CN105384905A - TPU (Thermoplastic Polyurethane Elastomer) material and preparation method thereof - Google Patents
TPU (Thermoplastic Polyurethane Elastomer) material and preparation method thereof Download PDFInfo
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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
- C08G18/6633—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
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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
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
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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
- C08G18/42—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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of TPU (Thermoplastic Polyurethane Elastomer), and in particular relates to a TPU material and a preparation method thereof. The TPU material is prepared from the following raw materials in percentage by weight: 44 to 56 percent of polymer polyol, 27 to 42 percent of diisocyanate, 11 to 16.5 percent of chain extender, 0.3 to 1 percent of wear-resistant fortifier, 0.3 to 0.5 percent of lubricating agent, 0.2 to 0.4 percent of antioxidant and 0.02 to 0.05 percent of catalyst. According to the preparation method provided by the invention, a continuous process is adopted, the quality of a product is stable, and a higher production efficiency is realized in comparison with that of a casting TPU; the polymer polyol is adopted as a raw material, the high cost of a PTMG type polyurethane material is reduced and meanwhile, the elastomer is endowed with good mechanical properties.
Description
Technical field
The invention belongs to technical field of polyurethane elastomer, be specifically related to a kind of TPU material and preparation method thereof.
Background technology
Thermoplastic polyurethane elastomerics (TPU), because having special soft or hard section block copolymer structure, has high strength, high-modulus and excellent mechanical property.Compare with other elastomer materials, TPU durometer level is wide, in wear resisting property, elasticity and mechanical property etc., have good over-all properties, therefore obtains paying close attention to more and more widely in fields such as castor, axle sleeve or sieve plates.TPU is applied to the field such as castor or axle sleeve, requires that it has good supporting capacity and rigidity, also needs to have good resilience and wear resisting property simultaneously.Polyester type TPU increases along with hardness, and the tensile strength of TPU, tear strength and rigidity can increase, but the elasticity of TPU and elongation at break can reduce simultaneously.Maintain good rebound performance while selecting polyether-type TPU that high rigidity can be obtained, but polyether-type TPU wear resistance is relative with mechanical property poor.
The casting type polyurethane elastomer that it is Material synthesis that patent CN101633717B reports with polytetrahydrofuran polyol (PTMG), its hardness is 86 ~ 93A, and rebound degree is greater than 70%, and tear strength is greater than 100KN/m; It is the performed polymer of 5 ~ 15% that JP8231669 reports PTMG blending and MDI synthesis NCO content, then adopts alcohol chain extension to obtain polyurethane elastomer, and its rebound degree is greater than 70%, and hardness is 70-85A, and tear strength is 63 ~ 70KN/m.
The polyurethane elastomer of above-mentioned data synthesis take PTMG as raw material, all obtains higher rebound resilience and mechanical property.But its sintetics is casting type polyurethane elastomer, belongs to thermoset polyurethane material, when for processing the product such as castor or axle sleeve, there is the problems such as operation efficiency is low, scrap rate is high and cannot reuse.Soft section of polyurethane elastomer adopts pure PTMG to be raw material, the Shortcomings such as the mechanical property of product, wear resisting property and rigidity.
Summary of the invention
The object of this invention is to provide a kind of TPU material, there is excellent wear resisting property and rigidity, excellent mechanical property; Invention also provides the preparation method of TPU material, scientific and reasonable, simple, process for processing efficiency is high.
TPU material of the present invention, be made up of the raw material of following weight percent:
Described polymer polyatomic alcohol is polyester polyol, and number-average molecular weight is 2000.The preferred polybutylene glyool adipate of polyester polyol or polyhexamethylene adipate glycol.
Described vulcabond is 4,4'-diphenylmethanediisocyanate (MDI-100), phenylene-Isosorbide-5-Nitrae-vulcabond, naphthalene-1,5-vulcabond or ditane-3,3 '-dimethoxy-4 ', the one in 4 '-vulcabond.
Described chainextender is one or more in BDO (Isosorbide-5-Nitrae-BDO), quinhydrones-bis-(beta-hydroxyethyl) ether (HQEE) or 1,6-hexylene glycol (1,6HG).
Described resistance to grinding reinforcing agent is that organic silicon polyether is polymer-modified, one or more in aralkyl modified polyorganosiloxane or silicone plastics lubricant.
Described lubricant is one or more in stearic acid acyl, amine hydroxybenzene, erucicamide or ethylene bis stearic acid amide.
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol (BHT), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), poly-(dipropylene glycol) phenyl phosphites (PDP) or 4,4'-split in isopropyl diphenyl base C12-15-alcohol phosphorous acid ester (PDAP) one or more.
Described catalyzer is organic tin catalyzer.
Described organic tin catalyzer is one or more in stannous octoate (T-9), dibutyl tin laurate (T-12) or 100E.
The durometer level of TPU material of the present invention in 90-98A, DIN abrasion performance at 22-28mm
3.
The preparation method of TPU material of the present invention, step is as follows:
(1) polymer polyatomic alcohol, antioxidant, lubricant, resistance to grinding reinforcing agent and catalyzer are joined and be furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 95-105 DEG C; Be positioned over by vulcabond in B reactor, set temperature is 60-75 DEG C; Be positioned over by chainextender in C reactor, set temperature is 40-60 DEG C;
(2) treat that each temperature of reaction kettle is stablized; by the filling system with accurate measurement; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixture is homogeneous reaction conveying in twin screw cylindrical shell, is cut into the elliptical particles of uniform particle sizes after plasticizing through underwater pelletizer.
The present invention compared with prior art, has following beneficial effect:
The present invention adopts continuous process to produce, product with stable quality, has the process for processing efficiency higher than casting type polyurethane elastomer; Employing polyester polyol is raw material, reduces the high cost of PTMG type polyurethane material, gives elastomerics excellent mechanical property simultaneously.By introducing preferred composite plastic lubricant, under compared with the condition of few additive, obtain excellent wear resisting property and rigidity, product abrasion performance is lower than 28mm
3, obtain a wide range of applications in fields such as castor, axle sleeve and wearing-resistant sieve boards.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Raw material is composed as follows, according to weight percent meter:
Preparation technology: weigh each component raw material by weight percentage, by the polybutylene glyool adipate of precise, amine hydroxybenzene, 1010, PDP, R-170S and catalyzer join is furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 100 DEG C; Be positioned over by MDI-100 in B reactor, set temperature is 60 DEG C; Be positioned over by Isosorbide-5-Nitrae-BG in C reactor, set temperature is 45 DEG C; Treat that each temperature of reaction kettle is stablized; by metering filling system; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixing head rotating speed is set to 5000rpm/min; extruder temperature 150 ~ 200 DEG C is set; screw speed 220rpm/min is set, makes mixture homogeneous reaction plasticizing in twin screw cylindrical shell, be cut into the elliptical particles of uniform particle sizes through underwater pelletizer.
Embodiment 2
Raw material is composed as follows, according to weight percent meter:
Preparation technology: weigh each component raw material by weight percentage, by the polybutylene glyool adipate of precise, amine hydroxybenzene, two ethylene stearic amide, 1010, PDP, SI-69 and catalyzer join is furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 100 DEG C; Be positioned over by MDI-100 in B reactor, set temperature is 60 DEG C; Be positioned over by Isosorbide-5-Nitrae-BG in C reactor, set temperature is 45 DEG C; Treat that each temperature of reaction kettle is stablized; by metering filling system; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixing head rotating speed is set to 5000rpm/min; extruder temperature 145 ~ 200 DEG C is set; screw speed 220rpm/min is set, makes mixture homogeneous reaction plasticizing in twin screw cylindrical shell, be cut into the elliptical particles of uniform particle sizes through underwater pelletizer.
Embodiment 3
Raw material is composed as follows, according to weight percent meter:
Preparation technology: weigh each component raw material by weight percentage, by the polybutylene glyool adipate of precise, amine hydroxybenzene, stearic amide, 1010, PDAP, R-170S, E-2203 and catalyzer join is furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 100 DEG C; Be positioned over by MDI-100 in B reactor, set temperature is 60 DEG C; Be positioned over by HQEE in C reactor, set temperature is 105 DEG C; Treat that each temperature of reaction kettle is stablized; by metering filling system; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixing head rotating speed is set to 5500rpm/min; extruder temperature 145 ~ 195 DEG C is set; screw speed 220rpm/min is set, makes mixture homogeneous reaction plasticizing in twin screw cylindrical shell, be cut into the elliptical particles of uniform particle sizes through underwater pelletizer.
Comparative example 1
Raw material is composed as follows, according to weight percent meter:
Preparation technology: weigh each component raw material by weight percentage, by the polybutylene glyool adipate of precise, 1010, PDP and catalyzer join is furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 100 DEG C; Be positioned over by MDI-100 in B reactor, set temperature is 60 DEG C; Be positioned over by Isosorbide-5-Nitrae-BG in C reactor, set temperature is 45 DEG C; Treat that each temperature of reaction kettle is stablized; by metering filling system; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixing head rotating speed is set to 5000rpm/min; extruder temperature 145 ~ 200 DEG C is set; screw speed 220rpm/min is set, makes mixture homogeneous reaction plasticizing in twin screw cylindrical shell, be cut into the elliptical particles of uniform particle sizes through underwater pelletizer.
The mechanical property of the said products is according to following standard detection: shore a hardness presses GB/T531.1-2008 test; Tensile strength is tested according to GB/T528-2009; Tear strength is according to GB/T529-2009; Rebound performance is tested according to GB/T1681-2009; Abrasion resistance is tested according to GB/T9867-2008.Properties detected result is in table 1.
Table 1TPU material property detected result
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Hardness (shore A) | 98 | 95 | 91 | 91 |
| Tensile strength (MPa) | 46 | 44 | 40 | 42 |
| Tear strength (MPa) | 172 | 156 | 152 | 141 |
| 100% tensile modulus (MPa) | 13 | 11 | 10.5 | 8.5 |
| Resilience (%) | 28 | 30 | 30 | 31 |
| Abrasion performance (mm 3) | 22 | 24 | 28 | 75 |
Polyurethane Thermoplastic Elastomer provided by the invention, hardness is greater than 90A, and have excellent mechanical property and higher rebound degree, product DIN abrasion performance is lower than 28mm
3, can be widely used in and the fields such as high castor, axle sleeve and sieve plate are required to carrying and abrasion performance.Product injectable or extrude processing, efficiently simple to operate, waste material is reusable, pollution-free waste.
Claims (10)
1. a TPU material, is characterized in that being made up of the raw material of following weight percent:
2. TPU material according to claim 1, it is characterized in that described polymer polyatomic alcohol is polyester polyol, number-average molecular weight is 2000.
3. TPU material according to claim 1, is characterized in that described vulcabond is 4,4'-diphenylmethanediisocyanate, phenylene-1,4-vulcabond, naphthalene-1,5-vulcabond or ditane-3,3 '-dimethoxy-4 ', the one in 4 '-vulcabond.
4. TPU material according to claim 1, is characterized in that described chainextender is one or more in BDO, quinhydrones-bis-(beta-hydroxyethyl) ether or 1,6-hexylene glycol.
5. TPU material according to claim 1, is characterized in that described resistance to grinding reinforcing agent is that organic silicon polyether is polymer-modified, one or more in aralkyl modified polyorganosiloxane or silicone plastics lubricant.
6. TPU material according to claim 1, is characterized in that described lubricant is one or more in stearic acid acyl, amine hydroxybenzene, erucicamide or ethylene bis stearic acid amide.
7. TPU material according to claim 1, it is characterized in that described antioxidant is 2,6-di-tert-butyl-4-methy phenol, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, poly-(dipropylene glycol) phenyl phosphites or 4,4'-split in isopropyl diphenyl base C12-15-alcohol phosphorous acid ester one or more.
8. TPU material according to claim 1, is characterized in that described catalyzer is organic tin catalyzer.
9. TPU material according to claim 1, is characterized in that its durometer level in 90-98A, DIN abrasion performance at 22-28mm
3.
10. a preparation method for the arbitrary described TPU material of claim 1-9, is characterized in that step is as follows:
(1) polymer polyatomic alcohol, antioxidant, lubricant, resistance to grinding reinforcing agent and catalyzer are joined and be furnished with in the A reactor of mechanical stirring and thermometer, set temperature is 95-105 DEG C; Be positioned over by vulcabond in B reactor, set temperature is 60-75 DEG C; Be positioned over by chainextender in C reactor, set temperature is 40-60 DEG C;
(2) treat that each temperature of reaction kettle is stablized; by the filling system with accurate measurement; feed composition in A/B/C reactor is injected twin screw reaction machine spout through the mixing of high speed rotating mixing head; mixture is homogeneous reaction conveying in twin screw cylindrical shell, is cut into the elliptical particles of uniform particle sizes after plasticizing through underwater pelletizer.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279633A (en) * | 2016-08-31 | 2017-01-04 | 温州东润新材料科技有限公司 | A kind of super abrasive Polyurethane Thermoplastic Elastomer and preparation method thereof |
| CN106397715A (en) * | 2016-08-31 | 2017-02-15 | 温州东润新材料科技有限公司 | Polishable thermoplastic polyurethane elastomer and preparation method thereof |
| CN106957523A (en) * | 2017-03-15 | 2017-07-18 | 东莞市吉鑫高分子科技有限公司 | It is a kind of for thermoplastic polyurethane of tire tread and preparation method thereof |
| CN107312154A (en) * | 2017-07-17 | 2017-11-03 | 中天科盛（上海）企业发展股份有限公司 | A kind of antibacterial hydrolysis TPUE |
| CN107778432A (en) * | 2016-08-29 | 2018-03-09 | 江苏绿艳高分子材料有限公司 | A kind of TPU materials |
| CN108034226A (en) * | 2017-12-27 | 2018-05-15 | 清远新力化机有限公司 | A kind of high wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN108659517A (en) * | 2018-05-29 | 2018-10-16 | 广东旭坤新特材料科技有限公司 | One kind is for the saturating lacquer painting protective film basement membranes of TPU high, TPU membrane and preparation method thereof |
| CN109266290A (en) * | 2018-08-31 | 2019-01-25 | 浙江华峰热塑性聚氨酯有限公司 | Response type thermoplastic polyurethane and preparation method thereof |
| WO2019213932A1 (en) * | 2018-05-11 | 2019-11-14 | Covestro Deutschland Ag | Thermoplastic polyurethane composition and use thereof |
| CN110903634A (en) * | 2019-11-29 | 2020-03-24 | 清远新力化机有限公司 | Low-shrinkage rapid-forming TPU (thermoplastic polyurethane) for rubber wheel injection molding and preparation method thereof |
| CN111434718A (en) * | 2019-01-11 | 2020-07-21 | 汉达精密电子(昆山)有限公司 | TPU conductive material and product thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778432A (en) * | 2016-08-29 | 2018-03-09 | 江苏绿艳高分子材料有限公司 | A kind of TPU materials |
| CN106397715A (en) * | 2016-08-31 | 2017-02-15 | 温州东润新材料科技有限公司 | Polishable thermoplastic polyurethane elastomer and preparation method thereof |
| CN106279633A (en) * | 2016-08-31 | 2017-01-04 | 温州东润新材料科技有限公司 | A kind of super abrasive Polyurethane Thermoplastic Elastomer and preparation method thereof |
| CN106957523A (en) * | 2017-03-15 | 2017-07-18 | 东莞市吉鑫高分子科技有限公司 | It is a kind of for thermoplastic polyurethane of tire tread and preparation method thereof |
| CN107312154A (en) * | 2017-07-17 | 2017-11-03 | 中天科盛（上海）企业发展股份有限公司 | A kind of antibacterial hydrolysis TPUE |
| CN108034226A (en) * | 2017-12-27 | 2018-05-15 | 清远新力化机有限公司 | A kind of high wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| WO2019213932A1 (en) * | 2018-05-11 | 2019-11-14 | Covestro Deutschland Ag | Thermoplastic polyurethane composition and use thereof |
| CN112771093A (en) * | 2018-05-11 | 2021-05-07 | 科思创知识产权两合公司 | Thermoplastic polyurethane composition and use thereof |
| CN108659517A (en) * | 2018-05-29 | 2018-10-16 | 广东旭坤新特材料科技有限公司 | One kind is for the saturating lacquer painting protective film basement membranes of TPU high, TPU membrane and preparation method thereof |
| CN108659517B (en) * | 2018-05-29 | 2021-03-02 | 广东旭坤新特材料科技有限公司 | Base film for TPU (thermoplastic polyurethane) high-transparency paint surface protective film, TPU film and preparation method of TPU film |
| CN109266290B (en) * | 2018-08-31 | 2020-11-24 | 浙江华峰热塑性聚氨酯有限公司 | Reactive thermoplastic polyurethane and preparation method thereof |
| CN109266290A (en) * | 2018-08-31 | 2019-01-25 | 浙江华峰热塑性聚氨酯有限公司 | Response type thermoplastic polyurethane and preparation method thereof |
| CN111434718A (en) * | 2019-01-11 | 2020-07-21 | 汉达精密电子(昆山)有限公司 | TPU conductive material and product thereof |
| CN110903634A (en) * | 2019-11-29 | 2020-03-24 | 清远新力化机有限公司 | Low-shrinkage rapid-forming TPU (thermoplastic polyurethane) for rubber wheel injection molding and preparation method thereof |
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Application publication date: 20160309 |