TWI606071B - Diblock copolymer and dispersion - Google Patents

Description

Double agglomerate copolymer and dispersion

The present disclosure relates to a double agglomerate polymer and a dispersion using the same.

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.

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.

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.

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

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. .

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:

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:

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.

Next, an acid is added to convert R' to H, and then a base neutralizing copolymer is added as follows:

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.

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.

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.

The above and other objects, features and advantages of the present invention will become more apparent and understood.

Example

Example 1

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.

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:

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:

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.

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:

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.

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:

Example 2

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:

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:

Example 3

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:

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:

Example 4

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:

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:

Comparative example 1

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:

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:

Comparative example 2

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:

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:

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.

Example 5-1 (dispersion)

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.

Example 5-2 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to BYK190 (purchased from BYK).

Example 5-3 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to the random copolymer A-20 prepared in Comparative Example 2.

Example 5-4 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to the random copolymer A-21 prepared in Comparative Example 1.

Example 5-5 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDP02 prepared in Example 2.

Example 5-6 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDE01 prepared in Example 1.

Example 5-7 (dispersion)

Similar to Example 5-1, the difference was that the dispersant was changed to the double-branched copolymer DBDH01 prepared in Example 4.

Table 7

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.

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.

Example 6 (dispersion)

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.

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.

Example 7-1 (dispersion)

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.

Example 7-2 (dispersion)

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.

Example 7-3 (dispersion)

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).

Example 7-4 (dispersion)

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.

Example 7-5 (dispersion)

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.).

Example 7-6 (dispersion)

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.

Example 7-7 (dispersion)

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).

Example 7-8 (dispersion)

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.

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.

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)

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. 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. The double-branched copolymer according to claim 1, wherein (a) the first briquettes . A double-branched copolymer as described in claim 1, wherein (b) the second agglomerate . A double-branched copolymer as described in claim 1, wherein (b) the second agglomerate . The double-branched copolymer according to claim 1, wherein (b) the second agglomerate . The double-branched copolymer according to claim 1, wherein (b) the second agglomerate . 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. 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. 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.