CN104817774A - Foaming master batch and preparation method thereof - Google Patents
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Abstract
The invention discloses a foaming master batch and a preparation method thereof. The foaming master batch comprises 65-70% of modified nanometer powder, 20-29% of carrier resin, 5-10% of cycloparaffin rubber filling oil, 0.2% of a heat stabilizer, 0.1% of an anti-oxidant and 0.1% of a coupling agent. The foaming master batch is used for foaming processing of EVA, LDPE and TPR shoe materials, improves production efficiency, reduces a raw material production cost and improves mechanical strength of the EVA, LDPE and TPR shoe materials.
Description
Technical field
The invention belongs to technical field of macromolecules, particularly relate to a kind of foaming master batch and preparation method thereof.
Background technology
Master batch, is made up of the chemical assistant of excess, vector resin and dispersion agent.Master batch is that the chemical assistant of super quantity is evenly attached to the aggregate obtained in resin.Conventional master batch is divided into cooling masterbatch, blast master batch, moisture absorption foam eliminating mother particle, fire-retardant master granule and foaming master batch.
Foaming master batch is a kind of heat absorbing type closed pore formula chemical nucleation whipping agent.Zhu Min discloses a kind of toughness reinforcing foaming master batch in 201110322117.8, comprise Low Density Polyethylene, linear low density polyethylene, ethylene/vinyl acetate copolymer, whipping agent, dispersion agent, nucleator and oxidation inhibitor, the master batch of preparation makes an addition in goods, under the prerequisite not changing technique, alleviates the weight of goods and enhances physical strength.The people such as Chen Yonghui disclose a kind of foaming master batch and preparation method thereof at 200910185736.X, and obtained master batch comprises superfine composite non-metal powder, composite modifier, ldpe resin and Tegin 55G, the master batch environmentally-friendly sanitary of preparation, cost-saving.The former achieves the effect increasing physical strength, but in production process costly; The latter's cost reduces, but products machinery intensity is not improved.How to improve the mechanical property of goods, cost-saving, reduce energy consumption, enhancing productivity is a problem demanding prompt solution simultaneously.
Summary of the invention
In order to solve the problems of the prior art, the object of this invention is to provide a kind of foaming master batch and preparation method thereof.Master batch provided by the invention be used for EVA(ethylene/vinyl acetate copolymer), LDPE(Low Density Polyethylene), TPR(thermoplastic elastomer) footwear material foaming the course of processing in, can enhance productivity, reduce the production cost of raw material, improve EVA, the physical strength of LDPE, TPR footwear material.
To achieve these goals, the technical solution used in the present invention: a kind of foaming master batch, is characterized in that, comprise the modified nano powder of 65%-70%, the vector resin of 20%-29%, the naphthenic hydrocarbon rubber filling oil of 5%-10%, the thermo-stabilizer of 0.2%, the oxidation inhibitor of 0.1%, the coupling agent of 0.1%.
Wherein, described modified nano powder is that inorganic nanometer powder is by the modified powder obtained of activeconstituents.
Wherein, described inorganic nanometer powder is nano-calcium carbonate.
Wherein, described activeconstituents is silicane tensio-active agent.
As preferably, the method for modifying of described inorganic nanometer powder comprises the steps: to be poured into by inorganic powder in high-speed stirring bucket, and heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes; In agitation vat, spray activeconstituents while stirring, spray time is 10-15 minute; Be cooled to room temperature, discharge material.
As preferably, described activeconstituents and the mass ratio of inorganic powder are 0.5%-0.7%.
As preferably, described vector resin is styrenic thermoplastic rubber.
As preferably, described thermo-stabilizer is zinc oxide or calcium stearate.
As preferably, described oxidation inhibitor is 1010 or 168.
As preferably, described coupling agent is silane coupling agent.
Prepare the method for aforesaid foaming master batch, comprise the steps:
S1. each material is taken according to afore-mentioned materials mass percent;
S2. be placed on by modified nano powder in A bucket, vector resin is placed in B bucket, naphthenic hydrocarbon rubber filling oil, thermo-stabilizer, and oxidation inhibitor and coupling agent are placed in C bucket;
S3. open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 160-250 kg/h, C bucket is 40-60 kg/h, stirring reaction;
S4. the mixture in S3 is added in twin screw extruder, extrude at 115 DEG C-140 DEG C, obtain master batch finished product.
The beneficial effect that the present invention realizes: the foaming master batch good dispersity that the present invention obtains, processing characteristics is excellent, at EVA, add this master batch in LDPE, the TPR footwear material foaming course of processing, the viscosity of mixed system can be reduced, make melt even, be beneficial to compound and extrude, enhance productivity; Reduce the consumption of bridging agent and white mother, reduce production cost; Improve tensile strength, stripping strength, tear strength and unit elongation, thus realize the effect strengthening footwear material mechanical property.
Accompanying drawing explanation
The present invention is further described below in conjunction with the drawings and specific embodiments:
Fig. 1 is under different master batch addition, and EVA extrudes system melt pressure change curve;
Fig. 2 is under different master batch addition, and LDPE extrudes system melt pressure change curve;
Fig. 3 is under different master batch addition, and TPR extrudes system melt pressure change curve.
Embodiment
One. the preparation of modified nano powder
First, joined by inorganic powder in high-speed stirring bucket, heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes; Then in high-speed stirring bucket, spray activeconstituents while stirring, spray time is 10-15 minute; Be cooled to room temperature, discharge material.Join in clear water by discharge material, clear water is 5:1 with the mass ratio of discharge material, stirs after 5 minutes, leaves standstill 30 seconds, observes the situation of particles settling.Described inorganic powder is nano-calcium carbonate, and described activeconstituents is silicane tensio-active agent.Described activeconstituents and the mass ratio of inorganic powder are 0.5%-0.7%.
Table 1:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Activeconstituents | Silicane tensio-active agent | Silicane tensio-active agent | Silicane tensio-active agent | Silicane tensio-active agent |
| Spray time/minute | 10 | 12 | 15 | 15 |
| Inorganic powder composition | Nano-calcium carbonate | Nano-calcium carbonate | Nano-calcium carbonate | Nano-calcium carbonate |
| The mass ratio of activeconstituents and inorganic powder | 0.7% | 0.5% | 0.6% | 0.7% |
| Particle sinks to the bottom situation | Nothing | Nothing | Nothing | Nothing |
Water is polar molecule, and oil is non-polar molecule, and according to the similar principle that mixes, water oil does not dissolve each other, and the density due to oil is less than the density of water, and the density of inorganic powder is greater than the density of water, and under normal conditions, oil wafts and keeps afloat, and inorganic powder sinks to the bottom.According to shown in table 1, embodiment 1,2, the modified nano powder of 3,4 preparations sinks to the bottom situation without particle, and illustrate nano powder modified respond well, periphery, all by active ingredient encases, when preparing master batch, has good consistency with vector resin.
Two. be that main body prepares master batch with modified nano powder
A kind of foaming master batch, comprises the modified nano powder of 65%-70%, the vector resin of 20%-29%, the naphthenic hydrocarbon rubber filling oil of 5%-10%, the thermo-stabilizer of 0.2%, the oxidation inhibitor of 0.1%, the coupling agent of 0.1%.
The modified nano powder prepared by embodiment 1-4 is main body, prepares master batch respectively according to embodiment 5-8.Each material is taken according to the mass percent of embodiment 5-8; Be placed on by modified nano powder in A bucket, vector resin is placed in B bucket, naphthenic hydrocarbon rubber filling oil, thermo-stabilizer, and oxidation inhibitor and coupling agent are placed in C bucket; Open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 160-250kg/h, C bucket is 40-60 kg/h, stirring reaction; Reacted mixture is added in twin screw extruder, extrudes at 115 DEG C-140 DEG C, obtain master batch finished product.Described vector resin is styrenic thermoplastic rubber, and described thermo-stabilizer is zinc oxide or calcium stearate, and described oxidation inhibitor is 1010 or 168, and described coupling agent is silane coupling agent.
Table 2:
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Modified nano powder/mass percent | 65% | 68% | 70% | 68% |
| Vector resin/per-cent | Styrenic thermoplastic rubber/20% | Styrenic thermoplastic rubber/25% | Styrenic thermoplastic rubber/29% | Styrenic thermoplastic rubber/29% |
| Naphthenic hydrocarbon rubber filling oil/per-cent | 8% | 5% | 5% | 10% |
| Coupling agent/per-cent | Silane coupling agent/0.1% | Silane coupling agent/0.1% | Silane coupling agent/0.1% | Silane coupling agent/0.1% |
| Thermo-stabilizer/per-cent | Calcium stearate/0.2% | Zinc oxide/0.2% | Calcium stearate/0.2% | Zinc oxide/0.2% |
| Oxidation inhibitor/per-cent | 1010/0.1% | 168/0.1% | 1010/0.1% | 168/0.1% |
| Granulating equipment | Twin screw extruder | Twin screw extruder | Twin screw extruder | Twin screw extruder |
| Prilling temperature | 115℃ | 125℃ | 135℃ | 140℃ |
In order to illustrate that the master batch prepared in embodiment 5-8 is applied to EVA better, in LDPE, TPR footwear material, can production efficiency be significantly improved, reducing the production cost of raw material, improving EVA, the physical strength of LDPE, TPR footwear material simultaneously.For the master batch that embodiment 5 is obtained, the EVA under the different master batch addition of DCO, the performance index of LDPE, TPR footwear material.
Table 3: under different master batch addition, the performance parameter variations of EVA shoe material
| Master batch addition/mass percent | Tensile strength/(kg/sq.cm) | Unit elongation/% | Tear strength/(kg/cm) | Stripping strength/(kg/cm) |
| 0 | 21.1 | 225 | 10.5 | 1.9 |
| 5% | 25.2 | 251 | 12.1 | 3.0 |
| 10% | 25.8 | 256 | 12.5 | 3.0 |
| 20% | 26.7 | 260.2 | 13 | 3.2 |
| 30% | 26.2 | 259.6 | 12.6 | 3.1 |
Table 4: under different master batch addition, the performance parameter variations of LDPE footwear material
| Master batch addition/mass percent | Tensile strength/(kg/sq.cm) | Unit elongation/% | Tear strength/(kg/cm) | Stripping strength/(kg/cm) |
| 0 | 22.5 | 219 | 11 | 1.6 |
| 5% | 25.5 | 250 | 12.2 | 3.1 |
| 10% | 25.8 | 256 | 12.5 | 3.2 |
| 20% | 26.5 | 261.5 | 14 | 3.5 |
| 30% | 26.0 | 258 | 13.6 | 3.2 |
Table 5: under different master batch addition, the performance parameter variations of TPR footwear material
| Master batch addition/mass percent | Tensile strength/(kg/sq.cm) | Unit elongation/% | Tear strength/(kg/cm) | Stripping strength/(kg/cm) |
| 0 | 22.1 | 220 | 10.8 | 1.9 |
| 5% | 25.3 | 253 | 12.1 | 3.2 |
| 10% | 25.8 | 257 | 12.6 | 3.5 |
| 20% | 26.8 | 262 | 13.8 | 3.8 |
| 30% | 26.0 | 259 | 13.2 | 3.6 |
Table 6: under different master batch addition, the Cost comparisons of EVA, LDPE, TPR footwear material
| Master batch addition | EVA | LDPE | TPR | Total cost yuan/ton |
| 0% | 100% | 100% | 100% | 10000 |
| 5% | 95% | 95% | 95% | 9875 |
| 10% | 90% | 90% | 90% | 9750 |
| 20% | 80% | 80% | 80% | 9500 |
| 30% | 70% | 70% | 70% | 9250 |
To test 5 obtained master batches, under measuring different master batch addition, EVA, LDPE and TPR extrude the change curve of system melt pressure, as Fig. 1, and 2, shown in 3.With TPR squeeze-up be example, when master batch addition is 0, TPR melt pressure is 550bar, and when addition is 5%, TPR melt pressure drops to 525bar by 550bar, and along with the continuation of master batch addition increases, melt pressure reduces further.
Master batch add the viscosity reducing mixed system, make melt even, melt pressure reduces.In melt, add master batch prepared by the present invention, be conducive to extruding of compound, add the extrusion capacity in the unit time, enhance productivity.
Table 3, table 4, table 5 is under different master batch addition, the mechanical property change of EVA, LDPE and TPR footwear material.Along with adding of master batch, the tensile strength of EVA, LDPE and TPR, unit elongation, tear strength and stripping strength increase thereupon, improve EVA, the physical strength of LDPE and TPR footwear material.In addition, it can also be seen that from table 6, adding of master batch also makes EVA, and the total cost of LDPE and TPR footwear material significantly reduces, its reason be master batch add the consumption that can reduce bridging agent and white mother, reduce production cost; But when master batch add-on is 30%, the tensile strength of EVA, LDPE and TPR, unit elongation, tear strength and stripping strength decrease on the contrary, therefore consider each side factor, and the addition of master batch in EVA, LDPE and TPR is about 20%.
Above-mentioned embodiment is exemplary, is to enable those skilled in the art understand this patent better, can not be interpreted as it is restriction this patent being comprised to scope; As long as according to this patent disclose any equivalent change done or the modification of spirit, all fall into the scope that this patent comprises.
Claims (8)
1. a foaming master batch, is characterized in that, comprises the modified nano powder of 65%-70%, the vector resin of 20%-29%, the naphthenic hydrocarbon rubber filling oil of 5%-10%, the thermo-stabilizer of 0.2%, the oxidation inhibitor of 0.1%, the coupling agent of 0.1%.
2. foaming master batch as claimed in claim 1, it is characterized in that, described modified nano powder is that inorganic nanometer powder is by the modified powder obtained of activeconstituents.
3. foaming master batch as claimed in claim 2, it is characterized in that, described inorganic nanometer powder is nano-calcium carbonate.
4. foaming master batch as claimed in claim 2, it is characterized in that, described activeconstituents is silicane tensio-active agent.
5. foaming master batch as claimed in claim 2, it is characterized in that, the method for modifying of inorganic nanometer powder comprises the steps: to be poured into by inorganic powder in high-speed stirring bucket, and heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes; In agitation vat, spray activeconstituents while stirring, spray time is 10-15 minute; Be cooled to room temperature, discharge material.
6. foaming master batch as claimed in claim 5, it is characterized in that, described activeconstituents and the mass ratio of inorganic powder are 0.5%-0.7%.
7. foaming master batch as claimed in claim 1, it is characterized in that, described vector resin is styrenic thermoplastic rubber; Described thermo-stabilizer is zinc oxide or calcium stearate; Described oxidation inhibitor is 1010 or 168; Described coupling agent is silane coupling agent.
8. prepare the method for foaming master batch according to claim 1, it is characterized in that, comprise the steps:
S1. mass percent according to claim 1 takes each material;
S2. be placed on by modified nano powder in A bucket, vector resin is placed in B bucket, naphthenic hydrocarbon rubber filling oil, thermo-stabilizer, and oxidation inhibitor and coupling agent are placed in C bucket;
S3. open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 160-250kg/h, C bucket is 40-60kg/h, stirring reaction;
S4. the mixture in S3 is added in twin screw extruder, extrude at 115 DEG C-140 DEG C, obtain master batch finished product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161150A (en) * | 2018-08-22 | 2019-01-08 | 扬州朗劲塑胶实业有限公司 | A kind of foaming master batch and preparation method thereof |
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