CN117467269B - High-strength high-elasticity PU material applied to soles and preparation method thereof - Google Patents
High-strength high-elasticity PU material applied to soles and preparation method thereof Download PDFInfo
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- CN117467269B CN117467269B CN202311419284.3A CN202311419284A CN117467269B CN 117467269 B CN117467269 B CN 117467269B CN 202311419284 A CN202311419284 A CN 202311419284A CN 117467269 B CN117467269 B CN 117467269B
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- calcium carbonate
- elasticity
- mixed solution
- strength
- whisker
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 170
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 45
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 41
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 41
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 239000004743 Polypropylene Substances 0.000 claims abstract description 33
- -1 polypropylene Polymers 0.000 claims abstract description 33
- 229920001155 polypropylene Polymers 0.000 claims abstract description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 48
- 229910001868 water Inorganic materials 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 34
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 238000013329 compounding Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000003014 reinforcing effect Effects 0.000 description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
Abstract
The invention relates to the technical field of PU materials, and particularly discloses a high-strength high-elasticity PU material applied to soles and a preparation method thereof. The high-strength high-elasticity PU material applied to the sole comprises the following components in parts by weight: 100 parts of TPU resin; 3-5 parts of polypropylene; 1-2 parts of an antioxidant; 15-20 parts of calcium carbonate whisker; the preparation method of the calcium carbonate whisker comprises the following steps: step 1), preparing a calcium hydroxide suspension; step 2), adding a crystal form control solution into the calcium hydroxide suspension, and uniformly mixing to obtain a mixed solution; step 3), keeping the temperature of the mixed solution at 80-100 ℃, then introducing carbon dioxide into the mixed solution, reacting until the pH value of the mixed solution is reduced, and filtering out precipitate to obtain calcium carbonate whiskers; the crystal form control liquid is an aqueous solution at least comprising magnesium ions, potassium ions and permanganate ions. The invention has the advantage of improving the strength of the PU material.
Description
Technical Field
The invention relates to the field of PU materials, in particular to a high-strength high-elasticity PU material applied to soles and a preparation method thereof.
Background
PU, namely polyurethane, is an artificial synthetic material, is widely applied to sole manufacture, and soles made of PU have the advantages of light weight, comfort, wear resistance, durability, breathing ventilation and the like, and PU soles are very soft, wear resistance and are deeply favored by consumers due to high elasticity.
The sports shoes are shoes special for sports, in the fierce sports, the soles are frequently and fiercely bent, and the soles are subjected to severe pulling force due to foot force application while bending, the prior PU materials are high in comfort level, but when applied to the sports soles, the strength is difficult to meet the requirements, the soles are easy to crack due to sudden stress in the fierce sports, and once crack fine lines appear, serious cracks can be rapidly developed in the process of subsequent stress, so that the soles cannot be continuously used, and therefore, the improvement space is provided.
Disclosure of Invention
In order to improve the strength of the PU material, the application provides a high-strength high-elasticity PU material applied to soles and a preparation method thereof.
In a first aspect, the application provides a high-strength high-elasticity PU material applied to soles, which adopts the following technical scheme: the high-strength high-elasticity PU material applied to the sole comprises the following components in parts by weight:
100 parts of TPU resin;
3-5 parts of polypropylene;
1-2 parts of an antioxidant;
15-20 parts of calcium carbonate whisker;
the preparation method of the calcium carbonate whisker comprises the following steps:
step 1), preparing a calcium hydroxide suspension;
Step 2), adding a crystal form control solution into the calcium hydroxide suspension, and uniformly mixing to obtain a mixed solution;
Step 3), keeping the temperature of the mixed solution at 80-100 ℃, then introducing carbon dioxide into the mixed solution, reacting until the pH value of the mixed solution is reduced, and filtering out precipitate to obtain calcium carbonate whiskers;
the crystal form control liquid is an aqueous solution at least comprising magnesium ions, potassium ions and permanganate ions.
Through adopting above-mentioned technical scheme, through adding special calcium carbonate whisker for the molecular weight of TPU resin can entangle the calcium carbonate whisker well for the calcium carbonate whisker plays fine reinforcement effect, effectively improves the intensity of TPU resin, and because the calcium carbonate whisker is not square lattice structure, but needle crystal, can not show the elasticity that influences the TPU resin after the calcium carbonate whisker is incorporated, can promote intensity well when making the TPU resin keep soft high bullet, makes the sole of making difficult fracture.
Through incorporating a certain amount of polypropylene, the molecular chain of TPU resin can be disturbed to a certain extent, and through entanglement of the polypropylene molecular chain and the TPU resin molecular chain, the entanglement effect of the calcium carbonate whisker by the polymer chain is better, and the entanglement is firmer, so that the polymer chain is not easy to disentangle, thereby the reinforcement effect is better, and the prepared high-strength high-elasticity PU material applied to soles has higher elasticity, higher strength and better quality.
When the calcium carbonate whisker is prepared, the whisker control liquid containing at least magnesium ions, potassium ions and permanganate ions is specifically selected, so that the calcium carbonate whisker can be induced to form a whisker structure which is more suitable for reinforcing the TPU resin, and the whisker structure can generate more branches, so that the firmness of molecular chain entanglement on the whisker is higher, and the whisker is not easy to unwrap, and the reinforcing effect of the calcium carbonate whisker prepared by a special process on the TPU resin is far higher than that of the conventional common calcium carbonate whisker.
Preferably, the crystal form control liquid is prepared by compounding water, magnesium chloride and potassium permanganate.
Through adopting above-mentioned technical scheme, through the compound of specific selection water, magnesium chloride, potassium permanganate for contain magnesium ion, potassium ion, permanganate ion simultaneously in the crystal form control liquid, the impurity of introducing is less moreover, has only introduced the chloride ion, reduces the influence to calcium carbonate whisker crystal form induction effect, and the effect that the calcium carbonate whisker of preparation improves TPU intensity is better.
Preferably, the mass ratio of the magnesium chloride to the potassium permanganate is 18-20:4-5.
Through adopting above-mentioned technical scheme, through the proportion of specifically selecting magnesium chloride, potassium permanganate, the proportion of magnesium ion and potassium ion, magnesium ion and permanganate ion has been controlled to make the effect that induces the crystal form change of calcium carbonate whisker better, prepare the calcium carbonate whisker that is comparatively fit for being used for strengthening TPU resin, the intensity of the PU material of preparation is higher.
Preferably, the mass ratio of the water to the magnesium chloride to the potassium permanganate is 100:18-20:4-5.
Through adopting above-mentioned technical scheme, through the mass proportion of specific selection water, magnesium chloride, potassium permanganate for the concentration of magnesium ion, potassium ion, permanganate root ion in the crystal form control liquid is more suitable, thereby induces the fashioned effect of calcium carbonate whisker better, and the reinforcement effect of the calcium carbonate whisker of preparation to TPU resin is better.
Preferably, in the step 1), the calcium hydroxide suspension is formed by compounding water and calcium hydroxide, wherein the mass ratio of the water to the calcium hydroxide is 1000:7-8.
By adopting the technical scheme, the prepared calcium hydroxide suspension is more suitable for reacting to generate the calcium carbonate whisker by specifically selecting the mass ratio of water to calcium hydroxide, the reaction process is more stable, and the quality of the prepared calcium carbonate whisker is better.
Preferably, in the step 2), the mass ratio of the calcium hydroxide suspension to the crystal form control liquid is 100:1-2.
Through adopting above-mentioned technical scheme, through the mass proportion of concrete selection calcium hydroxide suspension, crystal form control liquid for the effect of inducing the change of calcium carbonate whisker crystal form is better, and the quality of the calcium carbonate whisker of knowing is higher, and the effect of modifying TPU resin is better.
Preferably, in the step 3), the flow rate of introducing carbon dioxide into the mixed solution is 30-35ml/min.
By adopting the technical scheme, the reaction for generating the calcium carbonate whisker is stable by specifically selecting the flow rate of carbon dioxide, and the quality of the prepared calcium carbonate whisker is stable.
In a second aspect, the application provides a preparation method of a high-strength high-elasticity PU material applied to soles, which adopts the following technical scheme:
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps of:
Step 1), adding TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers into a stirring kettle, and uniformly mixing to obtain a mixture; and 2) putting the mixture into a screw extruder for extrusion granulation to obtain the high-strength high-elasticity PU material applied to the sole.
Through adopting above-mentioned technical scheme, the high-strength high-elastic PU material that is applied to the sole of making has fine elasticity and fine intensity, and the PU sole of preparation formation is very soft comfortable, and intensity is higher moreover, is difficult for the fracture, and durable, the security is higher, and the quality is better.
In summary, the application has the following beneficial effects:
1. According to the application, the special calcium carbonate whisker is added, so that the molecular weight of the TPU resin can be well entangled with the calcium carbonate whisker, the calcium carbonate whisker plays a good role in reinforcing, the strength of the TPU resin is effectively improved, and the elasticity of the TPU resin is not obviously affected after the calcium carbonate whisker is doped because the calcium carbonate whisker is not in a square lattice structure but in a needle-shaped crystal, so that the TPU resin can be well improved while the TPU resin is kept soft and high-elastic, and the prepared sole is not easy to crack.
2. According to the application, a certain amount of polypropylene is preferably doped, so that the molecular chain of the TPU resin is disturbed to a certain extent, the entanglement effect of the calcium carbonate whisker by the high molecular chain is better and the entanglement is firmer through entanglement of the polypropylene molecular chain and the TPU resin molecular chain, and the high molecular chain is not easy to unwrap, so that the reinforcing effect is better, and the prepared high-strength high-elasticity PU material applied to the sole has higher elasticity, higher strength and better quality.
3. According to the application, the whisker control liquid containing at least magnesium ions, potassium ions and permanganate ions is preferably selected, so that the calcium carbonate whisker can be induced to form a whisker structure which is more suitable for reinforcing the TPU resin, and the whisker structure can generate more branches, so that the firmness of molecular chains entangled on the whisker is higher, and the whisker is not easy to unwrap, and the reinforcing effect of the calcium carbonate whisker prepared by a special process on the TPU resin is far higher than that of the conventional common calcium carbonate whisker.
Detailed Description
The present application will be described in further detail with reference to examples.
Example 1
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1g of crystal form control liquid, stirring for 3min at the rotating speed of 60r/min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 80 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 30ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium permanganate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 18g of magnesium chloride and 4g of potassium permanganate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
Step 01), 100kgTPU of resin, 3kg of polypropylene, 1kg of anti-aging agent 1010 and 15kg of calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Example 2
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium permanganate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 4.5g of potassium permanganate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control liquid is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 100kgTPU resin, 4kg polypropylene, 1.5kg anti-aging agent 1010 and 18kg calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Example 3
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 8g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 2g of crystal form control liquid, stirring for 3min at the rotating speed of 60r/min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 100 ℃, then introducing carbon dioxide into the mixed solution at a flow rate of 35ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium permanganate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 20g of magnesium chloride and 5g of potassium permanganate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
Step 01), 100kgTPU of resin, 5kg of polypropylene, 2kg of anti-aging agent 1010 and 20kg of calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Comparative example 1
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium phosphate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 4.5g of potassium phosphate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 100kgTPU resin, 4kg polypropylene, 1.5kg anti-aging agent 1010 and 18kg calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Comparative example 2
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium phosphate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 10g of potassium phosphate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 100kgTPU resin, 4kg polypropylene, 1.5kg anti-aging agent 1010 and 18kg calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Comparative example 3
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium nitrate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 4.5g of potassium nitrate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 100kgTPU resin, 4kg polypropylene, 1.5kg anti-aging agent 1010 and 18kg calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Comparative example 4
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium nitrate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 30g of potassium nitrate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control solution is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 100kgTPU resin, 4kg polypropylene, 1.5kg anti-aging agent 1010 and 18kg calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Comparative example 5
A high-strength high-elasticity PU material applied to soles is prepared from the following components:
TPU resin, antioxidant and calcium carbonate whisker.
Wherein, TPU resin is purchased from Basoff, germany, with the brand number of C70A10WH.
Wherein, polypropylene is purchased in China petrochemical industry with the brand F401.
Wherein, the antioxidant is purchased from Nanjing Milan New Material Co., ltd., antioxidant 1010.
Wherein, the calcium carbonate whisker is self-made, and the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), 1000g of deionized water is weighed, stirring is continuously carried out at the rotating speed of 60r/min, and 7.5g of calcium hydroxide is slowly added to prepare a calcium hydroxide suspension.
And 2) weighing 100g of calcium hydroxide suspension, adding 1.5g of crystal form control liquid, stirring at the rotating speed of 60r/min for 3min, and uniformly mixing to obtain a mixed liquid.
And 3) heating the mixed solution and keeping the temperature at 90 ℃, then introducing carbon dioxide into the mixed solution at the flow rate of 32ml/min, reacting until the pH value of the mixed solution is reduced to 6.8, and filtering out precipitate to obtain the calcium carbonate whisker.
Wherein the whisker control liquid is prepared by compounding water, magnesium chloride and potassium permanganate.
The preparation method of the whisker control liquid comprises the following steps:
100g of water is weighed, 19g of magnesium chloride and 4.5g of potassium permanganate are added into the water, the rotating speed is 60r/min, the stirring is carried out for 5min, and the whisker control liquid is obtained after uniform mixing.
The preparation method of the high-strength high-elasticity PU material applied to the sole comprises the following steps:
step 01), 104kgTPU resin, 1.5kg of anti-aging agent 1010 and 18kg of calcium carbonate whisker are put into a stirring kettle, stirred for 5min at the rotating speed of 120r/min, and uniformly mixed to obtain a mixture.
Step 02), putting the mixture into a double-screw extruder for extrusion, and granulating under water to obtain the high-strength high-elasticity PU material applied to soles, wherein the temperatures of all areas of the screw extruder are as follows: first 165 ℃, second 185 ℃, third 210 ℃, fourth 215 ℃, fifth 195 ℃, die 195 ℃.
Experiment 1
Determination of tensile Properties of plastics according to GB/T1040.2-2022 part 2: test conditions for molded extruded plastics test specimens prepared from the high-strength and high-elastic PU materials for shoe soles of the examples and comparative examples were tested for tensile strength and elongation at break.
The sample was type 1A.
The tensile test speed was 10mm/min.
The specific test data for experiment 1 are detailed in table 1.
TABLE 1
| Tensile Strength (MPa) | Elongation at break (%) | |
| Example 1 | 118 | 985 |
| Example 2 | 121 | 989 |
| Example 3 | 122 | 983 |
| Comparative example 1 | 91 | 969 |
| Comparative example 2 | 98 | 984 |
| Comparative example 3 | 86 | 957 |
| Comparative example 4 | 95 | 977 |
| Comparative example 5 | 112 | 998 |
According to the comparison of the data of each example in Table 1 with the data of comparative examples 1-4, the tensile elongation of each example is not greatly different from that of comparative examples 1-4, and the PU materials prepared by each example and comparative examples 1-4 are proved to have better elasticity, but the tensile strength of each example is obviously higher than that of comparative examples 1-4, so that the special calcium carbonate whisker prepared by adding each example can play a more obvious reinforcing modification effect on the TPU material, and the matching degree of the calcium carbonate whisker prepared by adopting the conventional whisker control agent and the TPU resin is more general, so that the reinforcing effect is more general.
According to the data comparison of each example in Table 1 and comparative example 5, a small amount of polypropylene is added into the TPU resin, and the polypropylene can be matched with the TPU molecular chain, so that the reinforcing and modifying effects of the calcium carbonate whisker are better, and the strength of the PU material is higher.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. The utility model provides a be applied to high-strength high-elastic PU material of sole which characterized in that: comprises the following components in parts by mass:
100 parts of TPU resin;
3-5 parts of polypropylene;
1-2 parts of an antioxidant;
15-20 parts of calcium carbonate whisker;
the preparation method of the calcium carbonate whisker comprises the following steps:
Step 1), preparing a calcium hydroxide suspension;
Step 2), adding a crystal form control solution into the calcium hydroxide suspension, and uniformly mixing to obtain a mixed solution;
Step 3), keeping the temperature of the mixed solution at 80-100 ℃, then introducing carbon dioxide into the mixed solution, reacting until the pH value of the mixed solution is reduced, and filtering out precipitate to obtain calcium carbonate whiskers;
The crystal form control liquid is prepared by compounding water, magnesium chloride and potassium permanganate;
The mass ratio of the water to the magnesium chloride to the potassium permanganate is 100:18-20:4-5.
2. The high-strength and high-elasticity PU material for shoe soles according to claim 1, wherein: in the step 1), the calcium hydroxide suspension is formed by compounding water and calcium hydroxide, wherein the mass ratio of the water to the calcium hydroxide is 1000:7-8.
3. The high-strength and high-elasticity PU material for shoe soles according to claim 2, wherein: in the step 2), the mass ratio of the calcium hydroxide suspension to the crystal form control liquid is 100:1-2.
4. The high-strength and high-elasticity PU material for shoe soles according to claim 1, wherein: in the step 3), the flow rate of introducing carbon dioxide into the mixed solution is 30-35ml/min.
5. A method for preparing the high-strength and high-elasticity PU material for shoe soles according to any one of claims 1-4, characterized in that: the method comprises the following steps:
Step 1), adding TPU resin, polypropylene, an antioxidant and calcium carbonate whiskers into a stirring kettle, and uniformly mixing to obtain a mixture;
And 2) putting the mixture into a screw extruder for extrusion granulation to obtain the high-strength high-elasticity PU material applied to the sole.
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