CN110922542A - Block copolymer and process for producing the same - Google Patents
Block copolymer and process for producing the same Download PDFInfo
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- CN110922542A CN110922542A CN201811099566.9A CN201811099566A CN110922542A CN 110922542 A CN110922542 A CN 110922542A CN 201811099566 A CN201811099566 A CN 201811099566A CN 110922542 A CN110922542 A CN 110922542A
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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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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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
- C08F4/00—Polymerisation catalysts
Abstract
The present disclosure provides a method for preparing a block copolymer, comprising the steps of: (A) mixing a compound of formula (I), a catalyst of formula (II), and a first solvent to obtain a first mixture; (B) adding a first monomer into the first mixture to react to obtain a second mixture; and (C) adding a second monomer into the second mixture to react to obtain a third mixture, wherein the compound of the formula (I) and the catalyst of the formula (II) are defined in the specification.
Description
Technical Field
The present invention relates to a block copolymer and a preparation method thereof, and more particularly, to a triblock copolymer and a method for catalyzing the synthesis of the block copolymer by using an oxygen metal complex as a catalyst.
Background
The pigment has better stability to light, heat, water and the like compared with the dye, so the pigment is widely applied to printing ink and coating, however, the pigment is a solid particle which is insoluble in water, and aggregation and uneven dispersion are easy to occur in the preparation, use or storage process, so the quality is influenced, and the dispersibility of the pigment is one of the key factors influencing the quality.
The dispersant is often used as a necessary additive, and has the advantages of promoting dispersion of pigment particles, improving stability and the like, while the traditional small molecular dispersant has poor stability and poor dispersion effect, and has been gradually replaced by a high molecular dispersant recently, wherein the block type high molecular dispersant is particularly emphasized. In general, the synthesis of the catalytic block copolymer requires a reaction using 1 to 2 equivalents of a catalyst, and the reaction efficiency is low and the cost is high.
Therefore, there is a need to continuously research the block copolymer to provide industrial utilization and develop a new preparation method to simplify the process or reduce the cost.
Disclosure of Invention
Accordingly, the present disclosure provides a block copolymer and a method for preparing the block copolymer, which can utilize an oxygen metal complex as a catalyst to catalyze the synthesis of the block copolymer, and only use a catalyst amount to perform the reaction, thereby saving the cost. In addition, the oxygen-metal complex is biochemically absorbable and metabolizable, thereby reducing environmental burden.
The present disclosure provides a method for preparing a block copolymer, comprising the steps of: (A) mixing a compound of formula (I), a catalyst of formula (II), and a first solvent to obtain a first mixture; (B) adding a first monomer into the first mixture to react to obtain a second mixture; and (C) adding a second monomer into the second mixture to react to obtain a third mixture.
Furthermore, the present disclosure also provides a block copolymer comprising the structure of the following formula (V):
[D]x-[E]y-[F]z(V)
wherein D, E, and F are each independently a compound of formula (VI), and D, E, and F are different from each other; and x, y, z are each independently an integer from 1 to 40, wherein the compound of formula (VI) is shown below:
wherein A is2Is O or S; r7Is H, or C1-6Alkyl groups of (a); and R8Is C1-12Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13. Wherein R is11、R12、R13Each independently is C1-6Alkyl groups of (a); q, r, s are each independently an integer of 1 to 10.
In the present disclosure, a compound of formula (I) is used as a starting material for synthesizing a block copolymer, wherein the compound of formula (I) is shown as follows:
wherein A is1Is a bond, O, or S; and R1、R2And R3Each independently is H, C1-6Alkyl of (a), -COOR4、-CH2P(＝O)R5R6(ii) a Or R1And R2Are bonded to each other to form C4-8Cycloalkyl of, or C3-7The heterocycloalkyl group of (a); or R2And R3Are bonded to each other to form C5-8A cycloalkyl group of (a). Wherein R is4、R5And R6Each independently is C1-6Alkyl of (C)1-6Alkoxy of, -OTMS, Via C1-6Alkyl-substituted amine group of (1).
In one embodiment of the present disclosure, the compound of formula (I) may be a1Is O; and R1、R2And R3Each independently is H, or C1-6But the present disclosure is not limited thereto.
In the present disclosure, the catalyst used in the preparation method of the block copolymer is represented by the following formula (II):
[M(O)a]m+Xb n-(II)
wherein M is an element of group IB, group IVB, group VB, group VIB, group VIIB, or group VIIIB; x is Cl, Br, I, OH, OAc, OC (O) Ar, OC (O) (CF)2)cCF3、OC(O)C12H25、[(OSO2C6H4-CHCH2)n]、OTf、OTs、SO4、SO3C12H25Acetylacetone (acac), or mixtures thereof; a is an integer of 0 to 3; b is an integer of 1 to 4; m is an integer of 2 to 4; n is an integer of 1 to 2; and c is an integer from 1 to 6. Wherein Ar is C6-20Aryl of (a); [ (OSO)2C6H4-CHCH2)n]Has the structural formula
In the catalysts of formula (II) disclosed herein, a can be 0, and M is Ti (IV), Zr (IV), Hf (IV), V (III), Fe (II/III), Cu (I/II), Mn (II/III), Co (II), or Ni (II).
In the catalysts of the formula (II) disclosed in the present disclosure, M (O)aCan be BiO, VO3、ZrO、HfO、WO2、MoO2、CrO2Or ReO3。
In the catalyst of formula (II) of the present disclosure, comprising Hf (O) Cl2、V(O)Cl2、V(O)[(O3SC6H4CHCH2)n]2、V(O)Cl3、V(O)(OTf)2、V(O)(OCOR)2、MoO2Cl2、Mn(O)(OCOR)、FeCl3、Zr(O)Cl2、Zr(OAc)x(OH)y(x+y＝4)、Ti(O)(acac)2、V(O)SO4、V(O)(acac)2、MoO2(acac)2、Mn(II)SO4Or FeSO4However, the present disclosure is not limited thereto, and the catalysts may be used alone or in combination. Wherein R is C6-20Aryl group of (1).
In one embodiment of the present disclosure, the content of the catalyst is not particularly limited as long as the catalytic synthesis of the block copolymer can be achieved. Preferably, the catalyst is present in an amount of 0.1 to 20 wt%, such as 0.1 to 15 wt%, 0.1 to 10 wt%, 0.1 to 5 wt%, based on the total weight of the first mixture, although the present disclosure is not limited thereto.
In one embodiment of the present disclosure, after the third mixture is obtained in step (C), a third monomer is added to the third mixture to react, so as to obtain a fourth mixture.
In the present disclosure, the first monomer, the second monomer, and the third monomer are each independently an acrylate compound or a diacrylate compound.
In one embodiment of the present disclosure, the acrylate compound may be a compound of the following formula (III):
wherein A is2Is O or S; r7Is H, or C1-6Alkyl groups of (a); and R8Is C1-12Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13. Wherein R is11、R12、R13Each independently is C1-6Alkyl groups of (a); q, r, s are each independently an integer of 1 to 10.
In one embodiment of the present disclosure, the compound of formula (III) may be a2Is O; r7And is H, or C1-6Alkyl groups of (a); and R8Is C1-10Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13. Wherein R is11、R12、R13Each independently is C1-6Alkyl groups of (a); q, r, s are each independently an integer of 1 to 6.
In one embodiment of the present disclosure, the diacrylate compound may be a compound of the following formula (IV):
wherein Y is O, NH or S; r9Is H, or C1-6Alkyl groups of (a); r10Is C1-6Alkyl of, or C6-20Aryl of (a); and p is an integer from 1 to 12.
In one embodiment of the present disclosure, the compound of formula (IV)Y can be O, or NH; r9Is H, or C1-6Alkyl groups of (a); r10Is C1-6Alkyl of, or C6-12Aryl of (a); and p is an integer from 1 to 8.
In one embodiment of the present disclosure, the method further comprises, after the step (C), a step (D) of adding the third mixture to a second solvent. Wherein the second solvent is not particularly limited as long as it can precipitate as an induced product, and for example, the second solvent may be water, alcohols, C5-10Or mixtures thereof. Wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, or a mixture thereof, but the disclosure is not limited thereto; the C is5-10The alkanes of (a) include pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or mixtures thereof, but the disclosure is not limited thereto.
In another embodiment of the present disclosure, the method further comprises the step (E) of adding the fourth mixture to a second solvent after the step (C). Wherein the second solvent is not particularly limited as long as it can precipitate as an induction product, and the second solvent is water, alcohols, C5-10Or mixtures thereof. Wherein the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, or a mixture thereof, but the disclosure is not limited thereto; the C is5-10The alkanes of (a) include pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or mixtures thereof, but the disclosure is not limited thereto.
In one embodiment of the present disclosure, the first solvent is not particularly limited as long as it can be used as a solvent for reaction. Preferably, the first solvent may be an ether solvent, such as tetrahydrofuran, diethyl ether, but the present disclosure is not limited thereto.
In one embodiment of the present disclosure, the compound of formula (V) may be x, y, and z are each independently an integer from 1 to 20, for example, x, y, and z are each independently an integer from 1 to 15, but the present disclosure is not limited thereto.
In one embodiment of the disclosure, the compound of formula (VI) may be a2Is O; r7Is H, or C1-3Alkyl groups of (a); r8Is C1-8Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13Wherein R is11、R12、R13Each independently is C1-3Alkyl groups of (a); q, r, s are each independently an integer of 1 to 6.
In one embodiment of the present disclosure, the block copolymer comprises an end portion represented by the following formula (VII):
wherein R is1Is C1-6Alkyl groups of (a); and R2And R3Each independently is H, or C1-6Alkyl group of (1).
In one embodiment of the present disclosure, at least one of D, E and F is a compound of formula (VIII):
wherein R is7Is H, or C1-6Alkyl groups of (a); r8Is (CH)2)qN(R11)2Or CH2(CH2OCH2)rCH2N(R12)2Wherein R is11、R12Each independently is C1-6Alkyl groups of (a); q and r are each independently an integer of 1 to 10.
In one embodiment of the block copolymer of the present disclosure, the compound of formula (VIII) can be R7Is H, or C1-3Alkyl groups of (a); r8Is (CH)2)qN(R11)2Or CH2(CH2OCH2)rCH2N(R12)2Wherein R is11、R12Each independently is C1-3Alkyl groups of (a); q and r are each independently an integer of 1 to 6.
Detailed Description
Other advantages and capabilities of the present disclosure will be readily apparent to those skilled in the art from the present disclosure by describing the embodiments of the present disclosure by specific embodiments. The disclosure is capable of other and different embodiments and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present disclosure.
Catalyst synthesis
In this example, the catalyst was synthesized according to the following reaction formula.
V(O)SO4(aq)+BaX2(aq)→V(O)X2(aq)+BaSO4(s)
V(O)SO4(aq)+Ba(OC(O)R)2(aq)→V(O)(OC(O)R)2(aq)+BaSO4(s)
V(O)5O4(aq)+Ba(OTf)2(aq)→V(O)(OTf)2(aq)+BaSO4(s)
V(O)SO4(aq)+Ba(OTs)2(aq)→V(O)(OTs)2(aq)+BaSO4(s)
V(O)SO4(aq)+Ba[(O3SC6H4CHCH2)n]2(aq)→V(O)[(O3SC6H4CHCH2)n]2(aq)+BaSO4(s)
Taking vanadyl sulfate (VOSO)4-5H2O, 2.5mmol) was added to a dry two-necked round bottomed plate (50mL), followed by addition of anhydrous methanol (2.5 mL). To the resulting solution was slowly added BaX-containing solution at room temperature2(1 eq, 2.5mmol) (e.g.: Ba (OAc))2、BaOTs2、BaOTf2Or Ba [ (O)3SC6H4CHCH2)n]2) After stirring for 30 minutes, the reaction mixture was cloudy with a large amount of barium sulfate precipitated. The mixture was filtered through a plug of celite (plug) and the resulting filtrate was evaporated to give a dark blue solid. The resulting solid was dried under vacuum at 120 ℃ for 4 hours. The product obtained can be stored in a drying cabinet for several weeks and can be used directly.
Synthesis of Block copolymer
Example 1
1-methoxy-2-methyl-1- (trimethylsilyl) propene (MTS, 0.20mL, 0.99mmol) in tetrahydrofuran (20mL) was injected into a vanadyl benzoic acid catalyst (2.5mg) in a round bottom flask (100mL) previously sealed with a membrane and purged with argon (purge). Then, butyl methacrylate (BuMA, 2.2mL, 11.2mmol) was injected, the temperature was raised from 20 ℃ to 33 ℃ and the exothermic reaction was reduced after 30 minutes, and 2 0.1mL aliquots of the reaction solution were extracted by GPC and1HNMR analysis. 2- (dimethylamino) ethyl methacrylate (DMAEMA, 2.65mL, 15.7mmol) was then added and the temperature was observed to rise from 22 ℃ to 34 ℃. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecular impurities to give the final product.
1H NMR(400MHz，CDCl3)δ0.88(br，55H)，0.94(br，56H)，1.04(br，39H)，1.40(br，40H)，1.61(br，35H)，1.81-1.90(br，82H)，2.28(br，107H)，2.56(br，36H)，3.94(br，33H)，4.06(br，35H).
Mn＝4104(THF)；Mw＝4785；PDI＝1.17.
Example 2
1-methoxy-2-methyl-1- (trimethylsilyl) propene (MTS, 0.20mL, 0.99mmol) in tetrahydrofuran (20mL) was injected into a vanadyl benzoic acid catalyst (2.5mg) in a round bottom flask (100mL) previously sealed with a membrane and purged with argon (purge). Then, hexyl methacrylate (HexMA, 2.2mL, 11.2mmol) was injected, the temperature was raised from 20 ℃ to 33 ℃ and the exothermic reaction was reduced after 30 minutes, and 2 aliquots of 0.1mL were extractedThe reaction solution was treated with GPC and1HNMR analysis. Subsequently PEGMA in tetrahydrofuran (0.95mL (50 vol% solution), 2.1mmol, MW 500) was added, the temperature was raised from 25 ℃ to 27 ℃, and 2 0.1mL aliquots were collected for GPC and1h NMR analysis. 2- (dimethylamino) ethyl methacrylate (DMAEMA, 2.65mL, 15.7mmol) was then added and the temperature was observed to rise from 22 ℃ to 34 ℃. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecular impurities to give the final product.
1H NMR(400MHz，CDCl3)δ0.90(br，50H)，1.00(br，21H)，1.32(br，46H)，1.61-1.68(br，23H)，1.81-1.98(br，31H)，2.28(br，58H)，2.56(br，19H)，3.38(br，3H)，3.55(br，3H)，3.64(br，18H)，3.92(br，14H)，4.06(br，21H).
Mn＝6249(THF)；Mw＝7811；PDI＝1.25.
Example 3
1-methoxy-2-methyl-1- (trimethylsilyl) propene (MTS, 0.20mL, 0.99mmol) in tetrahydrofuran (20mL) was injected into a vanadyl benzoic acid catalyst (2.5mg) in a round bottom flask (100mL) previously sealed with a membrane and purged with argon (purge). Then, a diacrylate in tetrahydrofuran (6.0mL (33.3 vol% solution), 2.9mmol) was added and the temperature was raised from 25 ℃ to 27 ℃ followed by collection of 2 0.1mL aliquots for GPC and1h NMR analysis. Then, hexyl methacrylate (HexMA, 1.0mL, 5.9mmol) was injected, the temperature was raised from 20 ℃ to 33 ℃, the exothermic reaction was reduced after 30 minutes, 2 reaction solutions of 0.1mL aliquots were extracted by GPC and1h NMR analysis. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecular impurities to give the final product.
1H NMR(400MHz，CDCl3)δ0.99-1.18(br，10H)，1.32-1.35(br，7H)，1.62(s，8H)，1.95(br，3H)，3.64-3.71(br，17H)，3.83(s，2H)，3.95(s，2H)，6.79(br，2H)，7.11(br，2H).
Mn＝6249(THF)；Mw＝7811；PDI＝1.25.
Test for Dispersion Effect
The copolymer (1g) of example 3 and a commercially available dispersant (1g) were dissolved in 1mL of tetrahydrofuran, 135uL of a yellow pigment (500mg of the yellow pigment in 3mL of tetrahydrofuran) was added, and the mixture was stirred by milling for 30 seconds to observe the dispersion of the yellow pigment, and the results are shown in Table 1.
TABLE 1
| Dispersing effect | Particle suspension situation | |
| Copolymer of example 2 | Superior food | Without particle suspension or dispersion inhomogeneity |
| Copolymer of example 3 | Superior food | Without particle suspension or dispersion inhomogeneity |
| Commercially available dispersant | Jia | With obvious particle suspension |
The particular embodiments described above are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
Claims (19)
1. A method of preparing a block copolymer comprising the steps of:
mixing a compound of formula (I), a catalyst of formula (II), and a first solvent to obtain a first mixture;
wherein A is1Is a bond, O, or S; and
R1、R2and R3Each independently is H, C1-6Alkyl of (a), -COOR4、-CH2P(＝O)R5R6(ii) a Or R1And R2Are bonded to each other to form C4-8Cycloalkyl of, or C3-7The heterocycloalkyl group of (a); or R2And R3Are bonded to each other to form C5-8Cycloalkyl groups of (a);
wherein R is4、R5And R6Each independently is C1-6Alkyl of (C)1-6Alkoxy of, -OTMS, Via C1-6Alkyl-substituted amino groups of (a);
[M(O)a]m+Xb n-(II)
wherein M is an element of group IB, group IVB, group VB, group VIB, group VIIB, or group VIIIB;
x is Cl, Br, I, OAc, OC (O) Ar, OC (O) (CF)2)cCF3、OC(O)C12H25、[(OSO2C6H4-CHCH2)n]、OTf、OTs、SO4、5O3C12H25Acetylacetone (acac), or mixtures thereof;
a is an integer of 0 to 3;
b is an integer of 1 to 4;
m is an integer of 2 to 4;
n is an integer of 1 to 2;
c is an integer from 1 to 6; and
ar is C6-20Aryl of (a);
adding a first monomer into the first mixture to react to obtain a second mixture; and
adding a second monomer into the second mixture to react to obtain a third mixture.
2. The method of claim 1, further comprising the step of (D) adding the third mixture to a second solvent.
3. The method of claim 2, wherein the second solvent is water, alcohol, C5-10Or mixtures thereof.
4. The method of claim 1, wherein a is 0 and M is Ti (IV), Zr (IV), Hf (IV), V (III), Fe (II/III), Cu (I/II), Mn (II/III), Co (II), or Ni (II).
5. The method according to claim 1, wherein M (O)aIs BiO, VO3、ZrO、HfO、WO2、MoO2、CrO2Or ReO3。
6. The method of claim 1, wherein the first monomer and the second monomer are each independently an acrylate compound or a diacrylate compound.
7. The method according to claim 6, wherein the acrylate compound is a compound of the following formula (III):
wherein A is2Is O or S;
R7and is H, or C1-6Alkyl groups of (a); and
R8is C1-12Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13，
Wherein R is11、R12、R13Each independently is C1-6Alkyl groups of (a); q, r, s are each independently an integer of 1 to 10.
8. The method according to claim 6, wherein the diacrylate compound is a compound of the following formula (IV):
wherein Y is O, NH or S;
R9is H, or C1-6Alkyl groups of (a);
R10is C1-6Alkyl of, or C6-20Aryl of (a); and
p is an integer of 1 to 12.
9. The method of claim 1, wherein after the third mixture is obtained in step (C), further comprising adding a third monomer to the third mixture to react and obtain a fourth mixture.
10. The method of claim 9, further comprising the step of (E) adding the fourth mixture to a second solvent.
11. The method of claim 10, wherein the second solvent is water, alcohol, C5-10Or mixtures thereof.
12. The method of claim 9, wherein the first monomer, the second monomer, and the third monomer are each independently an acrylate compound or a diacrylate compound.
13. The method according to claim 1, wherein the first solvent is an ether solvent.
14. The method of claim 1, wherein the catalyst is present in an amount of 0.1 to 20 wt% based on the total weight of the first mixture.
15. A block copolymer comprising the structure of the following formula (V):
[D]x-[E]y-[F]z(V)
wherein D, E, and F are each independently a compound of formula (VI) below, and D, E, and F are different from each other; and
x, y, z are each independently an integer from 1 to 40;
wherein A is2Is O or S;
R7is H, or C1-6Alkyl groups of (a); and
R8is C1-12Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13Wherein R is11、R12、R13Each independently is C1-6Alkyl groups of (a); q, r, s are each independently an integer of 1 to 10.
16. The block copolymer of claim 15, wherein x, y, z are each independently an integer from 1 to 20, and B is O; r7Is H, or C1-3Alkyl groups of (a); r8Is C1-8Alkyl group of (CH)2)qN(R11)2、CH2(CH2OCH2)rCH2N(R12)2Or CH2(CH2OCH2)sCH2OR13Wherein R is11、R12、R13Each independently is C1-3Alkyl groups of (a); q, r, s are each independently an integer of 1 to 6.
17. The block copolymer of claim 15, wherein the block copolymer comprises an end portion, the end portion being represented by formula (VII) below:
wherein R is1Is C1-6Alkyl groups of (a); and
R2and R3Each independently is H, or C1-6Alkyl group of (1).
18. The block copolymer of claim 15, wherein at least one of said D, E, and F is a compound of formula (VIII):
wherein R is7Is H, or C1-6Alkyl groups of (a);
R8is (CH)2)qN(R11)2Or CH2(CH2OCH2)rCH2N(R12)2Wherein R is11、R12Each independently is C1-6Alkyl groups of (a); q and r are each independently an integer of 1 to 10.
19. A block copolymer as claimed in claim 18, wherein R7Is H, or C1-3Alkyl groups of (a); r8Is (CH)2)qN(R11)2Or CH2(CH2OCH2)rCH2N(R12)2Wherein R is11、R12Each independently is C1-3Alkyl groups of (a); q and r are each independently integers of 1 to 6And (4) counting.
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| US4508880A (en) * | 1981-06-30 | 1985-04-02 | E. I. Du Pont De Nemours And Company | "Living" polymers and process for their preparation |
| US4806605A (en) * | 1987-01-27 | 1989-02-21 | E. I. Du Pont De Nemours And Company | Monomers and initiators for group transfer polymerization |
| CN1378576A (en) * | 1999-10-07 | 2002-11-06 | 纳幕尔杜邦公司 | Pigment dispersions containing ABC-block polymer dispersant |
| US20180094092A1 (en) * | 2016-10-04 | 2018-04-05 | Shin-Etsu Chemical Co., Ltd. | Copolymer of triisopropylsilyl (meth)acrylate with (meth)acrylic acid derivative and making method |
| CN107892729A (en) * | 2016-10-04 | 2018-04-10 | 信越化学工业株式会社 | The copolymer and manufacture method of (methyl) acrylic acid triisopropylsilyl ester and (methyl) acrylic acid derivative |
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