TWI453237B - Cross-linking composition for forming the quaternary ammonium salts - Google Patents
Cross-linking composition for forming the quaternary ammonium salts Download PDFInfo
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Description
本發明係有關於一種交聯配方，且特別是有關於一種形成四級銨鹽之交聯配方。This invention relates to a cross-linking formulation, and more particularly to a cross-linking formulation which forms a quaternary ammonium salt.
世界各大廠積極開發各種應用於海水、工業用水及廢水之脫鹽過濾材料，脫鹽過濾材料除了要能高效率處理水中鹽類外，更希望可以降低操作壓力，進而因低耗能而降低淨水處理成本。The world's major factories are actively developing various desalting filter materials for seawater, industrial water and wastewater. In addition to high-efficiency treatment of salt in water, desalting filter materials are expected to reduce operating pressure and reduce water purification due to low energy consumption. Processing costs.
有研究將離子性高分子作為脫鹽過濾材料，此材料能在低壓下仍具有高通量，然而，為了要加強脫鹽過濾材料之機械強度，通常會添加交聯劑與離子性高分子進行交聯，然而，交聯劑的種類及交聯反應速度的快慢都會影響脫鹽過濾材料之穩定性與品質。It has been studied to use ionic polymers as desalting filter materials, which can still have high flux at low pressure. However, in order to strengthen the mechanical strength of desalination filter materials, crosslinking agents are often added to crosslink with ionic polymers. However, the type of cross-linking agent and the speed of the cross-linking reaction rate will affect the stability and quality of the desalting filter material.
為了進一步改善脫鹽過濾材料之品質，本發明提出一種交聯配方，此交聯配方包括帶有胺基之可膨潤高分子、交聯劑與溶液，藉由該交聯配方進行之交聯反應所得到的四級銨鹽可作為脫鹽過濾材料。In order to further improve the quality of the desalination filter material, the present invention provides a cross-linking formulation comprising a swellable polymer with an amine group, a crosslinking agent and a solution, and a crosslinking reaction by the crosslinking formulation. The obtained quaternary ammonium salt can be used as a desalting filter material.
本發明提供一種形成四級銨鹽之交聯配方，包括：一帶有胺基之可膨潤高分子；一交聯劑，其中該交聯劑具有至少兩個鹵素取代基，且該些鹵素取代基不相等；以及一溶液，其中該溶液包括一溶解帶有胺基之可膨潤高分子之溶劑。The present invention provides a cross-linking formulation for forming a quaternary ammonium salt, comprising: a swellable polymer having an amine group; a crosslinking agent, wherein the crosslinking agent has at least two halogen substituents, and the halogen substituents Not equal; and a solution wherein the solution comprises a solvent which dissolves the swellable polymer bearing the amine group.
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：The above and other objects, features and advantages of the present invention will become more <RTIgt;
本發明提供一種形成四級銨鹽之交聯配方，包括：帶有胺基之可膨潤高分子；交聯劑，其中交聯劑具有至少兩個鹵素取代基，且該些鹵素取代基不相等；以及溶液，其中溶液包括溶解帶有胺基之可膨潤高分子之溶劑、質子溶劑(protic solvent)、非溶劑或上述之組合。此處所謂「可膨潤高分子(water-swellable)」意指高分子本身可藉由吸收水而膨脹，且此高分子可吸收大量水分而不會導致其在水中溶解。The present invention provides a cross-linking formulation for forming a quaternary ammonium salt, comprising: a swellable polymer having an amine group; a crosslinking agent, wherein the crosslinking agent has at least two halogen substituents, and the halogen substituents are not equal And a solution, wherein the solution comprises a solvent, a protic solvent, a non-solvent or a combination thereof in which a swelling polymer having an amine group is dissolved. The term "water-swellable" as used herein means that the polymer itself can be expanded by absorbing water, and the polymer can absorb a large amount of water without causing it to dissolve in water.
上述帶有胺基之可膨潤高分子由下述化學式(I-1)、化學式(I-2)與化學式(I-3)之單體所組成：(I-1)，其中R1 包括苯環磺酸基或烷鏈磺酸基；(I-2)，其中R2 包括或 (I-3)，其中R3 包括或；以及化學式(I-1)、化學式(I-2)與化學式(I-3)之莫耳數比為約(0.1-50)：(1-99)：(0.1-50)。The above-mentioned amine-containing swellable polymer is composed of the following chemical formula (I-1), chemical formula (I-2) and chemical formula (I-3): (I-1), wherein R 1 includes a benzene ring sulfonic acid group or an alkyl chain sulfonic acid group; (I-2), where R 2 includes or (I-3), where R 3 includes or And the molar ratio of the chemical formula (I-1), the chemical formula (I-2) and the chemical formula (I-3) is about (0.1-50): (1-99): (0.1-50).
上述之交聯劑包括多滷烷、多滷苯、多滷雜環或多滷高分子，例如化學式(II)、化學式(III)或化學式(IV)之化合物，The above crosslinking agent includes a polyhalogenane, a polyhalogenated benzene, a polyhalogenated heterocyclic ring or a polyhalogenated polymer, such as a compound of the formula (II), the formula (III) or the formula (IV),
其中A包括C1 -C25 亞烷基(alkylene)、C6 -C25 芳香基(aryl)或C7 -C25 芳烷基(aralkyl)；R1 、R2 各自獨立包括Cl、Br或I，且R1 ≠R2 。Wherein A includes C 1 -C 25 alkylene, C 6 -C 25 aryl or C 7 -C 25 aralkyl; R 1 and R 2 each independently include Cl, Br or I, and R 1 ≠ R 2 .
其中R3 、R4 、R5 各自獨立包括取代或未取代之芳基(aryl)或是壓克力系列(acrylic)結構，如 或；R6 、R9 各自獨立包括H或CH3 ；R7 、R8 各自獨立包括CH2 Cl、CH2 Br、CH2 I；R10 、R11 各自獨立包括H、CH3 、CH2 Cl、CH2 Br、CH2 I，其中R7 ≠R10 ，R8 ≠R11 ，其中a、b、c為重複單元之數目，且a、b、c各自獨立為1~1000之整數。Wherein R 3 , R 4 and R 5 each independently comprise a substituted or unsubstituted aryl or an acrylic structure, such as or ; R 6 , R 9 each independently include H or CH 3 ; R 7 and R 8 each independently include CH 2 Cl, CH 2 Br, CH 2 I; R 10 and R 11 each independently include H, CH 3 , CH 2 Cl And CH 2 Br, CH 2 I, wherein R 7 ≠R 10 , R 8 ≠R 11 , wherein a, b, c are the number of repeating units, and a, b, and c are each independently an integer of from 1 to 1000.
其中R12 、R13 各自獨立包括Cl、Br或I，且R12 ≠R13 ，其中d、e為重複單元之數目，且d、e各自獨立為1~1000之整數。Wherein R 12 and R 13 each independently comprise Cl, Br or I, and R 12 ≠ R 13 , wherein d and e are the number of repeating units, and d and e are each independently an integer of from 1 to 1000.
交聯劑與帶有胺基之可膨潤高分子之間的重量比例為0.01-10，然而，交聯劑之比例並不以此為限，熟知本領域之人士可依據實際應用之需求進行調整。當交聯劑比例較高時，可得到結構較為緻密的四級銨鹽，當交聯劑比例較低時，可得到結構較為鬆散之四級銨鹽。The weight ratio between the crosslinking agent and the swellable polymer with an amine group is 0.01-10. However, the ratio of the crosslinking agent is not limited thereto, and those skilled in the art can adjust according to the needs of practical applications. . When the proportion of the crosslinking agent is relatively high, a quaternary ammonium salt having a relatively dense structure can be obtained, and when the ratio of the crosslinking agent is low, a quaternary ammonium salt having a relatively loose structure can be obtained.
須注意的是，藉由本發明交聯配方製得之四級銨鹽可進一步經由紡絲步驟形成纖維(fiber)，由於紡絲時間可能需要幾小時，所以若交聯速度太快時，會造成黏度(viscosity)上升迅速，使得四級銨鹽無法進行紡絲步驟，因此，本發明藉由交聯劑中的該些鹵素取代基不相等，用以減緩交聯反應的速度。It should be noted that the quaternary ammonium salt prepared by the cross-linking formulation of the present invention can further form a fiber through a spinning step, and since the spinning time may take several hours, if the crosslinking speed is too fast, it may cause The viscosity rises rapidly, so that the quaternary ammonium salt cannot be subjected to the spinning step. Therefore, the present invention is used to slow down the crosslinking reaction by making the halogen substituents in the crosslinking agent unequal.
此外，藉由本發明交聯配方製得之四級銨鹽可進一步經由塗佈(coating)步驟形成於載體層上，以製作成脫鹽過濾材料，然而，若交聯速度太快時，會造成黏度(viscosity)上升迅速，會使得塗佈之厚度太厚或厚度不易控制，因此，本發明藉由交聯劑中的該些鹵素取代基不相等，用以調控交聯反應的速度。Further, the quaternary ammonium salt obtained by the cross-linking formulation of the present invention may be further formed on the carrier layer via a coating step to form a desalting filter material, however, if the crosslinking speed is too fast, viscosity may be caused. (viscosity) rises rapidly, making the thickness of the coating too thick or the thickness difficult to control. Therefore, the present invention uses the halogen substituents in the crosslinking agent to be unequal to regulate the speed of the crosslinking reaction.
於一實施例中，使用相同的高分子搭配不同的交聯劑，實驗結果發現於室溫條件下，使用1-溴-6氯己烷(1-bromo-6-chloro-hexane,BCH)之交聯速度慢於1,6-二溴己烷(1,6-dibrono hexane,DBH)，這是因為溴原子與氯原子進行交聯反應時，溴原子比氯原子較容易與高分子反應鍵結，因此，兩邊為溴原子的交聯劑之交聯速度會快於一邊溴一邊氯的交聯劑，由此可知，使用兩邊具有不同鹵素的交聯劑確實可減緩交聯反應之速度，因此，熟知本領域之人士可依據實際製程(紡絲製程或塗佈製程)之需要，添加不同類型之交聯劑，以調控交聯反應之速度。In one embodiment, the same polymer was used with different cross-linking agents, and the experiment found that 1-bromo-6-chloro-hexane (BCH) was used at room temperature. The crosslinking speed is slower than 1,6-dibrono hexane (DBH). This is because when a bromine atom is cross-linked with a chlorine atom, the bromine atom is more reactive with the polymer than the chlorine atom. Therefore, the cross-linking rate of the cross-linking agent having a bromine atom on both sides is faster than that of the bromine-side cross-linking agent, and it is understood that the use of a cross-linking agent having a different halogen on both sides can actually slow down the crosslinking reaction. Therefore, those skilled in the art can add different types of crosslinking agents to adjust the speed of the crosslinking reaction according to the actual process (spinning process or coating process).
上述之溶解帶有胺基之可膨潤高分子之溶劑為高極性之溶劑，例如N,N-二甲基乙胺(DMAc)、二甲基甲醯胺(Dimethylformamide,DMF)、二甲基亞碸(Dimethyl sulfoxide,DMSO)、醇類、N-甲基吡咯酮(N-methyl pyrrolidinone,NMP)等。The above solvent for dissolving the amine-containing swellable polymer is a highly polar solvent such as N,N-dimethylethylamine (DMAc), dimethylformamide (DMF), dimethyl amide. Dimethyl sulfoxide (DMSO), alcohols, N-methyl pyrrolidinone (NMP), and the like.
上述之質子溶劑包括水、酸或醇類。酸類包括甲酸(formic acid)、乙酸(acetic acid)、檸檬酸(citric acid)、琥珀酸(succinic acid)、鹽酸(hydrochloric acid)或上述之組合。The protic solvent described above includes water, an acid or an alcohol. The acid includes formic acid, acetic acid, citric acid, succinic acid, hydrochloric acid or a combination thereof.
醇類可以是單元醇或多元醇，單元醇例如甲醇(methanol)、乙醇(ethanol)、正丙醇(n-propanol)、異丙醇(isopropanol)、正丁醇(n-butanol)或正戊醇(n-pentanol)。The alcohol may be a unit alcohol or a polyol, and a unit alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol or n-pentane Alcohol (n-pentanol).
多元醇包括二醇類、多醇類、醚二醇類或上述之組合。二醇類例如乙二醇、丙二醇、丁二醇、戊二醇、己二醇、環己二醇、環己基二甲醇(Cyclohexyldimethanol，CHDM)、辛二醇、新戊二醇(Neopentyl glycol，NPG)、三甲基戊二醇(Trimethylpentanediol，TMPD)、苯二甲醇、苯二酚、甲苯二酚或雙酚A(Bisphenol-A)、丁二醇-己二酸共聚物[Poly(butanediol-co-adipate) glycol，PBA]、聚四亞甲基醚二醇(Polytetramethylene glycol，PTMEG)、聚丙二醇(Polypropylene glycol，PPG)、聚乙二醇(Polyethylene glycol，PEG)。Polyols include glycols, polyols, ether glycols or combinations of the foregoing. Glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol, cyclohexyldimethanol (CHDM), octanediol, neopentyl glycol (NPG) ), Trimethylpentanediol (TMPD), benzenedimethanol, benzenediol, toluenediol or bisphenol A (Bisphenol-A), butanediol-adipate copolymer [Poly (butanediol-co -adipate) glycol, PBA], polytetramethylene glycol (PTMEG), polypropylene glycol (PPG), polyethylene glycol (PEG).
多醇類包括聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚己內酯多元醇、聚丙烯酸酯多元醇，例如丙三醇、三甲基醇丙烷(Trimethylolpropane)、戊四醇(Pentaerythritol)、苯三酚。Polyols include polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyacrylate polyols such as glycerol, trimethylolpropane, pentaerythritol. (Pentaerythritol), benzenetriol.
醚二醇類例如包括二乙二醇、三乙二醇、二丙二醇、三丙二醇。The ether glycols include, for example, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
上述之非溶劑指的是與帶有胺基之可膨潤高分子不互溶之溶劑，由於帶有胺基之可膨潤高分子為離子性高分子，因此非溶劑為低極性之溶劑，非溶劑包括四氫呋喃(Tetrahydrofuran,THF)、二氯甲烷(dichloromethane,DCM)、三氯甲烷(chloroform)、直鏈或支鏈烷類(戊烷、己烷(hexane)、庚烷(heptane)、苯(benzene)、甲苯(toluene)或丙酮(acetone)等。The above non-solvent refers to a solvent which is immiscible with the amine-containing swellable polymer. Since the swellable polymer having an amine group is an ionic polymer, the non-solvent is a solvent having a low polarity, and the non-solvent includes Tetrahydrofuran (THF), dichloromethane (DCM), chloroform, linear or branched alkanes (pentane, hexane, heptane, benzene) , toluene or acetone.
上述溶解帶有胺基之可膨潤高分子之溶劑：質子溶劑(或非溶劑)之重量比例為約9/1-5/5。The above solvent for dissolving the amine-containing swellable polymer: protic solvent (or non-solvent) is in a weight ratio of about 9/1-5/5.
於一實施例中，溶解帶有胺基之可膨潤高分子之溶劑為N,N-二甲基乙胺(DMAc)，而質子溶劑為乙醇(ethanol)，前者與後者之混合重量比例為9:1。In one embodiment, the solvent for dissolving the amine-containing swellable polymer is N,N-dimethylethylamine (DMAc), and the protic solvent is ethanol. The former and the latter are in a weight ratio of 9 :1.
於另一實施例中，溶解帶有胺基之可膨潤高分子之溶劑為N,N-二甲基乙胺(DMAc)，而非溶劑為四氫呋喃(Tetrahydrofuran,THF)，前者與後者之混合重量比例為5:5。In another embodiment, the solvent for dissolving the amine-containing swellable polymer is N,N-dimethylethylamine (DMAc), and the non-solvent is tetrahydrofuran (THF). The former and the latter are mixed. The ratio is 5:5.
須注意的是，質子溶劑與帶有胺基之可膨潤高分子之間會形成氫鍵，此氫鍵可以減緩交聯反應速度。此外，由於非溶劑不會與可膨潤高分子互溶，因此，非溶劑的存在會降低交聯劑與可膨潤高分子兩者碰撞的機會，進而降低交聯反應速度。由此可知，本領域人士可依據實際製程之需要，混合一或多種質子溶劑或非溶劑，以調控所需之交聯反應速度。It should be noted that a hydrogen bond is formed between the protic solvent and the swellable polymer having an amine group, and the hydrogen bond can slow the crosslinking reaction rate. In addition, since the non-solvent does not dissolve with the swellable polymer, the presence of the non-solvent reduces the chance of collision between the cross-linking agent and the swellable polymer, thereby lowering the cross-linking reaction rate. It can be seen that one skilled in the art can mix one or more protic solvents or non-solvents according to the actual process to adjust the required crosslinking reaction rate.
再者，於一實施例中，本發明所提供之交聯配方係於室溫下(20-25℃)即開始進行部份交聯反應，可藉由加熱步驟，幫助交聯反應的進行。於另一實施例中，本發明所提供之交聯配方需藉由加熱步驟，才能進行交聯反應。Furthermore, in one embodiment, the cross-linking formulation provided by the present invention initiates a partial crosslinking reaction at room temperature (20-25 ° C), and the crosslinking step can be assisted by a heating step. In another embodiment, the cross-linking formulation provided by the present invention requires a heating step to carry out the crosslinking reaction.
綜上所述，本發明所提供之交聯配方可用以調控交聯反應速度，以利於後續離子高分子加工製程(例如紡絲形成纖維，或者是塗佈於載體層上形成塗佈層)，而後續製程所得之纖維或塗佈層可再經由加熱步驟，使高分子與交聯劑完全交聯，最後所得之材料可作為脫鹽過濾材料。In summary, the cross-linking formulation provided by the present invention can be used to regulate the cross-linking reaction speed to facilitate the subsequent ion-polymer processing process (for example, spinning to form fibers, or coating on a carrier layer to form a coating layer). The fiber or coating layer obtained in the subsequent process can be further cross-linked through the heating step to completely crosslink the polymer and the crosslinking agent, and finally the obtained material can be used as a desalting filter material.
【實施例】[Examples]
實施例1 合成交聯劑化學結構(III)：Poly(styrene-co-vinylbenzylhalide) copolymer Example 1 Synthesis of Crosslinking Agent Chemical Structure (III): Poly(styrene-co-vinylbenzylhalide) copolymer
苯乙烯(Styrene)/氯甲基苯乙烯(vinylbenzylchloride)/溴甲基苯乙烯(vinylbenzylbromide)分別取2g/1g/1g(各單體比例可視需求而訂)，並加入20ml四氫呋喃(THF)，於氮氣下進行反應，再將溫度升至70℃，接著加入起始劑過氧化苯(benzoperoxide,BPO)溶液(BPO溶液：0.04g/5ml THF)，於70℃下反應3小時。再將產物以甲醇沉降，過濾抽乾後即可得到Poly(styrene-co-vinylbenzylhalide) copolymer。Styrene / vinylbenzyl chloride / vinylbenzylbromide 2g / 1g / 1g respectively (the ratio of each monomer can be specified), and added 20ml of tetrahydrofuran (THF), The reaction was carried out under nitrogen, and the temperature was further raised to 70 ° C, followed by the addition of a benzoperoxide (BPO) solution (BPO solution: 0.04 g / 5 ml of THF), and the reaction was carried out at 70 ° C for 3 hours. The product was precipitated with methanol, filtered and dried to obtain a poly(styrene-co-vinylbenzylhalide) copolymer.
實施例2 合成交聯劑化學結構(IV)：Halide-methylated Polysulfone(PSF-X) Example 2 Synthesis of Crosslinking Agent Chemical Structure (IV): Halide-methylated Polysulfone (PSF-X)
將3克聚碸(polysulfone)(分子量35,000)與80ml氯仿(chloroform)，於氮氣下加熱至50℃使其完全溶解，以形成混合溶液。3 g of polysulfone (molecular weight: 35,000) and 80 ml of chloroform were heated to 50 ° C under nitrogen to completely dissolve to form a mixed solution.
將2 g甲醛(P-formaldehyde)，0.35g四氯化錫(SnCl4 )，4.3g一氯三甲基矽烷(trimethylsilylchloride,SiMe3 Cl)與5.9 g一溴三甲基矽烷(trimethylsilylbromide,SiMe3 Br)(SiMe3 Cl與SiMe3 Br比例視實際需要調整)溶於30 ml氯仿(chloroform)，上述藥品依序加入聚碸混合溶液中，50℃加熱迴流48小時。反應結束後，加入甲醇將產物沉澱，最後可得白色固體Halide-methylated Polysulfone(PSF-X)。2 g of formaldehyde (P-formaldehyde), 0.35 g of tin tetrachloride (SnCl 4 ), 4.3 g of trimethylsilylchloride (SiMe 3 Cl) and 5.9 g of trimethylsilylbromide (SiMe 3 ) Br) (the ratio of SiMe 3 Cl to SiMe 3 Br was adjusted as needed) was dissolved in 30 ml of chloroform, and the above-mentioned drugs were sequentially added to the polyfluorene mixed solution, and heated under reflux at 50 ° C for 48 hours. After completion of the reaction, the product was precipitated by adding methanol, and finally a white solid Halide-methylated Polysulfone (PSF-X) was obtained.
實施例3 合成可膨潤高分子Poly(sodium styrene sulfate-co-4-vinylpyridine-co-styrene) Example 3 Synthesis of swellable polymer Poly (sodium styrene sulfate-co-4-vinylpyridine-co-styrene)
取230g苯乙烯磺酸鈉(sodium styrene sulfate)，460g 4-乙烯吡啶(4-vinylpyridine)，230 g苯乙烯(styrene)(各單體比例可視情況調整)，1150ml去離子水，1150ml異丙醇(IPA)攪拌溶解，通入氮氣，恆溫70℃下反應30分鐘，以形成混合溶液。Take 230 g of sodium styrene sulfate, 460 g of 4-vinylpyridine, 230 g of styrene (adjusted for each monomer ratio), 1150 ml of deionized water, 1150 ml of isopropanol (IPA) was stirred and dissolved, and nitrogen gas was introduced thereto, and the mixture was reacted at 70 ° C for 30 minutes to form a mixed solution.
取9.2 g過硫酸鉀(potassium persulfate,KPS)溶於230ml去離子水中，再慢慢滴入上述混合溶液中，反應3小時即完成。反應完之高分子溶液以鹽水沉降，經烘乾、水洗純化後可得乳白色固體Poly(sodium styrene sulfate-co-4-vinylpyridine-co-styrene)。9.2 g of potassium persulfate (KPS) was dissolved in 230 ml of deionized water, and then slowly dropped into the above mixed solution, and the reaction was completed in 3 hours. The polymer solution after completion of the reaction is sedimented with brine, and dried and washed with water to obtain a milky white solid (Sodium styrene sulfate-co-4-vinylpyridine-co-styrene).
實施例4 合成四級銨鹽 Example 4 Synthesis of quaternary ammonium salt
將實施例3 高分子配置於N,N-二甲基乙胺(DMAc)溶劑中，固含量是20wt%，按照比例加入相當於高分子鏈吡啶(pyridine)莫耳含量之0.3倍(0.3當量)的交聯劑1-溴-6氯己烷(1-bromo-6-chloro-hexane,BCH)。The polymer of Example 3 was placed in a solvent of N,N-dimethylethylamine (DMAc) at a solid content of 20% by weight, and was added in proportion to 0.3 times the molar content of the polymer chain pyridine (0.3 equivalents). The crosslinker 1-bromo-6-chloro-hexane (BCH).
取上述適量樣品於黏度儀上進行黏度偵測，黏度測定與反應溫度都在室溫下進行，每隔固定時間紀錄黏度數值變化，實驗結果如表1所示。The appropriate amount of the sample was taken on a viscometer for viscosity detection. The viscosity measurement and the reaction temperature were all performed at room temperature, and the viscosity values were recorded at regular intervals. The experimental results are shown in Table 1.
比較例1Comparative example 1
實驗步驟、材料、測定方法與實施條件同實施例4 ，唯，交聯劑由BCH改為1,6-二溴己烷(1,6-dibrono hexane,DBH)，交聯劑當量數仍維持0.3當量。實驗結果如表2所示。The experimental procedures, materials, measurement methods and implementation conditions were the same as those in Example 4. However, the crosslinking agent was changed from BCH to 1,6-dibronohexane (DBH), and the number of crosslinkers was maintained. 0.3 equivalents. The experimental results are shown in Table 2.
由表1與表2之實驗結果可得知，相較於DBH，BCH於相同實驗條件下黏度上升緩慢許多。From the experimental results of Tables 1 and 2, it can be seen that the viscosity of BCH rises much more slowly under the same experimental conditions than DBH.
實施例5 利用質子溶劑或非溶劑控制交聯反應速度 Example 5 Controlling the crosslinking reaction speed by using a protic solvent or a non-solvent
將實施例3 高分子分別配置於顯示於表3之溶劑中(分別為N,N-二甲基乙胺(DMAc)、N,N-二甲基乙胺與四氫呋喃(THF)混合溶劑、以及N,N-二甲基乙胺與酒精混合溶劑)，其中溶液固含量固定在23.5wt%。The polymer of Example 3 was separately placed in a solvent shown in Table 3 (N,N-dimethylethylamine (DMAc), a mixed solvent of N,N-dimethylethylamine and tetrahydrofuran (THF), and N,N-dimethylethylamine mixed with alcohol), wherein the solution solid content is fixed at 23.5 wt%.
將上述各批溶液分別按照比例加入相當於高分子鏈吡矴(pyridine) 0.3當量的1-溴-6氯己烷(1-bromo-6-chloro-hexane,BCH)交聯劑，取適量樣品於黏度儀上進行線上黏度偵測，溫度設定在25℃，隨時間改變，每隔0.5小時紀錄黏度數值變化，實驗結果如表3所示。Each of the above batch solutions was added in proportion to a 1-bromo-6-chloro-hexane (BCH) cross-linking agent equivalent to 0.3 equivalent of a polymer chain pyridine, and an appropriate amount of the sample was taken. The viscosity was detected on the viscometer. The temperature was set at 25 ° C, and the viscosity value was changed every 0.5 hours. The experimental results are shown in Table 3.
由表3之數據可得知，添加質子溶劑(如酒精)或非溶劑(如四氫呋喃)，確實可減緩交聯反應速度。From the data in Table 3, it can be known that the addition of a protic solvent (such as alcohol) or a non-solvent (such as tetrahydrofuran) can slow down the crosslinking reaction rate.
實施例6Example 6
將實施例3 之可膨潤分子與實施例1(交聯劑) 之高分子依重量比例混合(75:25、60:40、50:50與40:60)，分別配置於N,N-二甲基乙胺溶劑中，高分子固含量均為20wt%。The swelling molecules of Example 3 and the polymer of Example 1 (crosslinking agent) were mixed in a weight ratio (75:25, 60:40, 50:50, and 40:60), respectively, in N,N-di In the methyl ethylamine solvent, the solid content of the polymer was 20% by weight.
將上述溶液充份混合後，再將溶液塗佈於玻璃基材上，經130℃交聯硬化後，再以FT-IR確認，實驗結果如請參見表5與第1A-1D圖所示，由1638cm-1 FT-IR特徵吸收峰可確定混合溶液已進行交聯反應。After the above solution is thoroughly mixed, the solution is applied to a glass substrate, cross-linked and hardened at 130 ° C, and then confirmed by FT-IR. The experimental results are shown in Table 5 and Figure 1A-1D. From the 1638 cm -1 FT-IR characteristic absorption peak, it was confirmed that the mixed solution had undergone a crosslinking reaction.
實施例7Example 7
實施步驟同實施例6 ，差別在於高分子材料改為實施例3 可膨潤高分子與實施例2(交聯劑) ，混合比例分別為70:30、63:37與37:63，由1638cm-1 FT-IR特徵吸收峰可確定混合溶液已進行交聯反應。The implementation steps are the same as those in Example 6 , except that the polymer material is changed to the swellable polymer of Example 3 and the second embodiment (crosslinking agent) , and the mixing ratios are 70:30, 63:37 and 37:63, respectively, from 1638 cm - 1 FT-IR characteristic absorption peak can confirm that the mixed solution has been cross-linked.
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，任何所屬技術領域中具有通常知識者，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 scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
第1A-1D圖為一系列傅立葉轉換紅外線光譜圖(FT-IR)，用以說明本發明實施例之交聯程度。1A-1D is a series of Fourier Transform Infrared Spectrograms (FT-IR) to illustrate the degree of crosslinking of embodiments of the present invention.
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