熱塑性聚氨酯泡珠水中造粒量產技術研究｜國立臺灣科技大學博碩士論文系統

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研究生：	Stephen Utomo Stephen Utomo
論文名稱：	熱塑性聚氨酯泡珠水中造粒量產技術研究 Foamed TPU Beads Made with the Underwater Pelletizing Process
指導教授：	葉樹開 Shu-Kai Yeh
口試委員:	蘇至善 Chie-Shaan Su 張浩 Hao Chang 楊銘乾 Ming-Chien Yang 葉樹開 Shu-Kai Yeh
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2020
畢業學年度：	108
語文別：	英文
論文頁數：	68
中文關鍵詞：	TPU 、泡珠材料、押出發泡、水中造粒
外文關鍵詞：	TPU, Bead Foam, Foam Extrusion, Underwater Pelletizing
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泡珠材料(bead foam)，或又稱可膨脹發泡材料(expandable foam)是迄今唯一可以製備低密度且形狀多變泡材的製程，且具有加工設備便宜、節能等特性。因此，在
近年來越來越受重視，由於發泡過程較不易控制，或是易以懸浮聚合，過去泡珠材
料多半採批式方式製備。而水中造粒(underwater pelletizing)是能以連續量產泡
珠珠粒的技術，但因設備較複雜，製程變數較多，較少人採用，由於泡珠材料最近
的市場需求越來越大，此技術也越來越受重視。
熱塑性聚氨酯(thermoplastic polyurethane)簡稱TPU，為一種共嵌聚合物，是由聚酯多元醇或聚醚多元醇與一定比例的二元異氰酸酯、催化劑混合，通過聚合反應而形成的聚合物。由於其可回復性及高彈性，TPU泡珠材料在鞋材上大受歡迎。
本實驗利用泡沫擠出和水中造粒工藝從TPU生產具有兩種不同硬度（85A和90A）的珠狀泡沫。結果表明，高硬度的TPU將產生高膨脹比的泡材。此外，將滑石粉添加到這些TPU中，有助於改善泡孔結構並增加珠狀泡沫的泡孔密度。
還研究了二氧化碳添加的影響。在該實驗中，最佳的CO2含量為約1〜1.5 wt%。因為泡孔聚併效應。因此，膨脹率沒有增加。添加更多的二氧化碳無助於增加膨脹率。
最後，改變冷卻水溫度，發現降低冷卻水溫度也將降低泡珠的泡孔尺寸和膨脹率。在這項研究中，使用TPU E390成功生產了膨脹比為4.75的TPU珠狀泡沫。

Bead foam or expandable/expanded foam is a foam material with low density that can be sintered into a three-dimensional shaped product by steam-chest molding. Besides, the equipment and energy cost of foam beads are much lower than other polymeric foam manufacturing processes. Due to those reasons, bead foam technology becomes more and more critical in recent years. In the past, bead foams were made by suspension polymerization or by batch foaming processes. Underwater pelletizing is the continuous process that can produce bead foam on a large scale. It was less adopted by industry because of its high equipment cost and multiple interacted processing variables. However, due to the growing market demands, this process becomes more and more attractive.
Thermoplastic polyurethane (TPU) is a linear segmented copolymer consist of hard and soft segments. Because of its high elasticity, high tear strength and high recovery ratio, expandable TPU (ETPU) foam beads become very popular in the shoe industry.
This experiment utilizes foam extrusion with an underwater pelletizing process to produce bead foams from TPU with two different hardness, 85A, and 90A. The results showed that high hardness TPU would produce a high expansion ratio foam. Furthermore, the addition of talc helps improve the cell structure and increase the cell density of the bead foams. In this experiment, the optimized CO2 content was about 1 ~ 1.5 wt%. Adding more CO2 did not help increase the expansion ratio. Besides, the cells ruptured and coalesced. Because of that, the expansion ratio did not increase.
Finally, the cooling water temperature was varied and it was found that decreasing the cooling water temperature would lower the cell size and expansion ratio of the beads. In this study, TPU bead foams with an expansion ratio of 4.75 were successfully produced.

CONTENTS
摘要    I
ABSTRACT    II
ACKNOWLEDGMENT    III
CONTENTS    IV
LIST OF FIGURES    VI
LIST OF TABLES    VIII
CHAPTER 1 INTRODUCTION    1
CHAPTER 2 LITERATURE REVIEW    4
2.1.    Polyurethane (PU)    4
2.1.1.    TPU    4
2.2.    Foaming Process    5
2.2.1.     Batch Foaming    5
2.2.2.    Foam Extrusion    6
2.3.    Foaming Mechanism    7
2.3.1.    Cell Nucleation    8
2.3.2.    Cell Growth and Coalescence    10
2.3.3.    Cell Stabilization    11
2.4.    Bead Foaming Technology    11
2.5.    Processes for Bead Foam Production    12
2.5.1.    Bead Foam Production by Batch Foaming Process    12
2.5.2.    Continuous Process to Produce Bead Foams    13
2.6    Foam Sintering    16
CHAPTER 3 EXPERIMENTAL METHOD    18
3.1.    Materials    18
3.2.    Instruments    19
3.3.    Experiment Procedures    20
3.3.1.    Pristine TPU Sample Preparation    20
3.3.2.    TPU/Talc Sample Preparation    20
3.3.3.    Extrusion Foaming and Underwater Pelletizing    21
3.4.    Analysis Methods    22
3.4.1.    Density Measurement    22
3.4.2.    Expansion Ratio    22
3.4.3.    Scanning Electron Microscope (SEM) Analysis    22
3.4.4.    Cell Size and Cell Density Calculation    22
3.4.5.    Open Cell Content    23
CHAPTER 4 RESULTS AND DISCUSSION    24
4.1.    Effect of CO2 Loading Level and Hardness    24
4.2.    Effect of Talc and Hardness to The Cell Morphology    30
4.2.1    Effect of Hardness to the Cell Morphology    34
4.3    Effect of Cooling Water Temperature to the Cell Morphology    36
CHAPTER 5 CONCLUSION    41
REFERENCES    42
APPENDIX A CO2 FLOWRATE CALCULATION    48
APPENDIX B EXPERIMENT VARIABLES    49

LIST OF FIGURES
Figure 1 1 Methods of Producing Bead Foams    2
Figure 1 2 Current EPP used in the Automobile Industry    2
Figure 1 3 ETPU Bead Foam from BASF    3
Figure 2 1 PU Synthesis Scheme    4
Figure 2 2 Schematic of Batch Foaming Setup    6
Figure 2 3 Schematic of Foam Extrusion Process    7
Figure 2 4 Variables and their relationship in Foam Extrusion    7
Figure 2 5 Foaming Mechanism    8
Figure 2 6 Cell Nucleation and Growth as a Function of ∆G and Cell Radius    8
Figure 2 7 Heterogeneous Nucleation on Smooth Surface    10
Figure 2 8 Heterogeneous Nucleation on Rough Surface    10
Figure 2 9 Beads and Molded EPS Foam    12
Figure 2 10 Schematic Diagram of Batch Foaming for Bead Foam Production    12
Figure 2 11 Strand Pelletizing System    14
Figure 2 12 Schematic Diagram of Perforated Plate Die    14
Figure 2 13 Underwater Pelletizing Extrusion Process    15
Figure 2 14 Foam Extrusion with Underwater Pelletizing Process    16
Figure 2 15 Amorphous Foam Beads Sintering Mechanism    16
Figure 2 16 Double Melting Peak of Foamed Polymer    17
Figure 3 1 Block Diagram of the Extruder    19
Figure 3 2 Experiment Overview    20
Figure 4 1 Pictures of TPU E385 Beads with (a) 1 wt% (b) 2 wt% and (c) 3 wt% CO2 Loading Level    25
Figure 4 2 SEM of TPU E385 with (a) 1 wt% (b) 2 wt% and (c) 3 wt% CO2 Loading Level     26
Figure 4 3 Pictures of TPU E390 with (a) 1 wt% (b) 2 wt% and (c) 3 wt% CO2 Content    27
Figure 4 4 SEM of TPU E390 with (a) 1 wt% (b) 2 wt% and (c) 3 wt% CO2 Content    28
Figure 4 5 Effect of CO2 Loading Level on OCC of TPU E385 & TPU E390    29
Figure 4 6 Effect of Expansion Ratio on OCC of TPU E385 & TPU E390    29
Figure 4 7 Effect of Solubility Pressure on Premature Nucleation.    30
Figure 4 8 Pictures of TPU E385/talc; Each picture (a-f) corresponds to experiments No. 7 - 12 described in Table 4-9    32
Figure 4 9 SEM of TPU E385/talc; Each picture (a-f) corresponds to experiments No. 7 - 12 described in Table 4-9    34
Figure 4 10 SEM Image of Beads of (a) TPU E385 and (b) TPU E390    35
Figure 4 11 Effect of CO2 Loading Level on OCC of TPU E385 and TPU E390 with Talc    36
Figure 4 12 Effect of Expansion Ratio OCC of TPU E385 and TPU E390 with Talc    36
Figure 4 13 Pictures of TPU E390/Talc; Each picture (a-e) corresponds to results (13-17) described in Table 4-15    38
Figure 4 14 SEM of TPU E390/Talc; Each picture (a-e) corresponds to results (13-17) described in Table 4-15    39
Figure 4 15 Effect of Cooling Water Temperature on OCC of TPU E390/Talc    40
Figure 4 16 Effect of Expansion Ratio on OCC of TPU E390/Talc    40
Figure A 1 CO2 Density at Different Pressures    48
 
LIST OF TABLES
Table 3 1 Physical Properties of TPU    18
Table 4 1 Zone Temperature of TPU E385 (°C)    24
Table 4 2 TPU E385 Experiment’s Controlled Speed    25
Table 4 3 Foam Analysis Results of TPU E385    25
Table 4 4 Zone Temperature of Pure TPU E390 (°C)    27
Table 4 5 TPU E390 Experiment’s Controlled Speed    27
Table 4 6 Foam Analysis Results of TPU E390    28
Table 4 7 Extruduer Temperature Profile of TPU E385/Talc (°C)    31
Table 4 8 TPU E385/Talc Experiment’s Controlled Speed    31
Table 4 9 Foam Analysis Results of TPU E385/Talc    33
Table 4 10 Extruder Temperature Profile of TPU E385 and E390 with Talc (°C)    34
Table 4 11 Controlled Variables of TPU E385 and E390 with Talc    34
Table 4 12 Foam Analysis Results of TPU E385 and E390 with Talc    35
Table 4 13 Extruder Temperature Profile of Cooling Water Temperature Experiments (°C)    37
Table 4 14 TPU E390/Talc Experiment’s Controlled Speed    37
Table 4 15 Foam Analysis Results of TPU E390/Talc    38
Table B 1 Controlled Variables and Expansion Ratio of TPU E385    49
Table B 2 Measured Variables of TPU E385    52
Table B 3 Controlled Variables and Expansion Ratio of TPU E390    54
Table B 4 Measured Variables of TPU E390    56


                                

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全文公開日期 2025/02/10 (校內網路)
全文公開日期 2025/02/10 (校外網路)
全文公開日期 2025/02/10 (國家圖書館：臺灣博碩士論文系統)

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