臺灣博碩士論文加值系統

由於全球氣候的變遷、環保是未來重要的課題之一，聚氨酯 (polyurethane, PU) 樹脂的發展由溶劑型的 PU轉為水性的聚氨酯分散液 (polyurethane dispersion, PUD)，PUD多使用丙酮法製程，製程中仍添加少量溶劑 (5 – 50 wt. %)，反應製程的最終階段須再進行減壓蒸餾去除溶劑，但成品中仍有相當的殘留量及氣味存在。
一般 PUD之固含量為 30 – 40 wt. %，若能有效提升固含量至 50 – 60 wt. %，則具有設備成本低、生產成本低，且產率提高等特色。PUD藉由親水基團的導入得以製成，一般多採用羧酸型陰離子劑，其羧酸型陰離子劑廣泛的搭配胺類中和劑生成鹽類，方可有效的在水中分散，此類 PUD塗層在烘膜後會有游離胺 (delocalized amine) 的生成造成環境汙染，因此研發無游離胺 PUD的課題勢在必行。
本實驗透過改良製程及特殊原料的使用，不需添加任何溶劑且選用非胺類中和劑製成無溶劑無游離胺全環保型高固含量 (50 wt. %) PUD。本研究 PUD計畫目標分別為 (1) 無溶劑製程，製程中不添加任何溶劑、(2) 固含量 ≧ 50 wt. %、(3) 黏度 < 3,000 cps、(4) 粒徑 < 200 nm、(5) 機械性質 > 30 MPa、(6) 儲存安定性 > 6 months、(7) 無游離胺，不添加胺類中和劑，共有七項計畫目標。
本實驗分為三大部分，分別探討高固含量 PUD的開發、提升高固含量 PUD的儲存安定性及無游離胺 PUD之開發。第一部分高固含量 PUD的開發共探討三個參數，分別探討 1). 鏈延伸率 (0 % – 100 %)、2). 親水基含量 (2.5 wt. % - 5.0 wt. %)、3). 摻混型多元醇組成 [ PBA 2000 (polybutylene adipate)與 PCD 4671 (polycarbonate diol) 以摻混當量數比為 10：0、5：5、4：6、3：7 及 0：10] 對高固含量 (≧ 50 wt.%) PUD成品之製備及其對物性的影響。第二部分提升高固含量 PUD的儲存安定性，以易相轉變之聚酯多元醇 [ PBA 2000 及 PHA 2000 (polyhexamethylene adipate) ] 為基材以及不同預聚物當量值 (3,900 g / eq. mol、4,517 g / eq. mol)，製備高固含量 (50 wt.%) PUD且提升成品的儲存安定性。第三部分無游離胺 PUD之開發，以不同莫耳數比例之 NaOH與 Na2CO3以摻混當量數比為 10：0、9：1、8：2、7：3、6：4 及 5：5 當作非胺類中和劑取代胺類中和劑，製備成高固含量 (≧ 50 wt.%) 無游離胺 PUD成品進行物性探討。
實驗結果顯示：本實驗選用 HDI (hexamethylene diisocyanate)：IPDI (isophorone diisocyanate) = 3：7為異氰酸酯、PBA 2000為多元醇、DMBA (dimethylol butanoic acid) 為陰離子劑、非胺類組成 NaOH：Na2CO3摻混莫耳比例為 8：2為非胺類中和劑、EDA (ethylene diamine) 為鏈延伸劑其鏈延伸率為 100 % 及親水基含量為 5 wt. %，以無溶劑製程製備固含量 50 wt. %之 PUD，成品之粒徑 182 nm、黏度 508 cps，具有良好的分散能力且拉力達 31.5 MPa、儲存安定性大於 6個月以上，成品其具有良好儲存安定性。非胺類中和劑組成已成功取代揮發性較高之胺類中和劑，此成品擁有無溶劑、無游離胺、高固含量、低生產成本、全環保特性，極具市場競爭力。

Environmental protection is an important issue to the future. It is an important challange to decrease the level of volatile organic concentration (VOC) recently. Therefore, solvent based PU resins will be gradually replaced by aqueous based polyurethane dispersions (PUDs). Acetone process is the most important manufacture process, which had 5 to 50 wt. % acetone added. Then, it also requires vacuum distillation to remove solvents from PUDs, but still has some residual and odd exist.

PUDs usually can be made to have 30 – 40 wt. % solid content. If we can increase the solid content to 50 – 60 wt. ％, it has the advantages of low capital investment, low product cost and high yield rate. The incorporation of anionic groups into polyurethanes and neutralizing the anionomer carboxylic group is the most widely used to make PUDs. Amine neutralizing agent contented PUDs evaporate delocalized amine after drying which cause the air pollution and health hazard. The development of non-delocalized amine PUDs is another essential topic for environmental friendly PUDs.

The purpose of this research is to creat a solvent free, high solid content (50 wt. %), non-delocalized amine PUDs fit the following criteria: (1) solvent free process, (2) solids content ≧ 50 wt. %, (3) viscosity < 3,000 cps, (4) particle size < 200 nm, (5) tensile strength > 30 MPa, (6) storage stability > 6 months, (7) non-delocalized amine.

There are three parts of this research focused on. Part I: investigate three parameters of high solid content PUDs: (1) chain extension ratio from 0 % to 100 %, (2) hydrophilic group content (HGC) : 2.5, 2.7, 3.0 and 5.0 wt. %, respectively. (3) incorporating of polyester polyol (PBA 2000) blend with polycarbonate diol (PCD 4671) with the equivalent ratio of 10:0, 5:5, 4:6, 3:7 and 0:10, respectively to reduce the viscosity of PUDs. Part II, high solid content (50 wt. %) PUDs based on polyester polyol (PBA 2000 and PHA 2000) can more easily occur phase inversion and prepolymer equivalent were controlled at 3,900 g/ eq. mol or 4,517 g/ eq. mol, and the storage stability of the PUDs and the properties of the PUDs are investigated. Part III, high solid content (50 wt. %) PUDs with non-delocalized amine of sodium hydroxide (NaOH) and soldium hydrogen carbonate (Na2CO3) as the non amine neutralizing agent. The non amine neutralizing agent was incorporated by NaOH and Na2CO3 with the molar ratio of 10:0, 9:1, 8:2, 7:3, 6:4 and 5:5, respectively. The properties of these PUDs were characterized by particle size, viscosity tests and tensile property.

From the experiments results, we adopted HDI:IPDI, PBA2000, DMBA, neutralizing agent that incorporating of NaOH and Na2CO3 with the molar ratio 8:2, chain extender EDA with a chain extension ratio of 100 % and HGC = 5 wt. %. We successfully synthesis a solid content 50 wt. % PUD product by solvent free process, with a particle size of 182 nm, viscosity of 508 cps, tensile strength of 31.5 MPa, and storage stability above 6 months were obtained. The product has fulfilled the seven criteria above. We have successfully developed a solvent free, non-delocalized amine, high solid content, low production costs and environment friendly PUD with competitive price.

摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VI
圖目錄 VIII
一、緒論 1
1-1 前言 1
1-2 研究方向 1
二、文獻回顧 4
2-1 聚氨酯 4
2-1.1 聚氨酯簡介 4
2-1.2 聚氨酯化學 5
2-2聚氨酯分散液 7
2-2.1 二異氰酸酯 7
2-2.2 聚多元醇 9
2-2.3 親水基團 10
2-2.4 中和劑 10
2-2.5 鏈延伸劑 12
2-2.6 製備方法 13
2-3 高固含量聚氨酯分散液 16
2-3.1 聚氨酯分散液極限固含量之研究 16
2-3.2 聚氨酯分散液儲存安定性之研究 17
2-3.3 相關論文探討 17
2-4 無游離胺聚氨酯分散液 28
2-4.1 無游離胺羧酸型聚氨酯分散液 28
2-4.2 無游離胺磺酸型聚氨酯分散液 30
三、實驗 35
3-1實驗藥品 35
3-1.1合成藥品 35
3-1.2 鑑定藥品 38
3-2 實驗設備與分析儀器 39
3-2.1 實驗設備 39
3-2.2 分析儀器 39
3-2.3 測試條件及 —NCO當量測定 39
3-3 實驗流程及製程檢驗點測定 40
3-3.1 實驗流程 40
3-3.2 製程檢驗點測定 42
3-4 實驗設計 42
3-4.1 無溶劑型高固含量 PUD之基礎研究設計 42
3-4.2 無溶劑型高固含量 PUD之儲存安定性研究成品之設計 44
3-4.3 無溶劑無游離胺全環保型高固含量 PUD研究成品之設計 44
3-5 實驗配方 45
3-5.1 無溶劑型高固含量 PUD之基礎研究配方 45
3-5.2 無溶劑型高固含量 PUD之儲存安定性研究成品之配方 48
3-5.3 無溶劑無游離胺全環保型高固含量 PUD研究成品之配方 49
3-6 實驗製程 50
3-6.1 無溶劑型高固含量 PUD之基礎研究製程 50
3-6.2 無溶劑型高固含量 PUD之儲存安定性研究成品之製程 52
3-6.3 無溶劑無游離胺全環保型高固含量 PUD研究成品之製程 53
3-7 樣品命名 53
3-7.1 無溶劑型高固含量 PUD之基礎研究命名 53
3-7.2無溶劑型高固含量 PUD之儲存安定性研究成品之命名 55
3-7.3 無溶劑無游離胺全環保型高固含量 PUD研究成品之命名 56
四、結果與討論 57
4-1 無溶劑型高固含量 PUD之基礎研究 57
4-1.1 探討不同鏈延伸率製成之無溶劑型高固含量 PUD成品 57
4-1.2 探討不同親水基含量製成之無溶劑型高固含量 PUD成品 64
4-1.3 探討不同摻混型多元醇組成製成之無溶劑型高固含量 PUD成品 70
4-2 無溶劑型高固含量 PUD之儲存安定性成品之研究 79
4-2.1 探討以不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品 79
4-2.2 探討以不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品對粒徑的影響 80
4-2.3 探討以不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品對黏度的影響 82
4-2.4 探討以不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品對拉力性質的影響 83
4-2.5 探討以不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品對儲存安定性的影響 85
4-2.6 探討不同預聚物當量值對聚酯型製成之無溶劑型高固含量 PUD成品綜合影響結論 86
4-3 無溶劑無游離胺全環保型高固含量 PUD 88
4-3.1 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品的物性影響 88
4-3.2 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品 pH值影響 88
4-3.3探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品之粒徑的影響 90
4-3.4 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品之黏度的影響 92
4-3.5 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品之拉力性質的影響 93
4-3.6 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品之儲存安定性的影響 94
4-3.7 探討以不同莫耳數比例之 NaOH與Na2CO3當非胺類中和劑對 PUD成品之綜合影響結論 95
五、結論 97
六、參考文獻 98
自述 102
發表期刊 102

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