good bullet due to it
Property more be applied to sneaker sole material, but because EVA shoe base pressure compression permanent deformation is big, after shoes have worn a period of time, sole
Can become very thin and lose elasticity.Additionally, EVA resin is low due to melt strength, certain chemistry must be carried out while foaming
Crosslinking, this causes EVA resin that melting recovery ability is just lost after foaming.EVA foaming all uses chemical blowing, on the one hand chemistry
Foaming agent discharges toxic gas, certain harm is caused to environment and operating personnel, in the EVA material after on the other hand foaming also
There is the CBA of residual, this can cause the unstable properties of material.
Polystyrene（PS）And low density polyethylene (LDPE)（LDPE）Expanded material is used for packaging industry, but due to PS foaming
Material is difficult to degrade, and is also easy to produce white pollution, and united nations environment tissue had determined to stop using PS expanded materials in recent years.
LDPE expanded material resistances to elevated temperatures are poor, it is impossible to used under high-temperature field, and these all seriously limit their development.
Polyurethane（PU）Automobile engine lid and inner decoration material being applied to soft and hard foam more, but
It is easy residual isocyanate during PU foams, this can know from experience generation harm to people, in addition generating of PU expanded materials
Crosslinking is learned, this just result in it and can not melt recovery.
Thermoplastic polyurethane（TPU）Polyester and polyether-type are can be generally divided into, its hardness range is very broad（50HA-
80HD）, and recycled etc. with excellent mechanical strength wear-resisting, high, good water-fast, oil resistant and melting excellent
Point.TPU expanded materials not only remain the excellent properties of protocorm material, but also have good resilience, low-density and
Can be used within the scope of broad temperature, based on above advantage, TPU expanded materials are in damping, packaging, toy for children, physical culture
The fields such as articles for use, model airplane, insulation and automotive trim have good application prospect.
So far, many researchers all use different foaming methods to prepare expanded material by matrix of TPU, bag
Include using suspension foaming, extrusion molding, low temperature dipping method etc..For expanded material, it is to avoid the contraction of expanded material is particularly
Important, blowing temperature is usually to be in matrix semi-molten state, and the contraction of product size is mainly by viscosity, the crystallinity of resin
And under blowing temperature resin segment locomitivity.
Chinese invention patent application CN103408922A and CN102276785A disclose TPU expanded material preparation technologies,
With TPU as matrix, TPU expanded materials are obtained by adding the auxiliary agents such as CBA, crosslinking agent and assistant crosslinking agent, foam work
Skill is similar with EVA foaming, there is also needs crosslinking and environmentally friendly sex chromosome mosaicism, in addition, abscess can be caused using CBA
Structure heterogeneity, the CBA of incomplete decomposing has harm to human body and material property.
WO2010136398A1 is with CO for world inventions patent application2、N2It is foaming agent Deng inert gas, using suspension method work
Skill obtains low-density TPU expanded beads.This patent of invention there is also clearly disadvantageous, be mainly manifested in the following aspects, hang
Floating process is with water as medium, it is well known that the TPU of the difference that TPU hydrolysis all compares, especially polyester-type, and suspension method is needed
To be boiled in 100-140 DEG C of hot water 2 hours, this prolonged water of high temperature is boiled easily makes TPU degrade, so as to cause hair
TPU hydraulic performance declines after bubble；On the other hand, all contain small-molecule substance in TPU particles after blending, such as：It is pigment, anti-old
Agent, filler etc., these small-molecule substances are boiled through the long-time of superheated water, and surface is easily separated out or moved to from particle,
There is a series of problem so as to cause TPU expanded particles.Chinese invention patent application CN103642200A and
CN104130439A there is also problem like above.
Chinese invention patent application CN101370861A and CN103804889A are disclosed and have been used C4-C10Aliphatic alkane is made
Be physical blowing agent, including butane, pentane, hexane and octane isomers, foamed using continuous extrusion or batch tank
Technique is prepared for TPU expanded particles.Although extrusion foaming yield is big, the structure of control TPU abscesses is difficult so that foaming grain
Sub- abscess heterogeneity, and the TPU expanded particles of opening are readily obtained, such that subsequent forming TPU expanded particles are received
Shrinkage is high.In addition, there is potential safety hazard using aliphatic hydrocarbon as foaming agent in large quantities, the danger of blast is easily produced.
Chinese invention patent application CN103951965A is disclosed and is used high-pressure fluid（CO2Or N2）Low temperature dipping TPU
Son, then short time heating, obtains TPU expanded particles.On the one hand, TPU strands free volume is small under low temperature, chain mobility
Than relatively low, and CO2And N2Diffusion coefficient is small, and this can cause dip time long, low production efficiency；Still further aspect, it is impregnated
Good TPU particles need at once carry out foamable, because the TPU particles for having impregnated completion can over time, inside it
CO2And N2Can be toward external diffusion, this can cause TPU particle expansion ratios to diminish or lose foaming capacity.
The content of the invention
It is an object of the invention to provide the preparation method and the bead moulding process of a kind of thermoplastic polyurethane bead, with
Solve the problems, such as to be proposed in above-mentioned background technology.
In order to overcome the above-mentioned deficiencies of the prior art, the invention discloses a kind of preparation method of thermoplastic polyurethane bead
And the bead moulding process, mainly solve prior art and there is TPU expanded bead abscesses heterogeneity, the dirt of foaming process generation environment
TPU expanded particles easily shrink under dye, high magnification, TPU expanded materials cannot be recycled again and suspension process is so that TPU sends out
The problems such as reduction of foam material performance and lower-molecular substance are migrated.
The present invention is from cleaning, cheap, environment-friendly CO2And/or N2High-pressure fluid is high by middle temperature as foaming agent
The techniques such as pressure dipping, dissolution equilibrium, pressure release prefoam, saturated vapor second time of foaming, are prepared for density for 0.02-0.3g/cm3、
Any surface finish, shrinkage factor are small, and abscess-size is 150 μm of TPU closed-cell foam particles.Compression molding skill is aided in using vapor
Art, thermal source and physical blowing agent are used as by vapor so that are produced between expanded particle and are bonded and reexpand, obtain TPU
Expanded bead formed body, it has, and density is low, caking property strong, resilience and wearability are good, can be widely applied to vibration-absorptive material,
The fields such as packaging material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material.
The technical solution adopted in the present invention is：
A kind of preparation method of thermoplastic polyurethane bead and the bead moulding process, comprise the following steps：
1）By TPU particles on the market and melt viscosity modifiers, filler, age resistor premix, then by the particle after premix
Extruded machine melt blending, granulation underwater or tank pelletizing are obtained thermoplasticity TPU blending particles, can be molded according to bead in addition
The different purposes of body, adds different auxiliary agents, such as：Formed body needs certain flame retardant effect, can add fire retardant.
2）By step 1）Obtained TPU blendings particle is put into autoclave, opens stirring, is passed through high pressure CO2And/or
N2Fluid, and particle softening temperature is heated to, high-pressure fluid is reached dissolution equilibrium with TPU particles；
3）By step 2）The TPU blending particles for reaching dissolution equilibrium carry out progressively pressure release, obtain prefoam TPU beads；
4）By step 3）The prefoam TPU beads for obtaining are put into autoclave, and to being passed through saturated steam in kettle
And pressure-air so that prefoam TPU beads reexpand and obtain expansion ratio TPU beads higher；
5）By step 4）In the high-foaming TPU beads injection vapor auxiliary compression molding forming machine mould for obtaining, matched moulds, then
Passage from mould is passed through the steam of certain pressure so that bead reexpands and clinkering is overall, now stops being passed through
Steam simultaneously sheds molding, and foaming product is just further expanded to full of whole mold cavity, is cooled down through cold water, is obtained after the demoulding
TPU expanded bead formed bodys.
The step 1）In, TPU particles are the mixing of the one or two kinds of in polyester-type TPU, polyether-type TPU, wherein
TPU density is 1-1.2g/cm3, hardness be shore A60-90, the weight of addition is 100 parts；Melt viscosity modifiers are second
Alkene-acetate ethylene copolymer（EVA）, low density polyethylene (LDPE)（LDPE）Or acrylonitrile-butadiene-styrene copolymer（ABS）In
The mixing of one or more, the weight of addition is 1-20 parts；Filler is one or more in calcium carbonate, talcum powder, clay
Mixture, the weight of addition is 0-20 parts；The weight that age resistor is added is 0.1-2 parts；Wherein melt viscosity modifiers, auxiliary agent
It is that on the basis of TPU particle weights, the TPU blending particles obtained by extruding pelletization are circular, oval, grain with the addition of filler
Sub- length is in 1-4mm, draw ratio 1-2.
The step 2）In, foaming agent is CO2、N2In one or two kinds of mixture, the pressure of its high pressure fluid
It is 6-30MPa, preferably 7-26MPa；The temperature of autoclave is 70-190 DEG C, preferably 90-180 DEG C；High-pressure spray
The body dipping TPU blending particle times are 0.5-6h, preferably 1-5h.
The step 3）In, pressure release is to implement progressively pressure release under middle temperature, venting duration be 1-30s, preferably 5-
20s。
The step 4）In, the pressure of saturated steam is 0.2-1 MPa, and the heat time is 60-300 s, preferably
0.3-0.8 MPa, 140-250 s；The pressure of the pressure-air is 0.2-0.8MPa, and temperature is room temperature, preferably
0.4—0.8 MPa；The TPU particle densities that the secondary steam foaming is obtained are 0.02-0.3g/cm3, expansion ratio be 5-
60 times.
The step 5）In, the clamping pressure of mould is 0.5-8MPa, and the temperature of saturated steam is 100-160 DEG C,
Heat time is 50-300s；The obtained TPU expanded beads shaping volume density is 0.04-0.7g/cm3, hardness is shore
C 30-60, obtained formed body can be widely applied to vibration-absorptive material, packaging material, toy for children, sports goods, boat
The fields such as empty model, heat preserving and insulating material and automotive interior material.
Beneficial effects of the present invention are as follows compared with prior art：
1）Using cleaning, cheap high pressure CO2And/or N2Fluid, middle temperature dipping TPU blending particles, can not only shorten height
The time of fluid and TPU blending particle dippings, improve production efficiency are pressed, but also other patents can be efficiently solved and used
CBA and aliphatic alkane foaming agent pollution on the environment.
2）The present invention can efficiently solve variety of problems of the existing patent using suspension method production, such as in water slurry
In, small-molecule substance is easily migrated out and the easy hydrolysising aging of TPU particles from TPU particles.
3）Using melt viscosity modifiers, TPU Melt processing temperatures are on the one hand improved, it is to avoid TPU melt viscosities are too high,
On the other hand in blowing temperature and molded temperature, TPU is in semi-molten state, and the addition of melt viscosity modifiers can increase
The locomitivity of segment, it is to avoid TPU hard sections are produced when foaming and consumingly torn or larger strain, so as to avoid hair
Contraction and the fold of bubble bead and product.
4）Using the technological means such as high-pressure fluid prefoam and steam second time of foaming, other patented technologies are efficiently solved
Produced foam structure heterogeneity, shrinkage crack and a series of low shortcomings of expansion rate.
5）Moulding process of the present invention prepares TPU expanded bead formed bodys using vapor auxiliary mould pressing technology, prepares
Formed body has that density is low, shrinkage factor is small, surface texturisation is uniform, while also there is the distinctive performance of TPU resins, such as：It is wear-resisting
, permanent compression set very excellent with resilience is small and chemical stability is strong, is particularly suitable for vibration-absorptive material, packing timber
The fields such as material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material.
Brief description of the drawings：
The present invention is further elaborated with reference to the accompanying drawings and detailed description.
Fig. 1 is the thermoplastic polyurethane elastomer blended particle DSC curve of embodiment 1
Fig. 2 is the thermoplastic polyurethane elastomer blended particle FT-IR curves of embodiment 1
Fig. 3 is the high-foaming TPUE expanded bead digital photograph obtained by embodiment 1
Fig. 4 is the high-foaming TPUE expanded bead scanning electron microscope (SEM) photograph obtained by embodiment 1.
Specific embodiment
In order to technical scheme is explained further, the present invention is done further with specific embodiment below
It is bright, but protection scope of the present invention not limited to this.
In each embodiment, TPUE is as shown in table 1 with the addition of each component：
Table 1
Note：1st, the addition of melt viscosity modifiers, filler and age resistor is with TPU percentage by weights.
2nd, TPUE A：Bayer 786E；TPUE B：BASF 1190A；Thermoplasticity
Polyurethane elastomer C：BASF 1180A；TPUE D：Yantai Wanhua WHT-1185；Thermoplastic polyurethane bullet
Gonosome E：BASF 60A.
3rd, age resistor is purchased from Shanghai Ren Fu Chemical Co., Ltd.s.
Embodiment 1
100kg TPU particles, 15Kg EVA melt viscosity modifiers, 10kg calcium carbonate and 1.2kg age resistor in table 1 are existed
Premix in homogenizer, extruded machine melt blending granulation underwater is made the ellipse that length is 1.3 mm, draw ratio is 1.2
TPU blending particles G1.As shown in Figure 1, this curve is bent secondary temperature elevation to thermoplastic polyurethane elastomer blended particle DSC curve
Line, is, in order to eliminate thermal history, to understand that TPU glass transition temperatures are -37.39 DEG C by curve, and melting range is 111.5-176.4
DEG C, this TPU optimal foaming temperature can be speculated, melting range peak is typically set to optimal foaming temperature.TPUE
Particle infrared spectrum is blended as shown in Figure 2,3327cm-1It is imino group infrared absorption peak, 2956 and in carbamate
2861cm-1It is methyl and methylene infrared absorption peak, strong 1724cm-1Infrared absorption peak is carbonyl peak, 1724cm in ester bond-1
Infrared absorption peak polyester-type is eager to excel than polyether-type TPU absworption peaks（DSC and FT-IR curves, following examples are not just illustrated one by one）.
Weigh 10 kgTPU blendings particle G1 to be put into autoclave, autoclave is warming up to 155 DEG C, be passed through high pressure CO2Stream
Body causes that autoclave pressure reaches 18MPa, in order that TPU blending particles G1 impregnates and is uniformly heated, autoclave is opened low
Speed is stirred, and dip time is 2 h.Treat high pressure CO2Fluid reaches dissolution equilibrium in TPU resins, carries out progressively pressure release, pressure release
Time is 20s, obtains prefoam TPU particles Y1.Above-mentioned pre-expanded beads Y1 is moved into second time of foaming autoclave, 0.4 is passed through
MPa saturated vapors, the saturated vapor heat time is 200 s, closes saturated vapor intake valve, while opening autoclave covers end
Air bleeding valve discharges rapidly the steam in autoclave, is passed through 0.6MPa pressure-airs and progressively cools to normal temperature, drives kettle and obtains density
It is 0.038 g/cm3, the high-foaming spheroid shape TPU beads F1 that expansion ratio is 30.As shown in figures 3 and 4, F1 high-foamings bead
Any surface finish, bead size are uniformly full, expanded bead inner cell even compact, and abscess belongs to hole-closing structure, and abscess is straight
Footpath is 150 μm（Thermoplastic polyurethane foam's bead profile and section electron microscope and accompanying drawing 3,4 classes obtained by following examples
Seemingly, so not providing one by one）.
Above-mentioned high-foaming TPU beads F1 is filled into vapor auxiliary compression molding captain 260mm × 125mm × thickness wide
In 10mm moulds, matched moulds makes clamping pressure reach 8MPa, 160 DEG C of vapor is passed through from mould passage, when vapor is heated
Between 120 s, shed molding, carry out cold water cooling to mould, die sinking obtains final product TPU expanded bead formed body M1, also dependent on mould
Different shape obtain different expanded bead formed bodys.Bonded preferably between expanded bead in formed body M1, and surface distributed
Uniformly, its density is 0.25g/cm3, hardness is shore C50, wear-resisting and resilience preferably, can be widely applied to vibration-absorptive material,
The fields such as packaging material, toy for children, sports goods, model airplane, heat preserving and insulating material and automotive interior material.
Embodiment 2
100kg TPU particles, 15Kg LDPE melt viscosity modifiers, 13kg talcum powder and 1kg age resistor in table 1 are existed
Premix in homogenizer, extruded machine melt blending granulation underwater is made the circular TPU that length is 1.5 mm, draw ratio is 1
Blending particle G2.
Weigh 15kgTPU blendings particle G2 to be put into autoclave, autoclave is warming up to 180 DEG C, be passed through high pressure CO2And N2
Fluid causes that autoclave pressure reaches 20MPa, in order that TPU blending particles G2 impregnates and is uniformly heated, autoclave is opened
Low rate is stirred, and dip time is 1 h.Treat that high-pressure fluid reaches dissolution equilibrium in TPU resins, carry out progressively pressure release, pressure release
Time is 10s, obtains prefoam TPU particles Y2.Above-mentioned pre-expanded beads Y2 is moved into second time of foaming autoclave, 0.6 is passed through
MPa saturated vapors, the saturated vapor heat time is 180s, closes saturated vapor intake valve, while opening autoclave covers end
Air bleeding valve discharges rapidly the steam in autoclave, is passed through 0.5MPa pressure-airs and progressively cools to normal temperature, drives kettle and obtains density
It is 0.045 g/cm3, the high-foaming spheroid shape TPU beads F2 that expansion ratio is 25.
Above-mentioned high-foaming TPU beads F2 is filled into vapor auxiliary compression molding captain 260mm × 125mm × thickness wide
In 10mm moulds, matched moulds makes clamping pressure reach 5MPa, 150 DEG C of vapor is passed through from mould passage, when vapor is heated
Between 200s, shed molding, carry out cold water cooling to mould, die sinking obtains final product TPU expanded bead formed bodys M2.By detecting formed body
Bonded preferably between expanded bead in M2, and surface distributed is uniform, its density is 0.5g/cm3, hardness is shore C60, it is wear-resisting and
Resilience is preferable.
Embodiment 3
By 100kg TPU particles, 12Kg ABS melt viscosity modifiers, 12kg clays and 2kg age resistor in table 1 at a high speed
Premix in mixer, extruded machine melt blending granulation underwater is made the oval TPU that length is 3 mm, draw ratio is 1.7 and is total to
Mixed particle G3.
Weigh 14kgTPU blendings particle G3 to be put into autoclave, autoclave is warming up to 130 DEG C, be passed through high pressure CO2And N2
Fluid causes that autoclave pressure reaches 19 MPa, in order that TPU blending particles G3 impregnates and is uniformly heated, autoclave is opened
Low rate is stirred, and dip time is 1.5 h.Treat that high-pressure fluid reaches dissolution equilibrium in TPU resins, carry out progressively pressure release, let out
The pressure time is 13s, obtains prefoam TPU particles Y3.Above-mentioned pre-expanded beads Y3 is moved into second time of foaming autoclave, 0.4 is passed through
MPa saturated vapors, the saturated vapor heat time is 170s, closes saturated vapor intake valve, while opening autoclave covers end
Air bleeding valve discharges rapidly the steam in autoclave, is passed through 0.7MPa pressure-airs and progressively cools to normal temperature, drives kettle and obtains density
It is 0.05 g/cm3, the high-foaming spheroid shape TPU beads F3 that expansion ratio is 22.
Above-mentioned high-foaming TPU particles F3 is filled into vapor auxiliary compression molding captain 260mm × 125mm × thickness wide
In 10mm moulds, matched moulds makes clamping pressure reach 2.5MPa, and 135 DEG C of vapor, vapor heating are passed through from mould passage
Time 150s, sheds molding, and cold water cooling is carried out to mould, and die sinking obtains final product TPU expanded bead formed bodys M3.It is molded by detection
Bonded preferably between expanded bead in body M3, and surface distributed is uniform, its density is 0.4g/cm3, hardness is shore C55, wear-resisting
It is preferable with resilience.
Embodiment 4
By 100kg TPU particles, 14Kg EVA+LDPE melt viscosity modifiers, 15kg calcium carbonate and clay in table 1,
In being premixed in homogenizer, extruded machine melt blending granulation underwater is made length for 1.6 mm, draw ratio to 0.8kg age resistor
It is 1.5 oval TPU blending particles G4.
Weigh 20kgTPU blendings particle G4 to be put into autoclave, autoclave is warming up to 120 DEG C, be passed through high pressure N2Fluid
So that autoclave pressure reaches 18 MPa, in order that TPU blending particles G4 impregnates and is uniformly heated, autoclave opens low speed
Rate is stirred, and dip time is 1.8 h.Treat that high-pressure fluid reaches dissolution equilibrium in TPU resins, progressively pressure release is carried out, during pressure release
Between be 12s, obtain prefoam TPU particles Y4.Above-mentioned pre-expanded beads Y4 is moved into second time of foaming autoclave, 0.5 MPa is passed through
Saturated vapor, the saturated vapor heat time is 190s, closes saturated vapor intake valve, while opening the exhaust that autoclave covers end
Valve discharges rapidly the steam in autoclave, is passed through 0.5MPa pressure-airs and progressively cools to normal temperature, drives kettle and obtains density and is
0.06 g/cm3, the high-foaming spheroid shape TPU beads F4 that expansion ratio is 20.
Above-mentioned high-foaming TPU beads F4 is filled into vapor auxiliary compression molding captain 260mm × 125mm × thickness wide
In 10mm moulds, matched moulds makes clamping pressure reach 3MPa, 130 DEG C of vapor is passed through from mould passage, when vapor is heated
Between 180s, shed molding, carry out cold water cooling to mould, die sinking obtains final product TPU expanded bead formed bodys M4.By detecting formed body
Bonded preferably between expanded bead in M4, and surface distributed is uniform, its density is 0.3g/cm3, hardness is shore C47, it is wear-resisting and
Resilience is preferable.
Embodiment 5
By 100kg TPU particles, 15Kg EVA+ABS melt viscosity modifiers, 15kg talcum powder and clay in table 1,
In being premixed in homogenizer, extruded machine melt blending granulation underwater is made length for 1.3 mm, draw ratio to 1.5kg age resistor
It is 2 oval TPU blending particles G5.
Weigh 18kgTPU blendings particle G5 to be put into autoclave, autoclave is warming up to 110 DEG C, be passed through high pressure N2Fluid
So that autoclave pressure reaches 16 MPa, in order that TPU blending particles G5 impregnates and is uniformly heated, autoclave opens low speed
Rate is stirred, and dip time is 2.4 h.Treat that high-pressure fluid reaches dissolution equilibrium in TPU resins, progressively pressure release is carried out, during pressure release
Between be 15s, obtain prefoam TPU particles Y5.Above-mentioned pre-expanded beads Y5 is moved into second time of foaming autoclave, 0.35MPa is passed through
Saturated vapor, the saturated vapor heat time is 140s, closes saturated vapor intake valve, while opening the exhaust that autoclave covers end
Valve discharges rapidly the steam in autoclave, is passed through 0.7MPa pressure-airs and progressively cools to normal temperature, drives kettle and obtains density and is
0.03 g/cm3, the high-foaming spheroid shape TPU beads F5 that expansion ratio is 40.
Above-mentioned high-foaming TPU particles F5 is filled into vapor auxiliary compression molding captain 260mm × 125mm × thickness wide
In 10mm moulds, matched moulds makes clamping pressure reach 2MPa, 120 DEG C of vapor is passed through from mould passage, when vapor is heated
Between 100s, shed molding, carry out cold water cooling to mould, die sinking obtains final product TPU expanded bead formed bodys M5.By detecting formed body
Bonded preferably between expanded bead in M5, and surface distributed is uniform, its density is 0.07g/cm3, hardness is shore C40, wear-resisting
It is preferable with resilience.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires to be limited rather than described above, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as the claim involved by limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each implementation method is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Specification an as entirety, the technical scheme in each embodiment can also be formed into those skilled in the art through appropriately combined
May be appreciated other embodiment.
Claims (4)
1. a kind of preparation method of thermoplastic polyurethane bead, using following steps：
The first step：By TPUE, melt viscosity modifiers, filler and age resistor in pre- in high-speed mixer
It is mixed, melting mixing in extruder is put into after being well mixed, underwater cutpellet or tank pelletizing are obtained thermoplastic polyurethane blending particle；
Described TPUE is polyester-type and/or polyether-type, and its density is 1-1.2g/cm3, hardness be shore
A60-90, the weight of addition is 100 parts；
Described melt viscosity modifiers are low density polyethylene (LDPE), ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-benzene second
The mixing of one or more in alkene copolymer, the weight of addition is 12-15 parts；
Described filler is the mixture of one or more in calcium carbonate, talcum powder, clay, and the weight of addition is 10-15 parts；
The weight that age resistor is added is 0.8-2 parts；
Second step：The thermoplastic polyurethane blending particle that above-mentioned steps are obtained is added in autoclave, and stirring is passed through high-pressure fluid
And the softening of polyurethane comixing particle is warming up to, high-pressure fluid is reached with polyurethane comixing particle by middle temperature high-pressure impregnation 1-5h
Dissolution equilibrium, then implements progressively pressure release under middle temperature, obtains prefoam thermoplastic polyurethane bead, then full to being passed through in kettle
With vapor and pressure-air so that prefoam thermoplastic polyurethane bead reexpands and obtains high-foaming thermoplastic polyurethane pearl
Grain；
Described high-pressure fluid is CO2And/or N2；
Described middle temperature high pressure, its temperature is 90-180 DEG C, and pressure is 7-26MPa；
The venting duration for implementing progressively pressure release under middle temperature is 10-20s；
The pressure of described saturated steam is 0.2-1MPa, and the heat time is 60-300s；The pressure of described pressure-air is
0.2-0.8MPa, temperature is room temperature；
Described high-foaming thermoplastic polyurethane bead density is 0.02-0.3g/cm3, expansion ratio is 5-60 times.
2. the preparation method of thermoplastic polyurethane bead according to claim 1, it is characterised in that：Described thermoplastic poly
Urethane blending particle is circular, oval, and particle length is 1-4mm, draw ratio 1-2.
3. the preparation method of thermoplastic polyurethane bead according to claim 1, it is characterised in that：Described saturation water steams
The pressure of gas is 0.3-0.8MPa, and the heat time is 140-250s；The pressure of described pressure-air is 0.4-0.8MPa.
4. a kind of thermoplastic polyurethane bead, it is characterised in that preparation side of the bead as any one of claim 1-3
Method is obtained.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510024941.3A CN104974370B (en) | 2015-01-19 | 2015-01-19 | A kind of preparation method of thermoplastic polyurethane bead and the bead moulding process |
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| CN201510024941.3A CN104974370B (en) | 2015-01-19 | 2015-01-19 | A kind of preparation method of thermoplastic polyurethane bead and the bead moulding process |
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