CN110922511A - Method for esterifying a copolymer - Google Patents
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- CN110922511A CN110922511A CN201811099765.XA CN201811099765A CN110922511A CN 110922511 A CN110922511 A CN 110922511A CN 201811099765 A CN201811099765 A CN 201811099765A CN 110922511 A CN110922511 A CN 110922511A
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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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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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
- C08F8/14—Esterification
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Abstract
The present disclosure provides a method for esterifying a copolymer compound, comprising the steps of: (A) mixing a copolymer with a carboxylic acid group, an alcohol or an amine alcohol compound, a catalyst of formula (I), and a first solvent to obtain a first mixture; (B) reacting the first mixture at a predetermined temperature to obtain a second mixture; and (C) adding the second mixture to a second solvent; wherein the catalyst of formula (I) is as follows: [ M (O)a]m+Xb n‑(I) Wherein M, X, a, b, M, and n are as defined in the specification.
Description
Technical Field
The present disclosure relates to a method for esterifying a copolymer, and more particularly, to a method for catalyzing esterification of a copolymer by using an oxygen metal complex as a catalyst.
Background
Generally, the esterified polymer product is obtained by esterifying small molecular fragments and then performing polymerization reaction, so that the method has the disadvantages of complicated steps, long time consumption, high cost, low transesterification rate and the like, and the environmental pollution is caused because strong acid is often used for catalysis in the process.
Therefore, there is a need to develop a new method for esterifying a copolymerization compound, which can simplify the process, save time, reduce cost, or reduce environmental burden.
Disclosure of Invention
In view of the above, the present disclosure utilizes an oxygen metal complex as a catalyst to directly catalyze a copolymerization compound for esterification reaction, thereby simplifying the process and saving time or cost. Wherein the oxygen-metal complex is biochemically absorbable and metabolizable to reduce environmental burden.
The present disclosure provides a catalyst for catalyzing esterification of a co-compound, as shown in formula (I):
[M(O)a]m+Xb n-(I)
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
Furthermore, the present disclosure provides a method for esterifying a copolymer, comprising the following steps: (A) mixing a copolymer with a carboxylic acid group, an alcohol or amine alcohol compound, a catalyst of formula (I), and a first solvent to obtain a first mixture; (B) reacting the first mixture at a predetermined temperature to obtain a second mixture; and (C) adding the second mixture to a second solvent.
In the catalysts of formula (I) 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 (I) disclosed in the present disclosure, M (O)aCan be BiO, VO3、ZrO、HfO、WO2、MoO2、CrO2Or ReO3。
In the catalyst of formula (I) 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 copolymer with carboxylic acid groups may have the following structure of formula (II):
wherein R is1Is hydrogen or C1-6Alkyl groups of (a); r2Is C1-12Alkyl of, or CH2(CH2OCH2)pCH2OR3(ii) a And d and e are each an integer from 5 to 150; wherein R is3Is C1-6And p is an integer of 0 to 12; the weight average molecular weight of the carboxylic acid group-containing copolymer was 3000-12000.
In one embodiment of the present disclosure, the carboxylic acid group-containing copolymer having the structure of formula (II) is preferably R1Is hydrogen or methyl; r2Is C1-8Alkyl of, or CH2(CH2OCH2)pCH2OR3(ii) a And d and e are each an integer of 10 to 90, wherein R3Is C1-3And p is an integer of 1 to 8, the weight average molecular weight of the copolymer with carboxylic acid groups being 3000-10000.
In another embodiment of the present disclosure, the copolymer with carboxylic acid groups may have the following structure of formula (III):
wherein R is1Is hydrogen or C1-6Alkyl groups of (a); r4Is C1-6Alkyl of, or C6-20Aryl of (a); y is O, NH, or S; q is an integer of 1 to 12; and f and g are each independently an integer from 1 to 80; wherein the weight average molecular weight of the copolymer with carboxylic acid groups is 3000-12000.
In another embodiment of the present disclosure, the carboxylic acid group-containing copolymer having the structure of formula (III) is preferably R1Is hydrogen or methyl; r4Is C6-18Aryl of (e.g. R)4May include, but is not limited to, phenyl, naphthyl, anthryl, phenanthryl (phenanthryl), or pyrenyl (pyrenyl); y is O or NH; q is an integer of 1 to 10; and f and g are each independently an integer of 3 to 50, wherein the weight average molecular weight of the carboxylic acid group-bearing copolymer is 4000-12000.
In the esterification method of the copolymer disclosed in the present disclosure, the alcohol compound comprises C1-10Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol (2-methyl butanol), secondary pentanol (sec-amyl alcohol), n-hexanol (n-hexyl alcohol), 2-methylpentanol (2-methyl pentanol), 2-ethylbutanol (2-ethyl butanol), n-heptanol (n-heptyl alcohol), n-octanol (n-octyl alcohol), 2-ethylhexanol (2-ethyl hexanol), n-nonanol, n-decanol (n-decylalchol), cyclohexanol (cyclohexanol), cyclohexanemethanol (cyclohexanol), 2-methylcyclohexanol (2-methylcyclohexanol), and benzyl alcohol (benzyl alcohol), but are not limited thereto. In the present disclosure, the alcohol compound is preferably C5-10Alcohols of (2).
In the esterification method of the copolymer disclosed in the present disclosure, the aminoalcohol compound may be a compound of the following formula (IV) or formula (V):
HO(CH2)rN(R5)2(IV)HO(CH2)2O(CH2)2N(R5)2(V)
wherein R is5Is C1-6Alkyl groups of (a); and r is an integer from 2 to 10.
In one embodiment of the present disclosure, the aminoalcohol compound may beA compound of formula (IV) or (V), wherein R is preferred5Is C1-3Alkyl groups of (a); r is an integer of 2 to 6, and may be, for example, 2-dimethylethanolamine (2-dimethylethanone), but the present disclosure is not limited thereto.
The term "alkyl" and "aryl" as used in this disclosure includes alkyl and aryl groups which are unsubstituted or substituted with halo, alkenyl, aryl, heteroaryl.
In the method for esterifying the copolymer of the present disclosure, the first solvent is not particularly limited as long as it can serve as a solvent for the reaction. Aromatic solvents such as benzene, toluene, or xylene are preferred, but the present disclosure is not limited thereto.
In the esterification method of the copolymer of the present disclosure, the second solvent is not particularly limited as long as it can precipitate as an induced product. Preferably water or C1-5Alcohols of (2), C5-10Or an alkane, petroleum ether, or a mixture thereof. Wherein, the C1-5The alcohols of (a) include methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, or mixtures 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 the method for esterifying the copolymer of the present disclosure, the predetermined temperature of the reaction is not particularly limited as long as the reaction is facilitated. Preferably, the predetermined temperature is between 0 ℃ and 180 ℃, and more preferably, the predetermined temperature is between 50 ℃ and 120 ℃.
In the method for esterifying the copolymer of the present disclosure, the content of the catalyst is not particularly limited as long as the esterification reaction of the copolymer can be catalyzed. 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.
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)SO4(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)5O4(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.
Esterification of copolymers
Embodiments of the present disclosure may perform esterification of copolymers according to scheme I or scheme II below.
[ Process I ]
Example 1
Taking copolymers (R) bearing carboxylic acid groups1＝CH3，R2＝C6H13MW 4172, 1.0g), 2-dimethylethanolamine (2-dimethylethanone, 0.5mL, 5.0mmol), the catalyst of formula (I) (0.1mmol), and toluene (15mL) in a flask equipped with Dean-Stark (1mL H)2O) and condenser, the reaction mixture was refluxed and purified by TLC or1H nmr spectroscopy monitored the reaction every 12 hours. The reaction mixture of the copolymer was poured into hexane to induce precipitation. The purified product was dissolved in chloroform, and small molecular impurities were removed by filtration to obtain the product. The catalyst used here is ZrOCl2Or TiO (acac)2。
1H NMR(400MHz，CDCl3)δ0.90(s，6H)，1.04(s，2H)，1.32(s，5H)，1.61(s，2H)，1.85-1.90(br，4H)，2.28(s，6H)，2.56(s，2H)，3.93(s，2H)，4.06(s，2H).
Mn＝4796(THF)；Mw＝5684；PDI＝1.19.
Example 2
Taking copolymers (R) bearing carboxylic acid groups1＝CH3，R2＝CH2(CH2OCH2)4CH2OCH3，MW＝6304，1.0g)、C6H13OH (2.2mL, 11.2mmol), catalyst of formula (I) (0.1mmol), and toluene (15mL) in a column supplemented with Dean-Stark (1mL H)2O) and condenser, the reaction mixture was refluxed and purified by TLC or1H nmr spectroscopy monitored the reaction every 12 hours. The reaction mixture of the copolymer was poured into hexane to induce precipitation. The purified product was dissolved in chloroform and the fractions were removed by filtrationImpure seed to obtain the product. The catalyst used here is ZrOCl2Or TiO (acac)2。
1H NMR(400MHz，CDCl3)δ0.85-0.90(br，9H)，1.03(s，3H)，1.32(s，10H)，1.61(s，9H)，1.89-1.91(br，5H)，3.38(s，3H)，3.55(s，2H)，3.66(s，15H)，3.92(s，3H)，4.09(s，2H).
Mn＝6286(THF)；Mw＝7732；PDI＝1.23.
[ Process II ]
Example 3
Taking copolymers (R) bearing carboxylic acid groups1＝CH3，R4Is phenyl, Y ═ O, q ═ 7, MW ═ 6364, 1.0g), C6H13OH (1.0mL, 5.9mmol), catalyst of formula (I) (0.1mmol), and toluene (15mL) in a column supplemented with Dean-Stark (1mL H)2O) and condenser, the reaction mixture was refluxed and purified by TLC or1H nmr spectroscopy monitored the reaction every 12 hours. The reaction mixture of the copolymer was poured into hexane to induce precipitation. The purified product was dissolved in chloroform, and small molecular impurities were removed by filtration to obtain the product. The catalyst used here is ZrOCl2Or TiO (acac)2。
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 1 | 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 (15)
1. A process for the esterification of a co-polymer comprising the steps of:
mixing a copolymer with a carboxylic acid group, an alcohol or amine alcohol compound, a catalyst of formula (I), and a first solvent to obtain a first mixture;
[M(O)a]m+Xb n-(I)
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;
c is an integer from 1 to 6; and
ar is C6-20 aryl;
reacting the first mixture at a predetermined temperature to obtain a second mixture; and
adding the second mixture to a second solvent.
2. The esterification process 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).
3. The esterification process according to claim 1, wherein M (O)aIs BiO, VO3、ZrO、HfO、WO2、MoO2、CrO2Or ReO3。
4. The esterification process according to claim 1, wherein the copolymer having a carboxylic acid group has the following structure of formula (II):
wherein R is1Is hydrogen or C1-6 alkyl;
R2is C1-12Alkyl of, or CH2(CH2OCH2)pCH2OR3Wherein R is3Is C1-6And p is an integer of 0 to 12; and
d and e are each an integer of 5 to 150;
wherein the weight average molecular weight of the copolymer with carboxylic acid groups is 3000-12000.
5. The esterification process according to claim 4, wherein R1Is hydrogen or methyl, R2Is C1-8Alkyl of, or CH2(CH2OCH2)pCH2OR3Wherein R is3Is C1-3And p is an integer of 1 to 8.
6. An esterification process according to claim 1, wherein the copolymer bearing carboxylic acid groups has the following structure of formula (III):
wherein R is1Is hydrogen or C1-6Alkyl groups of (a);
R4is C1-6Alkyl of, or C6-20Aryl of (a);
y is O, NH, or S;
q is an integer of 1 to 12; and
f and g are each independently an integer from 1 to 80;
wherein the weight average molecular weight of the copolymer with carboxylic acid groups is 3000-12000.
7. The esterification process according to claim 6, wherein R1Is hydrogen or methyl; r4Is C6-18Aryl of (a); y is O or NH; q is an integer of 1 to 10.
8. The esterification method according to claim 1, wherein the alcohol compound is C1-10Alcohols of (2).
9. The method of claim 8An esterification process wherein the alcohol compound is C5-10Alcohols of (2).
10. An esterification process according to claim 1, wherein the aminoalcohol-based compound is a compound of the following formula (IV) or formula (V):
HO(CH2)rN(R5)2(IV) HO(CH2)2O(CH2)2N(R5)2(V)
wherein R is5Is C1-6Alkyl groups of (a); and
r is an integer from 2 to 10.
11. The esterification process of claim 10, wherein R5Is C1-3Alkyl groups of (a); r is an integer from 2 to 6.
12. The esterification process of claim 1, wherein the first solvent is an aromatic solvent.
13. The esterification process according to claim 1, wherein the second solvent is water, C1-5Alcohols of (2) C5-10Or a petroleum ether, or a mixture thereof.
14. The esterification process according to 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. The esterification process according to claim 1, wherein the predetermined temperature is between 0 ℃ and 180 ℃.
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| TW200704767A (en) * | 2005-07-22 | 2007-02-01 | Chien-Tien Chen | Nucleophilic acyl substitutions of acids or esters catalyzed by metal oxide complex, and the applications in fabricating biodiesel |
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| CN103492428A (en) * | 2010-12-30 | 2014-01-01 | 科莱恩金融(Bvi)有限公司 | Continuous process for esterifying polymers bearing acid groups |
| RU2608819C1 (en) * | 2015-11-05 | 2017-01-24 | Андрей Сергеевич Малинин | Catalyst of esterification of polyacrylic acid, method of producing catalyst and method of esterification with its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101076509A (en) * | 2004-12-13 | 2007-11-21 | 国立大学法人岐阜大学 | Process for producing carboxylic acid ester and esterification catalyst |
| TW200704767A (en) * | 2005-07-22 | 2007-02-01 | Chien-Tien Chen | Nucleophilic acyl substitutions of acids or esters catalyzed by metal oxide complex, and the applications in fabricating biodiesel |
| CN103228680A (en) * | 2010-12-10 | 2013-07-31 | Sika技术股份公司 | Production of comb polymers by means of esterification |
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