CN103642200A - Foaming thermoplastic polyurethane bead and preparation method thereof - Google Patents
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Abstract
The invention discloses a foaming thermoplastic polyurethane bead. The foaming bead comprises 100 parts of thermoplastic polyurethane particles, 1-10 parts of cell size stabilizer, and 1-35 parts of melt viscosity modifier. The bead is prepared through the following steps: steeping the thermoplastic polyurethane particles containing a cell size stabilizer and a melt viscosity modifier in an aqueous suspension and foaming by volatilizing foaming agent. The melt viscosity of the foaming thermoplastic polyurethane bead is 8000-15000 poise below 180 DEG C, the size of the prepared foaming thermoplastic polyurethane bead is stable, the diameter of the cell is uniform, the surface is bright, the yield of the product is high, the foaming thermoplastic polyurethane bead has good sintering property even under lower vapor pressure, and the molding foam product deforms slightly and has low shrinking percentage compared with the size of the die, good dimensional stability and attractive appearance.
Description
Technical field:
The present invention relates to foam material technical field, be a kind of foamed thermoplastic polyurethane bead and preparation method thereof specifically, the molding foaming goods of being made by 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, by physics or chemical process, in plastics inner, fill a large amount of bubbles, obtain polymer foaming 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 produces " white pollution " problem, and united nations environment is organized and 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, and excellent wear resistance, physical strength, water-fast, oil resistant, resistance to chemical attack, resistance to mould are 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 molding foaming goods.This kind of goods, retaining outside the performance of protocorm excellence, have excellent rebound resilience simultaneously, shape diversity, and low density can be used in more wide in range temperature range.Based on above-mentioned advantage, TPU moulded foam goods have application prospect very 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 the shortcoming of the foamed thermoplastic polyurethane bead of this report is that foam structure size is thicker, there is " wrinkle " in particle surface, and product yield is low, in its foaming process, adopts normal butane as whipping agent, easily produces problem of environmental pollution.
On the other hand, for foamed thermoplastic polyurethane bead and moulded parts thereof, the TPU(Thermoplastic polyurethanes) melt temperature scope adopting is narrower, melt viscosity is higher, in macromolecular chain, soft section is mixed existence with hard section, hard section, due to the hydrogen bond effect between molecular chain, can produce hard section of crystallization, also belongs to those semi-crystalline materials.At subsequent forming, add man-hour, need to be softened to the semi-melting state of suitable degree and carry out.Therefore, the dimensional contraction of molding foaming goods, the impact of the factors such as mobility of macromolecular chain when metamorphism can be subject to resin melt viscosity, degree of crystallinity, semi-melting.For the goods of high foamability, be more vulnerable to above-mentioned factor impact especially.Present inventor also once attempted by adjusting resin crystallinity, and the methods such as soft segment molecule amount and molecular weight distribution are controlled, but in particle manufacture and product molding process, can be produced variety of issue the contraction of expanded bead and goods, distortion.
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 molding foaming goods mostly.Because foaming product adopts water vapour heating prepared by mutual clinkering between expanded bead, so the place of the clinkering face between expanded bead may produce the vestige of finedraw, hole, wrinkle or tortoise plastron line.In order to address the above problem, generally by employing, improve the method for moulding water vapour pressure, impel the clinkering between expanded particle.But the pressure that improves moulding water vapour relates to and will consume more energy consumption, and then causes the increase of forming process cost; In addition, need accordingly higher withstand voltage mould, equipment cost also can increase thereupon.
Summary of the invention:
The object of the invention is to overcome the deficiency of 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 has mainly solved that existing thermoplastic urethane foam bead foam structure size is thick, foaming process easily produces the problems such as vestige that clinkering face place between environmental pollution and moulded parts bead can produce finedraw, hole, wrinkle or tortoise plastron line.
Technical scheme of the present invention is: a kind of foamed thermoplastic polyurethane bead, and its special character is, the raw material that contains following weight proportioning, by raw material, through foaming, made, 100 parts of thermoplastic polyurethane particles, abscess-size stablizer 1-10 part, melt viscosity modifiers 1-35 part; The melt viscosity of described foamed thermoplastic polyurethane bead at 180 ℃ is 8000-15000 pool, between 10000-13000 pool; Bead cell diameter is 500-800um.
Further, described thermoplastic polyurethane particle's shore hardness is 55A-95A.
Further, described thermoplastic polyurethane particle's melt flow rate (MFR) (MI) is 5-50g/10 minute, and it records 190 ℃ of weight that 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 thermoplastic polyurethane particle, abscess-size stablizer and melt viscosity modifiers after weighing, by high-speed mixer, mix in rear input twin-screw extrusion and carry out melting mixing, melting mixing thing is extruded into strip from forcing machine, then cooling and shaping in tank, with dicing machine, cut, thereby obtain thermoplastic polyurethane particle;
B joins thermoplastic polyurethane particle obtained above and water in autoclave, and thermoplastic polyurethane particle is immersed in aqeous suspension, adds volatile foaming agent when stirring; 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, thereby obtains foamed thermoplastic polyurethane bead; Resulting foamed thermoplastic polyurethane bead density 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:
According to the foaming density p of the standard A STM D792-2008 of U.S. test materials association test expanded bead
f.Foaming density calculation formula is: ρ
f=W1/ (W1+W2-W3)
Wherein, W1 is the aerial quality of expanded beads, and W2 makes expanded bead be immersed in the weight of the metal cap in water, the quality of W3 expanded bead in water.
Bead expansion ratio calculation formula: n=ρ
p/ ρ
f.Wherein, n represents bead expansion ratio, ρ
pthe density that represents matrix resin, ρ
fthe density that represents expanded bead.
Bead cell diameter calculation formula: D=L/n.
Wherein, adopt microscope to gather thermoplastic polyurethane expanded bead along the image of diametric(al) cut surface, in diametric(al), calculate 2 intersection point distances (L) on thermoplastic polyurethane expanded bead surface and the abscess number (n) on this straight line.
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 thicker, the problem that abscess is inhomogeneous; 2, add after melt viscosity modifiers, expanded its melt temperature range, improved the motor capacity of macromolecular chain under melt state, thereby avoided the problem of foaming product dimensional contraction and expanded bead surface folding; 3, in order to facilitate the operation of subsequent thermal plastic polyurethane foam process, adopt in advance forcing machine its melt-processed to be become to the thermoplastic polyurethane particle of desired shape, thereby 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 deformation of resulting moulded foam goods is little, low with respect to the dimensional contraction rate of mould, excellent in dimensional stability, surface aesthetic.
Embodiment:
Below by embodiment, the present invention is carried out to more detailed explanation; Illustrated embodiment is only for explaining the present invention, not for limiting the present invention.
In embodiment and comparative example the thermoplastic polyurethane particle types of using and each component add-on as shown in table 1; The manufacturing condition of foamed thermoplastic polyurethane bead, the performance evaluation of physicals and molding foaming goods 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 evaluations are implemented as follows.
1, foam article distortion:
Outward appearance for molded foam article has been carried out visual inspection, wherein by substantially observing the foam article shrinking with wrinkle (striped more than 1cm), be not evaluated as zero, the foam article that will only have wrinkle but do not observe contraction is evaluated as △, wrinkle is many, and the whole irregular foam forming body of shape is evaluated as *.
2, foam article superficiality is evaluated:
Surface to molded foam article is observed, and calculates every 10cm
2in area, there is 1mm
2the mean number in gap between above expanded bead, and this is judged as follows:
Be less than 100 places and count zero;
100 places count above *.
Embodiment 1, by the 100Kg TPU particle A shown in table 1, and 1Kg dihydroxypropyl octadecane acid esters, 1Kg EVA is mixed in rear input twin-screw extrusion and is carried out melting mixing by high-speed mixer; The die head that is 2mm from forcing machine diameter by melting mixing thing, be extruded into strip, then cooling and shaping in tank, cuts with dicing machine, thereby obtains thermoplastic polyurethane particle T1;
Thermoplastic polyurethane particle T1 100Kg obtained above, 400Kg water are joined in autoclave, when stirring, add 40Kg carbon dioxide foaming agent, autoclave is warming up to 118 ℃, then constant temperature 2 hours at this temperature, finally open autoclave bottom dispensing valve, mixed solution in autoclave is discharged in atmospheric environment, thereby obtains foamed thermoplastic polyurethane bead F1; Resulting foamed thermoplastic polyurethane bead density 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 molding bonded along mold thickness direction compression 10%, finally obtain foamed thermoplastic polyurethane moulded foam goods; After resulting foam article is placed 2 hours under 50 ℃ * 50%RH, in the isoperibol of 80 ℃, be dried 2 hours, finally at 25 ℃ * 50%RH, place after 2 hours, evaluate its performance, as shown in table 2.
Embodiment 2, by the 100Kg TPU particle B shown in table 1, and 5Kg anhydrous sorbitol lauric acid monoester, 15Kg PVC is mixed in rear input twin-screw extrusion and is carried out melting mixing by high-speed mixer; The die head that is 2mm from forcing machine diameter by melting mixing thing, be extruded into strip, then cooling and shaping in tank, cuts with dicing machine, thereby obtains thermoplastic polyurethane particle T2;
Except adopting thermoplastic polyurethane particle T2, blowing temperature is set as 116 ℃, constant temperature 3 hours, 1Kg nitrogen is as whipping agent, outside the water vapour of 1.1bar, according to the method identical with embodiment 1, obtain foamed thermoplastic polyurethane bead F2 and foamed thermoplastic polyurethane moulded foam goods, performance evaluation is as shown in table 2.
Embodiment 3, by the 100Kg TPU particle C shown in table 1, and 10Kg fatty acid cane sugar ester, 35Kg ABS is mixed in rear input twin-screw extrusion and is carried out melting mixing by high-speed mixer; The die head that is 2mm from forcing machine diameter by melting mixing thing, be extruded into strip, then cooling and shaping in tank, cuts with dicing machine, thereby obtains thermoplastic polyurethane particle T3;
Except adopting thermoplastic polyurethane particle T3, blowing temperature is set as to 115 ℃, constant temperature 4 hours, 28Kg carbonic acid gas and nitrogen mixture body are as whipping agent, outside the water vapour of 1.0bar; According to the method identical with embodiment 1, obtain foamed thermoplastic polyurethane bead F3 and foamed thermoplastic polyurethane moulded foam goods, performance evaluation is as shown in table 2.
Comparative example 1, by the 100Kg TPU particle A shown in table 1,1Kg dihydroxypropyl octadecane acid esters, is mixed in rear input twin-screw extrusion and is carried out melting mixing by high-speed mixer; The die head that is 2mm from forcing machine diameter by melting mixing thing, be extruded into strip, then cooling and shaping in tank, cuts with dicing machine, thereby obtains thermoplastic polyurethane particle T4;
Adopt outside thermoplastic polyurethane particle T4, according to the method identical with embodiment 1, obtain foamed thermoplastic polyurethane bead F4 and foamed thermoplastic polyurethane moulded foam goods, performance evaluation is as shown in table 2.
Comparative example 2, by the 100Kg TPU particle B shown in table 1,15Kg PVC is mixed in rear input twin-screw extrusion and is carried out melting mixing by high-speed mixer; The die head that is 2mm from forcing machine diameter by melting mixing thing, be extruded into strip, then cooling and shaping in tank, cuts with dicing machine, thereby obtains thermoplastic polyurethane particle T5;
Except adopting thermoplastic polyurethane particle T5, according to the method identical with embodiment 2, obtain foamed thermoplastic polyurethane bead F5 and foamed thermoplastic polyurethane moulded foam goods, 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, according to the method identical with embodiment 3, obtain foamed thermoplastic polyurethane bead F6 and foamed thermoplastic polyurethane moulded foam goods, performance evaluation is as shown in table 2.
In the above-described embodiments, the density of resulting expanded bead, cell diameter and melt viscosity are all in the scope limiting, and moulding deformation and the superficiality of moulded foam goods are all good; In comparative example 1, the density of expanded bead and cell diameter are in the scope limiting, but melt viscosity is in the scope limiting, and the moulding deformation of resulting moulded foam goods is good, but superficiality is poor; In comparative example 2, the density of expanded bead and melt viscosity be in the scope limiting, but cell diameter is in the scope limiting, and resulting moulded foam goods demonstrate 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 limiting, and serious distortion occurs resulting moulded foam article shape, and demonstrates more wrinkle, and superficiality is poor.
Foamed thermoplastic polyurethane bead size of the present invention is stable, and cell diameter is even, surface-brightening, and product yield is high; The moulded foam goods deformation obtaining is little, low with respect to the dimensional contraction rate of mould, excellent in dimensional stability, surface aesthetic; In addition, because the deformation of moulded foam goods is little, therefore can also shorten digestion time, can adopt the water vapour of lower pressure to carry out forming process, be applicable to Eco-power industrial production simultaneously.
A kind of foamed thermoplastic polyurethane bead of the present invention, according to design, 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., consumption is conventional amount used.
Claims (7)
1. a foamed thermoplastic polyurethane bead, is characterized in that, the raw material that contains following weight proportioning is made 100 parts of thermoplastic polyurethane particles, abscess-size stablizer 1-10 part, melt viscosity modifiers 1-35 part through foaming by raw material; The melt viscosity of described foamed thermoplastic polyurethane bead at 180 ℃ is 8000-15000 pool, and bead cell diameter is 500-800um.
2. a kind of foamed thermoplastic polyurethane bead according to claim 1, is characterized in that, described thermoplastic polyurethane particle's shore hardness 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. a kind of foamed thermoplastic polyurethane bead according to claim 1, it is characterized in that, 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.
5. a kind of foamed thermoplastic polyurethane bead according to claim 1, it is characterized in that, described melt viscosity modifiers is ethylene-vinyl acetate copolymer, polyvinyl chloride, polypropylene-butadiene styrene resin or polystyrene-polyethylene-polybutene-polystyrene.
6. the preparation method of any one foamed thermoplastic polyurethane bead of the claims 1-5, is characterized in that, comprises following processing step:
A is by thermoplastic polyurethane particle, abscess-size stablizer and melt viscosity modifiers after weighing, by high-speed mixer, mix in rear input twin-screw extrusion and carry out melting mixing, melting mixing thing is extruded into strip from forcing machine, then cooling and shaping in tank, with dicing machine, cut, thereby obtain thermoplastic polyurethane particle;
B joins thermoplastic polyurethane particle obtained above and water in autoclave, and thermoplastic polyurethane particle is immersed in aqeous suspension, adds volatile foaming agent when stirring; 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, thereby obtains foamed thermoplastic polyurethane bead; Resulting foamed thermoplastic polyurethane bead density is 0.08-0.2g/cm
3.
7. the preparation method of foamed thermoplastic polyurethane bead according to claim 6, 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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