TWI694988B - Preparation of five-carbon epoxy nitrogen benzocyclohexane polyurethane damping material - Google Patents

Preparation of five-carbon epoxy nitrogen benzocyclohexane polyurethane damping material Download PDF

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TWI694988B
TWI694988B TW108112411A TW108112411A TWI694988B TW I694988 B TWI694988 B TW I694988B TW 108112411 A TW108112411 A TW 108112411A TW 108112411 A TW108112411 A TW 108112411A TW I694988 B TWI694988 B TW I694988B
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carbon epoxy
diisocyanate
item
diol
benzocyclohexane
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TW202037590A (en
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江淑媜
吳建欣
葉世傑
鍾昀澄
鄭如忠
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國家中山科學研究院
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Abstract

一種含五碳環氧氮苯并環己烷雙醇及其聚胺酯之製備方法，步驟包括：將含五碳環化合物與胺基醇及聚甲醛反應，得到含五碳環氧氮苯并環己烷雙醇。將該雙醇與二元醇預聚物及二異氰酸酯進一步反應，可得到含五碳環氧氮苯并環己烷之聚胺酯。本發明可將該聚胺酯交聯，藉此，結合五碳環及氧氮苯并環己烷兩種分子結構的優點，該聚胺酯可應用在阻尼材料的領域。 A method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane diol and its polyamine ester. The steps include: reacting a five-carbon ring-containing compound with an amino alcohol and polyoxymethylene to obtain a five-carbon epoxy nitrogen-containing benzocyclohexane Alkanediol. The diol is further reacted with a diol prepolymer and a diisocyanate to obtain a five-carbon epoxy-nitrobenzocyclohexane-containing polyamine ester. In the present invention, the polyurethane can be cross-linked, thereby combining the advantages of two molecular structures of five-carbon ring and oxynitrobenzocyclohexane, the polyurethane can be applied in the field of damping materials.

Description

製備含五碳環氧氮苯并環己烷聚胺酯阻尼材料 Preparation of five-carbon epoxy nitrogen benzocyclohexane polyurethane damping material

本發明係關於一種聚胺酯材料之製備方法，特別是關於一種含五碳環氧氮苯并環己烷聚胺酯阻尼材料之製備方法。 The invention relates to a method for preparing a polyurethane material, in particular to a method for preparing a five-carbon epoxy-nitrogen-benzocyclohexane polyurethane damping material.

聚胺酯(PU)高分子具有良好的強韌性和耐油性，透過各種原料組成改變，可製得具有不同性能和用途的聚氨酯產品，包括彈性體、纖維、泡沫塑料、塗料和膠黏劑等。透過透過導入化學交聯官能基，可近一步提升產品性質，增加產品使用用途。其中氧氮苯并環己烷(Benzoxazine，BZ)合成簡易，反應不需添加觸媒，無副產物、性質良好且成本低廉，藉由氧氮苯并環己烷開環，即可提升材料的特性效能。 Polyurethane (PU) polymer has good strength and toughness and oil resistance. Through changes in the composition of various raw materials, polyurethane products with different properties and uses can be prepared, including elastomers, fibers, foams, paints and adhesives. The introduction of chemical cross-linking functional groups can further improve product properties and increase the use of products. Among them, benzoxazine (BZ) is easy to synthesize, the reaction does not need to add a catalyst, no by-products, good properties and low cost. By opening the ring of oxynitrobenzocyclohexane, the material can be improved. Feature efficiency.

國內外已有專利揭露BZ混摻至PU高分子中，如CN107083146A及WO2011041625A1所示，將BZ直接混摻PU高分子製作超疏水且耐磨的材料，主要就是利用氧氮苯并環己烷的低介電及低表面能的性質，並結合聚胺酯的優點而得。由於氧氮苯并環己烷在熱處理之後，可以進行交聯，如此 可以在分子鏈中型成一些網狀結構，以提高材料的機械性質及品質安定性。此類材料在熱交聯後沒有其他副產物產生也兼具尺寸安定性，並有高強度的機械性質。 Domestic and foreign patents have disclosed that BZ is blended into PU polymers. As shown in CN107083146A and WO2011041625A1, BZ is directly blended with PU polymers to make super-hydrophobic and wear-resistant materials, mainly using oxynitrobenzocyclohexane Low dielectric and low surface energy properties, combined with the advantages of polyurethane. Since oxynitrobenzocyclohexane can be cross-linked after heat treatment, so It can be formed into some network structure in the molecular chain to improve the mechanical properties and quality stability of the material. This kind of material has no other by-products after thermal cross-linking, and has both dimensional stability and high-strength mechanical properties.

另外，透過組成或交聯程度變化，能夠調整性質使聚氨酯達到阻尼材料應用的目的。中華民國專利公開號I460196的發明，揭露一種形成黏彈性阻尼聚合物之聚胺酯壓克力材料，其包含至少一種聚胺酯壓克力聚合物與至少一熱起始劑，上述至少一種聚胺酯壓克力聚合物包含至少一聚胺酯結構與至少一具雙鍵交聯結構。另外，US20110034578A1，揭露一種微孔狀聚胺酯材料的裝備系統包括發泡體；可溶於CMP漿液中之填料；及固化劑，較佳為包括芳族二胺及三醇者。為要產製微孔狀材料，泡體可以與填料(諸如PVP)結合，接著固化所得之混合物。微孔狀材料具有低的彈回率，且能消散不規則之能量及安定化磨光已產生經改良之均勻性及較少之碟化現象。中華民國專利公開號I540169，揭露一種嵌段共聚物，其包含：至少一種單烯基芳烴單體聚合物嵌段(A)及包含月桂烯之共聚物嵌段(B)所形成的共聚物，該嵌段共聚物可用於製備黏著劑及振動阻尼組合物。 In addition, through changes in composition or degree of cross-linking, properties can be adjusted so that polyurethane can achieve the purpose of damping material application. The invention of Republic of China Patent Publication No. I460196 discloses a polyurethane acrylic material forming a viscoelastic damping polymer, which comprises at least one polyurethane acrylic polymer and at least one thermal initiator, and the above at least one polyurethane acrylic polymerization The substance includes at least one polyurethane structure and at least one double bond cross-linked structure. In addition, US20110034578A1 discloses a microporous polyurethane material equipment system including a foam; a filler soluble in CMP slurry; and a curing agent, preferably including aromatic diamines and triols. To produce a microporous material, the foam can be combined with a filler (such as PVP) and the resulting mixture is then cured. The microporous material has a low rebound rate, and can dissipate irregular energy and stabilize the polishing. It has produced improved uniformity and less dishing. Republic of China Patent Publication No. I540169, discloses a block copolymer comprising: a copolymer formed by at least one monoalkenyl aromatic monomer polymer block (A) and a copolymer block containing myrcene (B), The block copolymer can be used to prepare adhesives and vibration damping compositions.

因此，目前業界需要一種聚胺酯阻尼材料之製備方法，其製備出來的聚胺酯可兼具彈性與黏性的性質，以製備出符合業界需求的阻尼聚胺酯材料。 Therefore, at present, the industry needs a method for preparing polyurethane damping materials. The prepared polyurethanes can have the properties of both elasticity and viscosity to prepare damping polyurethane materials that meet the needs of the industry.

本發明之主要目的在於提供一種製備含五碳環氧氮苯并環己烷聚胺酯阻尼材料之方法，可將氧氮苯并環己烷為主鏈的高分子單獨應用或是與其他材料形成複合材料。由於氧氮苯并環己烷的性能與製備程序與酚醛樹脂材料相類似，其成本亦具競爭優勢。 The main object of the present invention is to provide a method for preparing a five-carbon epoxy-nitrobenzocyclohexane polyurethane damping material, which can be used alone or in combination with other materials to form a polymer of oxynitrobenzocyclohexane as the main chain material. Since the properties and preparation procedures of oxynitrobenzocyclohexane are similar to phenolic resin materials, its cost is also competitive.

本發明之一種製備含五碳環氧氮苯并環己烷聚胺酯阻尼材料之方法，可利用石油烴產生乙烯過程中的副產物五碳稀烴為原料，製作出含五碳環氧氮苯并環己烷雙醇單體，再將此單體以不同比例導入聚胺酯高分子主鏈中，再藉由交聯反應調整聚胺酯的機械性質。五碳側環在分子鏈上可防止分子間堆疊，增加高分子自由體積，作為降低交聯溫度提升機械性質的方法，以符合實際產品的應用規格。 A method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane polyurethane damping material of the present invention can use the by-product five-carbon dilute hydrocarbon as a raw material in the process of producing ethylene from petroleum hydrocarbons to produce a five-carbon epoxy nitrogen-containing benzo Cyclohexane diol monomer, and then introduce the monomer into the polyurethane main chain in different proportions, and then adjust the mechanical properties of the polyurethane through the cross-linking reaction. The five-carbon side ring on the molecular chain can prevent the intermolecular stacking and increase the free volume of the polymer. It is used as a method to reduce the cross-linking temperature and improve the mechanical properties to meet the actual product application specifications.

為了達上述目的，根據本發明所提出的方案，提供含五碳環氧氮苯并環己烷雙醇之製備方法，步驟包括：將如式(a)之含五碳環化合物與胺基醇及聚甲醛反應，得到如式(I)之含五碳環氧氮苯并環己烷雙醇。 In order to achieve the above object, according to the solution proposed by the present invention, a method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane diol is provided. The steps include: combining the five-carbon ring-containing compound of formula (a) with an amino alcohol It reacts with polyoxymethylene to obtain a five-carbon epoxy nitrogen-containing benzocyclohexane diol of formula (I).

Figure 108112411-A0101-12-0003-1
Figure 108112411-A0101-12-0003-1

Figure 108112411-A0101-12-0004-2
其中，n為2至10之正整數。
Figure 108112411-A0101-12-0004-2
 Where n is a positive integer from 2 to 10.

上述中，該反應之溶劑係選自於由四氫呋喃、苯***、甲乙酮、丙酮、丁酮、甲苯、甲醇、乙醇、異丙醇及丁二醇所組成之群組之一；該反應之溫度為50℃至80℃。 In the above, the solvent of the reaction is one selected from the group consisting of tetrahydrofuran, phenethyl ether, methyl ethyl ketone, acetone, methyl ethyl ketone, toluene, methanol, ethanol, isopropyl alcohol and butylene glycol; the temperature of the reaction is 50℃ to 80℃.

上述中，該式(a)之含五碳環化合物可採用以下製程製備：將二環戊二烯(Dicyclopentadiene，DCPD)裂解成單五環之環戊二烯(Cyclopentadiene，CPD)二稀前驅物，再透過一系列反應，包括轉位、烷基化與加成反應，利用CPD製備出式(a)之五碳環化合物二醇單體。 In the above, the five-carbon ring-containing compound of formula (a) can be prepared by the following process: Dicyclopentadiene (DCPD) is cracked into a mono-pentacyclic dicyclopentadiene (Cyclopentadiene, CPD) dilute precursor Then, through a series of reactions, including transposition, alkylation and addition reaction, the five-carbon ring compound diol monomer of formula (a) is prepared by CPD.

上述中，該胺基醇可為

Figure 108112411-A0101-12-0004-3
，其中n值可為2至10之正整數。 In the above, the amino alcohol may be
Figure 108112411-A0101-12-0004-3
, Where the value of n can be a positive integer from 2 to 10.

本發明進一步提供一種含五碳環氧氮苯并環己烷之聚胺酯之製備方法，步驟包括：(A)將二元醇預聚物與二異氰酸酯於溫度30℃~130℃進行預聚反應；(B)加入式(I)之含五碳環氧氮苯并環己烷雙醇，於催化劑下持續反應2小時~5小時，生成含五碳環氧氮苯并環己烷之聚胺酯。 The present invention further provides a method for preparing a five-carbon epoxy-nitrobenzocyclohexane-containing polyurethane ester. The steps include: (A) Prepolymerization of a diol prepolymer and a diisocyanate at a temperature of 30°C to 130°C; (B) Add the five-carbon epoxy-nitrogen-containing benzocyclohexane diol of formula (I) and continue to react for 2 hours to 5 hours under the catalyst to produce a five-carbon epoxy-nitrogen-containing benzocyclohexane polyamine ester.

上述中，該含五碳環氧氮苯并環己烷之聚胺酯可具有如式(II)之結構。 In the above, the five-carbon epoxy nitrogen-containing benzocyclohexane polyamine ester may have the structure of formula (II).

Figure 108112411-A0101-12-0005-4
其中，x介於20至100之間、y介於30至150之間、n為2至10之正整數、-O-R1-O-為二元醇預聚物參與聚合反應後相應之結構單元、
Figure 108112411-A0101-12-0005-5
為二異氰酸酯參與聚合反應後相應之結構單元。
Figure 108112411-A0101-12-0005-4
 Where x is between 20 and 100, y is between 30 and 150, n is a positive integer from 2 to 10, and -OR 1 -O- is the corresponding structural unit after the diol prepolymer participates in the polymerization reaction ,
Figure 108112411-A0101-12-0005-5
It is the corresponding structural unit after diisocyanate participates in the polymerization reaction.

上述中，該含五碳環氧氮苯并環己烷之聚胺酯的分子量介於45,000(g/mol)至180,000(g/mol)之間。 In the above, the molecular weight of the five-carbon epoxy nitrogen-containing benzocyclohexane polyamine ester is between 45,000 (g/mol) and 180,000 (g/mol).

上述中，步驟(B)之催化劑可為辛酸亞錫(stannous octoate)或二月桂酸二丁基錫(dibutyltin dilaurate)。 In the above, the catalyst in step (B) may be stannous octoate or dibutyltin dilaurate.

上述中，該二元醇預聚物可為聚酯二醇(polyester diol)或聚醚醇。該聚酯二醇(polyester diol)可為聚己內酯二醇(polycaprolactone diol，PCL)或聚丙二醇(polypropylene glycol，PPG)；該聚醚醇可為聚四氫呋喃(polytetramethylene ether glycol，PTMEG)。 In the above, the diol prepolymer may be polyester diol or polyether alcohol. The polyester diol may be polycaprolactone diol (PCL) or polypropylene glycol (PPG); the polyether alcohol may be polytetramethylene ether glycol (PTMEG).

上述中，該二異氰酸酯係為脂肪族二元異氰酸酯或芳香族二元異氰酸酯。該脂肪族二元異氰酸酯係選自於由六亞甲基二異氰酸酯(hexamethylene diisocyanate，HDI)、異佛爾酮二異氰酸酯(isophorone diisocyanate，IPDI)及4,4’-二環己基甲烷二異氰酸酯(4,4'-methylene dicyclohexyl diisocyanate，H12MDI)所組成之群組之一；該芳香族二元異氰酸酯係選自於 由二苯基甲烷二異氰酸酯(methylenediphenyl diisocyanate，MDI)、雙異氰酸甲苯酯(toluene diisocyanate，TDI)及萘二異氰酸酯(naphthalene diisocyanate，NDI)所組成之群組之一。 In the above, the diisocyanate system is an aliphatic diisocyanate or an aromatic diisocyanate. The aliphatic diisocyanate is selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (4 , 4'-methylene dicyclohexyl diisocyanate (H12MDI) is one of the groups; the aromatic diisocyanate is selected from It is one of the groups composed of methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI) and naphthalene diisocyanate (NDI).

上述中，步驟(A)或步驟(B)之溶劑係選自於由二甲基乙酰胺(DMAc)、二甲基甲醯胺(DMF)及N-甲基吡咯烷酮(NMP)所組成之群組之一；步驟(B)之聚合溶劑濃度為10wt%~35wt%。 In the above, the solvent of step (A) or step (B) is selected from the group consisting of dimethylacetamide (DMAc), dimethylformamide (DMF) and N-methylpyrrolidone (NMP) One of the groups; the concentration of the polymerization solvent in step (B) is 10wt%~35wt%.

本發明進一步提供一種交聯型聚胺酯，係將如式(II)之聚胺酯於溫度140℃~300℃進行熱交聯反應，得到如式(III)之交聯型聚胺酯。 The present invention further provides a cross-linked polyurethane, wherein the polyamine ester of formula (II) is thermally cross-linked at a temperature of 140° C. to 300° C. to obtain the cross-linked polyurethane of formula (III).

Figure 108112411-A0101-12-0006-7
其中，x介於20至100之間、y介於30至150之間、n為2至10之正整數、-O-R1-O-為二元醇預聚物參與聚合反應後相應之結構單元、
Figure 108112411-A0101-12-0006-8
為二異氰酸酯參與聚合反應後相應之結構單元。
Figure 108112411-A0101-12-0006-7
 Where x is between 20 and 100, y is between 30 and 150, n is a positive integer from 2 to 10, and -OR 1 -O- is the corresponding structural unit after the diol prepolymer participates in the polymerization reaction ,
Figure 108112411-A0101-12-0006-8
It is the corresponding structural unit after diisocyanate participates in the polymerization reaction.

上述中，該式(III)之交聯型聚胺酯可作為適用溫度範圍在-20℃至40℃之間的阻尼材料。 In the above, the cross-linked polyurethane of formula (III) can be used as a damping material with a temperature range of -20°C to 40°C.

本發明是一種製備含五碳環氧氮苯并環己烷聚胺酯阻尼材料之方法，可利用石油烴產生乙烯過程中的副產物五碳稀烴作為原料，結合氧氮苯并環己烷，製備聚胺酯主鏈帶有五碳環及氧氮苯并環己烷之高分子結構。本發明所製備之含五碳環氧氮苯并環己烷聚胺酯，結合五碳環及氧氮苯并環己烷兩種分子結構的優點，可應用在阻尼材料的領域。 The invention is a method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane polyurethane damping material, which can use the by-product five-carbon dilute hydrocarbon in the process of producing petroleum hydrocarbon as ethylene as a raw material, combined with oxygen-nitrobenzobenzocyclohexane to prepare The polyurethane main chain has a polymer structure of five-carbon ring and oxynitrobenzocyclohexane. The five-carbon epoxy nitrogen-containing benzocyclohexane polyurethane prepared by the invention combines the advantages of two molecular structures of five-carbon ring and oxynitrobenzoxane, and can be applied in the field of damping materials.

以上之概述與接下來的詳細說明及附圖，皆是為了能進一步說明本發明達到預定目的所採取的方式、手段及功效。而有關本發明的其他目的及優點，將在後續的說明及圖式中加以闡述。 The above summary, the following detailed description and the accompanying drawings are intended to further illustrate the methods, means and effects of the present invention to achieve the intended purpose. The other objects and advantages of the present invention will be explained in the subsequent description and drawings.

S101‧‧‧步驟 S101‧‧‧Step

S201-S202‧‧‧步驟 S201-S202‧‧‧Step

第一圖係為本發明一種含五碳環氧氮苯并環己烷雙醇及其聚胺酯之製備方法流程圖；第二圖係為本發明實施例含五碳環氧氮苯并環己烷雙醇之合成示意圖；第三圖係為本發明實施例含五碳環氧氮苯并環己烷雙醇之1H-NMR圖譜；第四圖係為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之合成示意圖；第五圖係為本發明實施例含五碳環氧氮苯并環 己烷之聚胺酯之FT-IR分析圖；第六圖係為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之DSC分析圖；第七圖係為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之拉力分析圖；第八圖係為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯交聯測試之DSC分析圖；第九圖係為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯交聯前後之動態熱機械分析圖。 The first figure is a flow chart of a method for preparing a five-carbon epoxy-nitrogen-containing benzocyclohexane diol and its polyamine ester; the second figure is a five-carbon epoxy-nitrogen-containing benzocyclohexane. Schematic diagram of the synthesis of diol; the third picture is the 1 H-NMR spectrum of the five-carbon epoxy nitrogen-containing benzocyclohexane diol in the embodiment of the present invention; the fourth picture is the five-carbon epoxy nitrogen in the embodiment of the present invention Schematic diagram of the synthesis of the polyamine ester of benzocyclohexane; the fifth figure is the FT-IR analysis diagram of the polyamine ester containing five carbon epoxynitrobenzoxane; the sixth figure is the example of the present invention The DSC analysis chart of the five-carbon epoxy-nitrobenzobenzohexane polyamine ester; the seventh figure is the tensile analysis chart of the five-carbon epoxy-nitrobenzobenzohexane polyamine ester; the eighth figure is the DSC analysis chart of cross-linking test of polyurethane containing five-carbon epoxy-nitrobenzocyclohexane in the embodiment of the invention; the ninth figure is before and after cross-linking of polyurethane containing five-carbon epoxy-nitrobenzocyclohexane in the embodiment of the invention Dynamic thermomechanical analysis chart.

以下係藉由特定的具體實例說明本發明之實施方式，熟悉此技藝之人士可由本說明書所揭示之內容輕易地了解本發明之優點及功效。 The following is a description of the embodiments of the present invention by specific specific examples. Those skilled in the art can easily understand the advantages and effects of the present invention from the contents disclosed in this specification.

請參閱第一圖，為本發明一種含五碳環氧氮苯并環己烷雙醇及其聚胺酯之製備方法流程圖。如圖所示，本發明之一種含五碳環氧氮苯并環己烷雙醇之製備方法，步驟包括：將如式(a)之含五碳環化合物與胺基醇及聚甲醛反應，得到如式(I)之含五碳環氧氮苯并環己烷雙醇。本發明進一步提供一種含五碳環氧氮苯并環己烷聚胺酯之製備方法，步驟包括：(A)將二元醇預聚物與二異氰酸酯於溫度30℃~130℃進行預聚反應；(B)加入式(I)之含五碳環氧氮苯并環己烷雙醇，於催化劑下持續反應2小時~5小時，生成含五碳環氧氮苯并環己烷之 聚胺酯。 Please refer to the first figure, which is a flow chart of a method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane diol and its polyamine ester. As shown in the figure, a method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane diol of the present invention includes the steps of: reacting a five-carbon ring-containing compound of formula (a) with an amino alcohol and polyoxymethylene, A five-carbon epoxy nitrogen-containing benzocyclohexane diol as in formula (I) is obtained. The present invention further provides a method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane polyurethane ester. The steps include: (A) Prepolymerization of a diol prepolymer and a diisocyanate at a temperature of 30°C to 130°C; ( B) Add the five-carbon epoxy-nitrogen-containing benzocyclohexane diol of formula (I), and continue to react under the catalyst for 2 hours to 5 hours to form the five-carbon epoxy-nitrogen-containing benzocyclohexane Polyurethane.

本發明進一步提供一種交聯型聚胺酯，係以如式(II)之結構於溫度140℃~300℃進行熱交聯反應，得到如式(III)之交聯型聚胺酯。 The present invention further provides a cross-linked polyurethane, which undergoes a thermal cross-linking reaction at a temperature of 140° C. to 300° C. with the structure of formula (II) to obtain the cross-linked polyurethane of formula (III).

Figure 108112411-A0101-12-0009-9
Figure 108112411-A0101-12-0009-9

Figure 108112411-A0101-12-0009-10
Figure 108112411-A0101-12-0009-10

Figure 108112411-A0101-12-0009-11
Figure 108112411-A0101-12-0009-11

Figure 108112411-A0101-12-0009-12
其中，x介於20至100之間、y介於30至150之間、n為2至10之正整數、-O-R1-O-為二元醇預聚物參與聚合反應後相 應之結構單元、
Figure 108112411-A0101-12-0010-13
為二異氰酸酯參與聚合反應後相應之結構單元。
Figure 108112411-A0101-12-0009-12
 Where x is between 20 and 100, y is between 30 and 150, n is a positive integer from 2 to 10, and -OR 1 -O- is the corresponding structural unit after the diol prepolymer participates in the polymerization reaction ,
Figure 108112411-A0101-12-0010-13
It is the corresponding structural unit after diisocyanate participates in the polymerization reaction.

實施例： Example:

實施例1：請參閱第二圖，為本發明實施例含五碳環氧氮苯并環己烷雙醇之合成示意圖。如圖所示，於此實施例中，取0.3088克胺基醇置入50mL雙頸圓底瓶中，加入2ml的溶劑(如IPA、THF、DMF等)，再加入0.16g聚甲醛(聚合度3)，以磁石均勻攪拌，通入流通氮氣，在60℃下反應。再加入0.61克之4,4'-(cyclopentane-1,1-diyl)diphenol(CPDP)反應物溶於10ml的溶劑，以進料管緩慢滴入，加熱迴流，反應時間超過10小時。反應完後用將溶劑用濃縮迴旋儀抽乾，把剩餘的粗產物加入15ml氯仿(CHCl3)，用稀釋過的氫氧化鈉與純水萃取數次。再加入無水硫酸鎂除水後過濾，再把氯仿(CHCl3)抽乾，所得產物為含五碳環氧氮苯并環己烷雙醇單體(CPDP-C6BZ)之暗棕色黏稠油狀物。請參閱第三圖之含五碳環氧氮苯并環己烷雙醇之1H-NMR圖譜，該雙醇溶在CDCl3溶劑中，以超導核磁共振光譜儀(1H-NMR)分析(δ/ppm,400Hz,CDCl3-d1)，所得化學位移為：8.00(m,2H,Ar-H),6.83(d,2H,Ar-H),6.66(d 2H,Ar-H),4.81(s,4H,-N-CH2-O-),3.94(s,4H,-N-CH2-),3.65(t,4H,-CH2-OH),2.73(t,4H,-N-CH2-),2.20(m,4H,-CH2-),1.68(s,4H,-CH2-) 1.57~1.38(m,18H,-(CH2)4-,-OH)。 Embodiment 1: Please refer to the second figure, which is a schematic diagram of the synthesis of a five-carbon epoxy nitrogen-containing benzocyclohexane diol. As shown in the figure, in this example, 0.3088 g of amino alcohol was put into a 50 mL double-necked round bottom bottle, 2 ml of solvent (such as IPA, THF, DMF, etc.) was added, and then 0.16 g of polyoxymethylene (degree of polymerization) 3) Stir uniformly with a magnet, pass nitrogen gas through it, and react at 60°C. Then add 0.61g of 4,4'-(cyclopentane-1,1-diyl)diphenol (CPDP) reactant dissolved in 10ml of solvent, slowly drop into the feed tube, heat to reflux, and the reaction time exceeds 10 hours. After the reaction was completed, the solvent was drained with a convolution gyroscope, the remaining crude product was added to 15 ml of chloroform (CHCl 3 ), and extracted several times with diluted sodium hydroxide and pure water. After adding anhydrous magnesium sulfate to remove water and filtering, the chloroform (CHCl 3 ) is pumped to dryness, and the resulting product is a dark brown viscous oil containing a five-carbon epoxy nitrogen benzocyclohexane diol monomer (CPDP-C6BZ) . See FIG containing the third of the five carbon nitrogen-benzo epoxy-cyclohexane bis 1 H-NMR spectrum of an alcohol, the alcohol dual solvent in CDCl 3, superconducting magnetic resonance spectroscopy (1 H-NMR) analysis ( δ/ppm, 400Hz, CDCl 3 -d 1 ), the resulting chemical shifts are: 8.00 (m, 2H, Ar-H), 6.83 (d, 2H, Ar-H), 6.66 (d 2H, Ar-H), 4.81 (s, 4H, -N-CH 2 -O-), 3.94 (s, 4H, -N-CH 2 -), 3.65 (t, 4H, -CH 2 -OH), 2.73 (t, 4H,- N-CH 2 -), 2.20 (m, 4H, -CH 2 -), 1.68 (s, 4H, -CH 2 -) 1.57 ~ 1.38 (m, 18H,-(CH 2 ) 4 -, -OH).

實施例2：請參閱第四圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之合成示意圖。請參閱表一之添加量，取7.159克聚四氫呋喃雙醇(PTMEG)置入250mL雙頸圓底瓶中，加入2ml的溶劑(如DMAc、NMP、DMF等)當作溶劑，再加入0.77至1.42克的二苯基甲烷二異氰酸酯(MDI)，以磁石均勻攪拌，通入流通氮氣，在60℃下開始進行預聚反應1小時。再把不同比例的CPDP-C6BZ溶於20ml的溶劑，並由進料管緩慢滴入，加熱迴流溫度，穩定之後加入觸媒二月桂酸二丁基錫(DBTL,Dibutyltin dilaurate)，反應時間2小時，並將溫度逐漸升至75℃。反應完後用將溶液倒在鐵氟龍(PTFE)盤上後放入烘箱，在60℃下放置超過10小時即得代號為CPBZ-PU25(BZ及MDI屬於硬鏈段，比例為25wt%)、CPBZ-PU35(BZ及MDI屬於硬鏈段，比例為35wt%)、CPBZ-PU45(BZ及MDI屬於硬鏈段，比例為45wt%)薄膜。其餘商用之聚雙醇如聚己內酯二醇(polycaprolactone diol,PCL)及二異氰酸酯如異佛爾酮二異氰酸酯(isophorone diisocyanate,IPDI)及4,4’-二環己基甲烷二異氰酸酯(4,4'-methylene dicyclohexyl diisocyanate,H12MDI)、雙異氰酸甲苯酯(toluene diisocvanate,TDI)等單體亦適用於製備此類聚胺酯。 Embodiment 2: Please refer to the fourth figure, which is a schematic diagram of the synthesis of a polyurethane containing five-carbon epoxy-nitrobenzocyclohexane. Please refer to Table 1 for the amount of addition, take 7.159 grams of polytetrahydrofurandiol (PTMEG) into a 250mL double neck round bottom bottle, add 2ml of solvent (such as DMAc, NMP, DMF, etc.) as a solvent, then add 0.77 to 1.42 Grams of diphenylmethane diisocyanate (MDI) were evenly stirred with a magnet, flowed with nitrogen gas, and prepolymerization reaction was started at 60°C for 1 hour. Then dissolve CPDP-C6BZ in different proportions in 20ml of solvent, slowly drop into the feed tube, heat to reflux temperature, after stabilization, add catalyst dibutyltin dilaurate (DBTL, Dibutyltin dilaurate), the reaction time is 2 hours, and The temperature was gradually increased to 75°C. After the reaction is completed, pour the solution on a Teflon (PTFE) plate and place it in an oven. Place it at 60 ℃ for more than 10 hours to get the code name CPBZ-PU25 (BZ and MDI belong to the hard segment, the proportion is 25wt%) , CPBZ-PU35 (BZ and MDI belong to the hard segment, the proportion is 35wt%), CPBZ-PU45 (BZ and MDI belong to the hard segment, the proportion is 45wt%) film. Other commercial polyglycols such as polycaprolactone diol (PCL) and diisocyanates such as isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (4, 4'-methylene dicyclohexyl diisocyanate (H12MDI), toluene diisocyanate (toluene diisocvanate, TDI) and other monomers are also suitable for the preparation of such polyurethanes.

Figure 108112411-A0101-12-0012-14
Figure 108112411-A0101-12-0012-14

請參閱第五圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之FT-IR分析圖。如圖所示，利用紅外線光譜儀(FT-IR)分析聚胺酯(urethane)及氧氮苯并環己烷(benzoxazine)之官能基團，監控聚合過程。以第五圖(a)的CPBZ-PU45為例，胺酯的N-H不對稱和對稱伸展吸收峰出現在3534cm-1、3315cm-1，-CH2的伸展峰在2934cm-1及2850cm-1，-C=O伸展峰出現在1730cm-1，1220cm-1則有-NH及-CN特徵峰，1102cm-1則為C-O-C伸展峰。重要的氧氮并環己烷(benzoxazine)則在930cm-1附近，證明已成功聚合含氧氮并環己烷的聚胺酯材料。 Please refer to the fifth figure, which is an FT-IR analysis diagram of a polyurethane containing five-carbon epoxy-nitrobenzocyclohexane according to an embodiment of the present invention. As shown in the figure, the functional groups of urethane and benzoxazine were analyzed by infrared spectroscopy (FT-IR) to monitor the polymerization process. Taking the CPBZ-PU45 in Figure 5(a) as an example, the NH asymmetric and symmetric stretching absorption peaks of urethanes appear at 3534cm -1 , 3315cm -1 , the stretching peaks of -CH 2 are at 2934cm -1 and 2850cm -1 , The -C=O stretching peak appears at 1730cm -1 , 1220cm -1 has -NH and -CN characteristic peaks, and 1102cm -1 is the COC stretching peak. The important benzoxazine is near 930cm -1 , which proves that the urethane material containing oxazepine has been successfully polymerized.

本發明利用熱差掃描分析儀(DSC)分析此一系列的CPBZ-PU的熱性質，由DSC的數據可以初步了解這一類高分子的相轉移溫度範圍。另一方面，從TGA的數據可觀察高分子鏈在高溫下裂解及重量損失的情形，由於本系列之高分子在氧氮并環己烷的交聯並沒重量損失，所以有重量損失的訊號發生時，皆可以視為斷鍵後所發生的重量損失。如表二所示， 此一系列CPBZ-PU高分子的裂解溫度(Td)大致在233-283℃之間，並隨著CPDP-C6BZ在主鏈的含量減少，呈現增加的趨勢。 In the present invention, a thermal differential scanning analyzer (DSC) is used to analyze the thermal properties of this series of CPBZ-PU, and the phase transition temperature range of this type of polymer can be preliminarily understood from the data of DSC. On the other hand, from the TGA data, it can be observed that the polymer chain is cleaved at high temperature and the weight is lost. There is no weight loss due to the cross-linking of oxazepine in this series of polymers, so there is a signal of weight loss When it occurs, it can be regarded as the weight loss that occurs after the key is broken. As shown in Table 2, the cracking temperature (T d ) of this series of CPBZ-PU polymers is roughly between 233-283°C, and as CPDP-C6BZ content in the main chain decreases, it shows an increasing trend.

Figure 108112411-A0101-12-0013-15
Figure 108112411-A0101-12-0013-15

請參閱第六圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之DSC分析圖。掃描的速度為10℃/min，經過反覆升降溫的過程，結果可以發現到CPBZ-PU45在28.8℃左右有一個熔點(Tm)。其餘的樣品皆呈現相同的趨勢，此結果顯示這一系列的高分子相轉移的區間在0℃至40℃之間，即軟鏈段及硬鏈段的交互排列在此區間發生。 Please refer to the sixth figure, which is a DSC analysis chart of the polyurethane containing five-carbon epoxy-nitrobenzocyclohexane. The scanning speed is 10℃/min. After repeated temperature rise and fall, it can be found that CPBZ-PU45 has a melting point (T m ) around 28.8℃. The rest of the samples showed the same trend. This result shows that the range of phase transition of this series of polymers is between 0°C and 40°C, that is, the alternating arrangement of soft and hard segments occurs in this interval.

請參閱第七圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯之拉力分析圖。藉由調整軟硬鏈段的比例，可以改變材料的抗拉強度及伸長量。氧氮并環己烷(BZ)及二苯基甲烷二異氰酸酯(MDI)在PU鏈段中屬於硬鏈段，而聚四氫呋喃雙醇(PTMEG)為軟鏈段，本發明測試了硬鏈段比例25wt%、35wt%與45wt%的聚胺酯，樣品名分別為CPBZ-PU25、CPBZ-PU35、CPBZ-PU45。經測試後，以BZ的量為最多CPBZ-PU45抗拉強度及伸長量皆為最佳，其抗拉力更可以達到16.8MPa，且 伸長量超過原來的17倍。伸長量隨著拉力呈正比的現象，是表現出彈性的性質。此結果也呈現隨著BZ的比例增加，則機械性質有提升的趨勢。也證明本研究設計的材料，可符合兼具彈性與黏性的性質是相當有潛力符合阻尼材料的應用需求。 Please refer to the seventh figure, which is a drawing of the tensile analysis of the polyurethane containing five-carbon epoxy-nitrobenzocyclohexane. By adjusting the proportion of soft and hard segments, the tensile strength and elongation of the material can be changed. Oxyazinocyclohexane (BZ) and diphenylmethane diisocyanate (MDI) are hard segments in the PU segment, and polytetrahydrofuran diol (PTMEG) is the soft segment. The present invention tested the proportion of the hard segment 25wt%, 35wt% and 45wt% polyurethane, the sample names are CPBZ-PU25, CPBZ-PU35, CPBZ-PU45. After testing, the amount of BZ is the most CPBZ-PU45 tensile strength and elongation are the best, its tensile strength can reach 16.8MPa, and The elongation exceeds 17 times the original. The phenomenon that the amount of elongation is proportional to the tensile force is the property of showing elasticity. This result also shows that as the proportion of BZ increases, the mechanical properties tend to improve. It also proves that the material designed in this study can meet the properties of both elasticity and viscosity, which has great potential to meet the application requirements of damping materials.

氧氮并環己烷(BZ)交聯溫度可以熱差掃描分析儀(DSC)來進行觀察。首先，將已製備的單體CPDP-C6BZ從常溫加熱至250℃以上的高溫，以10℃/min的掃描速度進行觀察。當溫度到達交聯的溫度時，即可看到放熱的訊號。請參閱第八圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯交聯測試之DSC分析圖。由第八圖可以發現到CPDP-C6BZ的交聯起始溫度為100-250℃，可以了解Cardo結構的CPDP-C6BZ使得分子間堆疊後的自由體積(free volume)可達成較低溫度進行熱交聯反應，而CPBZ-PU交聯降至128℃，顯示導入Cardo結構可有效降低交聯溫度。 The cross-linking temperature of oxazepine (BZ) can be observed with a thermal differential scanning analyzer (DSC). First, the prepared monomer CPDP-C6BZ was heated from normal temperature to a high temperature of 250°C or higher, and observed at a scanning speed of 10°C/min. When the temperature reaches the cross-linking temperature, you can see the exothermic signal. Please refer to the eighth figure, which is a DSC analysis chart of the cross-linking test of the polyurethane containing five-carbon epoxy-nitrobenzocyclohexane according to an embodiment of the present invention. It can be found from the eighth figure that the CPDP-C6BZ has a cross-linking starting temperature of 100-250°C. It can be understood that the CPDP-C6BZ of the Cardo structure allows the free volume after the intermolecular stacking to reach a lower temperature for thermal cross-linking The cross-linking reaction, and CPBZ-PU cross-linking dropped to 128 ℃, showing that the introduction of Cardo structure can effectively reduce the cross-linking temperature.

阻尼材料的最終使用標準，可以利用動態機械性質分析儀(DMA)的tan δ數據結果進行觀察。依照拉力測試的結果，以CPBZ-PU45的樣品所呈現的機械性質為最佳。因此，DMA分析也選擇此比例的樣品進行測試。請參閱第九圖，為本發明實施例含五碳環氧氮苯并環己烷之聚胺酯交聯前後之動態熱機械分析圖。如圖所示，CPBZ-PU45在-41℃，1.8℃，50℃有較高的tan δ，在低溫下的tan δ為聚四氫呋喃雙醇(PTMEG)所貢獻。而樣品的tan δ大約在0.16至0.2左右已顯現 出其阻尼性質。 The final use standard of the damping material can be observed using the tan δ data results of the Dynamic Mechanical Properties Analyzer (DMA). According to the results of the tensile test, the mechanical properties exhibited by the CPBZ-PU45 sample are the best. Therefore, DMA analysis also selects this proportion of samples for testing. Please refer to the ninth figure, which is a dynamic thermomechanical analysis diagram of a five-carbon epoxy-nitrobenzoxane-containing polyurethane before and after crosslinking. As shown in the figure, CPBZ-PU45 has a higher tan δ at -41°C, 1.8°C, and 50°C. The tan δ at low temperature is contributed by polytetrahydrofurandiol (PTMEG). And the tan δ of the sample has appeared around 0.16 to 0.2 Out its damping properties.

CPBZ-PU經過高溫進行交聯交聯反應後，從第五圖的FT-IR圖譜顯示，三種比例的CPBZ-PUX在930cm-1附近的benzoxazine特徵峰已消失，可判斷本實施例CPDP-C6BZ可作為鏈延長劑，其中的BZ在PU主鏈中已交聯完成。交聯後的DMA動態機械性質分析如第九圖所示，材料在交聯處理之後的CPBZ-PUX45，經過熱交聯之後，tan δ最高值從-18℃平移至17℃左右，顯示BZ交聯後，材料阻尼性質也隨之改變。這也讓此一概念在製程改善性質上，提供一個可變參數。 After the CPBZ-PU undergoes crosslinking and crosslinking reaction at high temperature, the FT-IR spectrum of the fifth figure shows that the benzoxazine characteristic peak of the CPBZ-PUX at three ratios near 930 cm -1 has disappeared. It can be judged that the CPDP-C6BZ of this example Can be used as a chain extender, in which BZ has been cross-linked in the PU main chain. The analysis of dynamic mechanical properties of DMA after cross-linking is shown in the ninth figure. The CPBZ-PUX45 of the material after cross-linking treatment, after thermal cross-linking, the maximum value of tan δ shifts from -18 ℃ to about 17 ℃, showing BZ cross-linking After coupling, the damping properties of the material also change. This also allows this concept to provide a variable parameter in the nature of process improvement.

本發明之製備含五碳環氧氮苯并環己烷聚胺酯阻尼材料，可利用裂解石油烴之副產物雙環戊二烯及氧氮苯并環己烷(Benzoxazine，BZ)當作起始物，製備新的含五碳環氧氮苯并環己烷雙醇單體，做為聚胺酯的鏈延長劑。將所得的聚胺酯經由交聯反應後，開發高拉伸特性的聚胺酯，改善氧氮苯并環己烷原本硬脆無彈性的限制，結合兩種材料優點，可提供航空複材或運動用品等材料的阻尼性質調整，使其在未來的應用領域更加寬廣。 The preparation of the five-carbon epoxy nitrogen-containing benzocyclohexane polyurethane damping material of the present invention can use by-products of cracking petroleum hydrocarbons, dicyclopentadiene and oxynitrobenzocyclohexane (Benzoxazine, BZ), as starting materials. Preparation of a new five-carbon epoxy nitrogen-containing benzocyclohexane diol monomer as a chain extender for polyurethane. After the obtained polyurethane is cross-linked, the polyurethane with high tensile properties is developed to improve the original hard, brittle and inelastic limitation of oxynitrobenzocyclohexane. Combining the advantages of the two materials, it can provide materials such as aviation composites or sports products. Adjustment of the damping properties makes the application area wider in the future.

上述之實施例僅為例示性說明本發明之特點及功效，非用以限制本發明之實質技術內容的範圍。任何熟悉此技藝之人士均可在不違背發明之精神及範疇下，對上述實施例進行修飾與變化。因此，本發明之權利保護範圍，應如後述之申請專利範圍所列。 The above-mentioned embodiments are merely illustrative of the features and effects of the present invention, and are not intended to limit the scope of the essential technical content of the present invention. Anyone who is familiar with this skill can modify and change the above embodiments without departing from the spirit and scope of the invention. Therefore, the scope of protection of the rights of the present invention should be as listed in the scope of patent application mentioned later.

S101‧‧‧步驟 S101‧‧‧Step

S201-S202‧‧‧步驟 S201-S202‧‧‧Step

Claims (12)

一種含五碳環氧氮苯并環己烷雙醇之製備方法，步驟包括：將如式(a)之含五碳環化合物與胺基醇及聚甲醛反應，得到如式(I)之含五碳環氧氮苯并環己烷雙醇，
Figure 108112411-A0305-02-0019-1
Figure 108112411-A0305-02-0019-3
 其中，n為2至10之正整數。 A method for preparing a five-carbon epoxy nitrogen-containing benzocyclohexane diol, the steps include: reacting a five-carbon ring-containing compound of formula (a) with an amino alcohol and polyoxymethylene to obtain a compound of formula (I) Five carbon epoxy nitrogen benzocyclohexane diol,
Figure 108112411-A0305-02-0019-1
Figure 108112411-A0305-02-0019-3
 Where n is a positive integer from 2 to 10. 如申請專利範圍第1項所述之含五碳環氧氮苯并環己烷雙醇之製備方法，其中，反應之溶劑係選自於由四氫呋喃、苯***、甲乙酮、丙酮、丁酮、甲苯、甲醇、乙醇、異丙醇及丁二醇所組成之群組之一。 The preparation method of five-carbon epoxy-nitrogen-containing benzocyclohexane diol as described in item 1 of the patent application scope, wherein the reaction solvent is selected from tetrahydrofuran, phenethyl ether, methyl ethyl ketone, acetone, methyl ethyl ketone, toluene , Methanol, ethanol, isopropanol and butanediol. 一種含五碳環氧氮苯并環己烷之聚胺酯之製備方法，步驟包括：(A)將二元醇預聚物與二異氰酸酯於溫度30℃~130℃進行預聚反應； (B)加入如申請專利範圍第1項所述之式(I)之含五碳環氧氮苯并環己烷雙醇，於催化劑下持續反應2小時~5小時，生成含五碳環氧氮苯并環己烷之聚胺酯。 A method for preparing a polyamine ester containing five carbon epoxy-nitrobenzocyclohexane, the steps include: (A) Prepolymerization of a diol prepolymer and a diisocyanate at a temperature of 30°C to 130°C; (B) Add the five-carbon epoxy nitrogen-containing benzocyclohexane diol of formula (I) as described in item 1 of the patent application scope, and continue to react under the catalyst for 2 hours to 5 hours to generate a five-carbon epoxy resin Polyurethane ester of nitrobenzocyclohexane. 如申請專利範圍第3項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，該含五碳環氧氮苯并環己烷之聚胺酯具有如式(II)之結構，
Figure 108112411-A0305-02-0020-4
 其中，x介於20至100之間、y介於30至150之間；n為2至10之正整數；-O-R1-O-為二元醇預聚物參與聚合反應後相應之結構單元，R1為聚酯基團或聚醚基團；
Figure 108112411-A0305-02-0020-5
為二異氰酸酯參與聚合反應後相應之結構單 元，R2為脂肪族基團或芳香族基團。 The preparation method of the five-carbon epoxy-nitrobenzobenzocyclohexane-containing polyamine ester as described in Item 3 of the patent application scope, wherein the five-carbon epoxy-nitrobenzobenzocyclohexane-containing polyamine ester has the formula (II) structure,
Figure 108112411-A0305-02-0020-4
 Among them, x is between 20 and 100, y is between 30 and 150; n is a positive integer from 2 to 10; -OR 1 -O- is the corresponding structural unit after the diol prepolymer participates in the polymerization reaction , R 1 is a polyester group or a polyether group;
Figure 108112411-A0305-02-0020-5
It is the corresponding structural unit after the diisocyanate participates in the polymerization reaction, R 2 is an aliphatic group or an aromatic group. 如申請專利範圍第3項或第4項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，該含五碳環氧氮苯并環己烷之聚胺酯的分子量介於45,000g/mol至180,000g/mol之間。 The preparation method of the five-carbon epoxy nitrogen-containing benzocyclohexane polyamine ester as described in Item 3 or Item 4 of the patent application scope, wherein the molecular weight of the five-carbon epoxy nitrogen-containing benzocyclohexane polyamine ester is Between 45,000g/mol and 180,000g/mol. 如申請專利範圍第3項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，步驟(B)之催化劑可為辛酸亞錫(stannous octoate)或二月桂酸二丁基錫(dibutyltin dilaurate)。 The preparation method of the polycarbamate containing five-carbon epoxy-nitrobenzocyclohexane as described in item 3 of the patent application scope, wherein the catalyst in step (B) may be stannous octoate or dibutyltin dilaurate (dibutyltin dilaurate). 如申請專利範圍第4項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，該二元醇預聚物係為聚己內酯二醇(polycaprolactone diol，PCL)或聚丙二醇(polypropylene glycol，PPG)或聚四氫呋喃(polytetramethylene ether glycol，PTMEG)。 The preparation method of polycarbamate containing five carbon epoxy-nitrobenzocyclohexane as described in item 4 of the patent application scope, wherein the glycol prepolymer is polycaprolactone diol (PCL) Or polypropylene glycol (PPG) or polytetramethylene ether glycol (PTMEG). 如申請專利範圍第4項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，該二元異氰酸酯係選自於由六亞甲基二異氰酸酯(hexamethylene diisocyanate，HDI)、異佛爾酮二異氰酸酯(isophorone diisocyanate，IPDI)及4,4’-二環己基甲烷二異氰酸酯(4,4'-methylene dicyclohexyl diisocyanate，H12MDI)、二苯基甲烷二異氰酸酯(methylenediphenyl diisocyanate，MDI)、雙異氰酸甲苯酯(toluene diisocyanate，TDI)及萘二異氰酸酯(naphthalene diisocyanate，NDI)所組成之群組之一。 The preparation method of polycarbamate containing five-carbon epoxy-nitrobenzocyclohexane as described in item 4 of the patent application scope, wherein the binary isocyanate is selected from hexamethylene diisocyanate (HDI) , Isophorone diisocyanate (IPDI) and 4,4'-dicyclohexyl diisocyanate (4,4'-methylene dicyclohexyl diisocyanate (H12MDI), methylenediphenyl diisocyanate (MDI) , Toluene diisocyanate (TDI) and naphthalene diisocyanate (NDI). 如申請專利範圍第3項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，步驟(A)或步驟(B)之溶劑係選自於由二甲基乙酰胺(DMAc)、二甲基甲醯胺(DMF)及N-甲基吡咯烷酮(NMP)所組成之群組之一。 The preparation method of polyamine ester containing five-carbon epoxy-nitrobenzocyclohexane as described in item 3 of the patent application scope, wherein the solvent in step (A) or step (B) is selected from dimethylacetamide (DMAc), dimethylformamide (DMF) and N-methylpyrrolidone (NMP). 如申請專利範圍第3項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，步驟(B)之聚合溶劑濃度為10wt%~35wt%。 The method for preparing a five-carbon epoxy-nitrobenzocyclohexane-containing polyurethane ester as described in item 3 of the patent application scope, wherein the concentration of the polymerization solvent in step (B) is 10 wt% to 35 wt%. 如申請專利範圍第4項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，係進一步將如式(II)之聚胺酯於溫度140℃~300℃進行熱交聯反應，得到如式(III)之交聯型聚胺酯，
Figure 108112411-A0305-02-0022-7
 其中，x介於20至100之間、y介於30至150之間；n為2至10之正整數；-O-R1-O-為二元醇預聚物參與聚合反應後相應之結構單元，R1為聚酯基團或聚醚基團；
Figure 108112411-A0305-02-0022-6
為二異氰酸酯參與聚合反應後相應之結構單 元，R2為脂肪族基團或芳香族基團。 The preparation method of the polycarbamate containing five-carbon epoxy-nitrobenzocyclohexane as described in item 4 of the patent application scope, wherein the polyurethane of formula (II) is further thermally cross-linked at a temperature of 140°C to 300°C The reaction yields a cross-linked polyurethane of formula (III),
Figure 108112411-A0305-02-0022-7
 Among them, x is between 20 and 100, y is between 30 and 150; n is a positive integer from 2 to 10; -OR 1 -O- is the corresponding structural unit after the diol prepolymer participates in the polymerization reaction , R 1 is a polyester group or a polyether group;
Figure 108112411-A0305-02-0022-6
It is the corresponding structural unit after the diisocyanate participates in the polymerization reaction, R 2 is an aliphatic group or an aromatic group. 如申請專利範圍第11項所述之含五碳環氧氮苯并環己烷之聚胺酯之製備方法，其中，該式(III)之交聯型聚胺酯可作為適用溫度範圍在-20℃至40℃之間的阻尼材料。 The preparation method of the five-carbon epoxy-nitrobenzobenzohexane-containing polyamine ester as described in item 11 of the patent application scope, wherein the cross-linked polyamine ester of formula (III) can be used as the applicable temperature range from -20°C to 40 Damping material between ℃.
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