TWI434860B - Synthesis and Application of Novel Amphoteric Monomers, Their Synthesis, and Their Derivative Amphoteric Copolymer and Copolymer - Google Patents
Synthesis and Application of Novel Amphoteric Monomers, Their Synthesis, and Their Derivative Amphoteric Copolymer and Copolymer Download PDFInfo
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本發明係有關一種具有結構式(1)的兩性單體,及其兩性型共聚物,且特別者,有關一種具有結構式(2)的兩性型共聚物,其製備方法及其作為陶瓷粉末漿體分散劑之用途。The present invention relates to an amphoteric monomer having the structural formula (1), and an amphoteric copolymer thereof, and particularly, to an amphoteric copolymer having the structural formula (2), a preparation method thereof and a ceramic powder slurry thereof The use of bulk dispersants.
陶瓷粉末如鈦酸鋇、鋯鈦酸鉛等廣泛應用於電子工業,例如以鈦酸鋇為原料可製造電容器、電感器、熱阻器等。在製程上鈦酸鋇粉末須先加入溶劑以配成漿料,目前工業上所使用的溶劑分為水及有機溶劑兩類,基於環保與降低成本,近年來致力於發展水系鑄造(casting)系統。Ceramic powders such as barium titanate and lead zirconate titanate are widely used in the electronics industry. For example, capacitors, inductors, and thermistors can be fabricated using barium titanate as a raw material. In the process, barium titanate powder must be added to the solvent to form a slurry. Currently, the solvent used in the industry is divided into water and organic solvents. Based on environmental protection and cost reduction, in recent years, efforts have been made to develop a water system casting system. .
陶瓷粉末在溶劑中分散效果的好壞,對於製程品質有極大的影響。分散性差的漿料經乾燥後其生胚的密度較小,燒結胚體孔隙率大,容易斷裂,導致產品良率偏低及電性較差。所以工業上配製陶瓷漿料常須添加分散劑,以利其後的製程與獲得良好品質的產品。以水系陶瓷粉末漿料而言,目前工業上大多使用丙烯酸為主的聚合物或共聚物為分散劑,典型的例子為聚甲基丙烯酸銨鹽(PMAAN)。近年來有許多關於以PMAAN或丙烯酸衍生的聚合物作為陶瓷粉末如鈦酸鋇、氧化鋁、氧化鋯、二氧化鈦等分散劑的研究,結果雖然顯示PMAAN或丙烯酸衍生的聚合物呈現好的分散效果,惟仍有很大的改善空間;例如,以PMAAN 為分散劑的鈦酸鋇漿料,鋇離子溶出量多;過量的鋇離子溶出,在乾燥過程中會再沈積於陶瓷粉末表面,此對燒結胚體的電性會有負面影響。The dispersion effect of the ceramic powder in the solvent has a great influence on the process quality. After the slurry with poor dispersibility is dried, the density of the green embryo is small, and the sintered embryo body has a large porosity and is easily broken, resulting in low product yield and poor electrical properties. Therefore, it is often necessary to add a dispersing agent to the ceramic slurry in the industry to facilitate the subsequent process and obtain a good quality product. In the case of an aqueous ceramic powder slurry, an acrylic-based polymer or copolymer is often used in the industry as a dispersing agent, and a typical example is polyammonium methacrylate (PMAAN). In recent years, there have been many studies on dispersants using PMAAN or acrylic acid-derived polymers as ceramic powders such as barium titanate, alumina, zirconia, titania, etc., although the results show that PMAAN or acrylic acid-derived polymers exhibit good dispersion effects. But there is still much room for improvement; for example, with PMAAN As the dispersant barium titanate slurry, the amount of barium ions eluted is excessive; the excess barium ions are eluted and re-deposited on the surface of the ceramic powder during the drying process, which has a negative influence on the electrical properties of the sintered body.
近年來電子工業急速發展,電子陶瓷的市場需求量日益增加,以鈦酸鋇為例,因其具有高介電特性,為製造電容器之重要原料。目前電子元件需求趨向輕、薄、短、小與功能性強,積層陶瓷電容(MLCC)已成市場主流。為得到介電層數多、高電容且體積小的產品,介電層必須薄且緻密,因此如何製備高固含量且分散良好的漿體為一重要環節,致使分散劑被廣泛應用於各種陶瓷粉末的分散。陶瓷粉末分散劑多為高分子型界面助劑,分散劑在漿料中,靠高分子解離、吸附於粉末表面來達成分散粒子目的。分散劑之帶電荷官能基解離吸附於粉體表面後,因粉體表面吸附許多高分子助劑,彼此帶同性電荷,因電荷斥力而減少粒子凝聚;另一分散機制則因吸附於粒子表面的高分子助劑產生立體阻障使粉體達到分散。In recent years, the electronics industry has developed rapidly, and the market demand for electronic ceramics is increasing. Taking barium titanate as an example, it has high dielectric properties and is an important raw material for capacitor manufacturing. At present, the demand for electronic components tends to be light, thin, short, small and functional, and multilayer ceramic capacitors (MLCC) have become the mainstream in the market. In order to obtain a product with a large number of dielectric layers, high capacitance and small volume, the dielectric layer must be thin and dense. Therefore, how to prepare a slurry with high solid content and good dispersion is an important link, so that the dispersant is widely used in various ceramics. Dispersion of the powder. Most of the ceramic powder dispersant is a polymer type interface auxiliaries. The dispersant is dispersed in the slurry and adsorbed on the surface of the powder to achieve the purpose of dispersing particles. After the dissociation of the charged functional group of the dispersant is adsorbed on the surface of the powder, many polymer additives are adsorbed on the surface of the powder, and they have the same charge, which reduces the aggregation of the particles due to the charge repulsion; another dispersion mechanism is adsorbed on the surface of the particles. The polymer additive produces a stereoscopic barrier to achieve dispersion of the powder.
目前商用分散劑多為聚丙烯酸系列型分散劑,其中較著名有聚甲基丙烯酸鹽及丙烯酸衍生的聚合物,學術上也發表過許多相關論文。此型助劑做為陶瓷粉末分散劑,雖分散效果不錯,惟仍存有改善空間,例如,粉末沈降速度快,鋇離子溶出量多等,過量的鋇離子溶出將對燒結胚體的電性或其它性質有負面的影響。本新型分散劑則改善了上述缺點,且使漿體達到均勻的分散。At present, commercial dispersants are mostly polyacrylic acid series dispersants, among which polymethacrylates and acrylic acid-derived polymers are well known, and many related papers have been published in the academic field. This type of auxiliaries is used as a ceramic powder dispersant. Although the dispersion effect is good, there is still room for improvement. For example, the powder has a high sedimentation rate and a large amount of cerium ions. The excess cerium ion dissolution will affect the electrical properties of the sintered body. Or other properties have a negative impact. The novel dispersant improves the above disadvantages and achieves uniform dispersion of the slurry.
本發明的一項目的為提供一種如下式(1)之兩性單體:
本發明的另一項目的為提供一種該兩性單體的製備方法,其包括氯醋酸鈉與N-(4-乙烯基苯基)-N,N-二甲基胺或N-(4-α-C1-C5-烷基-乙烯基苯基)-N,N-二甲基胺反應。Another object of the present invention is to provide a process for the preparation of the amphoteric monomer comprising sodium chloroacetate and N-(4-vinylphenyl)-N,N-dimethylamine or N-(4-α -C1-C5-Alkyl-vinylphenyl)-N,N-dimethylamine reaction.
本發明的另一項目的為提供一種式(2)之兩性型共聚物
其中R1 為H、Cx H2x+1 ,x為1到5的整數,R2 為H、NH4 + 或鹼金屬離子;m為10到1000之整數,n為10到1000之整數;R為丙烯酸、丙烯醯胺、甲基丙烯酸、甲基丙烯醯胺或前述任二者之組合物及其衍生物所衍生之聚合單位,即為一起始共單體。Wherein R 1 is H, C x H 2x+1 , x is an integer from 1 to 5, R 2 is H, NH 4 + or an alkali metal ion; m is an integer from 10 to 1000, and n is an integer from 10 to 1000; R is an acrylic acid, acrylamide, methacrylic acid, methacrylamide or a combination of the foregoing and a derivative thereof, and is a starting comonomer.
本發明的另一項目的為該等水溶性兩性型共聚物之製備方法,包括該兩性單體與起始共單體於一反應容器內, 以過硫酸銨作為起始劑,甲基丙烯磺酸鈉作為鏈轉移劑,於氮氣、恆溫系統下,進行水溶液反應,最後以溶劑萃取分離出該水溶性兩性型共聚物。Another item of the present invention is a method for preparing the water-soluble amphoteric copolymer, comprising the amphoteric monomer and the starting comonomer in a reaction vessel, Ammonium persulfate was used as a starting agent, sodium methacrylate sulfonate was used as a chain transfer agent, and an aqueous solution was reacted under nitrogen and a constant temperature system. Finally, the water-soluble amphoteric copolymer was separated by solvent extraction.
本發明的另一項目的為提供該等水溶性兩性型共聚物作為陶瓷粉末漿體分散劑之用途,其可以降低陶瓷粉末漿體諸如鈦酸鋇漿料的黏度、減少粉體粒子彼此的聚集、且增長粒子懸浮的時間,對於鈦酸鋇漿體具有良好的分散效果。另外,添加本發明的兩性型共聚物更可以降低鈦酸鋇漿料中鋇離子溶出量,改善添加PMAAN會增加鈦酸鋇漿料中鋇離子溶出量的缺點,進而提高燒結體的介電常數值同時降低介電損失值。Another object of the present invention is to provide the use of the water-soluble amphoteric copolymers as a ceramic powder slurry dispersant, which can reduce the viscosity of a ceramic powder slurry such as barium titanate slurry and reduce the aggregation of powder particles. And the time of increasing the particle suspension has a good dispersion effect on the barium titanate slurry. In addition, the addition of the amphoteric copolymer of the present invention can reduce the amount of cerium ions eluted in the barium titanate slurry, and the improvement of the addition of PMAAN increases the disadvantage of the strontium ion elution amount in the barium titanate slurry, thereby improving the dielectric of the sintered body. The value simultaneously reduces the dielectric loss value.
據此,本發明的另一目的為提供一種陶瓷粉末漿體,其包含上面所述本發明兩性型共聚物,將其溶於水中,並加入陶瓷粉末形成漿體後可降低陶瓷粉末漿體的黏度。Accordingly, another object of the present invention is to provide a ceramic powder slurry comprising the above-described amphoteric copolymer of the present invention, which is dissolved in water and added to a ceramic powder to form a slurry, which can reduce the ceramic powder slurry. Viscosity.
於本發明一方面中,提供一種兩性單體,其具有如下之通式:
於一較佳具體實例中,R1 為H,亦即,該兩性單體為N-(4-乙烯基苯基)-N,N-二甲基甘胺酸或其鹽。In a preferred embodiment, R 1 is H, that is, the amphoteric monomer is N-(4-vinylphenyl)-N,N-dimethylglycine or a salt thereof.
於另一較佳具體實例中,R1 為Cx H2x+1 ,x為1到5的整數,亦即,R1 為C1-C5-烷基諸如甲基、乙基、丙基、丁基或戊基。該兩性單體為N-(4-α-C1-C5-烷基-乙烯基苯基)-N,N-二甲基甘胺酸或其鹽。In another preferred embodiment, R 1 is C x H 2x+1 , and x is an integer from 1 to 5, that is, R 1 is a C1-C5-alkyl group such as methyl, ethyl, propyl or butyl. Base or pentyl. The amphoteric monomer is N-(4-α-C1-C5-alkyl-vinylphenyl)-N,N-dimethylglycine or a salt thereof.
於該式(1)兩性單體中,R2 為H、NH4 + 或鹼金屬離子,亦即該式(1)兩性單體可為酸形式或鹽形式。該鹽可為銨鹽或鹼金屬鹽,諸如鈉鹽或鉀鹽。In the amphoteric monomer of the formula (1), R 2 is H, NH 4 + or an alkali metal ion, that is, the amphoteric monomer of the formula (1) may be in an acid form or a salt form. The salt can be an ammonium salt or an alkali metal salt such as a sodium or potassium salt.
於下文中,為簡明起見,以N-(4-乙烯基苯基)-N,N-二甲基甘胺酸代表該式(1)兩性單體來闡釋本發明。Hereinafter, for the sake of simplicity, the present invention is illustrated by the N-(4-vinylphenyl)-N,N-dimethylglycine representing the amphoteric monomer of the formula (1).
於本發明另一方面中,提供一種式(1)兩性單體的製備方法,其包括將反應物氯醋酸鈉與N-(4-乙烯基苯基)-N,N-二甲基胺或N-(4-α-C1-C5-烷基-乙烯基苯基)-N,N-二甲基胺於兩者的莫耳比為1:1,反應溫度60-90℃,恆溫反應時間為8-16小時等之條件下進行反應,然後以溶劑萃取所得產物,其中該萃取溶劑較佳者為丙酮或甲醇。In another aspect of the invention, there is provided a process for the preparation of an amphoteric monomer of formula (1) which comprises reacting the reactant sodium chloroacetate with N-(4-vinylphenyl)-N,N-dimethylamine or N-(4-α-C1-C5-alkyl-vinylphenyl)-N,N-dimethylamine has a molar ratio of 1:1 in both, a reaction temperature of 60-90 ° C, and a constant reaction time The reaction is carried out under conditions of 8-16 hours, etc., and then the obtained product is extracted with a solvent, wherein the extraction solvent is preferably acetone or methanol.
式(1)兩性單體係以1 H-NMR和IR光譜術予以鑑定。其1 H-NMR光譜圖如圖1所示,分別在δ=7.4-7.7,6.8-6.9,5.9-6.0,5.4-5.5,4.7,3.7-3.8,和3.2ppm處有共振峰。IR光譜圖如圖2所示,分別在3200-3600cm-1 ,1680cm-1 ,1650cm-1 ,1595cm-1 ,1398cm-1 ,和887cm-1 處有吸收峰。The amphoteric single system of formula (1) was identified by 1 H-NMR and IR spectroscopy. The 1 H-NMR spectrum thereof is shown in Fig. 1. There are resonance peaks at δ = 7.4 - 7.7, 6.8 - 6.9, 5.9 - 6.0, 5.4 - 5.5, 4.7, 3.7 - 3.8, and 3.2 ppm, respectively. IR spectrum shown in Figure 2, respectively, 3200-3600cm -1, 1680cm -1, 1650cm -1 , 1595cm -1, 1398cm -1, 887cm -1, and the absorption peak.
於另一方面中,本發明提供具有如下通式(2)之兩性型
共聚物:
於該式(2)中,R較佳者為丙烯醯胺、甲基丙烯醯胺、丙烯酸、甲基丙烯酸或彼等的衍生物諸如酯或鹽,或前述任二者之組合物所衍生的聚合單位。In the formula (2), R is preferably acrylamide, methacrylamide, acrylic acid, methacrylic acid or a derivative thereof such as an ester or a salt, or a combination of any of the foregoing. Aggregation unit.
據此,於另一方面中,本發明提供一種兩性型共聚物,其為一種本發明兩性單體與甲基丙烯酸經聚合反應所得聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/甲基丙烯酸鹽)(PVM)之水溶性兩性型共聚物。Accordingly, in another aspect, the present invention provides an amphoteric copolymer which is a poly(N-(4-vinylphenyl)-N,N obtained by polymerization of an amphoteric monomer of the present invention and methacrylic acid. a water-soluble amphoteric copolymer of -dimethylglycine/methacrylate (PVM).
於本發明另一方面中,本發明提供一種兩性型共聚物,其為本發明兩性單體與(甲基)丙烯酸鹽和(甲基)丙烯醯胺經聚合反應所得聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/(甲基)丙烯醯胺/(甲基)丙烯酸鹽)(PVMM)之水溶性兩性型共聚物。In another aspect of the present invention, the present invention provides an amphoteric copolymer which is a poly(N-(4-) obtained by polymerizing an amphoteric monomer with a (meth) acrylate and a (meth) acrylamide. A water-soluble amphoteric copolymer of vinylphenyl)-N,N-dimethylglycine/(meth)acrylamide/(meth)acrylate) (PVMM).
該等共聚物係以1 H-NMR和IR光譜術予以鑑定。如下 面的實施例中所闡釋者。These copolymers were identified by 1 H-NMR and IR spectroscopy. As explained in the examples below.
於另一方面中,本發明提供一種該等本發明水溶性兩性型共聚物之製備方法,包括該兩性單體與起始共單體於一反應容器內,以過硫酸銨作為起始劑,甲基丙烯磺酸鈉作為鏈轉移劑,於氮氣、恆溫系統下,進行水溶液反應。In another aspect, the present invention provides a process for preparing the water-soluble amphoteric copolymer of the present invention, comprising the amphoteric monomer and the starting comonomer in a reaction vessel, using ammonium persulfate as a starting agent, Sodium methacrylate sulfonate is used as a chain transfer agent, and an aqueous solution is reacted under a nitrogen gas and a constant temperature system.
於本發明製備方法中,本質上為一種自由基起始聚合反應,所使用之起始劑較佳者為過硫酸鉀或過硫酸銨;其中為調節分子量所用的鏈轉移劑較佳者為甲基丙烯磺酸鈉;反應溫度較佳者為60-90℃;恆溫反應時間為6-10小時;且所得產物之萃取溶劑較佳者為丙酮或甲醇。In the preparation method of the present invention, it is essentially a radical initiation polymerization reaction, and the initiator used is preferably potassium persulfate or ammonium persulfate; wherein the chain transfer agent used for adjusting the molecular weight is preferably A. Sodium propylene sulfonate; the reaction temperature is preferably 60-90 ° C; the constant temperature reaction time is 6-10 hours; and the extraction solvent of the obtained product is preferably acetone or methanol.
本發明的另一項目的為提供該等水溶性兩性型共聚物作為陶瓷粉末漿體分散劑之用途,其可以降低陶瓷粉末漿體諸如鈦酸鋇漿料的黏度、減少粉體粒子彼此的聚集、且增長粒子懸浮的時間,對於鈦酸鋇漿體具有良好的分散效果。另外,添加本發明的兩性型共聚物更可以降低鈦酸鋇漿料中鋇離子溶出量,改善添加PMAAN會增加鈦酸鋇漿料中鋇離子溶出量的缺點,進而提高燒結體的介電常數值同時降低介電損失值。Another object of the present invention is to provide the use of the water-soluble amphoteric copolymers as a ceramic powder slurry dispersant, which can reduce the viscosity of a ceramic powder slurry such as barium titanate slurry and reduce the aggregation of powder particles. And the time of increasing the particle suspension has a good dispersion effect on the barium titanate slurry. In addition, the addition of the amphoteric copolymer of the present invention can reduce the amount of cerium ions eluted in the barium titanate slurry, and the improvement of the addition of PMAAN increases the disadvantage of the strontium ion elution amount in the barium titanate slurry, thereby improving the dielectric of the sintered body. The value simultaneously reduces the dielectric loss value.
據此,於另一方面中,本發明提供一種陶瓷粉末漿體,其包含上面所述本發明兩性型共聚物,將其溶於水中,並加入陶瓷粉末形成漿體後可降低陶瓷粉末漿體的黏度。Accordingly, in another aspect, the present invention provides a ceramic powder slurry comprising the above-described amphoteric copolymer of the present invention, which is dissolved in water and added to a ceramic powder to form a slurry to reduce the ceramic powder slurry Viscosity.
於本發明陶瓷粉末漿體中,該陶瓷粉末包括鈦酸鋇、氧化鋁及二氧化鈦。In the ceramic powder slurry of the present invention, the ceramic powder comprises barium titanate, alumina and titania.
於本發明陶瓷粉末漿體中,該兩性型共聚物的添加量係 在0.05~1.0重量%之間。In the ceramic powder slurry of the present invention, the addition amount of the amphoteric copolymer is Between 0.05 and 1.0% by weight.
於一較佳具體實例中,該陶瓷粉末為鈦酸鋇,且其中該陶瓷粉末之鋇離子溶出量低於未添加兩性型共聚物之陶瓷粉末漿體。In a preferred embodiment, the ceramic powder is barium titanate, and wherein the ceramic powder has a lower amount of cerium ions eluted than the ceramic powder slurry to which the amphoteric copolymer is not added.
於一較佳具體實例中,該陶瓷粉末漿體的特徵在於其黏度低於未添加該兩性型共聚物之陶瓷粉末漿體,其穩定度優於未添加該兩性型共聚物之陶瓷粉末漿體,其粉末粒徑小於未添加該兩性型共聚物之陶瓷粉末漿體。In a preferred embodiment, the ceramic powder slurry is characterized in that its viscosity is lower than that of a ceramic powder slurry to which the amphoteric copolymer is not added, and its stability is superior to that of a ceramic powder slurry to which the amphoteric copolymer is not added. The powder particle size is smaller than the ceramic powder slurry to which the amphoteric copolymer is not added.
於一較佳具體實例中,該含有兩性型共聚物之陶瓷粉末漿體之特徵在於將該漿體球磨後,將樣品烘乾、研磨成粉末並過篩,再將其壓成圓盤狀,所得樣品以1000-1300℃恆溫燒結4-8小時後,所得燒結體之介電常數值高於未添加該兩性型共聚物之燒結體而介電損失值低於未添加該兩性型共聚物之燒結體。In a preferred embodiment, the ceramic powder slurry containing the amphoteric copolymer is characterized in that after the slurry is ball milled, the sample is dried, ground into a powder, sieved, and pressed into a disk shape. After the obtained sample is sintered at a constant temperature of 1000-1300 ° C for 4-8 hours, the dielectric constant value of the obtained sintered body is higher than that of the sintered body to which the amphoteric copolymer is not added, and the dielectric loss value is lower than that of the amphoteric copolymer not added. Sintered body.
下面諸實施例之敘述有助於本發明之進一步闡釋,該等實施例在此僅作為說明之用,而非用於限制本發明範圍。The following examples are intended to be illustrative of the invention, and are not intended to limit the scope of the invention.
取0.3莫耳氯醋酸鈉溶於200克去離子水中且與0.3莫耳N-(4-乙烯基苯基)-N,N-二甲基胺一同置入四頸反應瓶中,以1N HCl調整溶液pH值至3,通氮氣1小時,並以70℃恆溫持續反應12小時,將所得產物經迴旋濃縮去除大部分溶劑,再以大量丙酮萃取,純化後置於85℃的烘箱2小時去除殘餘的丙酮,最後可得約62.5克橘紅色黏稠液體 N-(4-乙烯基苯基)-N,N-二甲基甘胺酸,產率為75%。Dissolve 0.3 mol of sodium chloroacetate in 200 g of deionized water and place it in a four-necked reaction flask with 0.3 mol of N-(4-vinylphenyl)-N,N-dimethylamine to 1 N HCl Adjust the pH of the solution to 3, pass nitrogen for 1 hour, and continue to react at 70 ° C for 12 hours. The obtained product is concentrated by swirling to remove most of the solvent, and then extracted with a large amount of acetone. After purification, it is placed in an oven at 85 ° C for 2 hours to remove. Residual acetone, finally get about 62.5 grams of orange-red viscous liquid N-(4-vinylphenyl)-N,N-dimethylglycine, 75% yield.
N-(4-乙烯基苯基)-N,N-二甲基甘胺酸(VBDMGly)之1 H-NMR光譜圖如圖1所示,分別在δ=7.4-7.7、6.8-6.9、5.9-6.0、5.4-5.5、4.7、3.7-3.8、和3.2ppm處有共振峰。IR光譜圖如圖2所示,分別在3200-3600cm-1 、1680cm-1 、1650cm-1 、1595cm-1 、1398cm-1 、和887cm-1 處有吸收峰。The 1 H-NMR spectrum of N-(4-vinylphenyl)-N,N-dimethylglycine (VBDMGly) is shown in Figure 1, at δ = 7.4 - 7.7, 6.8 - 6.9, 5.9, respectively. There are resonance peaks at -6.0, 5.4-5.5, 4.7, 3.7-3.8, and 3.2 ppm. IR spectrum shown in Figure 2, respectively, 3200-3600cm -1, 1680cm -1, 1650cm -1 , 1595cm -1, 1398cm -1, 887cm -1, and the absorption peak.
秤取8.6克甲基丙烯酸溶於20毫升去離子水,以1N氨水調整pH值至10,持續攪拌30分鐘,得一甲基丙烯酸銨鹽水溶液。將所得甲基丙烯酸銨鹽水溶液置於500毫升四頸反應容器內,取20.5克N-(4-乙烯基苯基)-N,N-二甲基甘胺酸(VBDMGly)溶於100毫升去離子水中,再從進料管中逐滴加入1.37克過硫酸銨作為起始劑,在氮氣、恆溫(70℃)系統下,再加入0.95克甲基丙烯磺酸鈉,進行恆溫反應8小時可得黏稠液體產物。將產物自然冷卻至室溫,以丙酮純化三次,經抽氣過濾後,置於85℃的烘箱2小時以去除殘餘的丙酮,可得到22.7克橘紅色固體產物,聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/甲基丙烯酸酯)(PVM),產率約為78%。結構式如下:
圖3為PVM之1 H-NMR圖,分別在δ=6.8-7.4、3.5-3.8、1.5-2.2和0.7-1.2ppm處有共振峰。圖4為PVM之IR圖,分別在2700-3600cm-1 、1656cm-1 、1562cm-1 、1480cm-1 、1399cm-1 、和1200cm-1 處有吸收峰。Figure 3 is a 1 H-NMR chart of PVM with resonance peaks at δ = 6.8-7.4, 3.5-3.8, 1.5-2.2, and 0.7-1.2 ppm, respectively. FIG 4 is a IR chart of PVM, respectively, 2700-3600cm -1, 1656cm -1, 1562cm -1 , 1480cm -1, 1399cm -1, and the absorption peak at 1200cm -1.
秤取8.6克甲基丙烯酸溶於20毫升去離子水中,以1N氨水調整pH值至10,持續攪拌30分鐘,得一甲基丙烯酸銨鹽水溶液。將所得甲基丙烯酸銨鹽水溶液置於500毫升四頸反應容器內。另製備二溶液,溶液一為20.5克N-(4-乙烯基苯基)-N,N-二甲基甘胺酸溶於100毫升去離子水中;溶液二為8.6克甲基丙烯醯胺溶於25.8克去離子水中。將溶液一、二分別從進料管中逐滴加入,另加入2.05克過硫酸銨作為起始劑,在氮氣、恆溫(70℃)系統下,再加入1.42克甲基丙烯磺酸鈉,進行恆溫反應8小時可得黏稠液體產物。將產物自然冷卻至室溫,以丙酮純化三次,經抽氣過濾後,置於85℃的烘箱2小時以去除殘餘的丙酮,可得到24.5克橘黃色固體產物,聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/甲基丙烯醯胺/甲基丙烯酸酯)(PVMM),產率約為65%。結構式如下:
圖5為PVMM之1 H-NMR圖,分別在δ=6.6-7.5、3.5-3.8、1.3-2.1、和0.7-1.2ppm處有共振峰。圖6為PVMM之IR圖,分別在2800-3700cm-1 、3160cm-1 、1709cm-1 、1547cm-1 、1399cm-1 、1261cm-1 、和1186cm-1 處有吸收峰。Figure 5 is a 1 H-NMR chart of PVMM with resonance peaks at δ = 6.6 - 7.5, 3.5 - 3.8, 1.3 - 2.1, and 0.7 - 1.2 ppm, respectively. 6 is the IR chart PVMM, respectively 2800-3700cm -1, 3160cm -1, 1709cm -1 , 1547cm -1, 1399cm -1, 1261cm -1, and the absorption peak at 1186cm -1.
本實施例使用三種不同分散劑及一種鈦酸鋇粉末分別進行三種鈦酸鋇粉末水分散液之配置。所使用之次微米鈦酸鋇粉末為信昌電子陶瓷公司所提供,使用之分散劑,二種為本發明之實體,另一為PMAAN(Darvan C)由S.T.Vanderbilt公司製造。In this embodiment, three different dispersing agents and one barium titanate powder were used to respectively configure the three barium titanate powder aqueous dispersions. The submicron barium titanate powder used was supplied by Xinchang Electronic Ceramics Co., Ltd., the dispersing agent used, two of which were the entities of the present invention, and the other was PMAAN (Darvan C) manufactured by S.T. Vanderbilt.
以鈦酸鋇粉末與去離子水之重量百分比為3:2配製分散液,並改變分散劑添加量與粉末之重量百分比為0.5:1000,1:1000,2:1000,3:1000,5:1000,調整混合漿料至pH=9,球磨24小時後,使用Broodfield DV-Ⅱ黏度儀測定不同分散劑添加量和黏度的關係。實驗結果如第7圖所示。由第7圖得知當分散劑添加量為2毫克/克BT時,其黏度值降為10mPa.s左右,顯示添加PVM、PVMM作為分散劑可使鈦酸鋇漿體黏度值大為降低,相較於PMAAN分散劑,同樣使漿體具有良好的流動性。The dispersion is prepared by adding 3:2 by weight of barium titanate powder and deionized water, and changing the amount of the dispersant added and the weight percentage of the powder is 0.5:1000, 1:1000, 2:1000, 3:1000, 5: 1000, the mixed slurry was adjusted to pH=9, and after ball milling for 24 hours, the relationship between the amount of dispersant added and the viscosity was determined using a Brodfield DV-II viscometer. The experimental results are shown in Figure 7. It can be seen from Fig. 7 that when the dispersant is added in an amount of 2 mg/g BT, the viscosity value is reduced to about 10 mPa·s, which indicates that the addition of PVM and PVMM as a dispersing agent can greatly reduce the viscosity of the barium titanate slurry. The slurry also has good fluidity compared to the PMAAN dispersant.
首先將三種分散劑分別溶於去離子水中,然後加入鈦酸鋇粉末;另設一對照實驗為不添加任何分散劑,三種鈦酸鋇溶液均以1N氫氧化鈉調整pH值至9。本實施例所配置之分散液中,分散劑對鈦酸鋇粉末的重量百分比分別為0.5:1000,1:1000,2:1000,3:1000,5:1000,而水對鈦酸鋇粉末的重量百分比為2:3。將配置之樣品球磨24小時,取適量樣品經稀釋後,使用雷射粒徑分析儀(Mastersizer 2000,Malvern,UK)測其粒徑分佈。First, the three dispersants were separately dissolved in deionized water, and then barium titanate powder was added; another control experiment was carried out without adding any dispersant, and the three barium titanate solutions were adjusted to pH 9 with 1N sodium hydroxide. In the dispersion liquid configured in this embodiment, the weight percentage of the dispersant to the barium titanate powder is 0.5:1000, 1:1000, 2:1000, 3:1000, 5:1000, respectively, and the water is applied to the barium titanate powder. The weight percentage is 2:3. The configured sample was ball milled for 24 hours, and an appropriate amount of the sample was diluted, and the particle size distribution was measured using a laser particle size analyzer (Mastersizer 2000, Malvern, UK).
由第8圖得知未添加本發明兩性型共聚物的漿體其平均粒徑(d 50 )為1.15微米(μm),而添加新型PVM、PVMM作為分散劑者,在添加量為2毫克/克BT(每克鈦酸鋇粉末所添加的分散劑之毫克數)時,其分散液可達之最小平均粒徑(d 50 )分別為0.90與0.94微米,且添加PMAAN作為分散劑時,其分散液最小平均粒徑(d 50 )為0.95微米,顯示PVM、PVMM對於鈦酸鋇粒子有良好的分散效果,去除溶劑後可得堆積更為緻密的胚體。It is understood from Fig. 8 that the slurry having no addition of the amphoteric copolymer of the present invention has an average particle diameter ( d 50 ) of 1.15 μm (μm), and the addition of the new PVM and PVMM as a dispersing agent is added in an amount of 2 mg/克 BT (the number of milligrams of dispersant added per gram of barium titanate powder), the minimum average particle size ( d 50 ) of the dispersion is 0.90 and 0.94 μm, respectively, and when PMAAN is added as a dispersant, The minimum average particle size ( d 50 ) of the dispersion is 0.95 μm, which shows that PVM and PVMM have good dispersion effect on the barium titanate particles, and the denser embryo bodies can be accumulated after solvent removal.
分散液之配製為重量百分比1:9的鈦酸鋇粉末與去離子水,並改變分散劑添加量與粉末之重量百分比為0.5:1000,1:1000,1.5:1000,2:1000,3:1000,調整混合漿料至pH=9,球磨24小時後,將鈦酸鋇漿體倒入量筒中,封口並靜置,觀察其沉降高度的變化。The dispersion is prepared as a weight ratio of 1:9 barium titanate powder and deionized water, and the amount of the dispersant added and the weight percentage of the powder are changed to 0.5:1000, 1:1000, 1.5:1000, 2:1000, 3: 1000, the mixed slurry was adjusted to pH=9, and after ball milling for 24 hours, the barium titanate slurry was poured into a measuring cylinder, sealed and allowed to stand, and the change in the sedimentation height was observed.
第9、10圖為添加PVM、PVMM之鈦酸鋇漿體沉降時 間與分散體積的關係圖。當鈦酸鋇漿體不添加任何分散劑或添加0.5毫克/克BT的PVM、PVMM時,由於粒子凝聚,分散不佳,沉降速度快,在1天內,絕大部分粒子皆已沉降,且可觀察出量筒中明顯分成水與沉降體兩層。而PVM、PVMM添加量大於2mg/g BT以上時,由於分散效果佳,發現鈦酸鋇粒子大多懸浮於量筒中呈混濁狀,即使14天後仍有多數粒子未沉降。第11圖為添加PMAAN之鈦酸鋇漿體沈降時間與分散體積的關係圖。由於粒子凝聚,受重力影響而較易沈降。可知添加本發明之PVM、PVMM作為鈦酸鋇漿體之分散劑,確實有良好的分散效果。Figures 9 and 10 show the sedimentation of barium titanate slurry with PVM and PVMM. A diagram of the relationship between the volume and the dispersion volume. When the barium titanate slurry is added with no dispersant or PVM or PVMM with 0.5 mg/g BT, the particles are agglomerated, the dispersion is not good, and the sedimentation speed is fast. In one day, most of the particles have settled, and It can be observed that the measuring cylinder is clearly divided into two layers of water and sediment. When the addition amount of PVM and PVMM is more than 2 mg/g BT or more, the dispersion effect is good, and it is found that most of the barium titanate particles are suspended in the measuring cylinder to be turbid, and even after 14 days, most of the particles are not sedimented. Figure 11 is a graph showing the relationship between the settling time and the dispersion volume of the barium titanate slurry to which PMAAN is added. Due to the aggregation of particles, it is easier to settle due to the influence of gravity. It can be seen that the addition of the PVM and PVMM of the present invention as a dispersant for the barium titanate slurry does have a good dispersion effect.
使用本發明之分散劑進行分散劑添加量和氧化鋁漿料黏度的關係。以氧化鋁粉末(A21-SG,Alcoa USA)與去離子水之重量百分比為3:1配製分散液,並改變分散劑添加量與粉末之重量百分比為0.5:1000,1:1000,2:1000,3:1000,5:1000,球磨24小時後,使用Broodfield DV-Ⅱ黏度儀測定不同分散劑添加量和黏度的關係,得到實驗結果如第12圖所示。由第12圖得知當PVM、PVMM添加量為2毫克/克BT時,其分散液黏度值分別降為69、77mPa.s左右,顯示添加PVM、PVMM作為分散劑可使氧化鋁漿體黏度值大為降低。The relationship between the amount of the dispersant added and the viscosity of the alumina slurry is carried out using the dispersant of the present invention. The dispersion was prepared by the alumina powder (A21-SG, Alcoa USA) and deionized water in a weight ratio of 3:1, and the amount of the dispersant added and the weight of the powder were changed to 0.5:1000, 1:1000, 2:1000. 3:1000, 5:1000, after ball milling for 24 hours, the relationship between the amount of dispersant added and the viscosity was measured using a Brookfield DV-II viscometer. The experimental results are shown in Fig. 12. It can be seen from Fig. 12 that when the amount of PVM and PVMM added is 2 mg/g BT, the viscosity of the dispersion is reduced to about 69 and 77 mPa·s, respectively. It shows that the addition of PVM and PVMM as dispersant can make the viscosity of alumina slurry. The value is greatly reduced.
使用本發明分散劑進行分散劑添加量和二氧化鈦漿料黏度的關係。以二氧化鈦粉末(PT401M,ISK company,Japan) 與去離子水之重量百分比為5:6配製分散液,並改變分散劑添加量與粉末之重量百分比為0.5:1000,1:1000,2:1000,3:1000,5:1000,球磨24小時後,使用Broodfield DV-Ⅱ黏度儀測定不同分散劑添加量和黏度的關係,得到實驗結果如第13圖所示。由第13圖得知分散劑的添加量愈高,黏度值愈低,當分散劑添加量為3毫克/克BT時,其分散液黏度值分別降為17、15mPa.s左右,顯示添加PVM、PVMM作為分散劑可使二氧化鈦漿體黏度值降低,且具有良好的分散效果。The relationship between the amount of the dispersant added and the viscosity of the titanium dioxide slurry is carried out using the dispersant of the present invention. Titanium dioxide powder (PT401M, ISK company, Japan) Prepare the dispersion with a weight percentage of deionized water of 5:6, and change the amount of dispersant added and the weight percentage of the powder to 0.5:1000, 1:1000, 2:1000, 3:1000, 5:1000, ball milling for 24 hours. Thereafter, the relationship between the amount of dispersant added and the viscosity was measured using a Brodfield DV-II viscometer, and the experimental results were obtained as shown in Fig. 13. From Fig. 13, it is found that the higher the amount of dispersant added, the lower the viscosity value. When the amount of dispersant added is 3 mg/g BT, the viscosity of the dispersion is reduced to about 17,15 mPa.s, indicating that PVM is added. PVMM as a dispersing agent can reduce the viscosity of the titanium dioxide slurry and have a good dispersion effect.
使用本發明之分散劑以及PMAAN分散劑進行不同分散劑添加量與鈦酸鋇懸浮液中鋇離子濃度的關係。分散液之配製為粉末對去離子水之重量百分比為3:2,改變分散劑添加量對粉末之重量百分比為1:1000,2:1000,3:1000,5:1000,調整混合漿料至pH=9,球磨24小時後,以轉速8000rpm將之離心60分鐘,取離心後之澄清液,以感應耦合電漿原子發射光譜儀(ICP-AES,optima 2000 DV,Perkin Elmer Instruments,USA)做量測。測量的方法是先用電漿使樣品離子化,樣品離子化後再經過光源激發,可放出各種不同波長的原子放射光譜,由光譜強度大小判定離子濃度。The dispersant of the present invention and the PMAAN dispersant were used to determine the relationship between the amount of different dispersant added and the concentration of cerium ions in the barium titanate suspension. The dispersion is prepared by weighting the powder to deionized water by 3:2, and changing the amount of the dispersant added to the powder by 1:1000, 2:1000, 3:1000, 5:1000, adjusting the mixed slurry to After pH=9, after ball milling for 24 hours, it was centrifuged at 8000 rpm for 60 minutes, and the centrifuged clear liquid was taken for inductively coupled plasma atomic emission spectrometry (ICP-AES, optima 2000 DV, Perkin Elmer Instruments, USA). Measurement. The measurement method is to first ionize the sample with plasma, and after ionizing the sample and then exciting by the light source, atomic emission spectra of various wavelengths can be emitted, and the ion concentration is determined by the intensity of the spectrum.
第14圖為不同分散劑添加量與鋇離子濃度的關係圖。當以PMAAN為分散劑時,隨分散劑添加量增加,漿體鋇離子溶出量增加,顯示添加PMAAN為分散劑會造成鈦酸 鋇鋇離子溶出量增加;而以PVM、PVMM為分散劑則會減少溶液中鋇離子濃度,且隨分散劑添加量增加並不會大幅增加鋇離子溶出量。由此可見,本發明之新型分散劑可抑制鋇離子從鈦酸鋇粒子表面溶出,對燒結體電性有很大的幫助。Figure 14 is a graph showing the relationship between the amount of different dispersants added and the concentration of cerium ions. When PMAAN is used as a dispersing agent, as the amount of dispersant added increases, the amount of slurry cerium ion elution increases, indicating that adding PMAAN as a dispersing agent causes titanic acid. The amount of cesium ion elution increases, while the use of PVM and PVMM as dispersants reduces the concentration of strontium ions in the solution, and the amount of cesium ion eluted does not increase greatly with the addition of the dispersant. It can be seen that the novel dispersant of the present invention can inhibit the elution of cerium ions from the surface of barium titanate particles, which greatly contributes to the electrical properties of the sintered body.
使用本發明分散劑及PMAAN分散劑進行不同分散劑添加量與燒結體電性的關係之評估。分散液之配製為粉末對去離子水之重量百分比為3:2,改變分散劑添加量對粉末之重量百分比為0.5:1000,1:1000,2:1000,3:1000,5:1000,調整混合漿料至pH=9,經球磨後,將樣品烘乾、研磨成粉末並過篩,利用單軸加壓成型機將其壓成圓盤狀。所得樣品以1280℃恆溫燒結6小時後,表面塗上銀膠製得銀電極,使用阻抗分析儀(HP 4284,Palo Alto,California,USA),將試片夾上電極,測試頻率1KHz,可測得電容值及介電損失因子,經計算可得燒結體之介電常數值與介電損失值。The evaluation of the relationship between the amount of different dispersant added and the electrical properties of the sintered body was carried out using the dispersant of the present invention and the PMAAN dispersant. The dispersion is prepared by weighting the powder to deionized water by 3:2, and changing the amount of the dispersant added to the weight of the powder is 0.5:1000, 1:1000, 2:1000, 3:1000, 5:1000, adjusted The slurry was mixed until pH = 9, and after ball milling, the sample was dried, ground into a powder and sieved, and pressed into a disk shape by a uniaxial press molding machine. After the sample was sintered at a constant temperature of 1280 ° C for 6 hours, the surface was coated with silver glue to obtain a silver electrode, and the test piece was sandwiched with an electrode using an impedance analyzer (HP 4284, Palo Alto, California, USA), and the test frequency was 1 KHz, which was measurable. The capacitance value and the dielectric loss factor are calculated to obtain the dielectric constant value and the dielectric loss value of the sintered body.
第15圖為分散劑添加量對燒結體介電常數的關係。未添加分散劑的胚體其介電常數值為約1512。當摻入分散劑時,三種分散劑使燒結體具有最高介電常數值之最佳劑量分別為:PVM,3毫克/克BT,1972;PVMM,2毫克/克BT,2003;PMAAN,3毫克/克BT,1952。第16圖為分散劑添加量對燒結體介電損失的關係。未添加分散劑的胚體其介電損失值最高,達到0.047,當加入分散劑時,三種分散劑使 胚體得一最低介電損失值之最佳劑量分別為:PVM,1毫克/克BT,0.023;PVMM,2毫克/克BT,0.023;PMAAN,2毫克/克BT,0.02。顯示添加PVM、PVMM能改善胚體介電性質。Figure 15 is a graph showing the relationship between the amount of dispersant added and the dielectric constant of the sintered body. The embryo body to which no dispersant was added had a dielectric constant value of about 1512. When the dispersant is incorporated, the optimum dosages of the three dispersants for the highest dielectric constant of the sintered body are: PVM, 3 mg/g BT, 1972; PVMM, 2 mg/g BT, 2003; PMAAN, 3 mg /g BT, 1952. Figure 16 is a graph showing the relationship between the amount of dispersant added and the dielectric loss of the sintered body. The embryo body without added dispersant has the highest dielectric loss value of 0.047. When the dispersant is added, the three dispersants make The optimal doses for the lowest dielectric loss value of the embryo body were: PVM, 1 mg/g BT, 0.023; PVMM, 2 mg/g BT, 0.023; PMAAN, 2 mg/g BT, 0.02. It shows that adding PVM and PVMM can improve the dielectric properties of the embryo body.
根據測試結果顯示,添加本發明兩性型共聚物於鈦酸鋇漿料,可同時產生靜電排斥與立體障礙兩種分散模式,故可以降低鈦酸鋇漿料的黏度、減少粉體粒子彼此的聚集、且增長粒子懸浮的時間,對於鈦酸鋇漿體具有良好的分散效果。另外,添加本發明兩性型共聚物更可以降低鈦酸鋇漿料中的鋇離子溶出量,改善添加PMAAN會增加鈦酸鋇漿料中鋇離子溶出量的缺點,進而改善燒結體的電性。因此本發明水溶性兩性型共聚物實為一種性能優越的陶瓷粉末漿體分散劑。According to the test results, the addition of the amphoteric copolymer of the present invention to the barium titanate slurry can simultaneously produce two dispersion modes of electrostatic repulsion and steric hindrance, thereby reducing the viscosity of the barium titanate slurry and reducing the aggregation of the powder particles. And the time of increasing the particle suspension has a good dispersion effect on the barium titanate slurry. In addition, the addition of the amphoteric copolymer of the present invention can reduce the amount of cerium ions eluted in the barium titanate slurry, and the improvement of the addition of PMAAN increases the disadvantage of the amount of cerium ions eluted in the barium titanate slurry, thereby improving the electrical properties of the sintered body. Therefore, the water-soluble amphoteric copolymer of the present invention is a ceramic powder slurry dispersing agent having superior properties.
圖1為N-(4-乙烯基苯基)-N,N-二甲基甘胺酸(VBDMGly)或其鹽之1 H-NMR光譜。Fig. 1 is a 1 H-NMR spectrum of N-(4-vinylphenyl)-N,N-dimethylglycine (VBDMGly) or a salt thereof.
圖2為VBDMGly之IR光譜。Figure 2 shows the IR spectrum of VBDMGly.
圖3為聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/甲基丙烯酸酯)(PVM)之1 H-NMR光譜。Figure 3 is a 1 H-NMR spectrum of poly(N-(4-vinylphenyl)-N,N-dimethylglycine/methacrylate) (PVM).
圖4為PVM之IR光譜。Figure 4 shows the IR spectrum of PVM.
圖5聚(N-(4-乙烯基苯基)-N,N-二甲基甘胺酸/甲基丙烯醯胺/甲基丙烯酸酯)(PVMM)之1 H-NMR光譜。Figure 5 1 H-NMR spectrum of poly(N-(4-vinylphenyl)-N,N-dimethylglycine/methacrylamide/methacrylate) (PVMM).
圖6為PVMM之IR光譜。Figure 6 shows the IR spectrum of PVMM.
圖7為顯示不同分散劑添加量對鈦酸鋇漿體黏度之影 響的圖解。Figure 7 is a graph showing the effect of different dispersant additions on the viscosity of barium titanate paste. The illustration of the ringing.
圖8為顯示出不同分散劑添加量對鈦酸鋇漿體粒子平均粒徑(d 50 )的影響之圖解。Figure 8 is a graph showing the effect of different dispersant additions on the average particle size ( d 50 ) of barium titanate slurry particles.
圖9為顯示出PVM添加量對10重量%鈦酸鋇漿體分散體積的影響之圖解。Figure 9 is a graph showing the effect of the amount of PVM added on the dispersion volume of a 10% by weight barium titanate slurry.
圖10為顯示出PVMM添加量對10重量%鈦酸鋇漿體分散體積的影響之圖解。Figure 10 is a graph showing the effect of the amount of PVMM added on the dispersion volume of a 10% by weight barium titanate slurry.
圖11為顯示出PMAAN添加量對10重量%鈦酸鋇漿體分散體積的影響之圖解。Figure 11 is a graph showing the effect of the amount of PMAAN added on the dispersion volume of a 10% by weight barium titanate slurry.
圖12為顯示出分散劑添加量對75重量%氧化鋁漿體黏度的影響之圖解。Figure 12 is a graph showing the effect of the amount of dispersant added on the viscosity of a 75 wt% alumina slurry.
圖13為顯示出分散劑添加量對45重量%二氧化鈦漿體黏度的影響之圖解。Figure 13 is a graph showing the effect of the amount of dispersant added on the viscosity of a 45% by weight titanium dioxide slurry.
圖14為顯示出分散劑添加量對漿體鋇離子溶出量的影響之圖解。Fig. 14 is a graph showing the effect of the amount of dispersant added on the amount of slurry cerium ion eluted.
圖15為顯示出分散劑添加量對燒結體介電常數的影響之圖解。Fig. 15 is a graph showing the effect of the amount of dispersant added on the dielectric constant of the sintered body.
圖16為顯示出分散劑添加量對燒結體介電損失的影響之圖解。Figure 16 is a graph showing the effect of the amount of dispersant added on the dielectric loss of the sintered body.
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