CN102617820A - Continuous production method of thermoplastic polyurethane elastic body and special system of continuous production method - Google Patents
Continuous production method of thermoplastic polyurethane elastic body and special system of continuous production method Download PDFInfo
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- CN102617820A CN102617820A CN2012101009220A CN201210100922A CN102617820A CN 102617820 A CN102617820 A CN 102617820A CN 2012101009220 A CN2012101009220 A CN 2012101009220A CN 201210100922 A CN201210100922 A CN 201210100922A CN 102617820 A CN102617820 A CN 102617820A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
Abstract
The invention discloses a continuous production method of a thermoplastic polyurethane elastic body TPU and a special system of the continuous production method, which are characterized in that an extruder and a belt reactor gradually react to synthesize the thermoplastic polyurethane elastic body; the extruder is used for finishing early-stage mixing and initial-stage reaction; the belt reactor provides post-stage reaction and crystallization; through a sectioned reaction, the material staying time can be adjusted so as to give sufficient crystallization time to the materials; and the molecular weight of the TPU can be controlled, so as to effectively eliminate a gelatinization phenomenon; and the manufactured TPU granules are uniform and have very good physical and mechanical properties.
Description
Technical field:
The present invention relates to the high molecular polymer preparing technical field, is a kind of continuous production method and dedicated system of TPUE specifically.
Background technology:
TPUE (TPU) but have good elasticity body performance and thermoplastic processibility, be widely used in fields such as trolley part, sealing member, medical instruments, cable, tubing, fire hose, footwear material.As write in Shanxi-Prov Inst of Chemical Industry " the polyurethane elastomer handbook (and Chemical Industry Press, 2005, introduced relevant TPU preparation, performance and application in detail in P398).
Well-known preparation technology is a twin screw extruder technology, and this method is that raw material is metered into polymerization and granulation in the double-screw reactor.There is following problem in traditional twin screw extruder technology: 1, this expressing technique is fairly simple, and mixing and reaction are carried out simultaneously, but the product homogeneity that makes by this way is poor; 2, the residence time of material in forcing machine limited, be generally less than 1 minute, make reaction restive, cause product reaction not exclusively or gel occurs; 3, starting raw material temperature of reaction in reactor drum is higher, and generation is not hoped and uncontrollable crosslinked allophanate secondary reaction easily.
In order to improve constantly the quality of TPU, satisfy many-sided demand, a lot of TPU manufacturing enterprises all actively are devoted to the improvement of production technique.Bayer company produces TPU through prepolymer process in CN1281474; Mainly be earlier with polyvalent alcohol and isocyanic ester at the tubular reactor reaction prepolymer; Later stage reacts with chainextender prepolymer and generates TPU in double-screw reactor; But the later stage chain extending reaction all through the Couble screw rod high-temp reaction, causes producing heterogeneity and uncontrollable secondary reaction.Because prepolymer viscosity is big, influence is measured simultaneously, complicated operation, and the cleaning difficulty causes obtaining satisfied effect.
Germany Bayer AG has announced continuous technology of preparing of a kind of TPUE multistage in patent CN1289561C.The main process of this technology is following: at first the part polyvalent alcohol is mixed generating prepolymer by static mixer with isocyanic ester; React through tubular reactor after then this prepolymer being mixed by static mixer with the residue polyvalent alcohol; Resultant directly joins the ingress of twin screw and reacts in twin screw with chainextender, and the most all the material extruding pelletization makes finished product TPU.The twin screw technology that this technology is more traditional can prepare the complicated more TPU of composition, but this method operating procedure very complicated is had higher requirement to actual production control aspect.Also can't avoid simultaneously the generation of the pyroreaction and the crosslinking reaction in later stage.Yantai Wanhua New Material Technology Co., Ltd attempts to prolong the residence time in screw rod through two rank machine in patent CN101020737, but because pyroreaction causes gel more, the product homogeneity is poor.
Present twin screw technology and prepolymer process are not all controlled the TPU late phase reaction effectively, therefore are easy to generate the super large molecule, and the product heterogeneity generates insolubles and gel easily.
Summary of the invention:
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and a kind of continuous production method of TPUE is provided.
Another order of the present invention provides a kind of dedicated system of TPUE continuous production method.
The present invention mainly solves existing twin screw technology and prepolymer process continuous production TPUE owing to effectively the TPU late phase reaction is not controlled; Be easy to generate the super large molecule; The product heterogeneity generates problems such as insolubles and gel easily.
Technical scheme of the present invention is: a kind of continuous production method of TPUE, and its special character is to comprise following process step:
A mixes and initial reaction in earlier stage, and feed composition is measured in proportion, is poured into forcing machine first heating zone by casting molding machine, regulates the Heating temperature in forcing machine rotating speed He Ge district, and material is further mixed, and carries out initial reaction;
B late phase reaction and crystallization, the material of initial reaction gets into belt reactor through junctor, the heating of belt reactor leading portion; The later stage cooling; Temperature is respectively distinguished in control, in belt reactor, carries out late phase reaction and crystallization, obtains the flap that reacts completely of higher molecular weight;
The c finished product is pulverized flap through kibbler, obtain finished product TPU particle.
Further, said forcing machine machine section first Heating Zone Temperature is 90 ℃, and all the other several Heating Zone Temperature are 140-180 ℃.
Further, said belt reactor heating zone temperature is 80-210 ℃, and the cooling section temperature-stable is 70 ℃, and the residence time is 8-30 minute in belt reactor.
The continuous production method of a kind of TPUE of the present invention is a surface reaction owing to produce isocyanate material, polyvalent alcohol, the chainextender of TPUE, need three contacted fully and can react completely.Forcing machine machine section mainly is that mixture makes the material initial reaction, and actual material is lower in this elementary reaction degree, and molecular weight does not also reach the numerical value that needs.Therefore this section controlled temperature mainly is in order to satisfy the needs of mixing of materials and initial reaction.According to the reaction characteristics of TPU self, controlled temperature will guarantee that material can initiation reaction in the well-mixed while, therefore, and low about 90 ℃ of forcing machine machine section first Heating Zone Temperature; Because TPU is thermopositive reaction, so the temperature of several heating zone, back reaches 140-180 ℃.Therefore forcing machine provides pyroreaction, and enough strong shearing is provided, and each component mixing of TPU and initial reaction are increased chain, and the residence time of material is shorter; Less than 1 minute, the material of complete reaction was not extruded on belt reactor with certain thickness through T type mouth mould, added at band on the belt reactor of temperature function to accomplish late phase reaction; The sheet to the belt of trickling is thick to be 1-10mm, and with the sheet material heating, heating zone can adopt the thermopair heating in course of conveying; Heating temperature is 80-210 ℃, and cooling section can adopt cold wind to cool off, and temperature-stable is 70 ℃; The heat-up time of TPU on belt is 5-20 minute, and be 3-10 minute cooling time, and the reaction times was controlled at 8-30 minute; Slowly accomplish late phase reaction and crystallization, then cooled sheet material is pulverized through kibbler, obtain the TPU pulverized particles.
Realize the dedicated system of TPUE continuous production method, its special character is that it comprises storage tank, casting molding machine, forcing machine, belt reactor, kibbler and wrapping machine, connects through junctor between said forcing machine and the belt reactor; Said forcing machine is twin screw extruder or single screw extrusion machine, and screw extrusion press provides mix and initial reaction early stage; Said belt reactor is the steel band or the teflin tape of band temperature controlling function, and belt reactor provides late phase reaction and crystallization.
Further; Said single screw rod and twin screw extruder all can be used for reaction and extrude; The degree of mixing that begins material because of reaction is great to the reaction result influence; Make the material initial reaction and forcing machine machine section mainly plays a part mixture, so the optimal selection of forcing machine machine section is a twin screw extruder; Twin screw extruder is any one in type, incorgruous type, engagement type, the non-engagement type in the same way; Preferred tight engagement type twin screw extruder in the same way.
Further, described junctor is a T type mouth mould.
The TPU that continuation method of the present invention and dedicated system are fit to can be an any kind, like polyester type TPU, and polyether-type TPU, types such as polycarbonate type TPU.
Compared with present technology the continuous production method of a kind of TPUE of the present invention and dedicated system have outstanding substantive features and marked improvement, mix and initial reaction through the preferred twin screw extruder of forcing machine, and late phase reaction reacts product and secondary crystallization through the belt reactor of band temperature controlling function; Material reaction is more abundant, and the degree that is separated height has increased the product crystallization; The tensile strength and the Tc of product have been improved; And carry out through reacting in batches, suppressed the generation of super large molecule, reduced product gel and insolubles effectively; Improve the use range of product, can meet the demands than high product.
Description of drawings:
Fig. 1 is a connection synoptic diagram of the present invention.
Embodiment:
In order to understand better and to implement, provide specific embodiment below in conjunction with accompanying drawing and specify the present invention.
The present invention describes through following embodiment and reference examples:
The TPU prescription that following reference examples and embodiment adopt:
Ditan 4,4 '-vulcabond (MDI) 32.6% (weight)
Gather hexanodioic acid 1,4 butyleneglycol-ester (PBA, molar mass 2000g/mol) 58.1% (weight)
1,4-butyleneglycol (BDO) (molar mass is 90.123g/mol, and functionality is 2) 8.8% (weight)
Catalyzer: stannous octoate 0.011% (weight)
Oxidation inhibitor: Irganox
1,010 0.5% (weight)
Reference examples 1; With the polyester polyol (catalyzer and oxidation inhibitor directly join in the polyvalent alcohol) that is stored in the mechanical storage tank, vulcabond MDI (diphenylmethanediisocyanate) (43 ℃ of storing temps), chainextender BDO (1; The 4-butyleneglycol) (60 ℃ of storing temp); Through winning the forcing machine machine section that the thunder casting molding machine is poured into forcing machine, the mixing head rotating speed is 3600RPM, and control forcing machine machine section first Heating Zone Temperature is 180 ℃; All the other several Heating Zone Temperature are 200 ℃ ± 5 ℃, and screw speed is controlled to be 40Hz; Obtain the TPU particle through granulation underwater.
Reference examples 2; With the polyester polyol (catalyzer and oxidation inhibitor directly join in the polyvalent alcohol) that is stored in the mechanical storage tank; Vulcabond MDI (diphenylmethanediisocyanate) is pre-mixed through tubular reactor and generates prepolymer, is poured into the forcing machine machine section of forcing machine then by rich thunder casting molding machine with chainextender BDO (1, the 4-butyleneglycol); The mixing head rotating speed is 3600RPM; Control forcing machine machine section first Heating Zone Temperature is 180 ℃, and all the other several Heating Zone Temperature are 200 ℃ ± 5 ℃, and screw speed is controlled to be 40Hz; Obtain the TPU particle through granulation underwater.
Embodiment 1; Referring to Fig. 1, select storage tank 1 according to the raw material storage amount, select rich thunder casting molding machine 2; Selection length is that 2320mm, diameter are that 71mm, screw slenderness ratio L/D are 32; The type of the tight engagement in the same way twin screw extruder 3 that 8 heating zone are arranged, select wide cut be 1.2 meters T type mouth mould as junctor 7, to select length be 20 meters steel bands or adopt teflin tape, add the baking oven runner as belt reactor 4; Select conventional kibbler 5 simultaneously; With connecting through T type mouth mould junctor 7 between forcing machine 3 and the belt reactor 4; Pack through wrapping machine 6 at last, form dedicated system of the present invention by aforesaid device.
Embodiment 2; Adopt the system of embodiment 1; With polyester polyol (catalyzer and oxidation inhibitor directly join in the polyvalent alcohol), vulcabond MDI (diphenylmethanediisocyanate) and the chainextender BDO (1, the 4-butyleneglycol) that are stored in the storage tank, be poured into the forcing machine section of forcing machine with rich thunder casting molding machine; The mixing head rotating speed is 3600RPM; Control forcing machine machine section first Heating Zone Temperature is 90 ℃, and all the other several Heating Zone Temperature are 140 ℃-180 ℃, and screw speed is controlled to be 40Hz; Through T type mouth mould TPU is cast on the belt reactor, cast thickness is 4mm, and wide cut is 1.2 meters a sheet material; Preceding 5 sections heating in the baking oven runner, temperature are 130 degree, back 3 district's wind cooling temperature lowerings; Temperature-stable is 70 degree, and the residence time is 20 minutes in the baking oven runner; At last sheet material is pulverized, obtained the TPU pulverized particles, pack through wrapping machine.
Embodiment 3; Adopt the system of embodiment 1; With polyester polyol (catalyzer and oxidation inhibitor directly join in the polyvalent alcohol), vulcabond MDI (diphenylmethanediisocyanate) and the chainextender BDO (1, the 4-butyleneglycol) that are stored in the storage tank, be poured into the forcing machine section of forcing machine with rich thunder casting molding machine; The mixing head rotating speed is 3600RPM; Control forcing machine machine section first Heating Zone Temperature is 90 ℃, and all the other several Heating Zone Temperature are 140 ℃-180 ℃, and screw speed is controlled to be 40Hz; Through T type mouth mould TPU is cast on the belt reactor, cast thickness is 1mm, and wide cut is 1.2 meters a sheet material; Preceding 5 sections heating in the baking oven runner, temperature are 80 degree, back 3 district's wind cooling temperature lowerings; Temperature-stable is 70 degree, and the residence time is 8 minutes in the baking oven runner; At last sheet material is pulverized, obtained the TPU pulverized particles, pack through wrapping machine.
Embodiment 4; Adopt the system of embodiment 1; With polyester polyol (catalyzer and oxidation inhibitor directly join in the polyvalent alcohol), vulcabond MDI (diphenylmethanediisocyanate) and the chainextender BDO (1, the 4-butyleneglycol) that are stored in the storage tank, be poured into the forcing machine section of forcing machine with rich thunder casting molding machine; The mixing head rotating speed is 3600RPM; Control forcing machine machine section first Heating Zone Temperature is 90 ℃, and all the other several Heating Zone Temperature are 140 ℃-180 ℃, and screw speed is controlled to be 40Hz; Through T type mouth mould TPU is cast on the belt reactor, cast thickness is 10mm, and wide cut is 1.2 meters a sheet material; Preceding 5 sections heating in the baking oven runner, temperature are 210 degree, back 3 district's wind cooling temperature lowerings; Temperature-stable is 70 degree, and the residence time is 30 minutes in the baking oven runner; At last sheet material is pulverized, obtained the TPU pulverized particles, pack through wrapping machine.
The TPU product rerum natura of the foregoing description and reference examples production is contrasted, and the result sees table 1.
Table 1
Above-mentioned, the film gel is judged in the following manner: the TPU granule materials is extruded 4.5-6 centimetre wide at diameter for the fusing of 30mm single screw extrusion machine and through T type mouth mould, and the film of 6-10 mm thick is rectangular.
Compression set is tested through ASTMD395 B method, and test bars is that diameter is 13mm, the cylinder of 6mm.70 ℃ of temperature controls, placed 22 hours, compress under 25% ℃ the condition and test.
Can find out by above result, adopt the product of system's production of forcing machine and belt reactor can improve intensity, effectively reduce the product gel, enlarge the product use range.
Claims (7)
1. the continuous production method of a TPUE is characterized in that comprising following process step:
A mixes and initial reaction in earlier stage, feed composition is measured by casting molding machine in proportion be poured into forcing machine first heating zone, regulates the Heating temperature in forcing machine rotating speed He Ge district, and material is further mixed, and carries out initial reaction;
B late phase reaction and crystallization, the material of initial reaction gets into belt reactor through junctor, and temperature is respectively distinguished in control, in belt reactor, carries out late phase reaction and crystallization, obtains higher molecular weight;
The c finished product is pulverized through kibbler, obtains finished product TPU particle.
2. the continuous production method of a kind of TPUE according to claim 1 is characterized in that said forcing machine machine section first Heating Zone Temperature is 90 ℃, and all the other several Heating Zone Temperature are 140-180 ℃.
3. the continuous production method of a kind of TPUE according to claim 1; It is characterized in that said belt reactor heating zone temperature is 80-210 ℃; The cooling section temperature-stable is 70 ℃, and the residence time is 8-30 minute in belt reactor.
4. realize the dedicated system of the TPUE continuous production method that claim 1-3 is any; It is characterized in that it comprises storage tank (1), casting molding machine (2), forcing machine (3), belt reactor (4), kibbler (5) and wrapping machine (6), connect through junctor (7) between said forcing machine (3) and the belt reactor (4); Said forcing machine (3) is twin screw extruder or single screw extrusion machine; Said belt reactor (4) adds the steel band or the teflin tape of temperature function for band.
5. dedicated system according to claim 4 is characterized in that described twin screw extruder is in type, incorgruous type, engagement type, the non-engagement type in the same way any one.
6. dedicated system according to claim 5 is characterized in that described twin screw extruder screw-type is engagement type in the same way.
7. dedicated system according to claim 4 is characterized in that described junctor is a T type mouth mould.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160989A (en) * | 2018-08-23 | 2019-01-08 | 周朝功 | A kind of production system and production technology of thermoplastic polyurethane |
| CN110272528A (en) * | 2018-03-16 | 2019-09-24 | 浙江华峰热塑性聚氨酯有限公司 | The preparation method of thermoplastic polyurethane |
| CN114426686A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for forming ultra-low viscosity polyvinyl alcohol solid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19754885C1 (en) * | 1997-12-10 | 1999-09-16 | Basf Ag | Process for the continuous production of granules from thermoplastic polyurethane elastomers |
| JP2007130775A (en) * | 2005-11-08 | 2007-05-31 | Kaneka Corp | Tandem type reactive extruder and reactive extrusion method |
| CN101020737A (en) * | 2007-03-01 | 2007-08-22 | 烟台万华新材料科技有限公司 | Continuous production process of thermoplastic polyurethane elastomer |
| CN202543125U (en) * | 2012-04-09 | 2012-11-21 | 烟台美瑞化学材料有限公司 | System for producing TPU (Thermoplastic Polyurethane Elastomer) by continuous method |
-
2012
- 2012-04-09 CN CN2012101009220A patent/CN102617820B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19754885C1 (en) * | 1997-12-10 | 1999-09-16 | Basf Ag | Process for the continuous production of granules from thermoplastic polyurethane elastomers |
| JP2007130775A (en) * | 2005-11-08 | 2007-05-31 | Kaneka Corp | Tandem type reactive extruder and reactive extrusion method |
| CN101020737A (en) * | 2007-03-01 | 2007-08-22 | 烟台万华新材料科技有限公司 | Continuous production process of thermoplastic polyurethane elastomer |
| CN202543125U (en) * | 2012-04-09 | 2012-11-21 | 烟台美瑞化学材料有限公司 | System for producing TPU (Thermoplastic Polyurethane Elastomer) by continuous method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272528A (en) * | 2018-03-16 | 2019-09-24 | 浙江华峰热塑性聚氨酯有限公司 | The preparation method of thermoplastic polyurethane |
| CN110272528B (en) * | 2018-03-16 | 2021-07-16 | 浙江华峰热塑性聚氨酯有限公司 | Process for preparing thermoplastic polyurethanes |
| CN109160989A (en) * | 2018-08-23 | 2019-01-08 | 周朝功 | A kind of production system and production technology of thermoplastic polyurethane |
| CN114426686A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for forming ultra-low viscosity polyvinyl alcohol solid |
| CN114426686B (en) * | 2020-10-15 | 2024-02-09 | 中国石油化工股份有限公司 | Forming method of ultra-low viscosity polyvinyl alcohol solid |
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