CN111286011A - Carbon dioxide-based polycarbonate polyester copolymer and preparation method thereof - Google Patents
Carbon dioxide-based polycarbonate polyester copolymer and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Abstract
The invention relates to a carbon dioxide-based polycarbonate polyester copolymer and a preparation method thereof, wherein a catalyst is adopted to catalyze the copolymerization of carbon dioxide, an epoxy compound with a side group containing a double bond/ester group functional group and a cross-ester monomer to prepare the carbon dioxide-based polycarbonate polyester copolymer (FAPC-PEs) with the side group containing the double bond and/or the ester group functional group, the number average molecular weight of the copolymer is 6000-100000, the molecular weight distribution is 1.1-1.5, the mole percentage content of a polycarbonate APC chain segment in the copolymer is 40-80%, the total mole percentage content of the double bond and the ester group functional group in the side group in the copolymer is 15-40%, and the ammonium carboxylate-functionalized carbon dioxide-based polycarbonate polyester copolymer obtained after hydrophilic modification has good hydrophilicity and water dispersibility and wide application.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a carbon dioxide-based polycarbonate polyester copolymer and a preparation method thereof.
Background
With the development of industry, carbon dioxide (CO)2) The problems of 'greenhouse effect' caused by excessive emission of gas, urgent need for development of new renewable resources due to exhaustion of petroleum and coal resources, and 'white pollution' caused by heavy use of disposable packaging materials gradually attract extensive attention of global environmental scientists and chemists. The use of cheap and abundant carbon dioxide resources for the copolymerization of propylene oxide to produce PPC is considered as a potential utilization of CO2The most efficient route. The PPC not only has better mechanical strength, toughness and biocompatibility, but also has excellent performance of blocking oxygen and water, is expected to be widely applied to the aspects of disposable medicines, food packaging materials and the like, and the polymer can be photodegraded after being used, is a full-biodegradable plastic and can be degraded to release carbon dioxide, thereby relieving the huge pressure of resources and environment. However, the PPC has no rigid group in the segment and the main chain shows flexibility, resulting in lower glass transition temperature (38 ℃) and thermal degradation temperature (200 ℃). Meanwhile, PPC has poor hydrophilicity, and when the PPC is used as a biodegradable material, compared with polyester biodegradable plastics such as polylactic acid (PLA), Polycaprolactone (PCL), polybutylene succinate (PBS) and the like, the PPC has a longer degradation period, and the application of the PPC is limited. Polylactic acid (PLA) is prepared from renewable biomass resources such as corn, potato and sugarcane, has wide sources, excellent biocompatibility and high degradation speed, and is a biodegradable polymer material which is recognized as the most promising in the fields of medical treatment and tissue engineering, wherein degradation products in vivo are carbon dioxide and water. However, when polylactic acid is used as a biodegradable material, the polylactic acid has high brittleness and poor hydrophilicity, and the acidic degradation product in vivo easily causes non-infectious inflammation of patients, so that the application of the polylactic acid is limited to a certain extent.
The existing literature adopts blending of PPC and PLA to improve the mechanical property and biodegradability of a composite product and broaden the application range of the product, and the physical blending method has the defects of unstable interface property, poor biocompatibility and the like. At present, documents report that the terpolymer PPCLA prepared by the ternary copolymerization of carbon dioxide, propylene oxide and lactide obviously improves the mechanical property, the degradation property and the thermal stability of the PPC compared with the PPC, but the hydrophilicity of the terpolymer PPCLA is not obviously improved compared with the PPC (or PLA), and the terpolymer PPCLA is difficult to be applied to occasions requiring good hydrophilicity and hydrolysis property, such as drug sustained release carriers, degradable in-vivo implantation materials and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a carbon dioxide based polycarbonate polyester with a side group containing double bonds and/or ester functional groups, a hydrophilic carbon dioxide based polycarbonate polyester obtained by modification of the carbon dioxide based polycarbonate polyester and a preparation method thereof aiming at the defects in the prior art.
The invention aims to provide a carbon dioxide-based polycarbonate polyester copolymer with a side group containing double bonds and/or ester functional groups, which is a copolymer of carbon dioxide and an epoxy compound, an epoxy compound with a side group containing double bonds/ester functional groups and a cross-ester monomer, wherein the number average molecular weight of the copolymer is 6000-100000, the molecular weight distribution is 1.1-1.5, the mole percentage content of A Polycarbonate (APC) chain segment in the copolymer is 40-80%, and the mole percentage total content of the double bonds and the ester functional groups contained in the side group in the copolymer is 15-40%. The existence of double bonds/ester groups in the side groups of the copolymer enables the polycarbonate polyester copolymer to have better chemical modifiability, and the application range of the polycarbonate polyester copolymer is widened.
According to the scheme, the epoxy compound is propylene oxide or cyclohexene oxide.
According to the scheme, the epoxy compound with the side group containing the double bond/ester group functional group is one or more of allyl glycidyl ether, glycidyl methacrylate, tert-butyl 3, 4-epoxybutyrate, o-nitrobenzyl 2, 3-epoxypropionate, 1, 4-cyclohexadiene-1, 2-epoxide, 1, 2-epoxy-4-vinylcyclohexane, limonene epoxide and tert-butyl 3, 4-cyclohexene epoxide-1-carboxylate.
According to the scheme, the lactide monomer is racemic lactide or glycolide.
The second purpose of the invention is to provide a preparation method of the carbon dioxide based polycarbonate polyester copolymer with the pendant group containing double bond/ester based functional group, which comprises the following steps: adding a catalyst, an epoxy compound with a side group containing a double bond/ester functional group and a cross-ester monomer into a high-pressure reaction kettle, adding a solvent or not, quickly filling carbon dioxide into the high-pressure reaction kettle to maintain the pressure in the kettle at 1.0-5.0MPa, carrying out polymerization reaction for 10-48 hours at 20-90 ℃, adding a large amount of hydrochloric acid methanol solution to terminate the reaction after the polymerization reaction is finished, and washing the obtained product with a large amount of methanol to obtain the carbon dioxide-based polycarbonate polyester copolymer (FAPC-PEs) with the side group containing the double bond/ester functional group.
According to the scheme, the catalyst consists of a metalloporphyrin (PorphyrinM, M ═ Cr, Co, Al) catalyst and a cocatalyst, the molar ratio of the metalloporphyrin (PorphyrinM, M ═ Cr, Co, Al) catalyst to the cocatalyst is 1:0.5-2, wherein the metalloporphyrin (PorphyrinM, M ═ Cr, Co, Al) catalyst has the structural formula:
m ═ Cr or Co or Al; r2、R3、R4Each independently selected from hydrogen, fluoro, chloro, bromo, chloro-or bromo-substituted aliphatic groups; x is-Cl-OCH2CH3、-OCH(CH3)2、-Br、 CCl3COO-、CF3One of COO-, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy and 2,4, 6-trinitrophenol oxy;
the cocatalyst is one of bis- (triphenyl phosphoranylidene) ammonium chloride (PPNCl), 4-Dimethylaminopyridine (DMAP) and 2, 6-dimethylpyridine.
Under the catalytic action of metalloporphyrin catalyst, racemic lactide (or glycolide) monomer and CO2The epoxy compound monomer and the epoxy compound monomer with the side group containing double bond/ester group functional groups are subjected to random block copolymerization according to anion coordination polymerization, and the cocatalyst is coordinated in the center of the catalyst to promote the keying in of the monomers.
According to the scheme, the molar ratio of the metalloporphyrin (PorphyrinM, M ═ Cr, Co, Al) catalyst to the lactide monomer is 1:50-1000, the molar ratio of the epoxy compound to the lactide monomer is 1-20:1, and the molar ratio of the epoxy compound with the side group containing double bond/ester group functional group to the epoxy compound is 0.1-1: 1.
According to the scheme, the solvent is one of dichloromethane, toluene, tetrahydrofuran and 1, 4-dioxane.
The invention also aims to provide the carboxylic acid ammonium group functionalized carbon dioxide-based polycarbonate polyester obtained by hydrophilic modification of the carbon dioxide-based polycarbonate polyester copolymer with the side group containing double bonds/ester groups, wherein the surface water contact angle is lower than 45 degrees, and the particle size of emulsion particles in aqueous dispersion with the concentration of 1g/L is lower than 350 nm. The modified polymer shows good hydrophilicity and water dispersibility.
The fourth object of the present invention is to provide a method for preparing the above-mentioned carboxylic acid ammonium group functionalized carbon dioxide based polycarbonate polyester copolymer, which comprises the following steps: and carrying out carboxylation reaction on the carbon dioxide-based polycarbonate polyester with the side group containing double bonds/ester groups to convert the double bonds/ester functional groups of the side group into carboxyl, and then further reacting with ammonia water to prepare the carboxylic acid ammonium group functionalized carbon dioxide-based polycarbonate polyester.
Specifically, the method for performing carboxylation reaction on the carbon dioxide based polycarbonate polyester with the side group containing double bond/ester group comprises the following steps: and reacting double bonds contained in the carbon dioxide-based polycarbonate polyester side groups with thioglycolic acid, and reacting ester groups contained in the side groups with hydrochloric acid to convert the double bonds/ester groups into carboxyl groups, thereby obtaining the carboxyl functionalized copolymer. The reaction of mercapto groups with double bonds and the hydrolysis of ester groups are all referred to in the literature[5]The conversion was carried out at 100%. The carboxyl functional copolymer is further reacted with NH4The carboxylic acid ammonium group functionalized polycarbonate polyester is obtained after the OH reaction, and the copolymer has good hydrophilicity and biocompatibility and can be applied to the fields of drug sustained release, tissue engineering and the like.
The invention has the beneficial effects that: 1. the carbon dioxide based polycarbonate polyester with the side group containing double bonds or ester groups prepared by the invention has the number average molecular weight of 6000-100000 and the molecular weight distribution of less than 1.5, the mole percentage content of the polycarbonate chain segment in the copolymer is 40-80 percent, and the mole percentage content of the double bonds or ester functional groups contained in the side group in the copolymer is 15-40 percent. 2. According to the invention, the water contact angle of the carboxylic acid ammonium group functionalized polycarbonate polyester copolymer obtained after hydrophilic modification of the carbon dioxide group polycarbonate polyester copolymer is lower than 45 degrees, the particle size of emulsion particles in copolymer aqueous dispersion (with the concentration of 1g/L) is less than 350nm, the hydrophilic performance of the copolymer aqueous dispersion is improved compared with that of polypropylene carbonate PPC, polylactic acid PLA and polypropylene carbonate polylactic acid PPCLA polymers, and degradation (hydrolysis or enzymolysis) products are glyceric acid compounds, so that the biocompatibility is good, and the copolymer aqueous dispersion is expected to be applied to the aspects of drug sustained release carriers and degradable in-vivo implantation materials. 3. The preparation method provided by the invention has the advantages of simple steps, low cost, no generation of toxic and harmful intermediate substances in the polymerization process and no pollution to the environment.
Drawings
FIG. 1 is a schematic diagram of a process scheme for preparing an ammonium carboxylate-functionalized polycarbonate polyester copolymer in accordance with the present invention;
FIG. 2 is the nuclear magnetic hydrogen spectrum of the polycarbonate polyester with double bonds in the side groups prepared in example 11H NMR chart;
FIG. 3 is a nuclear magnetic carbon spectrum of the polycarbonate polyester with pendant double bonds prepared in example 113C NMR chart;
FIG. 4 is a graph of the water contact angle of the ammonium carboxylate-based functionalized polycarbonate polyester prepared in example 1;
FIG. 5 is a latex particle size distribution diagram (light scattering particle size test) of an aqueous dispersion of the ammonium carboxylate-functionalized polycarbonate polyester prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail below with reference to examples.
The carbon dioxide-based polycarbonate polyester with the side group containing double bonds or ester groups is a copolymer of carbon dioxide and an epoxy compound, an epoxy compound with the side group containing double bonds or ester functional groups and a cross-ester monomer, the number average molecular weight of the copolymer is 6000-100000, the molecular weight distribution is 1.1-1.5, the mole percentage content of a polycarbonate chain segment in the copolymer is 40-80%, and the mole percentage content of the double bonds or ester functional groups contained in the side group in the copolymer is 15-40%.
Preferably, the epoxide compound is propylene oxide or cyclohexene oxide.
Preferably, the epoxy compound with the side group containing double bonds or ester functional groups is one or more of allyl glycidyl ether, glycidyl methacrylate, tert-butyl 3, 4-epoxybutyrate, o-nitrobenzyl 2, 3-epoxypropionate, 1, 4-cyclohexadiene-1, 2-epoxide, 1, 2-epoxy-4-vinylcyclohexane, limonene epoxide and tert-butyl 3, 4-cyclohexene epoxide-1-carboxylate.
Among these references, tert-butyl 3, 4-epoxybutyrate[1]The preparation method comprises the steps of (1) preparing,1H NMR(CDCl3δ:1.46(s, 9H),2.47(t,2H),2.54(m,1H),2.82(t,1H),3.25(m,1H) ppm; 2, 3-Oxypropionic acid o-nitrobenzyl ester reference[2]The preparation method comprises the steps of (1) preparing,1H NMR(CDCl3δ) 2.94(d,1H),2.98(d,1H), 3.49(d,1H),5.25(d,2H),7.78(m,4H) ppm; 1, 4-cyclohexadiene-1, 2-epoxide reference[3]The preparation method comprises the steps of (1) preparing,1H NMR(CDCl3δ) 5.43(s,2H),3.23(s,2H),2.49(q,4H) ppm; 3, 4-cyclohexene epoxide-1-carboxylic acid tert-butyl ester reference[4]The preparation method comprises the steps of (1) preparing,1H NMR(CDCl3:δ)3.65 (s,5H),3.22,3.14(m,2H),2.49(m,1H),1.40-2.29(m,6H),1.40(s,9H)ppm。
preferably, the lactide monomer is racemic lactide or glycolide.
The process route for preparing the polycarbonate polyester copolymer with the pendant group containing the ammonium carboxylate group is shown in figure 1 (the raw material used on the left side of figure 1 is an epoxy compound with the pendant group containing the double-bond functional group, and the raw material used on the right side of figure 1 is an epoxy compound with the pendant group containing the ester functional group).
Example 1
47mg (0.07mmol) of porphyrinAlCl catalyst, 20mg (0.035mmol) of cocatalyst PPNCl, 0.5g (3.5mmol) of racemic lactide, 4.9mL (70mmol) of propylene oxide, 0.91mL (7mmol) of 1, 2-epoxy-4-vinylcyclohexane F and 5mL of dichloromethane are respectively added into a 25mL high-pressure reaction kettle (the molar ratio of porphyrinAlCl catalyst to cocatalyst to racemic lactide to propylene oxide to epoxy compound containing double bond/ester group functional group at the side group is 1:0.5:50:1000: 100), carbon dioxide is rapidly charged into the high-pressure reaction kettle, the pressure in the kettle is maintained at 4MPa, the polymerization temperature is 40 ℃, the reaction time is 22 hours, 100mL of methanol hydrochloride solution (HCl mass percent concentration is 1%) is added after the reaction is finished, the obtained product is washed by a large amount of methanol, and vacuum drying is carried out to obtain white double bond functionalized aliphatic polycarbonate polyester copolymer (FAPC-PEs)2.5g, the number average molecular weight M of the resulting copolymer as measured by GPC (THF)n10283 molecular weight distribution
Preparation of a double bond functionalized copolymer prepared in this example1The H NMR spectrum is shown in FIG. 2, wherein peaks at 5.14ppm and 1.55ppm are respectively attributed to the polyester PLA segment (-CH (CH)3) Peaks of methine and methyl hydrogens in COO-) units; the peaks at 5.03ppm, 4.20ppm, 1.30ppm were attributed to the polycarbonate APC segment (-CH) in the polymer2CH (R) OCOO-, R is CH3Or a group carried by a functional group monomer) of methine hydrogen, methylene hydrogen, and methyl hydrogen; the peaks at 5.78ppm, 4.86ppm, 2.38ppm, 2.11ppm and 1.59ppm are the peaks of double bond hydrogen and cyclohexane hydrogen introduced by the polymerization of 1, 2-epoxy-4-vinyl cyclohexane; peaks at 3.48ppm, 1.23ppm are a small amount of polyether segment (-CH) in the polymer2CH (R) O-, R is CH3Or a group introduced by a functional monomer) methine hydrogen, methylene hydrogen and methylPeak of radical hydrogen. The structural formula of the polymer is X (-CH (CH)3)COO-)n(-CH2CH(R)OCOO)m(-CH2CH(R)O)o-H(R＝CH3Or a group carried by a functional monomer, the specific structure of which is yet to be further confirmed), and the aliphatic polycarbonate having a molar percentage of APC segments of 0.5 a4.2*100％/(1/2A4.20+A5.14+1/3A3.50) The molar percentage of APC segments in the copolymer was calculated to be 67.4%. The molar percentage of the polyester chain segment PEs%5.1*100％/(1/2A4.20+A5.14+1/3A3.50) The molar percentage of polyester segments in the copolymer was calculated to be 23.1%, and the molar percentage of double bond functional groups contained in the pendant groups, F ═ A5.78*100％/(1/2A4.20+A5.14+1/3A3.50) The molar percentage of the double bond functional group contained in the side group in the copolymer is calculated to be 18.7 percent, and the molar percentage of the polyether chain segment PE percent is 1/3A3.5*100％/(1/2A4.20+A5.14+1/3A3.50) The molar percentage of polyether segments in the copolymer was calculated to be 9.5%. Of the polymers prepared in this example13The CNMR spectrum is shown in FIG. 3, in which the peak near 169.5ppm is the polyester (-CH (CH) in the polymer3) The peak of carbonyl carbon in COO-) unit is near 154.0ppm, and the polycarbonate chain segment (-CH) in the polymer2Peaks at carbonyl carbons in CH (R) OCOO-. The peaks near 141.53ppm and 113.82ppm are peaks at double bond carbons in the polymer.
Because of the number average molecular weight M of the copolymern10283 mol%, the side groups containing 18.7 mol% of vinyl functional groups, the repeat unit structure being as described above, so that the double bond content of the copolymer is approximately 1.8mmol/g, 0.5g of the resulting copolymer is dissolved in 50mL of THF, mercaptoacetic acid and AIBN (vinyl: mercapto: AIBN: 1:40:0.8, molar ratio) are added, the reaction is refluxed for 24h under nitrogen protection, a large amount of diethyl ether is added to precipitate a carboxyl-functionalized copolymer, the copolymer is washed with a large amount of water, THF is dissolved, the diethyl ether is precipitated 3 times, the copolymer is then dissolved in THF, a large amount of aqueous ammonia (COOH: NH) is added4OH 1:10 (molar ratio)), room temperatureStirring for 5 hours, adding a large amount of ether for precipitation to obtain a polycarbonate polyester copolymer with a side group containing an ammonium carboxylate group, dissolving ether in THF, and precipitating and purifying for 3 times to obtain 0.4 g. The copolymer was dissolved in THF (10% by mass/volume) and placed on a glass plate to form a film, which was then dried under vacuum, and the water contact angle was measured to be 42 ° (see FIG. 4: water contact angle: PPC, 90 ° (a); PPCLA (PLA%, 25%), 75 ° (b); PLA, 65 ° (c); d: ammonium carboxylate-functionalized polycarbonate polyester prepared in this example, 42 ° (d)). The copolymer was dispersed in water to give an emulsion having a concentration of 1g/L, and the particle size of the latex particles was measured by a light scattering particle size meter and was 300nm (see FIG. 5).
Example 2
47.8mg (0.07mmol) of aluminum porphyrin Al (OEt) catalyst, 40mg (0.07mmol) of cocatalyst PPNCl, 0.5g (3.5mmol) of racemic lactide, 4.9mL (70mmol) of propylene oxide, 0.91mL (7mmol) of 1, 2-epoxy-4-vinylcyclohexane F, 0.93mL (7mmol) of allyl glycidyl ether A, and 5mL of dichloromethane are added into a 25mL high-pressure reaction kettle respectively (aluminum porphyrin Al (OEt) catalyst: cocatalyst: racemic lactide: propylene oxide: epoxy compound containing double bond/ester functional group at the side group: 1:50:1000:200, molar ratio), carbon dioxide is rapidly charged into the high-pressure reaction kettle, the pressure in the kettle is maintained at 3.5MPa, the polymerization temperature is 20 ℃, the reaction time is 48 hours, 100mL of hydrochloric acid methanol solution (HCl concentration is 1 mass percent) is added after the reaction is finished, the resulting product was washed with a large amount of methanol and dried in vacuo to give 6.2g of a white double-bond-functionalized aliphatic polycarbonate polyester (FAPC-PEs) having a number average molecular weight of 88716 and a molecular weight distribution of 1.23. The mole percentage content of APC chain segment in the copolymer is 76.1%, the mole percentage content of polyester chain segment is 13.8%, the mole percentage content of polyether chain segment is 10.1%, and the mole percentage content of double bond functional group contained in the side group is 31.0%. The double bond of the pendant group in the copolymer was converted into an ammonium carboxylate group by the method of example 1, and the resulting copolymer had a water contact angle of 28 ℃ and a latex particle diameter of 150nm in an aqueous dispersion (1 g/L).
Example 3
Mixing the above PorphyrinAl (O (C)6H3(NO2)2) 26.6mg (0.035mmol) of catalyst, 4.27mg (0.035mmol) of cocatalyst DMAP4.27mg, 4.9mL of propylene oxide, 5.04 g of racemic lactide, 0.93mL (7mmol) of allyl glycidyl ether A, 0.95 mL (7mmol) of glycidyl methacrylate B, and 10mL of solvent dichloromethane are respectively added into a 100mL high-pressure reaction kettle (PorphyrinAl (O (C))6H3(NO2)2) Catalyst: and (3) a cocatalyst: racemic lactide: propylene oxide: epoxy compound with side group containing double bond/ester functional group is 1:1:1000:2000:400, molar ratio), quickly charging carbon dioxide into the kettle, maintaining the pressure in the kettle at 3.5MPa, the polymerization temperature at 60 ℃, the reaction time at 24 hours, after the reaction is finished, 100mL of hydrochloric acid methanol solution (HCl mass percentage content is 1%) is added to stop the reaction, the obtained product is washed by a large amount of methanol and dried in vacuum to obtain 4.5g of white double-bond functionalized aliphatic polycarbonate polyester copolymer (FAPC-PEs), the number average molecular weight is 95200, the molecular weight distribution is 1.5, the mole percentage content of APC chain segment in the copolymer is 46.1%, the mole percentage content of polyester chain segment is 46.8%, the mole percentage content of polyether chain segment is 7.1%, and the mole percentage content of double bond functional group contained in the side group is 25.2%. The double bond of the pendant group was converted to an ammonium carboxylate group by the method of example 1, and the resulting copolymer had a water contact angle of 35 ℃ and a latex particle diameter of 220nm in an aqueous dispersion (1 g/L).
Example 4
37.6mg (0.035mmol) of the PorphyrinCrCl catalyst, 7.5g (0.07mmol) of the cocatalyst 2, 6-lutidine, 12.2mL (0.175mol) of propylene oxide, 2.52g (0.0175mol) of racemic lactide, 1.38g (8.75mmol) of tert-butyl 3, 4-epoxybutyrate, 1.73g (8.75mmol) of 3, 4-cyclohexene epoxide-1-carboxylic acid tert-butyl ester, 10mL of the solvent 1, 4-dioxane were added to a 100mL autoclave (PorphyrinCrCl catalyst: cocatalyst: racemic lactide: propylene oxide having a double bond/ester functional group in a pendant group: epoxy compound: 1:2:500:5000:500, molar ratio), carbon dioxide was rapidly charged into the autoclave, the autoclave was maintained at 5MPa, the polymerization reaction temperature was 80 ℃ for 10 hours, and after the reaction was completed, 100mL of a methanol solution (HCl concentration: 1% by mass) was added to terminate the reaction, the obtained product is washed by a large amount of methanol and dried in vacuum to obtain 2.8g of white aliphatic polycarbonate polyester copolymer (FAPC-PEs), the number average molecular weight of the copolymer is 11170, the molecular weight distribution of the copolymer is 1.4, the mole percentage content of APC chain segments in the copolymer is 68.3 percent, the mole percentage content of polyester chain segments is 24.2 percent, the mole percentage content of polyether chain segments is 7.5 percent, and the mole percentage content of ester functional groups contained in the side groups is 24.0 percent.
0.5g of the obtained copolymer was dissolved in 50mL of THF, and a large amount of hydrochloric acid (carboxylate group: H) was added+1:20, molar ratio), under nitrogen, reflux for 24h, precipitation with a large amount of diethyl ether, washing with a large amount of water, dissolution in THF, 3-fold precipitation with diethyl ether, dissolution of the resulting carboxyl-functional copolymer in THF, addition of a large amount of aqueous ammonia (COOH: NH (NH)4OH ═ 1:10, molar ratio), stirred at room temperature for 5 hours, precipitated by addition of a large amount of diethyl ether, the resulting ammonium carboxylate-functionalized copolymer THF was dissolved, purified 3 times by diethyl ether precipitation, and dried under vacuum to give 0.45g of copolymer. The resulting copolymer was dissolved in THF (10% by mass/volume) and poured onto a glass plate to form a film, and the measured water contact angle was 38 ℃ and the particle diameter of the latex particles in the aqueous dispersion (1g/L) was 250 nm.
Example 5
The aforementioned PorphyrinCoCl catalyst 37.3mg (0.035mmol), cocatalyst PPNCl 20mg (0.035mmol), propylene oxide 0.98mL (14mmol), glycolide 1.624g (14mmol), 1, 4-cyclohexadiene-1, 2-epoxide E0.672 g (7mmol), limonene epoxide G1.064g (7mmol), and tetrahydrofuran 5mL as a solvent were added to a autoclave respectively (PorphyrinCoCl catalyst: cocatalyst: propylene oxide: glycolide: epoxy compound having a double bond/ester functional group in its pendant group 1:1:400:400, molar ratio), carbon dioxide was charged into the autoclave rapidly, the pressure in the autoclave was maintained at 3.5MPa, the polymerization temperature was 90 ℃ and the reaction time was 22 hours, after the reaction was completed, 100mL of hydrochloric acid was added to terminate the reaction, the resultant was washed with a large amount of methanol, vacuum-dried to obtain white aliphatic polycarbonate polyester copolymer (PEC-PEPs) 0.8g, the number average molecular weight is 6181, the molecular weight distribution is 1.23, the mole percentage content of APC chain segment in the copolymer is 53.1%, the mole percentage content of polyester chain segment is 43.8%, the mole percentage content of polyether chain segment is 3.1%, and the mole percentage content of double bond functional group contained in the side group is 38.5%. The double bond contained in the pendant group was converted into an ammonium carboxylate group by the method of example 1, and the resulting copolymer had a water contact angle of 20 ℃ and a latex particle diameter of 100nm in an aqueous dispersion (1 g/L).
Example 6
Mixing the above PorphyrinAl (OOCCCl)3) 39mg (0.035mmol) of catalyst, 20mg (0.035mmol) of cocatalyst PPNCl, 7.1mL (0.07mol) of cyclohexene oxide, 1.0g (0.007mol) of racemic lactide, 0.93mL (7mmol) of allyl glycidyl ether A, 0.449g (7mmol) of o-nitrobenzyl 2, 3-epoxypropionate and 5mL of toluene were added to a autoclave (PorphyrinAl (OOO CCCl)3) PPNCl, racemic lactide, propylene oxide, epoxy compound with a side group containing double bond/ester functional group, 1:1:200:2000:400, molar ratio), quickly charging carbon dioxide into a high-pressure reaction kettle, maintaining the pressure in the kettle at 1MPa, the polymerization temperature at 80 ℃, reacting for 22 hours, adding hydrochloric acid methanol solution to terminate the reaction after the reaction is finished, washing the obtained product with a large amount of methanol to obtain 4.5g of white aliphatic polycarbonate polyester copolymer (FAPC-PEs), wherein the number average molecular weight is 9703, the molecular weight distribution is 1.3, the mole percentage content of APC chain segment in the copolymer is 80.0%, and the mole percentage content of polyester chain segment is 80.0%12.5 percent, the molar percentage of the polyether chain segment is 7.5 percent, and the molar percentage of the (double bond + ester group) functional group contained in the side group is 19.8 percent. The obtained copolymer was converted into a carboxylic acid group from a double bond contained in the side group by the method of example 1, then converted into a carboxylic acid group from an ester group contained in the side group by the method of example 4, and then converted into an ammonium carboxylate group by the method of example 1, to obtain a polycarbonate polyester having an ammonium carboxylate group as the side group, wherein the water contact angle of the copolymer was 40 °, and the particle diameter of the latex particle in an aqueous dispersion (1g/L) was 280 nm.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Reference documents:
[1]Tsai F T,Wang Y Y,Darensbourg D J.J.Am.Chem.Soc.,2016,138: 4626-4633.
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Claims (10)
1. the carbon dioxide-based polycarbonate polyester copolymer with the side group containing double bonds and/or ester functional groups is characterized by being a copolymer of carbon dioxide and an epoxy compound, an epoxy compound with the side group containing double bonds/ester functional groups and a cross-ester monomer, wherein the number average molecular weight of the copolymer is 6000-100000, the molecular weight distribution is 1.1-1.5, the molar percentage content of a polycarbonate chain segment in the copolymer is 40-80%, and the total molar percentage content of the double bonds and the ester functional groups contained in the side group in the copolymer is 15-40%.
2. The carbon dioxide based polycarbonate polyester copolymer with pendant double bonds and/or ester based functional groups of claim 1, wherein the epoxy compound is propylene oxide or cyclohexene oxide.
3. The carbon dioxide-based polycarbonate polyester copolymer with pendant double bonds and/or ester-based functional groups as claimed in claim 1, wherein the epoxy compound with pendant double bonds/ester-based functional groups is one or more of allyl glycidyl ether, glycidyl methacrylate, tert-butyl 3, 4-epoxybutyrate, o-nitrobenzyl 2, 3-epoxypropionate, 1, 4-cyclohexadiene-1, 2-epoxide, 1, 2-epoxy-4-vinylcyclohexane, limonene epoxide, and tert-butyl 3, 4-cyclohexene epoxide-1-carboxylate.
4. The carbon dioxide-based polycarbonate polyester copolymer with pendant double bonds and/or ester-based functional groups according to claim 1, wherein the lactide-based monomer is racemic lactide or glycolide.
5. A method for preparing the carbon dioxide based polycarbonate polyester copolymer with the side group containing double bond/ester based functional group as the claim 1-4, which is characterized by comprising the following steps: adding a catalyst, an epoxy compound with a side group containing a double bond/ester functional group and a cross-ester monomer into a high-pressure reaction kettle, adding a solvent or not, quickly filling carbon dioxide into the high-pressure reaction kettle to maintain the pressure in the kettle at 1.0-5.0MPa, carrying out polymerization reaction for 10-48 hours at 20-90 ℃, adding a large amount of hydrochloric acid methanol solution to stop the reaction after the polymerization reaction is finished, and washing the obtained product with a large amount of methanol to obtain the carbon dioxide based polycarbonate polyester copolymer with the side group containing the double bond/ester functional group.
6. The preparation method of the carbon dioxide-based polycarbonate polyester copolymer with the pendant group containing the double bond/ester-based functional group as claimed in claim 5, wherein the catalyst is composed of a metalloporphyrin catalyst and a cocatalyst, the molar ratio of the metalloporphyrin catalyst to the cocatalyst is 1:0.5-2, wherein the metalloporphyrin catalyst has the structural formula:
m ═ Cr or Co or Al; r2、R3、R4Each independently selected from hydrogen, fluoro, chloro, bromo, chloro-or bromo-substituted aliphatic groups; x is-Cl-OCH2CH3、-OCH(CH3)2、-Br、CCl3COO-、CF3One of COO-, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy and 2,4, 6-trinitrophenol oxy;
the cocatalyst is one of bis- (triphenyl phosphorane) ammonium chloride, 4-dimethylamino pyridine and 2, 6-dimethyl pyridine.
7. The preparation method of the carbon dioxide-based polycarbonate polyester copolymer with the pendant group containing the double bond/ester functional group as claimed in claim 6, wherein the molar ratio of the metalloporphyrin catalyst to the lactide monomer is 1:50-1000, the molar ratio of the epoxy compound to the lactide monomer is 1-20:1, and the molar ratio of the epoxy compound with the pendant group containing the double bond/ester functional group to the epoxy compound is 0.1-1: 1; the solvent is one of dichloromethane, toluene, tetrahydrofuran and 1, 4-dioxane.
8. The carbon dioxide-based polycarbonate polyester copolymer with double bonds/ester groups on the side groups, which is obtained by hydrophilic modification of the carbon dioxide-based polycarbonate polyester copolymer according to any one of claims 1 to 4, wherein the surface water contact angle is lower than 45 degrees, and the particle size of latex particles in 1g/L aqueous dispersion is lower than 350 nm.
9. The method for preparing the ammonium carboxylate functionalized carbon dioxide based polycarbonate polyester copolymer according to claim 8, comprising the following steps: and carrying out carboxylation reaction on the carbon dioxide-based polycarbonate polyester copolymer with the side group containing double bonds/ester groups to convert the double bonds/ester functional groups of the side group into carboxyl groups, and then further reacting with ammonia water to prepare the carboxylic acid ammonium group functionalized carbon dioxide-based polycarbonate polyester copolymer.
10. The method for preparing the carbon dioxide-based polycarbonate polyester copolymer functionalized by ammonium carboxylate groups according to claim 9, wherein the method for performing the carboxylation reaction on the carbon dioxide-based polycarbonate polyester copolymer with the side groups containing double bonds/ester groups comprises the following steps: and reacting double bonds contained in the carbon dioxide-based polycarbonate polyester copolymer side groups with thioglycolic acid, and reacting ester groups contained in the side groups with hydrochloric acid to convert the double bonds/ester groups into carboxyl groups, thereby obtaining the carboxyl functionalized copolymer.
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| CN112062783A (en) * | 2020-08-17 | 2020-12-11 | 中国科学院长春应用化学研究所 | Ultraviolet-responsive metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate |
| CN113683764A (en) * | 2021-08-27 | 2021-11-23 | 中国科学院长春应用化学研究所 | Branched PPC-based membrane and preparation method thereof |
| CN114702656A (en) * | 2022-06-07 | 2022-07-05 | 欧尚元(天津)有限公司 | Carbon dioxide-based polylactic acid copolymer and preparation method thereof |
| CN116444974A (en) * | 2023-06-12 | 2023-07-18 | 山东联欣环保科技有限公司 | High-temperature-resistant carbon dioxide-based alloy, foaming material thereof and preparation method thereof |
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