CN113980219B - Preparation method of semitransparent antistatic TPU master batch - Google Patents
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- CN113980219B CN113980219B CN202111234476.8A CN202111234476A CN113980219B CN 113980219 B CN113980219 B CN 113980219B CN 202111234476 A CN202111234476 A CN 202111234476A CN 113980219 B CN113980219 B CN 113980219B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
A preparation method of a semitransparent antistatic TPU master batch comprises the following steps: preparing nonionic dihydric alcohol and preparing TPU by using the nonionic dihydric alcohol, wherein the preparation of the nonionic dihydric alcohol comprises the following steps: step 1, putting PEG, lithium salt, MMA, peroxide, styrene and first deionized water into a reaction container, heating to 65-75 ℃, and stirring for more than 0.5h; step 2, heating to 85-95 ℃, and stirring for more than 1h; step 3, putting MEHQ and second deionized water into a reaction container, and stirring for more than 0.3 h; step 4, raising the temperature to 100-110 ℃, reducing the pressure to 645-655 mmhg, and performing vacuum dehydration for more than 0.5h; step 5, raising the temperature to 135-145 ℃, boosting the temperature to 745-755 mmhg, and continuing to remove water in vacuum for more than 10 hours; and 6, recovering the normal pressure and cooling to form the nonionic dihydric alcohol. Compared with the prior permanent antistatic material only suitable for hard plastics, the semitransparent antistatic TPU master batch has a hard chain segment and a soft chain segment, is suitable for most plastics and elastomers, and has wide application range.
Description
Technical Field
The invention relates to the field of TPU (thermoplastic polyurethane), in particular to a preparation method of a semitransparent antistatic TPU master batch.
Background
Due to climate change, some of the world are in extremely cold or hot environments, some are in extremely dry or extremely humid environments, and these harsh environments cause static damage, for example, in factory workshops, home lives, outdoor sites, etc., which often causes damage to personnel, instruments and products due to static electricity generation.
In the various environments mentioned above, plastics are often used as an antistatic solution. Most of the equipment mainly adopts short-acting antistatic effect, and some equipment adopts plastic with permanent antistatic effect.
However, there are dozens of plastic varieties, and the plastic varieties are often compatible when prepared from different materials, resulting in delamination, fracture and the like. For permanent antistatic plastics, nylon or nylon elastomer is mostly used as a carrier, and nylon or nylon elastomer is only suitable for hard plastics, and has poor transparency (mostly black or dark materials) and cannot be toned, so that the application range of the plastic is narrow.
Disclosure of Invention
The technical scheme of the invention is to solve the above problems and provide a preparation method of a semitransparent antistatic TPU master batch, which comprises the following steps:
step 1, putting PEG, lithium salt, MMA, peroxide, styrene and first deionized water into a reaction container, heating to 65-75 ℃, and stirring for more than 0.5h;
step 2, heating to 85-95 ℃, and stirring for more than 1h;
step 3, putting MEHQ and second deionized water into a reaction container, and stirring for more than 0.3 h;
step 4, heating to 100-110 ℃, reducing the pressure to 645-655 mmhg, and performing vacuum dewatering for more than 0.5h;
step 5, raising the temperature to 135-145 ℃, boosting the temperature to 745-755 mmhg, and continuing to remove water in vacuum for more than 10 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
step 7, placing the polymeric diol, the nonionic diol, the chain extender, the isocyanate, the antioxidant, the yellowing-resistant agent and the catalyst into a reaction vessel, heating to 75-85 ℃, and stirring for more than 0.3 h;
step 8, baking the material at the baking temperature of 95-105 ℃ for more than 7 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material to form the semitransparent antistatic TPU master batch.
Further, the ratio of each component of the nonionic dihydric alcohol is as follows:
further, in the step 1, the lithium salt is one or a mixture of more of lithium hydroxide, lithium chloride, lithium tert-butoxide, lithium perchlorate, lithium phosphate and lithium acetate; the peroxide is one or more of BPO, AIBN and ABVN.
Further, the ratio of the components of the semitransparent antistatic TPU master batch is as follows:
further, in step 7, the polymeric diol is one or a mixture of two of PEG and PEG-PPG copolymer; the chain extender is one or a mixture of EG and 1,4BG; the isocyanate is MDI, HDI, TDI, IPDI and H 12 One or more of MDI; the antioxidant is one or a mixture of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant; the anti-yellowing agent is one or a mixture of UV-328, UV-327, UV-P and UV-765; the catalyst is one or the mixture of stannous octoate and amine catalyst.
Further, the polymeric diol has a molecular weight of 2000 or 3000 or 4000.
Further, in step 8, the material is poured on a tray coated with a release agent, and the tray is placed in an oven to bake the material.
Furthermore, an antifreeze agent is added in the granulation process, and the granulation temperature is 5-10 ℃.
The semitransparent antistatic TPU master batch prepared by the invention has the following advantages:
1. compared with the common precipitation type antistatic material which loses efficacy for a long time, the semitransparent antistatic TPU master batch has a permanent antistatic effect, the high-molecular carrier is not easy to rot and crack, and instruments and equipment which need to be antistatic can be continuously protected.
2. Compared with the traditional carbon black or carbon tube type antistatic material which can only be used for manufacturing black parts, the semitransparent antistatic TPU master batch can be used for manufacturing parts and finished products with any color.
3. Compared with the existing permanent antistatic material only suitable for hard plastics, the semitransparent antistatic TPU master batch has a hard chain segment and a soft chain segment, is suitable for most plastics and elastomers, and has a wide application range.
Detailed Description
The technical solution of the present invention is further described by the following examples:
the invention provides a preparation method of a semitransparent antistatic TPU master batch, which comprises the following steps:
first stage, preparation of non-ionic diols:
step 1, putting PEG (polyethylene glycol), lithium salt, MMA (methyl methacrylate), peroxide, styrene and first deionized water into a reaction container, heating to 65-75 ℃, and stirring for more than 0.5h;
step 2, heating to 85-95 ℃, and stirring for more than 1h;
step 3, putting MEHQ (p-hydroxyanisole) and second deionized water into a reaction container, and stirring for more than 0.3 h;
step 4, raising the temperature to 100-110 ℃, reducing the pressure to 645-655 mmhg, and performing vacuum dehydration for more than 0.5h;
step 5, raising the temperature to 135-145 ℃, boosting the temperature to 745-755 mmhg, and continuing to remove water in vacuum for more than 10 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
in the second stage, preparing semitransparent antistatic TPU master batch:
step 7, placing the polymeric diol, the nonionic diol, the chain extender, the isocyanate, the antioxidant, the anti-yellowing agent and the catalyst into a reaction vessel, heating to 75-85 ℃, and stirring for more than 0.3 h;
step 8, baking the material at the baking temperature of 95-105 ℃ for more than 7 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material to form the semitransparent antistatic TPU master batch.
The reason why the temperature is raised to 65 to 75 ℃ and the stirring is carried out for 0.5 hour or more in step 1 is to ensure that all lithium chloride is completely dissolved and the material solution is in a transparent state.
Wherein, two materials with weak polarity of styrene and MMA are added in the step 1, and the reaction forms a polypropylene styrene copolymer with a structure similar to IPN, the purpose is not physical property of the product, but compatibility, so that the product is suitable for various plastics with high and low polarity.
It is worth mentioning that the material is significantly exothermic when stirred for more than 1h in step 2, and MEHQ is then added in step 3 to stop the free radical polymerization, thereby terminating the reaction and allowing the polypropylene styrene copolymer to disperse in the non-ionic glycol.
Wherein, the vacuum water removal is continued for more than 10 hours when the pressure is increased to 745-755 mmhg in the step 5, so as to ensure that the water content is less than 500ppm to meet the standard of TPU preparation, and the material solution is kept clear. Because the material solution maintains a clear state, the subsequently prepared TPU master batch is in a semitransparent state and is easy to color adjust.
When the semitransparent antistatic TPU master batch is added into various plastics, lithium salt is dispersed in the materials to form ionized network charges, and the ionized network charges cannot be separated out, so that the effect of permanently eliminating static electricity is achieved.
Therefore, the semitransparent antistatic TPU master batch prepared by the invention has the following advantages:
1. compared with the common anti-static material which is precipitated and loses efficacy for a long time, the semi-transparent anti-static TPU master batch has a permanent anti-static effect, the high molecular carrier is not easy to rot and crack, and instruments and equipment which need static electricity resistance can be continuously protected.
2. Compared with the traditional carbon black or carbon tube type antistatic material which can only be used for manufacturing black parts, the semitransparent antistatic TPU master batch can be used for manufacturing parts and finished products with any color.
3. Compared with the existing permanent antistatic material only suitable for hard plastics, the semitransparent antistatic TPU master batch has a hard chain segment and a soft chain segment, is suitable for most plastics and elastomers, and has a wide application range.
Specifically, the ratio of each component of the nonionic dihydric alcohol is as follows:
specifically, in step 1, the lithium salt is one or a mixture of more of lithium hydroxide, lithium chloride, lithium tert-butoxide, lithium perchlorate, lithium phosphate and lithium acetate; the peroxide is one or more of BPO (benzoyl peroxide), AIBN (azodiisobutyronitrile) and ABVN (azodiisoheptanonitrile).
Specifically, the translucent antistatic TPU master batch comprises the following components in percentage by weight:
specifically, in step 7, the polymeric diol is one or a mixture of two of PEG (polyethylene glycol) and PEG-PPG copolymer (polyethylene glycol-polypropylene glycol copolymer); the chain extender is one or a mixture of EG (ethylene glycol) and 1,4BG (1, 4 butanediol); the isocyanate is MDI (diphenylmethane diisocyanate), HDI (hexamethylene diisocyanate), TDI (toluene diisocyanate), IPDI (isophorone diisocyanate) and H 12 One or more mixtures of MDI (hydrogenated phenyl methane diisocyanate); the antioxidant is one or two of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant; the anti-yellowing agent is one or more of UV-328, UV-327, UV-P and UV-765; the catalyst is one or the mixture of stannous octoate and amine catalyst.
More specifically, the polymeric glycol has a molecular weight of 2000 or 3000 or 4000. Molecular weights above 2000 help to aid charge formation and thus make the polymer stable.
Specifically, in step 8, the material is poured onto a tray coated with a release agent, and the tray is placed in an oven to bake the material. Therefore, the material can be conveniently discharged after being baked.
Specifically, in step 10, an antifreeze agent is added in the granulation process, and the granulation temperature is 5-10 ℃. Although the temperature of the granulation environment is 5-10 ℃, the temperature of the cooling water of the granulation equipment is 0 ℃, and the antifreeze agent is added to prevent the cooling water from solidifying to influence the particle crystallization.
[ example 1 ] A method for producing a polycarbonate
A preparation method of a semitransparent antistatic TPU master batch comprises the following steps:
first stage, preparation of non-ionic diol:
the following materials were prepared by weight:
step 1, putting PEG, lithium chloride, MMA, BPO, styrene and first deionized water into a reaction container, heating to 70 ℃, and stirring for 1h;
step 2, heating to 90 ℃, and stirring for 2 hours;
step 3, putting MEHQ and second deionized water into a reaction container, and stirring for 0.5h;
step 4, heating to 105 ℃, decompressing to 650mmhg, and performing vacuum dehydration for 1 hour;
step 5, raising the temperature to 140 ℃, boosting the pressure to 750mmhg, and continuing vacuum dewatering for 12 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
and in the second stage, preparing semitransparent antistatic TPU master batches:
the materials were prepared as follows by weight:
step 7, placing the PEG-PPG copolymer, the nonionic dihydric alcohol, EG, MDI, 1010 antioxidant, UV-328 and stannous octoate into a reaction vessel, heating to 80 ℃, and stirring for 0.5h;
step 8, pouring the material on a tray coated with a release agent, putting the tray into an oven, and baking the material at the baking temperature of 100 ℃ for 8 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material, adding an antifreeze agent in the granulating process, and forming the semitransparent antistatic TPU master batch at the granulating temperature of 5-10 ℃.
[ example 2 ]
A preparation method of a semitransparent antistatic TPU master batch comprises the following steps:
first stage, preparation of non-ionic diol:
the materials were prepared as follows by weight:
step 1, putting PEG, lithium hydroxide, MMA, BPO, styrene and first deionized water into a reaction vessel, heating to 70 ℃, and stirring for 1h;
step 2, heating to 90 ℃, and stirring for 2 hours;
step 3, putting MEHQ and second deionized water into a reaction container, and stirring for 0.5h;
step 4, heating to 105 ℃, decompressing to 650mmhg, and performing vacuum dehydration for 1 hour;
step 5, raising the temperature to 140 ℃, boosting the pressure to 750mmhg, and continuing vacuum dewatering for 12 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
and in the second stage, preparing semitransparent antistatic TPU master batches:
the following materials were prepared by weight:
step 7, placing the PEG-PPG copolymer, the nonionic dihydric alcohol, 1,4BG, MDI, 1010 antioxidant, UV-328 and stannous octoate into a reaction vessel, heating to 80 ℃, and stirring for 0.5h;
step 8, pouring the material on a tray coated with a release agent, placing the tray into a baking oven, and baking the material at the baking temperature of 100 ℃ for 8 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material, adding an antifreeze agent in the granulating process, wherein the granulating temperature is 5-10 ℃, and forming the semitransparent antistatic TPU master batch.
[ example 3 ]
A preparation method of a semitransparent antistatic TPU master batch comprises the following steps:
first stage, preparation of non-ionic diols:
the following materials were prepared by weight:
step 1, putting PEG, lithium tert-butoxide, MMA, BPO, styrene and first deionized water into a reaction vessel, heating to 70 ℃, and stirring for 1h;
step 2, heating to 90 ℃, and stirring for 2 hours;
step 3, putting MEHQ and second deionized water into a reaction container, and stirring for 0.5h;
step 4, heating to 105 ℃, decompressing to 650mmhg, and performing vacuum dehydration for 1 hour;
step 5, raising the temperature to 140 ℃, boosting the pressure to 750mmhg, and continuing vacuum dewatering for 12 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
in the second stage, preparing semitransparent antistatic TPU master batch:
the following materials were prepared by weight:
step 7, putting the PEG-PPG copolymer, the nonionic dihydric alcohol, EG, MDI, 1010 antioxidant, UV-328 and stannous octoate into a reaction vessel, heating to 80 ℃, and stirring for 0.5h;
step 8, pouring the material on a tray coated with a release agent, placing the tray into a baking oven, and baking the material at the baking temperature of 100 ℃ for 8 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material, adding an antifreeze agent in the granulating process, wherein the granulating temperature is 5-10 ℃, and forming the semitransparent antistatic TPU master batch.
[ basic Property test ]
The translucent antistatic TPU master batches of examples 1 to 3 were subjected to basic physical property tests, and the test results were as follows:
TABLE 1
As can be seen from table 1, the semi-transparent antistatic TPU masterbatch of examples 1-3 has somewhat lower hardness, elongation, tensile, 100% modulus, and tear resistance than conventional TPU, which allows better dispersion of the TPU masterbatch in various plastics. In addition, the lower the impedance value, the better the antistatic performance, and the antistatic performance of the translucent antistatic TPU master batches of examples 1 to 3 is all in the better index.
[ compatibility test ]
The translucent antistatic TPU master batches of examples 1 to 3 were subjected to compatibility tests, and were compatible with various plastics, the content of which was 85% of the total amount, and the impedance values after compatibility were measured, and the test results were as follows:
TABLE 2
As shown in Table 2, wherein "√" indicates no delamination, "Δ" is still usable and "X" indicates delamination. The translucent antistatic TPU master batches of examples 1 to 3 had good compatibility with most of the other except HDPE, and the resistance values after the compatibility were all on the best index. Furthermore, even if compatible with HDPE, no breakage occurs.
The above-described embodiments are merely preferred examples of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications in the structure, features and principles of the invention described in the claims should be included in the claims.
Claims (8)
1. A preparation method of semitransparent antistatic TPU master batches is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, putting PEG, lithium salt, MMA, peroxide, styrene and first deionized water into a reaction vessel, heating to 65-75 ℃, and stirring for more than 0.5h;
step 2, heating to 85-95 ℃, and stirring for more than 1h;
step 3, putting MEHQ and second deionized water into a reaction container, and stirring for more than 0.3 h;
step 4, heating to 100-110 ℃, reducing the pressure to 645-655 mmhg, and performing vacuum dewatering for more than 0.5h;
step 5, raising the temperature to 135-145 ℃, boosting the temperature to 745-755 mmhg, and continuing to remove water in vacuum for more than 10 hours;
step 6, recovering normal pressure and cooling to form nonionic dihydric alcohol;
step 7, placing the polymeric diol, the nonionic diol, the chain extender, the isocyanate, the antioxidant, the yellowing-resistant agent and the catalyst into a reaction vessel, heating to 75-85 ℃, and stirring for more than 0.3 h;
step 8, baking the material at the baking temperature of 95-105 ℃ for more than 7 hours;
step 9, crushing the material after cooling;
and step 10, granulating the material to form the semitransparent antistatic TPU master batch.
2. The method for preparing the translucent antistatic TPU master batch according to claim 1, characterized in that: the nonionic dihydric alcohol comprises the following components in percentage by weight:
3. the method of preparing the translucent antistatic TPU master batch of claim 2, wherein: in the step 1, the lithium salt is one or a mixture of more of lithium hydroxide, lithium chloride, lithium tert-butoxide, lithium perchlorate, lithium phosphate and lithium acetate; the peroxide is one or more of BPO, AIBN and ABVN.
4. The method for preparing the translucent antistatic TPU master batch according to claim 1, characterized in that: the ratio of the components of the semitransparent antistatic TPU master batch is as follows:
5. the preparation method of the translucent antistatic TPU master batch of claim 4, wherein: in step 7, the polymeric diol is one or a mixture of two of PEG and PEG-PPG copolymer; the chain extender is one or a mixture of EG and 1,4BG; the isocyanate is MDI, HDI, TDI, IPDI and H 12 One or more of MDI; the antioxidant is one or a mixture of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant; the tolerance isThe yellowing agent is one or more of UV-328, UV-327, UV-P and UV-765; the catalyst is one or the mixture of stannous octoate and amine catalyst.
6. The method of preparing the translucent antistatic TPU master batch of claim 5, wherein: the polymeric glycol has a molecular weight of 2000 or 3000 or 4000.
7. The method for preparing the translucent antistatic TPU master batch according to claim 1, characterized in that: in step 8, the material is poured onto the tray coated with the release agent, and the tray is placed in an oven to bake the material.
8. The preparation method of the translucent antistatic TPU master batch of claim 1, wherein: adding an antifreeze agent in the granulation process, wherein the granulation temperature is 5-10 ℃.
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| CA1127644A (en) * | 1980-01-28 | 1982-07-13 | Anupama Mishra | Isocyanurate products and polyurethanes therefrom |
| DE10356612A1 (en) * | 2003-12-01 | 2005-06-30 | Basf Ag | Thermoplastic polyurethane containing polymer polyols |
| CN100491428C (en) * | 2006-12-20 | 2009-05-27 | 中国科学院山西煤炭化学研究所 | Process for synthesis of polymer polyhydric alcohol |
| CN103275278A (en) * | 2013-06-19 | 2013-09-04 | 青岛新宇田化工有限公司 | Synthesis method for polyester polymer polyol dispersoid |
| CN110066377B (en) * | 2019-05-09 | 2020-05-12 | 中国科学技术大学 | Flexible semitransparent waterproof heat-insulation film and preparation method thereof |
| CN110627983A (en) * | 2019-08-29 | 2019-12-31 | 山东一诺威聚氨酯股份有限公司 | Low-density high-strength high-yellow-resistance TPU (thermoplastic polyurethane) for shoe sole and preparation method thereof |
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