TWI606071B - Diblock copolymer and dispersion - Google Patents

Diblock copolymer and dispersion Download PDF

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TWI606071B
TWI606071B TW105142918A TW105142918A TWI606071B TW I606071 B TWI606071 B TW I606071B TW 105142918 A TW105142918 A TW 105142918A TW 105142918 A TW105142918 A TW 105142918A TW I606071 B TWI606071 B TW I606071B
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dispersion
double
agglomerate
copolymer
branched copolymer
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TW201823285A (en
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張嘉文
張信貞
余若涵
陳佑蕙
陳貞伃
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財團法人工業技術研究院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Description

雙團塊共聚物與分散液 Double agglomerate copolymer and dispersion

本揭露關於雙團塊聚合物與採用其之分散液。 The present disclosure relates to a double agglomerate polymer and a dispersion using the same.

水性墨水具有優點如安全、無毒、無害、幾乎無揮發性有機氣體產生，因此水性顏料之分散劑開發極為重要。用於水性顏料分散安定化的分散劑，錨釘鏈段需能良好吸附顏料。如何使二氧化鈦等金屬氧化物微粉，分散性優且克服重力沉降而有高分散穩定性，分散劑扮演關鍵的角色。舉例來說，用於深色織物打底的水性白色墨水，其黏度低且主要的白色顏料(如氧化鈦)之內聚力大而易聚集產生沉降，分散不易。綜上所述，目前亟需針對微粉設計水性分散劑。 Aqueous inks have advantages such as safety, non-toxicity, harmlessness, and almost no volatile organic gas generation, so the development of dispersants for aqueous pigments is extremely important. A dispersant for the dispersion of aqueous pigments, the anchor segment needs to be able to adsorb the pigment well. How to make metal oxide powder such as titanium dioxide has excellent dispersibility and overcomes gravity sedimentation and has high dispersion stability, and dispersant plays a key role. For example, aqueous white inks for dark fabric priming have low viscosity and the main white pigments (such as titanium oxide) have a large cohesive force and tend to aggregate to cause sedimentation, which is not easy to disperse. In summary, there is an urgent need to design aqueous dispersants for micropowders.

本揭露一實施例提供之雙團塊共聚物，包括：(a)第一團塊，具有重複單元；以及(b) 第二團塊，具有重複單元，其中(a)第一團塊化學 鍵結至(b)第二團塊；R1係H或CH3；R2係H或CH3 基；R3係、、、或 ，R4係C1-10之烷基；M⊕係Na+、NH4 +、或NH(C2H4OH)3 +；m=10-20；n=2-20；以及x=0-4。 The present invention provides a bi-branched copolymer comprising: (a) a first agglomerate having repeating units And (b) the second mass with repeating units Wherein (a) the first mass is chemically bonded to (b) the second agglomerate; R 1 is H or CH 3 ; R 2 is H or CH 3 ; R 3 is , , ,or , R 4 is a C 1-10 alkyl group; M lanthanide Na + , NH 4 + , or NH(C 2 H 4 OH) 3 + ; m=10-20; n=2-20; and x=0 -4.

本揭露一實施例提供之分散液，包括：100重量份的粉體；1至80重量份的上述雙團塊共聚物；以及100至900重量份之極性溶劑。 The dispersion liquid provided in one embodiment comprises: 100 parts by weight of powder; 1 to 80 parts by weight of the above-mentioned double-branched copolymer; and 100 to 900 parts by weight of a polar solvent.

本揭露一實施例提供之雙團塊共聚物，包括：(a) 第一團塊，具有重複單元；以及(b)第 二團塊，具有重複單元。上述(a)第一團塊化學鍵結至(b)第二團塊，R1係H或CH3；R2係H或CH3；R3係 R4係C1-10之烷基；M⊕係Na+、NH4 +、或NH(C2H4OH)3 +；m=10-20；n=2-20；以及x=0-4。若m值過低，則共聚物所含之離子比例過低而無法使分散劑溶於水中。若m值過高，則易造成分散時所需的分散劑添加量過多。若n值過低，則無法使錨釘鏈段有效吸附至微粉上。若n值過高，則錨釘鏈易吸附另一個微粉造成聚集。若x值過高，則共聚物所含之羧酸鹽類過少，溶媒鏈段無法完全分散於水中，而無法提供有效的立體障礙。在一實施例中，m與n之比例介於7：1至1：2之間。若m/n值過低，則分散劑不易溶於水中。若m/n值過高，則分散時所需的分散劑添加量過多。上述共聚物之Mw可介於2000至8000之間，而Mn可介於1000至5000之間，且多分散指數(PDI)小於1.8且大於1。若共聚物之分子量過高，則過長的溶媒鏈段可能提供過度的立體障礙造成能分散的顏料量下降或是錨釘鏈過長易產生架橋現象造成凝集沉降不適用於奈米級微粒的分散，分散效果降低。若共聚物之分子量過低，則溶媒鏈段提供的立體障礙不夠或錨釘鏈無法有吸附粉體，造成分散效果不佳。若共聚物之PDI過高，在應用至分散微粉時可能造成分散後的微粉粒徑分佈過寬。在 一實施例中，(a)第一團塊係。在一 實施例中，(b)第二團塊係。在一實施例中， (b)第二團塊係。在一實施例中，(b)第二團 塊係。在一實施例中，(b)第二團塊係 The present invention provides a bi-branched copolymer comprising: (a) a first agglomerate having repeating units And (b) the second mass with repeating units . The above (a) first agglomerates are chemically bonded to (b) the second agglomerate, R 1 is H or CH 3 ; R 2 is H or CH 3 ; R 3 is R 4 is a C 1-10 alkyl group; M lanthanide Na + , NH 4 + , or NH(C 2 H 4 OH) 3 + ; m=10-20; n=2-20; and x=0- 4. If the value of m is too low, the proportion of ions contained in the copolymer is too low to dissolve the dispersant in water. If the value of m is too high, the amount of the dispersant required for dispersion is likely to be excessive. If the value of n is too low, the anchor segment cannot be effectively adsorbed onto the fine powder. If the value of n is too high, the anchor chain tends to adsorb another fine powder to cause aggregation. If the value of x is too high, the carboxylate contained in the copolymer is too small, and the solvent segment cannot be completely dispersed in water, and an effective steric hindrance cannot be provided. In an embodiment, the ratio of m to n is between 7:1 and 1:2. If the m/n value is too low, the dispersant is not easily soluble in water. If the m/n value is too high, the amount of the dispersant added during the dispersion is excessive. The above copolymer may have a Mw of between 2,000 and 8,000, and a Mn of between 1000 and 5,000 and a polydispersity index (PDI) of less than 1.8 and greater than 1. If the molecular weight of the copolymer is too high, an excessively long solvent segment may provide excessive steric hindrance, resulting in a decrease in the amount of pigment that can be dispersed or an excessively long anchor chain, which may cause bridging and collapse, which is not suitable for use in nanoscale particles. Dispersion, dispersion effect is reduced. If the molecular weight of the copolymer is too low, the steric barrier provided by the solvent segment is insufficient or the anchor chain cannot adsorb the powder, resulting in poor dispersion. If the PDI of the copolymer is too high, it may cause the particle size distribution of the dispersed fine powder to be too wide when applied to the dispersed fine powder. In an embodiment, (a) the first briquette system . In an embodiment, (b) the second briquette system . In an embodiment, (b) the second briquette system . In an embodiment, (b) the second briquette system . In an embodiment, (b) the second briquette system

在一實施例中，上述雙團塊共聚物之合成方式可如下說明。值得注意的是，本揭露之雙團塊共聚物並不限於下述合成方法，本技術領域中具有通常知識者自可依本揭露內容，自行挑選合適的合成方式以形成上述雙團塊共聚物。 In one embodiment, the synthesis of the above-described bi-branched copolymer can be as follows. It should be noted that the double-branched copolymer of the present disclosure is not limited to the following synthesis methods, and those skilled in the art can select a suitable synthesis method to form the above-mentioned double-bulk copolymer according to the disclosure. .

首先，先取溴化亞銅(CuBr)、溴化銅(CuBr2)、與N,N,N',N',N''-五甲基二乙三胺(N,N,N',N',N''-pentamethyl diethylenetriamine，PMDETA)溶於四氫呋喃(THF)後，將對甲苯磺醯氯(p-toluenesulfonyl chloride，TsCl)與丙烯酸酯加入上述溶液，並加熱進行ATRP聚合反應如下式： First, first take copper bromide (CuBr), copper bromide (CuBr 2 ), and N , N , N ', N ', N ''-pentamethyldiethylenetriamine ( N , N , N' , N after ', N''-pentamethyl diethylenetriamine, PMDETA) was dissolved in tetrahydrofuran (THF), toluene sulfonic will acyl chloride (p -toluenesulfonyl chloride, TsCl) acrylate added to the solution, and the reaction was heated for ATRP of the following formula:

待丙烯酸酯單體反應完後，接著將含R3之另一丙烯酸酯加入上述反應，繼續進行ATRP反應如下式： After the reaction of the acrylate monomer is completed, the other acrylate containing R 3 is then added to the above reaction, and the ATRP reaction is continued as follows:

可以理解的是，上述兩種丙烯酸酯的反應順序可顛倒，而不限於上述順序。需注意的是，不論採用哪種順序，在添加第二種丙烯酸酯前，需先確認反應物已無殘留第一種丙烯酸酯，以避免形成無規共聚物而非雙團塊共聚物。 It is to be understood that the reaction order of the above two acrylates may be reversed, and is not limited to the above order. It should be noted that, regardless of the order, it is necessary to confirm that the first acrylate remains in the reactants before the addition of the second acrylate to avoid formation of a random copolymer rather than a bi-branched copolymer.

接著加入酸使R'轉為H，再加入鹼中和共聚物如下式： Next, an acid is added to convert R' to H, and then a base neutralizing copolymer is added as follows:

在一實施例中，中和步驟可將溶液的pH值調至鹼性(如pH=8-10)，以確保所有的酸均轉為鹽(即x=0)。由於兩種丙烯酸酯係依序反應而非同時反應，因此形成之共聚物為團塊 共聚物而非無規共聚物。經由實驗證明，即使採用相同的反應物進行ATRP反應，本揭露之雙團塊共聚物在分散液中的效果優於無規共聚物。 In one embodiment, the neutralization step adjusts the pH of the solution to a basicity (e.g., pH = 8-10) to ensure that all of the acid is converted to a salt (i.e., x = 0). Since the two acrylates react sequentially rather than simultaneously, the copolymer formed is agglomerate Copolymers rather than random copolymers. It has been experimentally proved that the double-branched copolymer of the present invention is superior to the random copolymer in the dispersion even if the same reactant is used for the ATRP reaction.

本揭露一實施例亦提供分散液，其包括：100重量份的粉體；1至80重量份上述的雙團塊共聚物；以及100至900重量份之極性溶劑。若雙團塊共聚物之比例過低，則無法有效分散粉體。若雙團塊共聚物之比例過高，則易造成分散劑過剩。若極性溶劑之比例過低，則易造成分散劑的溶解度下降，無法提供有效的分散。在一實施例中，上述粉體可為無機顏料、有機顏料、金屬、金屬氧化物、或上述之組合。無機顏料可為TiO2(例如CR-80，購自石原產業株式會社)。有機顏料可為藍色顏料(例如B-432，購自貝斯特精密化學)、黃色顏料(例如Y-310，購自貝斯特精密化學)、紅色顏料(例如R-220，購自福大化學工業股份)、和黑色顏料(例如K-960，購自貝斯特精密化學)。金屬可為銀、銅、金、鋁、鉑、上述之合金、或上述之組合。金屬氧化物可為二氧化鈦、氧化鐵、氧化鋅、氧化鋁、或氧化鋯。在一實施例中，極性溶劑可為水、二乙二醇二***、二乙二醇二甲醚、丙二醇甲醚醋酸酯、二乙二醇丁醚醋酸酯、乙二醇丁醚、四乙二醇二甲醚、或上述之組合。 An embodiment of the present disclosure also provides a dispersion comprising: 100 parts by weight of a powder; 1 to 80 parts by weight of the above-mentioned double-branched copolymer; and 100 to 900 parts by weight of a polar solvent. If the proportion of the bi-branched copolymer is too low, the powder cannot be effectively dispersed. If the proportion of the double agglomerate copolymer is too high, it tends to cause excess of the dispersant. If the ratio of the polar solvent is too low, the solubility of the dispersant is liable to be lowered, and effective dispersion cannot be provided. In one embodiment, the powder may be an inorganic pigment, an organic pigment, a metal, a metal oxide, or a combination thereof. The inorganic pigment may be TiO 2 (for example, CR-80, available from Ishihara Sangyo Co., Ltd.). The organic pigment can be a blue pigment (eg B-432, available from Best Precision Chemicals), a yellow pigment (eg Y-310, available from Best Precision Chemicals), a red pigment (eg R-220, available from Fuda Chemical) Industrial shares), and black pigments (such as K-960, purchased from Best Precision Chemicals). The metal may be silver, copper, gold, aluminum, platinum, alloys of the above, or combinations thereof. The metal oxide can be titanium dioxide, iron oxide, zinc oxide, aluminum oxide, or zirconium oxide. In one embodiment, the polar solvent may be water, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, tetraethylene Diol dimethyl ether, or a combination thereof.

本揭露實施例提供之雙團塊共聚物，不僅具備立體障礙與靜電排斥力良好的溶媒鏈段(如(a)第一團塊)，亦具有錨釘微粉鏈段(如(b)第二團塊)。更重要的是，藉由調整雙團塊共聚物之(a)第一團塊與(b)第二團塊的分子量大小，與共聚物的分子量分布(如PDI)，可提高雙團塊共聚物對於分散液的粉 體分散容許量與安定性，並降低分散液黏度。 The double-branched copolymer provided by the embodiment not only has a solvent segment with good steric hindrance and electrostatic repulsive force (such as (a) the first agglomerate), but also has a anchor micro-powder segment (such as (b) second. Bump). More importantly, by adjusting the molecular weight of the (a) first agglomerate and (b) the second agglomerate of the double-branched copolymer, and the molecular weight distribution of the copolymer (such as PDI), the double-block copolymerization can be improved. Powder for dispersion The bulk dispersion tolerance and stability, and reduce the viscosity of the dispersion.

為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下： The above and other objects, features and advantages of the present invention will become more apparent and understood.

實施例 Example

實施例1 Example 1

將四頸瓶A抽真空通氮氣後，加入N,N,N',N',N''-五甲基二乙三胺(PMDETA，12.18g，70.32mmole)與THF(65mL)。將氮氣通入THF溶液中除氣30分鐘後，加入CuBr(10.08g，70.32mmole)並攪拌20分鐘。接著將CuBr2(3.14g，14.06mmole)加入THF溶液後，攪拌10分鐘。 After vacuuming the four-necked flask A through nitrogen, N , N , N ', N ', N ''-pentamethyldiethylenetriamine (PMDETA, 12.18 g, 70.32 mmole) and THF (65 mL) were added. After removing nitrogen gas into the THF solution for 30 minutes, CuBr (10.08 g, 70.32 mmole) was added and stirred for 20 minutes. Next, CuBr 2 (3.14 g, 14.06 mmole) was added to the THF solution, followed by stirring for 10 minutes.

將雙頸瓶B抽真空通氮氣後，加入tBMA(100.00g，703.23mmole)、p-TsCl(13.40g，70.32mmole)、與THF(65mL)，並將氮氣通入THF溶液中除氧30分鐘。接著將此溶液加入四頸瓶A後，在氮氣下加熱上述反應物至40℃並於40℃下反應22小時，形成PtBMA。上述聚合機制即ATRP，其反應式如下式所示： After vacuuming the double-necked bottle B with nitrogen, t BMA (100.00 g, 703.23 mmole), p- TsCl (13.40 g, 70.32 mmole), and THF (65 mL) were added, and nitrogen gas was introduced into the THF solution to remove oxygen 30. minute. After this solution was added to the four-necked flask A, the above reactant was heated to 40 ° C under nitrogen and reacted at 40 ° C for 22 hours to form P t BMA. The above polymerization mechanism is ATRP, and its reaction formula is as follows:

將雙頸瓶C抽真空通氮氣後，加入PhEA(81.10g，421.94mmole)，並將氮氣通入PhEA中除氧30分鐘。接著將除氧後的PhEA加入四頸瓶A，在氮氣下加熱上述反應物至40℃並於40℃下反應24小時，形成雙團塊共聚物PtBMA-b-PPhEA。可以 理解的是，由於tBMA與PhEA兩種單體係依序反應而非同時反應，因此形成之共聚物為團塊共聚物而非無規共聚物。上述聚合機制即ATRP，其反應式如下式所示： After vacuuming the double-necked flask C through nitrogen, PhEA (81.10 g, 421.94 mmole) was added, and nitrogen gas was bubbled through the PhEA for 30 minutes. Next, the deoxygenated PhEA was placed in a four-necked flask A, and the above reactant was heated to 40 ° C under nitrogen and reacted at 40 ° C for 24 hours to form a bi-branched copolymer PtBMA- b- PPhEA. It can be understood that since the two single systems of tBMA and PhEA react sequentially rather than simultaneously, the copolymer formed is agglomerate copolymer rather than random copolymer. The above polymerization mechanism is ATRP, and its reaction formula is as follows:

上述反應冷卻後，以中性氧化鋁管柱過濾上述反應後之粗產物溶液，並以正己烷再沉澱濾液，並收集白色固體(PtBMA-b-PPhEA，135.1g，產率約70%)。上述產物之Mw為7900，Mn為6100，且PDI為1.3。 After cooling the reaction described above, a neutral alumina column The crude product solution was filtered after the above reaction, and the filtrate was reprecipitated with n-hexane, and was collected as a white solid (P t BMA- b -PPhEA, 135.1g , a yield of about 70% ). The above product had a Mw of 7900, an Mn of 6100, and a PDI of 1.3.

接著取PtBMA-b-PPhEA(125g，36.16mmol)與二噁烷(260mL)於氮氣下混合攪拌，再將鹽酸(15.5mL，180mmol)加入上述混合液後，加熱至85℃並於85℃下反應18小時。冷卻反應後，濃縮除去溶劑。取THF溶解粗產物至具低黏度流動性後，過濾掉不溶物。再將溶液加入正己烷中再沈澱，並過濾取濾餅。乾燥濾餅後，即得白色固體PMAA-b-PPhMA(約76g，產率約79%)。PMAA-b-PPhMA之Mw=2700，Mn=1900，且PDI=1.4。接著將76g之PMAA-b-PPhMA粉末攪拌分散於75mL 的去離子水中，滴入28%之氨水溶液(22g)至上述分散液中，再加熱至70℃並於70℃反應5小時。溶解完全後，以氨水將上述溶液之pH值調整至8以上，即得雙團塊共聚物DBDE01，其未中和前的酸價為234mg KOH/g。上述反應如下式所示： Then, PtBMA- b- PPhEA (125 g, 36.16 mmol) and dioxane (260 mL) were mixed and stirred under nitrogen, and hydrochloric acid (15.5 mL, 180 mmol) was added to the above mixture, and then heated to 85 ° C at 85 ° C. Reaction for 18 hours. After cooling the reaction, the solvent was concentrated to remove. After the crude product was dissolved in THF to have a low viscosity fluidity, the insoluble matter was filtered off. The solution was again added to n-hexane to reprecipitate, and the filter cake was filtered. After drying the filter cake, a white solid PMAA- b- PPhMA (about 76 g, yield about 79%) was obtained. PMA- b- PPhMA has Mw = 2700, Mn = 1900, and PDI = 1.4. Next, 76 g of PMAA- b- PPhMA powder was stirred and dispersed in 75 mL of deionized water, and a 28% aqueous ammonia solution (22 g) was added dropwise to the above dispersion, and the mixture was further heated to 70 ° C and reacted at 70 ° C for 5 hours. After the dissolution was completed, the pH of the above solution was adjusted to 8 or more with aqueous ammonia to obtain a double-branched copolymer DBDE01, and the acid value before unneutralization was 234 mg KOH/g. The above reaction is as follows:

與上述步驟類似，改變反應物當量以調整m值與n值，得到雙團塊共聚物DBDE02。 Similar to the above procedure, the reactant equivalent was changed to adjust the m value and the n value to obtain a double agglomerate copolymer DBDE02.

上述反應產物(雙團塊共聚物)DBDE01與DBDE02之m/n，與其各階段中間產物PtBMA、PtBMA-b-PPhEA、PMAA-b-PPhEA之Mw、Mn、PDI、與酸價如第1表所示： The above reaction product (double-block copolymer) DB/01 and DBDE02 m/n, and its intermediate products P t BMA, P t BMA- b -PPhEA, PMAA- b -PPhEA Mw, Mn, PDI, and acid value As shown in Table 1:

實施例2 Example 2

與實施例1類似，差別在將PhEA置換為BzMA，並改變反應物當量以調整m值與n值，其反應如下式： Similar to Example 1, the difference was in replacing PhEA with BzMA and changing the reactant equivalents to adjust the m and n values, which reacted as follows:

上述反應產物(雙團塊共聚物)DBDP01-DBDP04之m/n，與其各階段之中間產物PtBMA、PtBMA-b-PBzMA、PMAA-b-PBzMA之Mw、Mn、PDI、與酸價如第2表所示： m/n of the above reaction product (double agglomerate copolymer) DBDP01-DBDP04, Mw, Mn, PDI, and acid with the intermediate products P t BMA, P t BMA- b -PBzMA, PMAA- b -PBzMA The price is as shown in the second table:

實施例3 Example 3

與實施例1類似，差別在將PhEA置換為BACA，並改變反 應物當量以調整m值與n值，其反應如下式： Similar to Example 1, the difference was in replacing PhEA with BACA and changing the reactant equivalents to adjust the m and n values, which reacted as follows:

上述反應產物(雙團塊共聚物)DBDN01之m/n，與其各階段之中間產物PtBMA、PtBMA-b-PBACA、PMAA-b-PBACA之Mw、Mn、PDI、與酸價如第3表所示： m/n of DBDN01 of the above reaction product (double agglomerate copolymer), Mw, Mn, PDI, and acid value of intermediate products P t BMA, P t BMA- b -PBACA, PMAA- b -PBACA Table 3 shows:

實施例4 Example 4

與實施例1類似，差別在將PhEA置換為HPPA，並改變反應物當量以調整m值與n值，其反應如下式： Similar to Example 1, the difference was in replacing PhEA with HPPA and changing the reactant equivalents to adjust the m and n values, which reacted as follows:

上述反應產物(雙團塊共聚物)DBDH01之m/n與其各階段之中間產物PtBMA、PtBMA-b-PHPPA、PMAA-b-PHPPA之Mw、Mn、PDI、與酸價如第4表所示： m/n of the above reaction product (double-block copolymer) DBDH01 and its intermediates P t BMA, P t BMA- b -PHPPA, PMAA- b -PHPPA Mw, Mn, PDI, and acid value 4 table shows:

比較例1 Comparative example 1

與實施例1類似，差別在於p-TsCl、tBMA、與PhEA一起反應成無規共聚物，而非依序反應成團塊共聚物。上述反應如下式所示： Similar to Example 1, the difference is that p-TsCl, t BMA, and PhEA are reacted together to form a random copolymer instead of sequentially reacting into agglomerated copolymer. The above reaction is as follows:

上述反應之中間產物P(MAA-co-PhEA)的酸價與Mw、Mn、PDI如第5表所示： The acid value and Mw, Mn, and PDI of the intermediate product P (MAA-co-PhEA) of the above reaction are shown in Table 5:

比較例2 Comparative example 2

取50.0g之BzMA、15.7g之MAA、42.5g之MMA、與1.8g之AIBN一起加入140mL之甲乙酮中，加熱至78℃後反應8小時， 得無規共聚物A-20。上述反應如下式所示： 50.0 g of BzMA, 15.7 g of MAA, 42.5 g of MMA, and 1.8 g of AIBN were added to 140 mL of methyl ethyl ketone, and heated to 78 ° C for 8 hours to obtain a random copolymer A-20. The above reaction is as follows:

上述反應之中間產物P(BzMA-co-MAA-co-MMA)的酸價與Mw、Mn、PDI如第6表所示： The acid value and Mw, Mn, and PDI of the intermediate product P (BzMA-co-MAA-co-MMA) of the above reaction are shown in Table 6:

由上述可知，比較例1之無規共聚物A-21的分子量分佈PDI窄，而比較例2之無規共聚物A-20的分子量分佈PDI寬且分子量大。 From the above, the molecular weight distribution PDI of the random copolymer A-21 of Comparative Example 1 was narrow, and the random copolymer A-20 of Comparative Example 2 had a broad molecular weight distribution PDI and a large molecular weight.

實施例5-1(分散液) Example 5-1 (dispersion)

取9g之市售分散劑BYK2010(購自BYK)加入9g之去離子水中，機械攪拌(400rpm)後加入12g的TiO2粉末(構自ISK石原產業之CR80)並持續攪拌1小時。接著將0.1mm之鋯珠(總重159g)加入上述分散液後，於20℃下以2000rpm之轉速進行球磨分散3 小時。過濾移去鋯珠後，取樣量測分散液中的TiO2粒徑。接著各取3mL的分散液量進行熱儲存(置於60℃ 7天)與低溫儲存(搭配10wt%的抗凍劑2-吡咯啶並置於-17℃ 7天)，再量測分散液中TiO2的平均粒徑(Dave)與D95，由儲存前後的△Dave以確認分散液的安定性，如第7表所示。 9 g of a commercially available dispersant BYK2010 (purchased from BYK) was added to 9 g of deionized water, and after mechanical stirring (400 rpm), 12 g of TiO 2 powder (CR80 constructed from ISK Ishihara Industries) was added and stirring was continued for 1 hour. Next, 0.1 mm of zirconium beads (total weight 159 g) was added to the above dispersion, and then ball-milled and dispersed at 20 ° C for 3 hours at 2000 rpm. After the zirconium beads were removed by filtration, the particle size of the TiO 2 in the dispersion was measured by sampling. Then take 3mL of each dispersion amount for thermal storage (placed at 60 ° C for 7 days) and low temperature storage (with 10wt% antifreeze 2-pyrrolidine and placed at -17 ° C for 7 days), and then measure the dispersion of TiO the average particle diameter of 2 (D ave) and D 95, the before and after storage △ D ave to confirm the stability of the dispersion as shown in table 7.

實施例5-2(分散液) Example 5-2 (dispersion)

與實施例5-1類似，差別在於分散劑改為BYK190(購自BYK)。 Similar to Example 5-1, the difference was that the dispersant was changed to BYK190 (purchased from BYK).

實施例5-3(分散液) Example 5-3 (dispersion)

與實施例5-1類似，差別在於分散劑改為比較例2製備之無規共聚物A-20。 Similar to Example 5-1, the difference was that the dispersant was changed to the random copolymer A-20 prepared in Comparative Example 2.

實施例5-4(分散液) Example 5-4 (dispersion)

與實施例5-1類似，差別在於分散劑改為比較例1製備之無規共聚物A-21。 Similar to Example 5-1, the difference was that the dispersant was changed to the random copolymer A-21 prepared in Comparative Example 1.

實施例5-5(分散液) Example 5-5 (dispersion)

與實施例5-1類似，差別在於分散劑改為實施例2製備之雙團塊共聚物DBDP02。 Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDP02 prepared in Example 2.

實施例5-6(分散液) Example 5-6 (dispersion)

與實施例5-1類似，差別在於分散劑改為實施例1製備之雙團塊共聚物DBDE01。 Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDE01 prepared in Example 1.

實施例5-7(分散液) Example 5-7 (dispersion)

與實施例5-1類似，差別在於分散劑改為實施例4製備之雙團塊共聚物DBDH01。 Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDH01 prepared in Example 4.

第7表 Table 7

註：比較例製備之無規共聚物在形成分散液後的初始粒徑過大，因此未進行熱儲存與低溫儲存測試。 Note: The random copolymer prepared in the comparative example had an excessive initial particle size after the formation of the dispersion, and thus no thermal storage and low temperature storage test were performed.

由第7表之比較可知，本揭露實施例之分散劑所形成的分散液中的TiO2，在熱儲存與低溫儲存後之平均粒徑變化(△Dave)較低。換言之，本揭露實施例之分散液的安定性較高。 As is apparent from the comparison of the seventh table, the average particle diameter change (ΔD ave ) of the TiO 2 in the dispersion formed by the dispersant of the present disclosure was low after heat storage and low temperature storage. In other words, the stability of the dispersion of the disclosed embodiment is high.

實施例6(分散液) Example 6 (dispersion)

取54.52g之實施例3製備之雙團塊共聚物DBDN01加入86.48g之去離子水與22g之乙二醇中，機械攪拌(400rpm)後加入66g的TiO2粉末(構自ISK石原產業之CR80)並持續攪拌1小時。接著將0.1mm之鋯珠(總重1100g)加入上述分散液後，於15℃下以2000rpm之轉速進行球磨分散5小時。過濾移去鋯珠後，取樣量測分散液中的TiO2粒徑。接著各取3mL的分散液量進行熱儲存(置於60℃ 7天)與低溫儲存(置於-17℃ 7天)，再量測分散液中TiO2的平均粒徑(Dave)與D95以確認分散液的安定性，如第8表所示。 54.52 g of the double-branched copolymer DBDN01 prepared in Example 3 was added to 86.48 g of deionized water and 22 g of ethylene glycol, and mechanically stirred (400 rpm) and then 66 g of TiO 2 powder (CR80 constructed from ISK Ishihara Industry) was added. ) and stirring for 1 hour. Next, 0.1 mm of zirconium beads (total weight 1100 g) was added to the above dispersion, and then ball-milled and dispersed at 15 ° C for 5 hours at 2000 rpm. After the zirconium beads were removed by filtration, the particle size of the TiO 2 in the dispersion was measured by sampling. Then take 3mL of each dispersion amount for thermal storage (placed at 60 ° C for 7 days) and low temperature storage (placed at -17 ° C for 7 days), and then measure the average particle size (D ave ) and D of TiO 2 in the dispersion. 95 to confirm the stability of the dispersion, as shown in Table 8.

由第8表之比較可知，本揭露實施例之分散劑所形成的分散液中的TiO2，在熱儲存與低溫儲存後之平均粒徑變化(△Dave)較低。換言之，本揭露實施例之分散液的安定性較高。 As is apparent from the comparison of the eighth table, the average particle diameter change (ΔD ave ) of the TiO 2 in the dispersion formed by the dispersant of the present embodiment is low after heat storage and low temperature storage. In other words, the stability of the dispersion of the disclosed embodiment is high.

實施例7-1(分散液) Example 7-1 (dispersion)

取6.75g之市售分散劑BYK2010加入12.75g之去離子水與1.5g之2-吡咯啶中，機械攪拌(400rpm)後加入9g之藍色有機顏料B432(購自貝斯特精密化學)並持續攪拌0.5小時。接著將0.1mm之鋯珠(總重195g)加入上述分散液後，於20℃下以2000rpm之轉速進行球磨分散2小時。過濾移去鋯珠後，取樣量測分散液中的TiO2粒徑。接著各取3mL的分散液量進行熱儲存(置於60℃ 7天)與低溫儲存(並置於-17℃ 7天)，再量測分散液中藍色有機顏料的平均粒徑(Dave)與D95，由儲存前後的△Dave以確認分散液的安定性，如第9表所示。 6.75 g of the commercially available dispersant BYK2010 was added to 12.75 g of deionized water and 1.5 g of 2-pyrrolidine. After mechanical stirring (400 rpm), 9 g of blue organic pigment B432 (purchased from Best Precision Chemicals) was added and continued. Stir for 0.5 hours. Next, 0.1 mm of zirconium beads (total weight 195 g) was added to the above dispersion, and then ball-milled at 2000 rpm for 2 hours at 20 °C. After the zirconium beads were removed by filtration, the particle size of the TiO 2 in the dispersion was measured by sampling. Then take 3mL of each dispersion for thermal storage (placed at 60 ° C for 7 days) and low temperature storage (and placed at -17 ° C for 7 days), and then measure the average particle size of the blue organic pigment in the dispersion (D ave ) With D 95 , the stability of the dispersion was confirmed by ΔD ave before and after storage, as shown in Table 9.

實施例7-2(分散液) Example 7-2 (dispersion)

與實施例7-1類似，差別在於市售分散劑BYK2010置換為實施例1製備之雙團塊共聚物DBDE01。 Similar to Example 7-1, the difference was that the commercially available dispersant BYK2010 was replaced with the double-branched copolymer DBDE01 prepared in Example 1.

實施例7-3(分散液) Example 7-3 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換為黃色有機顏料Y-301(購自貝斯特精密化學)。 Similar to Example 7-1, the difference was that the blue organic pigment B432 was replaced with the yellow organic pigment Y-301 (purchased from Best Precision Chemicals).

實施例7-4(分散液) Example 7-4 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換為黃色有機顏料Y-301(購自貝斯特精密化學)，且市售分散劑BYK2010置換為實施例1製備之雙團塊共聚物DBDE01。 Similar to Example 7-1, the difference was that the blue organic pigment B432 was replaced with the yellow organic pigment Y-301 (available from Best Precision Chemicals), and the commercially available dispersant BYK2010 was replaced with the double agglomerate copolymer prepared in Example 1. DBDE01.

實施例7-5(分散液) Example 7-5 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換紅色有機顏料R-220(購自福大化學工業股份)。 Similar to Example 7-1, the difference was that the blue organic pigment B432 replaced the red organic pigment R-220 (purchased from Fuda Chemical Industries Co., Ltd.).

實施例7-6(分散液) Example 7-6 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換為紅色有機顏料R-220(購自福大化學工業股份)，且市售分散劑BYK2010置換為實施例1製備之雙團塊共聚物DBDE01。 Similar to Example 7-1, the difference was that the blue organic pigment B432 was replaced with the red organic pigment R-220 (purchased from Fuda Chemical Industries Co., Ltd.), and the commercially available dispersant BYK2010 was replaced by the double agglomerate copolymer prepared in Example 1. Object DBDE01.

實施例7-7(分散液) Example 7-7 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換黑色有機顏料K-960(購自貝斯特精密化學)。 Similar to Example 7-1, the difference was that the blue organic pigment B432 replaced the black organic pigment K-960 (purchased from Best Precision Chemicals).

實施例7-8(分散液) Example 7-8 (dispersion)

與實施例7-1類似，差別在於藍色有機顏料B432置換為黑色有機顏料K-960(購自貝斯特精密化學)，且市售分散劑BYK2010置換為實施例1製備之雙團塊共聚物DBDE01。 Similar to Example 7-1, the difference was that the blue organic pigment B432 was replaced with the black organic pigment K-960 (available from Best Precision Chemicals), and the commercially available dispersant BYK2010 was replaced with the double agglomerate copolymer prepared in Example 1. DBDE01.

由第9表之比較可知，本揭露實施例之分散劑所形成的分散液中的有機顏料藍色、黃色和紅色粒子，初始粒徑與熱儲存與低溫儲存後之平均粒徑變化(△Dave)均較低。換言之，本揭露實施例之分散液的安定性較高。 As can be seen from the comparison of the ninth table, the blue, yellow and red particles of the organic pigment in the dispersion formed by the dispersant of the present disclosure, the initial particle diameter and the average particle size change after heat storage and low temperature storage (ΔD) Ave ) is lower. In other words, the stability of the dispersion of the disclosed embodiment is high.

雖然本揭露已以數個實施例揭露如上，然其並非 用以限定本揭露，任何本技術領域中具有通常知識者，在不脫離本揭露之精神和範圍內，當可作任意之更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。 Although the disclosure has been disclosed above in several embodiments, it is not In order to limit the disclosure, any person skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of the present disclosure is to be attached to the patent application scope. The definition is final.

Claims (10)

一種雙團塊共聚物，包括： (a)第一團塊，具有重複單元；以及 (b)第二團塊，具有重複單元，其中(a)第一團塊化學鍵結至(b)第二團塊；R1係H或CH3；R2係H或CH3； R3係、、、或 R4係C1-10之烷基；M⊕係Na+、NH4 +、或NH(C2H4OH)3 +；m=10-20；n=2-20；以及x=0-4，其中m與n之比例介於7：1至1：2之間，且雙團塊共聚物之Mn介於1000至5000之間。 A double agglomerate copolymer comprising: (a) a first agglomerate having repeating units And (b) the second mass with repeating units Wherein (a) the first mass is chemically bonded to (b) the second agglomerate; R 1 is H or CH 3 ; R 2 is H or CH 3 ; R 3 is , , ,or R 4 is a C 1-10 alkyl group; M lanthanide Na + , NH 4 + , or NH(C 2 H 4 OH) 3 + ; m=10-20; n=2-20; and x=0- 4, wherein the ratio of m to n is between 7:1 and 1:2, and the Mn of the double-branched copolymer is between 1000 and 5000. 如申請專利範圍第1項所述之雙團塊共聚物，其多分散 指數(PDI)小於1.8且大於1。 Polydisperse copolymer as described in claim 1 of the patent application, which is polydisperse The index (PDI) is less than 1.8 and greater than one. 如申請專利範圍第1項所述之雙團塊共聚物，其中(a)第一團塊係。 The double-branched copolymer according to claim 1, wherein (a) the first briquettes . 如申請專利範圍第1項所述之雙團塊共聚物，其中(b) 第二團塊係。 A double-branched copolymer as described in claim 1, wherein (b) the second agglomerate . 如申請專利範圍第1項所述之雙團塊共聚物，其中(b) 第二團塊係。 A double-branched copolymer as described in claim 1, wherein (b) the second agglomerate . 如申請專利範圍第1項所述之雙團塊共聚物，其中(b)第二團塊係。 The double-branched copolymer according to claim 1, wherein (b) the second agglomerate . 如申請專利範圍第1項所述之雙團塊共聚物，其中(b)第二團塊係。 The double-branched copolymer according to claim 1, wherein (b) the second agglomerate . 一種分散液，包括：100重量份的粉體； 1至80重量份的申請專利範圍第1項所述之雙團塊共聚物；以及100至900重量份之極性溶劑。 a dispersion comprising: 100 parts by weight of a powder; 1 to 80 parts by weight of the double-branched copolymer described in claim 1; and 100 to 900 parts by weight of a polar solvent. 如申請專利範圍第8項所述之分散液，其中該粉體包含無機顏料、有機顏料、金屬、金屬氧化物、或上述之組合。 The dispersion according to claim 8, wherein the powder comprises an inorganic pigment, an organic pigment, a metal, a metal oxide, or a combination thereof. 如申請專利範圍第8項所述之分散液，其中該極性溶劑包括水、二乙二醇二***、二乙二醇二甲醚、丙二醇甲醚醋酸酯、二乙二醇丁醚醋酸酯、乙二醇丁醚、四乙二醇二甲醚、或上述之組合。 The dispersion according to claim 8, wherein the polar solvent comprises water, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, Ethylene glycol butyl ether, tetraethylene glycol dimethyl ether, or a combination thereof.
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