CN103642200B - A kind of foamed thermoplastic polyurethane bead and preparation method thereof - Google Patents
A kind of foamed thermoplastic polyurethane bead and preparation method thereof Download PDFInfo
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- CN103642200B CN103642200B CN201310706444.2A CN201310706444A CN103642200B CN 103642200 B CN103642200 B CN 103642200B CN 201310706444 A CN201310706444 A CN 201310706444A CN 103642200 B CN103642200 B CN 103642200B
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Abstract
The invention discloses a kind of foamed thermoplastic polyurethane bead, this expanded bead comprises 100 parts of thermoplastic polyurethane particles, 1-10 part abscess-size stablizer, 1-35 part melt viscosity modifiers; These beads are that then foaming is produced by adopting volatile foaming agent to be immersed in aqeous suspension by the thermoplastic polyurethane particle comprising abscess-size stablizer and melt viscosity modifiers; The melt viscosity of this foamed thermoplastic polyurethane bead at 180 DEG C is 8000-15000 pool; The foamed thermoplastic polyurethane bead size of preparation is stablized, cell diameter is even, surface-brightening, product yield is high, even if foamed thermoplastic polyurethane bead also has good clinkering performance under lower water vapour pressure simultaneously, the mold foamed articles deformation obtained is little, low relative to the dimensional contraction rate of mould, excellent in dimensional stability, surface aesthetic.
Description
Technical field:
The present invention relates to foam material technical field, a kind of foamed thermoplastic polyurethane bead and preparation method thereof specifically, the molded foam article be made up of this expanded bead can be used for amortizing packaging material, heat preserving and insulating material, bedclothes (as pillow, mattress), Condom (as floor coating), damping energy-absorbing material (as bumper core).
Background technology:
Take plastics as matrix, fill a large amount of bubble by physics or chemical process in plastics inner, obtain polymeric foamable material.It is low that foam material has density, and row advantages such as heat-insulating sound-insulating, specific tenacity are high, buffering, are therefore used widely in fields such as packing business, industry, agricultural, transportation, war industry, space industry and daily necessities.Conventional porous plastics kind has the soft and rigid foam of urethane (PU), polystyrene (PS) porous plastics, polyethylene (PE) porous plastics, polypropylene (PP) porous plastics etc.But urethane foam is easy residual isocyanate in foaming process, harmful, and foam material cannot be recycled.Polystyrene foamed plastics product degraded difficulty, easily produce " white pollution " problem, united nations environment is organized and is determined to stop using PS foam article.Polyethylene foams resistance to elevated temperatures is poor, is not suitable for applying in high-temperature field.
Polyurethane Thermoplastic Elastomer (TPU) has more wide in range durometer level, excellent wear resistance, physical strength, water-fast, oil resistant, resistance to chemical attack, resistance to mould, environmentally friendly, the advantages such as recoverable.By foamed thermoplastic polyurethane bead is filled in mould, utilizes water vapour to carry out hot briquetting and can obtain molded foam article.This kind of goods are outside the performance retaining protocorm excellence, and have excellent rebound resilience, various shapes, low density, can use in more wide in range temperature range simultaneously.Based on above-mentioned advantage, TPU mold foamed articles has application prospect widely at many industrial circles (automotive industry, wrapping material) and daily life field (footwear material, pillow, mattress).
The mouldable foam beads of thermoplastic polyurethane is disclosed in WO2007082838.But it is comparatively thick that the shortcoming of the foamed thermoplastic polyurethane bead of this report is foam structure size, and " wrinkle " appears in particle surface, and product yield is low, adopts normal butane as whipping agent, easily produce problem of environmental pollution in its foaming process.
On the other hand, for foamed thermoplastic polyurethane bead and moulded parts thereof, the TPU(Thermoplastic polyurethanes) melt temperature scope adopted is narrower, melt viscosity is higher, in macromolecular chain, soft section to mix with hard section and exists, hard section, due to the hydrogen bond effect between molecular chain, can produce hard section crystallization, also belong to those semi-crystalline materials.Add man-hour at subsequent forming, need to be softened and carry out to the semi-melting state of suitable degree.Therefore, the dimensional contraction of molded foam article, the impact of the factor such as mobility of macromolecular chain when metamorphism can be subject to resin melt viscosity, degree of crystallinity, semi-melting.Especially for the goods of high foamability, be more vulnerable to the impact of above-mentioned factor.Present inventor also once attempted by adjustment Resin crystallization, and the methods such as soft segment molecule amount and molecular weight distribution control the contraction of expanded bead and goods, distortion, but in particle manufacture and product molding process, can produce various problem.
In addition, for daily life field (footwear material, pillow, mattress), during the purposes such as Condom (as floor coating), amortizing packaging material, user payes attention to the apparent property of molded foam article mostly.Because foaming product adopts water vapour heating to make mutual clinkering between expanded bead prepare, the clinkering face place therefore between expanded bead may produce the vestige of finedraw, hole, wrinkle or tortoise plastron line.In order to solve the problem, general by adopting the method improving shaping water vapour pressure, impel the clinkering between expanded particle.But the pressure improving shaping water vapour relates to and will consume more energy consumption, and then causes the increase of forming process cost; In addition, the higher withstand voltage mould of corresponding needs, equipment cost also can increase thereupon.
Summary of the invention:
The object of the invention is the deficiency overcoming above-mentioned prior art, and a kind of foamed thermoplastic polyurethane bead is provided.
Another object of the present invention is to provide a kind of preparation method of foamed thermoplastic polyurethane bead.
The present invention mainly solves that existing thermoplastic urethane foam bead foam structure size is comparatively thick, the foaming process clinkering face place easily produced between environmental pollution and moulded parts bead can produce finedraw, hole, wrinkle or tortoise plastron line the problem such as vestige.
Technical scheme of the present invention is: a kind of foamed thermoplastic polyurethane bead, and its special character is, the raw material containing following weight proportioning, be made up through foaming of raw material, thermoplastic polyurethane particle 100 parts, abscess-size stablizer 1-10 part, melt viscosity modifiers 1-35 part; The melt viscosity of described foamed thermoplastic polyurethane bead at 180 DEG C is 8000-15000 pool, between 10000-13000 pool; Bead cell diameter is 500-800um.
Further, the shore hardness of described thermoplastic polyurethane particle is 55A-95A.
Further, described thermoplastic polyurethane particle's melt flow rate (MFR) (MI) is 5-50g/10 minute, and it records in the weight that 190 DEG C apply 5Kg according to ASTM-1238.
Further, described abscess-size stablizer is dihydroxypropyl octadecane acid esters (GMS), anhydrous sorbitol lauric acid monoester, anhydrous sorbitol palmitinic acid monoesters, anhydrous sorbitol stearate monoesters or fatty acid cane sugar ester.
Further, described melt viscosity modifiers is ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride (PVC), polypropylene-butadiene styrene resin (ABS) or Polystyrene-Polyethylene-polybutene-polystyrene (SBS).
The preparation method of a kind of foamed thermoplastic polyurethane bead of the present invention, its special character is, comprises following processing step:
A is by the thermoplastic polyurethane particle after weighing, abscess-size stablizer and melt viscosity modifiers, mixed in rear input twin-screw extrusion by high-speed mixer and carry out melting mixing, melting mixing thing is extruded into strip from forcing machine, then cooling and shaping in the sink, cut with dicing machine, thus obtain thermoplastic polyurethane particle;
Thermoplastic polyurethane particle obtained above and water join in autoclave by b, and thermoplastic polyurethane particle is immersed in aqeous suspension, while carrying out stirring, add volatile foaming agent; Be warming up near thermoplastic polyurethane particle's softening temperature, after keeping high pressure temperature in the kettle, constant pressure 2-4 hour, open autoclave bottom dispensing valve, mixed solution in autoclave is discharged in atmospheric environment, thus obtains foamed thermoplastic polyurethane bead; The foamed thermoplastic polyurethane bead density obtained is 0.08-0.2g/cm
3.
Further, described volatile foaming agent is one or both mixing in carbonic acid gas, nitrogen; Adding weight is 1-40 part.
Performance test of the present invention:
The expansion density ρ of expanded bead is tested according to test materials association of U.S. standard A STMD792-2008
f.Expansion density calculation formula is: ρ
f=W1/ (W1+W2-W3)
Wherein, W1 is the aerial quality of expanded beads, and W2 is the weight making expanded bead be immersed in the metal cap in water, the quality of W3 expanded bead in water.
Bead foam multiplying power calculation formula: n=ρ
p/ ρ
f.Wherein, n represents bead foam multiplying power, ρ
prepresent the density of matrix resin, ρ
frepresent the density of expanded bead.
Bead cell diameter calculation formula: D=L/n.
Wherein, adopt microscope to gather the image of thermoplastic polyurethane foam bead diametrically cut surface, calculate 2 intersection points distance (L) and abscess number (n) on this straight line of thermoplastic polyurethane foam's surface of beads in diametric(al).
Compared with the prior art a kind of foamed thermoplastic polyurethane bead of the present invention and preparation method thereof has outstanding substantive distinguishing features and marked improvement, 1, adopt abscess-size stablizer to be conducive to volatile foaming agent and enter thermoplastic polyurethane particle inside, and can distribute equably, in thorough solution foaming process, whipping agent is at the inner skewness of resin, the cell size distribution of final expanded bead is comparatively thick, the problem that abscess is uneven; 2, after adding melt viscosity modifiers, expand its Melt processing temperatures scope, improve the motor capacity of macromolecular chain under melt state, thus avoid the problem of foaming product dimensional contraction and expanded bead surface folding; 3, conveniently subsequent thermal plastic polyurethane foam process operation, adopt forcing machine its melt-processed to be become the thermoplastic polyurethane particle of desired shape in advance, thus the foamed thermoplastic polyurethane bead abscess-size of preparation is even, product yield is high; 4, foamed thermoplastic polyurethane bead of the present invention, even if also have good clinkering performance under lower water vapour pressure, the mold foamed articles deformation obtained is little, low relative to the dimensional contraction rate of mould, excellent in dimensional stability, surface aesthetic.
Embodiment:
Below by embodiment, more detailed explanation is carried out to the present invention; Illustrated embodiment, only for explaining the present invention, is not for limiting the present invention.
In embodiment and comparative example use thermoplastic polyurethane particle types and each component add-on as shown in table 1; The manufacturing condition of foamed thermoplastic polyurethane bead, the performance evaluation of physicals and molded foam article is as shown in table 2.
Table 1
Note: 1, abscess-size stablizer and melt viscosity modifiers add-on are all with weight percent (based on thermoplastic polyurethane particle's weight).
2, thermoplastic polyurethane particle A:Mirathane E195, purchased from Yantai Mei Rui chemical material company limited; Thermoplastic polyurethane particle B:Mirathane E180, purchased from Yantai Mei Rui chemical material company limited; Thermoplastic polyurethane particle C:Mirathane E255, purchased from Yantai Mei Rui chemical material company limited.
3, MI represents melt flow rate (MFR), and unit is g/10 minute.
Table 2
Wherein, various evaluation is implemented as follows.
1, foam article distortion:
Outward appearance for molded foam article has carried out visual inspection, wherein be evaluated as zero by substantially not observing the foam article shunk with wrinkle (striped of more than 1cm), only will there is wrinkle but the foam article not observing contraction is evaluated as △, wrinkle is many, and the overall irregular foam forming body of shape is evaluated as ×.
2, foam article superficiality is evaluated:
The surface of molded foam article is observed, calculates every 10cm
21mm is there is in area
2the mean number in gap between above expanded bead, and this is judged as follows:
Be less than 100 places and count zero;
More than 100 places count ×.
Embodiment 1, by the 100KgTPU particle A shown in table 1,1Kg dihydroxypropyl octadecane acid esters, 1KgEVA is mixed in rear input twin-screw extrusion by high-speed mixer and carries out melting mixing; Be be extruded into strip the die head of 2mm by melting mixing thing from forcing machine diameter, then cooling and shaping in the sink, cuts with dicing machine, thus obtains thermoplastic polyurethane particle T1;
Thermoplastic polyurethane particle T1100Kg, 400Kg water obtained above is joined in autoclave, 40Kg carbon dioxide foaming agent is added while carrying out stirring, autoclave is warming up to 118 DEG C, then constant temperature 2 hours at this temperature, finally open autoclave bottom dispensing valve, mixed solution in autoclave is discharged in atmospheric environment, thus obtains foamed thermoplastic polyurethane bead F1; The foamed thermoplastic polyurethane bead density that obtains is 0.16g/cm
3, bubble diameter is 500um.
Foamed thermoplastic polyurethane bead F1 obtained above is filled in the mould of long 300mm × wide 250mm × thick 50mm; Adopt the water vapour of 1.2bar to make bead bond shaping along mold thickness direction compression 10%, finally obtain foamed thermoplastic polyurethane mold foamed articles; After being placed 2 hours under 50 DEG C × 50%RH by obtained foam article, in the isoperibol of 80 DEG C, drying 2 hours, finally after 25 DEG C × 50%RH places 2 hours, evaluates its performance, as shown in table 2.
Embodiment 2, by the 100KgTPU particle B shown in table 1,5Kg anhydrous sorbitol lauric acid monoester, 15KgPVC is mixed in rear input twin-screw extrusion by high-speed mixer and carries out melting mixing; Be be extruded into strip the die head of 2mm by melting mixing thing from forcing machine diameter, then cooling and shaping in the sink, cuts with dicing machine, thus obtains thermoplastic polyurethane particle T2;
Except adopting thermoplastic polyurethane particle T2, blowing temperature is set as 116 DEG C, constant temperature 3 hours, 1Kg nitrogen is as whipping agent, outside the water vapour of 1.1bar, obtain foamed thermoplastic polyurethane bead F2 and foamed thermoplastic polyurethane mold foamed articles according to the method identical with embodiment 1, performance evaluation is as shown in table 2.
Embodiment 3, by the 100KgTPU particle C shown in table 1,10Kg fatty acid cane sugar ester, 35KgABS is mixed in rear input twin-screw extrusion by high-speed mixer and carries out melting mixing; Be be extruded into strip the die head of 2mm by melting mixing thing from forcing machine diameter, then cooling and shaping in the sink, cuts with dicing machine, thus obtains thermoplastic polyurethane particle T3;
Except adopting thermoplastic polyurethane particle T3, blowing temperature is set as 115 DEG C, constant temperature 4 hours, 28Kg carbonic acid gas and nitrogen mixed gas as whipping agent, outside the water vapour of 1.0bar; Obtain foamed thermoplastic polyurethane bead F3 and foamed thermoplastic polyurethane mold foamed articles according to the method identical with embodiment 1, performance evaluation is as shown in table 2.
Comparative example 1, by the 100KgTPU particle A shown in table 1,1Kg dihydroxypropyl octadecane acid esters, is mixed in rear input twin-screw extrusion by high-speed mixer and carries out melting mixing; Be be extruded into strip the die head of 2mm by melting mixing thing from forcing machine diameter, then cooling and shaping in the sink, cuts with dicing machine, thus obtains thermoplastic polyurethane particle T4;
Adopt outside thermoplastic polyurethane particle T4, obtain foamed thermoplastic polyurethane bead F4 and foamed thermoplastic polyurethane mold foamed articles according to the method identical with embodiment 1, performance evaluation is as shown in table 2.
Comparative example 2, is mixed the 100KgTPU particle B shown in table 1,15KgPVC in rear input twin-screw extrusion by high-speed mixer and carries out melting mixing; Be be extruded into strip the die head of 2mm by melting mixing thing from forcing machine diameter, then cooling and shaping in the sink, cuts with dicing machine, thus obtains thermoplastic polyurethane particle T5;
Except employing thermoplastic polyurethane particle T5, obtain foamed thermoplastic polyurethane bead F5 and foamed thermoplastic polyurethane mold foamed articles according to the method identical with embodiment 2, performance evaluation is as shown in table 2.
Comparative example 3, adopt thermoplastic polyurethane particle C, do not add outside abscess-size stablizer and melt viscosity modifiers, obtain foamed thermoplastic polyurethane bead F6 and foamed thermoplastic polyurethane mold foamed articles according to the method identical with embodiment 3, performance evaluation is as shown in table 2.
In the above-described embodiments, obtain the density of expanded bead, cell diameter and melt viscosity are all in the scope limited, and the shaping deformation of mold foamed articles and superficiality are all good; In comparative example 1, the density of expanded bead and cell diameter are in the scope limited, but melt viscosity is not in the scope limited, and the shaping deformation of the mold foamed articles obtained is good, but superficiality is poor; In comparative example 2, the density of expanded bead and melt viscosity are in the scope limited, but cell diameter is not in the scope limited, and the mold foamed articles obtained demonstrates more wrinkle, and superficiality is poor; In comparative example 3, the cell diameter of expanded bead and melt viscosity be not all in the scope limited, and serious distortion occurs the mold foamed articles shape obtained, and demonstrates more wrinkle, and superficiality is poor.
Foamed thermoplastic polyurethane bead size of the present invention is stablized, and cell diameter is even, surface-brightening, and product yield is high; The mold foamed articles deformation obtained is little, low relative to the dimensional contraction rate of mould, excellent in dimensional stability, surface aesthetic; In addition, because mold foamed articles deformation is little, therefore can also shorten digestion time, the water vapour of lower pressure can be adopted to carry out forming process simultaneously, be applicable to Eco-power industrial production.
A kind of foamed thermoplastic polyurethane bead of the present invention, need also to add fire retardant, static inhibitor, tensio-active agent, lubricant, pigment, UV resistant absorption agent, hydrolysis-resisting agent, inorganic or organic filler, softening agent etc. according to design, consumption is conventional amount used.
Claims (5)
1. a foamed thermoplastic polyurethane bead, is characterized in that, the raw material containing following weight proportioning, is made up, thermoplastic polyurethane particle 100 parts, abscess-size stablizer 1-10 part, melt viscosity modifiers 1-35 part of raw material through foaming; The melt viscosity of described foamed thermoplastic polyurethane bead at 180 DEG C is 8000-15000 pool, and bead cell diameter is 500-800um; Described abscess-size stablizer is dihydroxypropyl octadecane acid esters, anhydrous sorbitol lauric acid monoester, anhydrous sorbitol palmitinic acid monoesters, anhydrous sorbitol stearate monoesters or fatty acid cane sugar ester; Described melt viscosity modifiers is ethylene-vinyl acetate copolymer, polyvinyl chloride, polypropylene-butadiene styrene resin or Polystyrene-Polyethylene-polybutene-polystyrene.
2. a kind of foamed thermoplastic polyurethane bead according to claim 1, is characterized in that, the shore hardness of described thermoplastic polyurethane particle is 55A-95A.
3. a kind of foamed thermoplastic polyurethane bead according to claim 1, is characterized in that, described thermoplastic polyurethane particle's melt flow rate (MFR) is 5-50g/10 minute.
4. the preparation method of any one foamed thermoplastic polyurethane bead of the claims 1-3, is characterized in that, comprises following processing step:
A is by the thermoplastic polyurethane particle after weighing, abscess-size stablizer and melt viscosity modifiers, mixed in rear input twin-screw extrusion by high-speed mixer and carry out melting mixing, melting mixing thing is extruded into strip from forcing machine, then cooling and shaping in the sink, cut with dicing machine, thus obtain thermoplastic polyurethane particle;
Thermoplastic polyurethane particle obtained above and water join in autoclave by b, and thermoplastic polyurethane particle is immersed in aqeous suspension, while carrying out stirring, add volatile foaming agent; Be warming up near thermoplastic polyurethane particle's softening temperature, after keeping high pressure temperature in the kettle, constant pressure 2-4 hour, open autoclave bottom dispensing valve, mixed solution in autoclave is discharged in atmospheric environment, thus obtains foamed thermoplastic polyurethane bead; The foamed thermoplastic polyurethane bead density obtained is 0.08-0.2g/cm
3.
5. the preparation method of foamed thermoplastic polyurethane bead according to claim 4, is characterized in that, described volatile foaming agent is one or both mixing in carbonic acid gas, nitrogen; Adding weight is 1-40 part.
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