TWI419906B - Biomass material having multi isocyanate groups and method for manufacturing the same - Google Patents
Biomass material having multi isocyanate groups and method for manufacturing the same Download PDFInfo
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- TWI419906B TWI419906B TW98145474A TW98145474A TWI419906B TW I419906 B TWI419906 B TW I419906B TW 98145474 A TW98145474 A TW 98145474A TW 98145474 A TW98145474 A TW 98145474A TW I419906 B TWI419906 B TW I419906B
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本發明係有關多異氰酸酯基之生質材料,更特別關於其形成方法及應用。The present invention relates to a polyisocyanate-based biomaterial, and more particularly to a method and application thereof.
聚胺基甲酸酯(polyurethane,以下簡稱PU)泡棉是重要民生或工業材料,廣泛應用於運輸、運動器材、傢俱、包裝、織物、及隔熱材料等產業。北美、歐洲、日本等地之PU泡棉年產量大於230萬噸,全球的每年成長率為2-3%。台灣泡棉廠每年產量近10萬噸,競爭激烈亟需新技術使泡棉品質升級,並開發高附加價值產品。Polyurethane (hereinafter referred to as PU) foam is an important material for people's livelihood or industry, and is widely used in transportation, sports equipment, furniture, packaging, fabrics, and insulation materials industries. The annual production of PU foam in North America, Europe, Japan and other places is more than 2.3 million tons, and the global annual growth rate is 2-3%. Taiwan's foam factory produces nearly 100,000 tons per year. The competition is fierce and new technologies are needed to upgrade the quality of foam and develop high value-added products.
隨PU工業發展及時代變遷,現代泡棉產品已開發多種技術如選用新發泡劑、開發耐黃化/安定助劑、強制發泡冷卻技術、變壓發泡技術、二氧化碳系統、及二異氰酸異佛爾酮(isophorone diisocyanate,以下簡稱IPDI)系PU泡棉材料及製程。目前的研究重心更趨於環保化(無鹵材料的選用)、非黃變化、以及高品質化。With the development of PU industry and the changing times, modern foam products have developed various technologies such as selecting new foaming agents, developing yellowing/stable additives, forced foaming cooling technology, variable pressure foaming technology, carbon dioxide system, and two different Isophorone diisocyanate (IPDI) is a PU foam material and process. The current research focus is more environmentally friendly (the choice of halogen-free materials), non-yellow changes, and high quality.
二異氰酸酯如二異氰酸異佛爾酮(isophorone diisocyanate,以下簡稱IPDI)或六亞甲基二異氰酸酯(hexamethylene diisocyanate,以下簡稱HDI)系之結構不含芳香環,不易產生黃變等劣化現象,已開始應用於發泡衣料,如內衣、衛生器材、交通器材、運動器材、及緩衝材料等領域,全球產值約為30至35億元新台幣。The structure of a diisocyanate such as isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI) does not contain an aromatic ring, and is less prone to yellowing and the like. It has been applied to foaming fabrics such as underwear, sanitary equipment, transportation equipment, sports equipment, and cushioning materials. The global output value is about NT$3 to 3.5 billion.
目前市售之泡棉預聚物均為雙官能基之線型分子,本身無法形成三次元立體結構,而需另外添加交聯劑以達三次元交聯硬化效果。此外為了符合環保需求,目前各國多制定法規鼓勵廠商將生質材料應用於各式石化產品中。以木質素為例,其結構具有大量羥基,可作為泡棉配方中的預聚物。然而木質素中位於烷基上的羥基其反應性遠低於位於苯環上的羥基,反應不均的結果將大幅降低產品物性。因此如何使木質素中不同取代位置之羥基的反應性一致,為本領域亟需克服的問題。At present, the commercially available foam prepolymers are all bifunctional linear molecules, which cannot form a three-dimensional three-dimensional structure by themselves, and an additional cross-linking agent is required to achieve a three-dimensional cross-linking hardening effect. In addition, in order to meet the environmental protection needs, many countries have enacted regulations to encourage manufacturers to apply raw materials to various petrochemical products. Taking lignin as an example, its structure has a large amount of hydroxyl groups and can be used as a prepolymer in a foam formulation. However, the hydroxyl group on the alkyl group in lignin is much less reactive than the hydroxyl group on the benzene ring, and the result of uneven reaction will greatly reduce the physical properties of the product. Therefore, how to make the reactivity of hydroxyl groups at different substitution positions in lignin consistent is a problem that needs to be overcome in the art.
本發明提供一種形成多異氰酸酯基生質材料的方法,包括配製二異氰酸酯溶液;以及將具有複數個羥基之生質材料溶解後,加入二異氰酸酯溶液中,使生質材料之羥基反應形成異氰酸酯基;其中二異氰酸酯包括脂肪族二異氰酸酯、芳香族二異氰酸酯、或上述之組合。The present invention provides a method for forming a polyisocyanate-based green material, comprising formulating a diisocyanate solution; and dissolving a raw material having a plurality of hydroxyl groups, adding a diisocyanate solution, and reacting a hydroxyl group of the green material to form an isocyanate group; Among them, the diisocyanate includes an aliphatic diisocyanate, an aromatic diisocyanate, or a combination thereof.
本發明亦提供一種多異氰酸酯基生質材料,其中每一異氰酸酯基係由生質材料之羥基與二異氰酸酯反應形成,且二異氰酸酯包括脂肪族二異氰酸酯、芳香族二異氰酸酯、或上述之組合。The present invention also provides a polyisocyanate-based green material in which each isocyanate group is formed by reacting a hydroxyl group of a raw material with a diisocyanate, and the diisocyanate includes an aliphatic diisocyanate, an aromatic diisocyanate, or a combination thereof.
本發明提供一種形成多異氰酸酯基生質材料的方法。首先,配製二異氰酸酯溶液,再將具有複數個羥基之生質材料溶液加入二異氰酸酯溶液,使該生質材料之羥基反應形成異氰酸酯基預聚物。以最常見之生質材料木質素為例,上述反應如式1所示,上述二異氰酸酯可以是脂肪族二異氰酸酯或芳香族二異氰酸酯。The present invention provides a method of forming a polyisocyanate based biomass material. First, a diisocyanate solution is prepared, and a solution of a raw material having a plurality of hydroxyl groups is added to the diisocyanate solution to react the hydroxyl groups of the raw material to form an isocyanate-based prepolymer. Taking the most common raw material lignin as an example, the above reaction is represented by Formula 1, and the above diisocyanate may be an aliphatic diisocyanate or an aromatic diisocyanate.
在式1中,一個單體的木質素(Ligin)含有不同脂肪族及芳香族羥基。經由分子量鑑定搭配滴定法可知木質素之分子量,同時推算出有幾個單體以及羥基。接著以上述羥基數目決定二異氰酸酯之使用量。木質素的每一羥基可與二異氰酸酯中一側的異氰酸酯基進行反應,形成異氰酸酯基如式2所示。In Formula 1, one monomeric lignin (Ligin) contains different aliphatic and aromatic hydroxyl groups. The molecular weight of lignin is known by molecular weight identification and titration, and several monomers and hydroxyl groups are derived. Next, the amount of the diisocyanate used is determined by the number of the above hydroxyl groups. Each of the hydroxyl groups of the lignin can be reacted with an isocyanate group on one side of the diisocyanate to form an isocyanate group as shown in Formula 2.
在這必需說明的是,木質素之羥基具有不同的反應速率。舉例來說,位於脂肪鍊上的羥基其反應速率比苯環上的羥基之反應速率快5倍左右。為了使所有的羥基均能反應形成異氰酸酯基,需加入兩倍羥基以上之異氰酸酯基。It must be stated here that the hydroxyl groups of the lignin have different reaction rates. For example, a hydroxyl group located on an aliphatic chain has a reaction rate about 5 times faster than a hydroxyl group on a benzene ring. In order to allow all of the hydroxyl groups to react to form an isocyanate group, it is necessary to add an isocyanate group of two or more hydroxyl groups.
適於作為本發明之二異氰酸酯為脂肪族異氰酸酯,包括二異氰酸異佛爾酮(IPDI)、六亞甲基二異氰酸酯(HDI)、甲烯雙(4-環已基異氰酸酯)、環已基甲烷二異氰酸(4,4'-dicyclohexylmethane diisocyante,以下簡稱H12 MDI)等脂肪族二異氰酸酯、或芳香族二異氰酸酯或上述之組合。在本發明一實施例中,二異氰酸酯之異氰酸酯基與木質素之羥基的莫耳比介於2:1至2.6:1之間。若二異氰酸酯之用量過少,則無法使木質所的所有羥基反應形成異氰酸酯基。若二異氰酸酯之用量過大,則未反應之二異氰酸酯將會殘留於產物中,生質材料所具有之堅硬特性降低。Diisocyanates suitable as the present invention are aliphatic isocyanates, including isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methene bis(4-cyclohexyl isocyanate), ring An aliphatic diisocyanate such as 4,4'-dicyclohexylmethane diisocyante (hereinafter abbreviated as H 12 MDI) or an aromatic diisocyanate or a combination thereof. In one embodiment of the invention, the molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of the lignin is between 2:1 and 2.6:1. If the amount of the diisocyanate is too small, it is impossible to react all the hydroxyl groups of the wood to form an isocyanate group. If the amount of the diisocyanate is too large, the unreacted diisocyanate will remain in the product, and the hard properties of the raw material will be lowered.
值得注意的是,上述方法並不限於改質木質素,亦可應用於其他含有兩種以上不同反應活性之羥基的生質材料如纖維素、半纖維素、或澱粉。It should be noted that the above method is not limited to modified lignin, and can also be applied to other raw materials such as cellulose, hemicellulose, or starch containing two or more different reactive hydroxyl groups.
將上述含有大量異氰酸酯基之生質材料、界面活性劑、發泡劑、二元醇、及水之混合物進行發泡反應(blowing)及交聯聚合反應,最後發泡體發泡固化成型為泡棉。與習知技藝相較,由於本發明之生質材料已預先使所有羥基反應形成異氰酸酯基,可有效改善生質材料不同位置之羥基反應活性不均的問題,在室溫下短時間即可完成發泡反應。此外,上述改質之生質材料本身已具有多個異氰酸酯基,因此泡棉配方不需添加交聯劑即可形成三次元立體結構。The above-mentioned raw material containing a large amount of isocyanate groups, a surfactant, a foaming agent, a glycol, and a mixture of water are subjected to a foaming reaction and a crosslinking polymerization reaction, and finally, the foam is foamed and solidified into a foam. cotton. Compared with the prior art, since the raw material of the present invention has previously reacted all the hydroxyl groups to form an isocyanate group, the problem of uneven reactivity of hydroxyl groups at different positions of the biomass material can be effectively improved, and the solution can be completed in a short time at room temperature. Foaming reaction. In addition, the above modified biomass material itself has a plurality of isocyanate groups, so that the foam formulation can form a three-dimensional structure without adding a crosslinking agent.
在本發明一實施例中,二元醇係一頭尾兩端具有羥基之聚合物,如重量平均分子量介於500至3000之聚酯(polyester),或聚醇(polyol)如聚乙二醇(PEG)、聚丙二醇(PPG)、或類似物。上述聚醇亦可稱之為聚醚(polyether)醇。In one embodiment of the present invention, the diol is a polymer having a hydroxyl group at both ends of the head, such as a polyester having a weight average molecular weight of 500 to 3,000, or a polyol such as polyethylene glycol ( PEG), polypropylene glycol (PPG), or the like. The above polyols may also be referred to as polyether alcohols.
在本發明一實施例中,預聚物與水之重量比較佳介於100:0.1至100:10之間。若水之比例過高,發泡體將會龜裂。若水之比例過低,發泡倍率將會不足。In one embodiment of the invention, the weight of the prepolymer and water is preferably between 100:0.1 and 100:10. If the proportion of water is too high, the foam will crack. If the proportion of water is too low, the expansion ratio will be insufficient.
將上述混合物高速攪拌均勻,經約1-300秒後,即可將混合物倒入模具或連續生產線如輸送帶上。經發泡0.1-10分鐘後,即可固化成型為泡棉。發泡反應可於室溫至200℃下完成,較佳介於20-100℃,最佳介於20-50℃。經上述方法形成之泡棉以UV照射後,其耐黃變級數可達到5級。The mixture is stirred at high speed at a high speed, and after about 1-300 seconds, the mixture can be poured into a mold or a continuous production line such as a conveyor belt. After foaming for 0.1-10 minutes, it can be solidified into foam. The foaming reaction can be carried out at room temperature to 200 ° C, preferably between 20 and 100 ° C, and most preferably between 20 and 50 ° C. After the foam formed by the above method is irradiated with UV, the yellowing resistance level can reach 5 levels.
與習知技藝相較,本發明之泡棉,其發泡時間(blowing time)只需1-300秒,較佳為5-100秒,更佳為10-50秒,交聯聚合時間(gelling time)只需0.1-10分鐘,較佳為0.5-5分鐘,更佳為0.5-2分鐘;且交聯反應不需高溫加熱,亦可於室溫至200℃之間進行反應,較佳介於20-100℃,最佳介於20-50℃下完成。由於本發明之預聚物之反應活性高,可簡化製程。Compared with the conventional art, the foaming time of the foam of the present invention takes only 1-300 seconds, preferably 5-100 seconds, more preferably 10-50 seconds, and cross-linking polymerization time (gelling). Time) only 0.1-10 minutes, preferably 0.5-5 minutes, more preferably 0.5-2 minutes; and the crosslinking reaction does not require high temperature heating, and can also be carried out between room temperature and 200 ° C, preferably between 20-100 ° C, best done at 20-50 ° C. Since the prepolymer of the present invention has high reactivity, the process can be simplified.
除了進行發泡反應形成泡棉外,本發明之含有複數個異氰酸酯基之生質材料亦可與二元醇直接進行交聯反應,以形成非發泡性產物如薄膜。In addition to the foaming reaction to form a foam, the raw material containing a plurality of isocyanate groups of the present invention may also be directly cross-linked with a glycol to form a non-foaming product such as a film.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例配合所附圖示,作詳細說明 如下:The above and other objects, features, and advantages of the present invention will become more apparent and understood. as follows:
本發明取200g之木質素(購自Borregaard LignoTech 之LS-103)溶於100ml之Polyol 1000(Bayer公司)中,形成木質素溶液,並取100g之HDI(購自Bayer公司之Desmodur H)。接著將木質素溶液慢慢滴入100℃之HDI溶液中攪拌反應,滴完後再反應6小時,以NCO滴定法確認木質素所有的羥基均反應形成異氰酸酯基。In the present invention, 200 g of lignin (LS-103 available from Borregaard LignoTech) was dissolved in 100 ml of Polyol 1000 (Bayer Co.) to form a lignin solution, and 100 g of HDI (Desmodur H from Bayer Co.) was taken. Then, the lignin solution was slowly dropped into a HDI solution at 100 ° C to stir the reaction, and after the completion of the dropwise addition, the reaction was further carried out for 6 hours, and it was confirmed by NCO titration that all the hydroxyl groups of the lignin reacted to form an isocyanate group.
取160g上述改質之木質素、40g之二元醇(購自Bayer公司之PPG-400)、2g之戊烷(發泡劑)、1g之L580(界面活性劑,美國Union Carbide公司產品)、及2g水充分混合20秒後,倒入開放空間模具,進行發泡交聯聚合反應,1分鐘後即得泡棉成品,此泡棉成品具有良好之機械強度,硬度為70、壓縮模數為90kgf/cm2 、氣泡密度為50孔/英吋、耐黃變級數為5級,密度為0.3g/cm3 。160 g of the above modified lignin, 40 g of glycol (PPG-400 available from Bayer Co., Ltd.), 2 g of pentane (foaming agent), 1 g of L580 (surfactant, product of Union Carbide, USA), After thoroughly mixing with 2g of water for 20 seconds, it is poured into an open space mold to carry out foaming cross-linking polymerization reaction. After 1 minute, the finished foam product is obtained. The foamed finished product has good mechanical strength, hardness of 70, and compression modulus. 90 kgf/cm 2 , a bubble density of 50 holes/inch, a yellowing resistance grade of 5, and a density of 0.3 g/cm 3 .
取80g木質素(購自Borregaard LignoTech之LS-103)、40g之HDI(購自Bayer公司之Desmodur H)、40ml之Polyol 1000、40g之二元醇(購自Bayer公司之PPG-400)、2g之戊烷(發泡劑)、1g之L580(界面活性劑,美國Union Carbide公司產品)、及2g水充分混合20秒後,倒入開放空間模具,直接進行發泡交聯聚合反應,1分鐘後即得泡棉成品,此泡棉成品之硬度為55、壓縮模數為75kgf/cm2 、氣泡密度為30孔/英吋、耐黃變級數為5級,密度為0.3g/cm3 。與實施例1相較,由於比較例1之木質素未經改質即進行發泡反應,因此反應不均且泡孔較粗。Take 80g lignin (LS-103 from Borregaard LignoTech), 40g of HDI (Desmodur H from Bayer), 40ml of Polyol 1000, 40g of glycol (PPG-400 from Bayer), 2g Pentane (foaming agent), 1 g of L580 (surfactant, product of Union Carbide, USA), and 2 g of water were thoroughly mixed for 20 seconds, poured into an open space mold, and directly subjected to foaming crosslinking polymerization for 1 minute. After that, the finished foam product has a hardness of 55, a compression modulus of 75 kgf/cm 2 , a bubble density of 30 holes/inch, a yellowing resistance grade of 5, and a density of 0.3 g/cm 3 . . Compared with Example 1, since the lignin of Comparative Example 1 was subjected to a foaming reaction without modification, the reaction was uneven and the cells were coarse.
雖然本發明已以數個較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
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