CN114656613A - High-performance TPU material and preparation method thereof - Google Patents
High-performance TPU material and preparation method thereof Download PDFInfo
- Publication number
- CN114656613A CN114656613A CN202210470634.8A CN202210470634A CN114656613A CN 114656613 A CN114656613 A CN 114656613A CN 202210470634 A CN202210470634 A CN 202210470634A CN 114656613 A CN114656613 A CN 114656613A
- Authority
- CN
- China
- Prior art keywords
- preparation
- chain extender
- nucleating agent
- parts
- tpu material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 3
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 claims description 2
- RUJLBGCWTMTXND-UHFFFAOYSA-N 4-hydroxy-2,3-bis(hydroxymethyl)but-2-enoic acid Chemical compound OCC(CO)=C(CO)C(O)=O RUJLBGCWTMTXND-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- -1 polyethylene adipate Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a high-performance TPU material, which comprises the following raw materials in parts by mass: 50-70 parts of polyol, 0.01-2 parts of nucleating agent, 30-55 parts of isocyanate, 0.5-10 parts of bifunctional chain extender and 0.02-1 part of polyfunctional chain extender with functionality being more than or equal to 3; the preparation method comprises the following steps: adding polyol, a bifunctional chain extender and isocyanate into a co-rotating double-screw reaction extruder from a pouring gate, adding a nucleating agent in a 3 rd zone of the double-screw reaction extruder in a side feeding manner, adding the polyfunctional chain extender in a 6 th zone of the double-screw reaction extruder in a side feeding manner, and performing reaction extrusion to obtain the high-performance TPU material. Starting from the synthesis of TPU raw materials, the invention controls the addition process and the addition amount of the nucleating agent and the polyfunctional chain extender, so that the tensile strength of the product can be improved by 20 percent or even higher on the basis of keeping higher elongation.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a high-performance TPU material and a preparation method thereof.
Background
The recycling of the finished thermoplastic polyurethane elastomer (TPU) is one of the characteristics, but in the markets of pipes, shoe materials and the like, when customers process and mold, the recycling of leftover materials has the following problems: firstly, the blending proportion cannot be too high, otherwise, the product performance can be influenced, the unqualified product rate can be increased due to the increase of the blending proportion, and the quality, particularly the strength and the transparency of the product are obviously reduced; secondly, the recycled materials are repeatedly mixed and used in the processing process, the degradation is serious, and the transparent product can become yellow and has a large influence on the appearance. The market popularization of TPU products is restricted by the above problems.
Aiming at the problems, the main measures of the current downstream customers of the TPU are that firstly, the products are classified, the finished products made of pure materials are sent to middle-high-end customers, the finished products made of reclaimed materials are sent to middle-low-end customers, but the measures are difficult to meet the requirements of the customers and improve the finished products of the customers because the problem of leftover materials cannot be avoided and the leftover materials are more; and secondly, color mixing is carried out by partially blending and then adding partial color master batch, so that the appearance problem of the product is solved, but the product performance is affected, the strength and the toughness are insufficient, and the delivery limit is large.
The patent specification with the publication number of CN 112430389A discloses a reinforced and toughened TPU material and a preparation method thereof, and the reinforced and toughened TPU material comprises the raw materials of TPU, a plasticizer and nylon; the melting point of the nylon is not lower than 225 ℃, and the particle size is not more than 10 mu m; the mass percentage of the nylon in the TPU is 0.1-2%. The preparation method comprises the following steps: and adding the TPU into the mixer, adding the plasticizer, uniformly mixing, adding the nylon, uniformly mixing again, adding the mixture into the extruder, and extruding to obtain the reinforced and toughened TPU material. This patent technique adds for TPU is the nylon powder of minute quantity specific melting point and particle diameter as the physics nucleation point, has accelerated TPU's crystallization rate in TPU course of working for TPU crystal nucleus figure increases, and the crystal nucleus size reduces, thereby makes the product fragility reduce, and toughness improves, and intensity improves, has improved the durability and the life-span that TPU used.
The patent specification with the publication number of CN 108484867A discloses a thermoplastic polyurethane elastomer, wherein double bond-containing polyol and/or common polyol are used as soft segments of the thermoplastic polyurethane elastomer, and diisocyanate and a micromolecular chain extender are used as hard segments of the thermoplastic polyurethane elastomer; the thermoplastic polyurethane elastomer comprises the following components in parts by weight: 3-50 parts of diisocyanate, 5-100 parts of double bond-containing polyol, 0.5-60 parts of common polyol and 0-20 parts of small molecular chain extender. The thermoplastic polyurethane elastomer has excellent heat resistance, excellent comprehensive performances such as mechanics and the like, and has wide application in the fields of cables, tires, sealing elements, shoes, medical appliances and the like.
Disclosure of Invention
The invention develops a new method starting from the synthesis of TPU raw materials, improves the performance of products in the same series through reasonable optimization of a formula and a synthesis process, improves the strength and the molecular weight of the products through the optimized matching of the formula and the process on the basis of ensuring the basic hardness and the transparency of the products, ensures that the products have better strength retention rate in extrusion processing, improves the tolerance of the TPU products to temperature and shearing in the extrusion processing, and can improve the performance of TPU leftover materials, thereby improving the mixing proportion and the cycle frequency on the premise of not influencing the comprehensive performance of the products.
The specific technical scheme is as follows:
a preparation method of a high-performance TPU material comprises the following raw materials in parts by mass:
the preparation method comprises the following steps: adding polyalcohol, bifunctional chain extender and isocyanate into a co-rotating double-screw reaction extruder from a pouring gate, adding nucleating agent in a 3 rd zone of the double-screw reaction extruder in a side feeding manner, adding polyfunctional chain extender in a 6 th zone of the double-screw reaction extruder in a side feeding manner, and performing reaction extrusion to obtain the high-performance TPU material.
The key point of the preparation method is the addition process and the addition amount control of the nucleating agent and the polyfunctional chain extender, the principle is that on the premise of ensuring the initial reaction of the TPU in the front 5 areas of the double-screw reaction extruder (ensuring the main body reaction, if the nucleating agent is directly added from a pouring gate and the like in advance, a more complex process is needed to solve the dispersion problem), the nucleating agent is added in a side feeding mode, the dispersion uniformity of the nucleating agent in the TPU can be ensured, the nucleating mode of the TPU is changed from homogeneous nucleation to heterogeneous nucleation, the crystallization rate is improved, the uniform crystal nucleus size is ensured, the product strength is favorably improved, the polyfunctional chain extender is added in the 6 th area (the polyfunctional chain extender is added in the temperature area to ensure the proceeding degree of the main body reaction and the length of the main body molecular chain, if the polyfunctional chain extender is directly added from the pouring gate and the like in advance, the excessive branching structure appears in the main body molecular chain growth process, the molecular chain length and the molecular weight distribution are influenced, the strength of a finished product is further influenced, if a polyfunctional chain extender is added in a later temperature zone, the reaction degree is more thorough, the polyfunctional chain extender is difficult to effectively improve the molecular chain length and increase the molecular weight, so that the semi-finished TPU product further reacts to present a micro-crosslinking structure, the molecular weight is improved, the aggregation structure of the product is optimized, the strength retention capacity of the TPU product under high-temperature shearing is greatly improved, namely, the strength retention rate of the TPU product under high-temperature shearing is improved while the strength of the TPU is improved, namely, the TPU product can still maintain enough strength after being processed and formed for many times.
In the preparation method, the types of the polyol, the bifunctional chain extender and the isocyanate are not specially limited, and all the materials can be common materials in the field of TPU synthesis. For example: the polyol may be at least one of polyester polyol and polyether polyol, such as polyethylene adipate glycol having a number average molecular weight (Mn) of 2000; the bifunctional chain extender can be 1, 4-butanediol and the like; the isocyanate may be 4, 4' -diphenylmethane diisocyanate or the like.
In a preferred embodiment, in the preparation method of the high-performance TPU material, the melting point of the nucleating agent is not lower than 180 ℃.
In a preferred embodiment, in the preparation method of the high-performance TPU material, the nucleating agent is in a powder form and has a particle size of 100nm-50 mu m.
In a preferred example, the nucleating agent comprises at least one of montmorillonite, silica, multi-walled carbon nanotubes, calcium carbonate, glass microspheres, thermoplastic polyester elastomer (TPEE) powder, nylon powder and diatomite.
In a preferred example, in the preparation method of the high-performance TPU material, the multifunctional chain extender includes one or a mixture of any several of glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolacrylate, pentaerythritol, and the like.
In a preferred embodiment, the preparation method of the high-performance TPU material further comprises the following raw materials in parts by mass:
0.1 to 0.7 portion of primary antioxidant,
0.1 to 0.5 portion of auxiliary antioxidant,
0.1-0.9 part of lubricant.
The primary antioxidant, the secondary antioxidant and the lubricant can be all of the types commonly used in the field.
Further preferably, in the preparation method, the polyol, the primary antioxidant, the secondary antioxidant and the lubricant are uniformly mixed and then added into the co-rotating twin-screw reaction extruder together with the bifunctional chain extender and the isocyanate from a pouring gate.
The invention also provides the high-performance TPU material prepared by the preparation method.
Compared with the prior art, the invention has the following remarkable technical effects:
starting from the synthesis of TPU raw materials, the strength and molecular weight of the product are improved by controlling the addition process and the addition amount of the nucleating agent and the polyfunctional chain extender, so that the tensile strength of the product can be improved by 20 percent or even higher on the basis of keeping higher elongation.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
In the following examples and comparative examples, "parts" means parts by mass unless otherwise specified.
Example 1
(1) Weighing the following raw materials in parts by mass: 57 parts of polyethylene glycol adipate (Mn ═ 2000), 34 parts of 4, 4' -diphenylmethane diisocyanate, 9 parts of 1, 4-butanediol, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, 0.4 part of polyethylene wax, 0.1 part of diatomite and 0.1 part of trimethylolpropane for later use;
(2) adding 0.2 part of 2, 6-tertiary butyl-4-methylphenol, 0.2 part of didodecyl alcohol ester, 0.35 part of dicyandiamide and 0.4 part of polyethylene wax into 57 parts of polyethylene glycol adipate glycol (Mn ═ 2000) and fully stirring to ensure that the additive is uniformly dispersed in the polyhydric alcohol for later use;
(3) injecting the mixed polyol component, isocyanate and 1, 4-butanediol into a co-rotating twin-screw reaction extruder by a metering pump according to a specified ratio, adding diatomite in a 3 rd zone of the reaction extruder in a side feeding manner, and adding trimethylolpropane in a 6 th zone of the reaction extruder in a side feeding manner; the temperature zones of the co-rotating twin-screw reaction extruder are controlled to be 190 ℃, 200 ℃, 205 ℃, 210 ℃, 190 ℃, 150 ℃, 130 ℃ and the rotating speed of 240r/min at the temperature of 1-10 zones.
(4) And carrying out reactive extrusion and underwater pelletizing to obtain a high-performance TPU finished product.
Comparative example 1
The preparation method is as in example 1, and no nucleating agent and polyfunctional chain extender are added in the production process.
Comparative example 2
The preparation method is as in example 1, and no polyfunctional chain extender is added in the production process.
Comparative example 3
The preparation method is as in example 1, and no nucleating agent is added in the production process.
Comparative example 4
The preparation method is as in example 1, and the nucleating agent and the polyfunctional chain extender are simultaneously added into the double-screw reaction extruder from a pouring gate in the production process.
Example 2
The procedure is as in example 1, with 0.2 part of diatomaceous earth being added.
Example 3
The procedure is as in example 1, with diatomaceous earth being added in an amount of 0.2 parts and trimethylolpropane in an amount of 0.15 parts.
The physical properties of the TPU finished samples of the above examples and comparative examples were compared and evaluated by baking and injection molding test pieces in the same baking process, and the specific data are shown in tables 1 and 2 below.
TABLE 1
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Hardness of | 90A | 90A | 91A | 90A | 91A |
| Tensile strength/MPa | 45 | 38 | 41 | 42 | 40 |
| Elongation/percent | 489 | 420 | 440 | 390 | 400 |
TABLE 2
| Example 1 | Example 2 | Example 3 | |
| Hardness of | 90A | 90A | 90A |
| Tensile strength/MPa | 45 | 48 | 50 |
| Elongation/percent | 489 | 460 | 440 |
The comparison between the example 1 and the comparative example 1 shows that the strength of the product can be obviously improved by using the optimized adding process and simultaneously matching the nucleating agent and the polyfunctional group chain extender, and the elongation rate is also improved, while the comparison between the example 1 and the comparative examples 1-3 shows that the addition of the nucleating agent and the independent use of the polyfunctional group chain extender are both beneficial to improving the tensile strength performance of the product, but the effect is not obvious, and the comparison between the example 1 and the comparative example 4 shows that the nucleating agent and the polyfunctional group chain extender are not added by adopting the optimized process, so that the effect on the strength of the product is limited, and the elongation rate is obviously reduced.
The comparison of the embodiments 1 to 3 shows that the usage amount of the nucleating agent and the polyfunctional chain extender is increased in a certain range, and the product strength can be further increased.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the high-performance TPU material is characterized by comprising the following raw materials in parts by mass:
the preparation method comprises the following steps: adding polyol, a bifunctional chain extender and isocyanate into a co-rotating double-screw reaction extruder from a pouring gate, adding a nucleating agent in a 3 rd zone of the double-screw reaction extruder in a side feeding manner, adding a polyfunctional chain extender in a 6 th zone of the double-screw reaction extruder in a side feeding manner, and performing reaction extrusion to obtain the high-performance TPU material.
2. The production method according to claim 1, wherein the melting point of the nucleating agent is not less than 180 ℃.
3. The method according to claim 1, wherein the nucleating agent is in the form of powder having a particle size of 100nm to 50 μm.
4. The method of claim 1, wherein the nucleating agent comprises at least one of montmorillonite, silica, multi-walled carbon nanotubes, calcium carbonate, glass microspheres, thermoplastic polyester elastomer powder, nylon powder, and diatomaceous earth.
5. The preparation method of claim 1, wherein the multifunctional chain extender comprises one or a mixture of any of glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolacrylate and pentaerythritol.
6. The preparation method according to claim 1, wherein the high-performance TPU material further comprises the following raw materials in parts by mass:
0.1 to 0.7 portion of primary antioxidant,
0.1 to 0.5 portion of auxiliary antioxidant,
0.1-0.9 part of lubricant.
7. The preparation method of claim 6, wherein in the preparation method, the polyol, the primary antioxidant, the secondary antioxidant and the lubricant are uniformly mixed and then added into the co-rotating twin-screw reaction extruder together with the bifunctional chain extender and the isocyanate from a pouring gate.
8. The high-performance TPU material prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210470634.8A CN114656613A (en) | 2022-04-28 | 2022-04-28 | High-performance TPU material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210470634.8A CN114656613A (en) | 2022-04-28 | 2022-04-28 | High-performance TPU material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114656613A true CN114656613A (en) | 2022-06-24 |
Family
ID=82036941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210470634.8A Pending CN114656613A (en) | 2022-04-28 | 2022-04-28 | High-performance TPU material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656613A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150210799A1 (en) * | 2012-08-06 | 2015-07-30 | Kuraray Co., Ltd. | Thermoplastic polyurethane and a composition thereof |
| CN105693971A (en) * | 2016-01-29 | 2016-06-22 | 上海益弹新材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN107141441A (en) * | 2017-06-02 | 2017-09-08 | 东莞市吉鑫高分子科技有限公司 | A kind of low-refraction high transparency TPUE and preparation method thereof |
| CN107474210A (en) * | 2017-06-28 | 2017-12-15 | 苏州奥斯汀新材料科技有限公司 | A kind of method for preparing thermoplastic polyurethane elastomer of resistance to flexion resistant to bending |
-
2022
- 2022-04-28 CN CN202210470634.8A patent/CN114656613A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150210799A1 (en) * | 2012-08-06 | 2015-07-30 | Kuraray Co., Ltd. | Thermoplastic polyurethane and a composition thereof |
| CN105693971A (en) * | 2016-01-29 | 2016-06-22 | 上海益弹新材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN107141441A (en) * | 2017-06-02 | 2017-09-08 | 东莞市吉鑫高分子科技有限公司 | A kind of low-refraction high transparency TPUE and preparation method thereof |
| CN107474210A (en) * | 2017-06-28 | 2017-12-15 | 苏州奥斯汀新材料科技有限公司 | A kind of method for preparing thermoplastic polyurethane elastomer of resistance to flexion resistant to bending |
Non-Patent Citations (1)
| Title |
|---|
| 山西省化工研究所编: "《聚氨酯弹性体手册》", vol. 1, 化学工业出版社, pages: 416 - 417 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3549983B1 (en) | Process for manufacturing tpu alloy material by in-situ compatibilization | |
| CN110229461B (en) | TPU (thermoplastic polyurethane) in-situ polymerization toughened polyformaldehyde material and preparation method thereof | |
| CN112812515A (en) | Degradable foaming material and preparation method thereof | |
| CN112778684B (en) | Talcum powder filled polypropylene material with high yield strain and low-temperature impact resistance and preparation method thereof | |
| CN102504504B (en) | High-impact-resistance heat-resistant polylactic acid alloy material and preparation method thereof | |
| CN111534099B (en) | Low-cost low-fiber-floating high-glass-fiber-content reinforced polyphenylene sulfide composite material and preparation method thereof | |
| CN112159564A (en) | Low-density and low-emission polypropylene material and preparation method thereof | |
| CN104910604A (en) | Matt polycarbonate styrene resin alloy and preparation method thereof | |
| CN113637283A (en) | High-strength high-resilience TPE (thermoplastic elastomer) thermoplastic elastomer and preparation method thereof | |
| CN110563912A (en) | High-transparency low-shrinkage thermoplastic polyurethane elastomer and preparation method thereof | |
| CN114656613A (en) | High-performance TPU material and preparation method thereof | |
| CN110272528B (en) | Process for preparing thermoplastic polyurethanes | |
| CN111875952B (en) | TPU (thermoplastic polyurethane) grafted-OBC (on-board diagnostics) modified thermoplastic polyurethane elastomer foam material and preparation method thereof | |
| CN113621132A (en) | High-melt-strength low-melt-index thermoplastic polyester elastomer and preparation method thereof | |
| CN113999518B (en) | Preparation method of TPU/POE alloy | |
| CN109705302B (en) | Thermoplastic polyurethane for producing high-resilience high-brightness foam beads and preparation method thereof | |
| CN114369359A (en) | High-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material and preparation method thereof | |
| CN112194891A (en) | Low-cost high-strength TPU film and preparation method thereof | |
| CN113502047A (en) | Carbon fiber reinforced TPU material and preparation method thereof | |
| CN113861379A (en) | Manufacturing method of TPU (thermoplastic polyurethane) medical cable and medical cable | |
| CN110922746A (en) | TPU plastic particle processing technology for improving peeling and watermark phenomena | |
| CN112430389B (en) | Reinforced and toughened TPU material and preparation method thereof | |
| CN118406351A (en) | Biodegradable film and preparation method thereof | |
| CN112480651B (en) | Colored ultrathin TPU film and preparation method thereof | |
| CN109721993A (en) | A kind of polycarbonate composite material and epoxy-functional graft polymers are in the application for improving polycarbonate glossiness and process window |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220624 |