CN113736001A - Application of Lewis base, sorbate polymer and derivative thereof - Google Patents
Application of Lewis base, sorbate polymer and derivative thereof Download PDFInfo
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Abstract
The invention provides application of Lewis base, a sorbate polymer and derivatives thereof, and belongs to the technical field of catalysts. The azacycloolefine with the structure shown in the formula I or the formula II has strong nucleophilicity, and can improve the initiation efficiency and the polymerization activity of the (E, E) -sorbate monomer polymerization; the organic aluminum compound has proper steric hindrance and acidity, avoids chain back biting and inactivation in the polymerization process of the (E, E) -sorbate monomer, and the Lewis base and the Lewis acid (the organic aluminum compound and/or the organic boron compound) are used together to be used as the polymerization catalyst of the (E, E) -sorbate to realize 100 percent of 1, 4-selective addition polymerization reaction at room temperature, so that the initiation efficiency is high.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to application of Lewis base, a sorbate polymer and derivatives thereof.
Background
The conjugated diene monomer (E, E) -sorbate (the structure is shown in formula a) can be polymerized to prepare a polymer by two modes of 1, 2-addition and 1, 4-addition, and if the polymerization mode of the (E, E) -sorbate can be completely controlled and the polymerization can be carried out only by the 1, 2-addition or 1, 4-addition, a polymer having a C ═ C double bond functional group on the main chain or side chain can be obtained.
Takasu et al (see J.Am.chem.Soc.2017,139,15005-15012) utilize N-heterocyclic carbene (NHC) as a Lewis Base (LB), (4-Me-2,6-tBu2-C6H2O)2AlMe((BHT)2AlMe) as Lewis Acid (LA) catalyzed (E, E) -Methyl Sorbate (MS) to synthesize cyclic PMS, where MS: NHC (molar ratio) is 20: 1. However, NHC has a strong basicity and a low nucleophilicity, and cannot well initiate polymerization, resulting in low initiation efficiency; furthermore, (BHT)2Chain back-biting occurs during polymerization of AlMe as LA at room temperature, resulting in chain deactivation, and 1, 4-addition polymerization of methyl sorbate at 100% at room temperature cannot be achieved.
Disclosure of Invention
In view of the above, the present invention aims to provide an application of a lewis base, a sorbate polymer and a derivative thereof, wherein the lewis base provided by the present invention can realize 100% 1, 4-selective addition polymerization of (E, E) -sorbate at room temperature, and has high initiation efficiency.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of Lewis base in catalyzing 1, 4-selective addition polymerization of sorbate, wherein the Lewis base is azacycloolefine which has a structure shown in a formula I or a formula II:
in the formula I, R1～R4Independently comprises hydrogen, methyl, isopropyl, tert-butyl, phenyl, 2,4, 6-trimethylphenyl or diisodecyl phthalate;
in the formula II, R1～R6Independently include hydrogen, methyl, isopropyl, t-butyl, phenyl, 2,4, 6-trimethylphenyl, or diisodecyl phthalate.
The invention provides a preparation method of a sorbate polymer, which comprises the following steps:
mixing (E, E) -sorbate, Lewis acid, Lewis base and an organic solvent, and carrying out 1, 4-selective addition polymerization reaction to obtain a sorbate polymer; the temperature of the 1, 4-selective addition polymerization reaction is-50-100 ℃;
the Lewis base is the Lewis base described in the technical scheme, and the Lewis acid is an organic aluminum compound and/or an organic boron compound.
Preferably, the organoaluminum compound comprises trimethylaluminum, tri-tert-butylaluminum, tris (pentafluorophenyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (methyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (isobutyl) aluminum or bis (2, 6-di-tert-butyl-4-methylphenoxy) (phenyl) aluminum;
the organoboron compound includes tris (pentafluorophenyl) boron.
Preferably, the organoaluminum compound comprises trimethylaluminum, tri-tert-butylaluminum, tris (pentafluorophenyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (methyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (isobutyl) aluminum or bis (2, 6-di-tert-butyl-4-methylphenoxy) (phenyl) aluminum;
the molar ratio of the Lewis base to the Lewis acid is 1 (1-10).
Preferably, the (E, E) -sorbate monomer has the structure shown in formula III:
in the formula III, R comprises methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triphenylmethyl or methyl ethyl ether.
Preferably, the molar ratio of the (E, E) -sorbate monomer to the Lewis base is (10-1600): 1.
Preferably, the organic solvent comprises toluene, tetrahydrofuran, N-dimethylformamide, fluorobenzene or chlorobenzene.
The invention provides a sorbate polymer prepared by the preparation method in the technical scheme, wherein the number average molecular weight of the sorbate polymer is 20-300 kg/mol, the weight average molecular weight is 22-350 kg/mol, and the molecular weight distribution is 1.06-1.32.
The invention provides a sorbate polymer derivative, which comprises a derivative A, a derivative B, a derivative C and a derivative D; the derivatives A, B, C and D have (AB)nA sequence;
the derivative A has a structure shown in a formula IV:
the derivative B has a structure shown as a formula V:
the derivative C has a structure shown in formula VI:
the derivative D has a structure shown in a formula VII:
the invention provides a preparation method of the sorbic acid ester polymer derivative in the technical scheme,
the preparation method of the derivative A comprises the following steps: mixing a sorbate polymer, an alkaline reagent and an organic solvent, carrying out a first hydrolysis reaction, and then acidifying to obtain a derivative A;
the preparation method of the derivative B comprises the following steps: mixing a sorbate polymer, a catalyst and an organic solvent, introducing hydrogen, and carrying out hydrogenation reduction reaction to obtain a derivative B;
the preparation method of the derivative C comprises the following steps: mixing the derivative B, an alkaline reagent and an organic solvent, carrying out a second hydrolysis reaction, and then acidifying to obtain a derivative C;
the preparation method of the derivative D comprises the following steps: mixing a sorbate polymer, a catalyst, a reducing agent and an organic solvent, and carrying out a deoxidation reaction to obtain a derivative D;
the sorbate polymer is the sorbate polymer in the technical scheme.
The invention also provides the application of the sorbate polymer in the technical scheme, the sorbate polymer derivative in the technical scheme or the sorbate polymer prepared by the preparation method in the technical scheme in preparing elastomers or adhesives.
The invention provides an application of Lewis base in catalyzing 1, 4-selective addition polymerization of sorbate, wherein the Lewis base is azacycloolefine which has a structure shown in a formula I or a formula II:
in the formula I, R1～R4Independently comprises hydrogen, methyl, isopropyl, tert-butyl, phenyl, 2,4, 6-trimethylphenyl or diisodecyl phthalate; in the formula II, R1～R6Independently include hydrogen, methyl, isopropyl, t-butyl, phenyl, 2,4, 6-trimethylphenyl, or diisodecyl phthalate. In the invention, the azacycloolefine with the structure shown in formula I or formula II has strong nucleophilicity, and can improve the initiation efficiency and polymerization activity of (E, E) -sorbate monomer polymerization. In the present invention, the above-mentioned azacyclic olefin and the organoaluminum compound are used in combinationAs a polymerization catalyst for (E, E) -sorbate, a 100% 1, 4-selective addition polymerization reaction can be achieved at room temperature, and the initiation efficiency is high. As shown by the results of the examples, the Lewis base provided by the invention catalyzes the 1, 4-selective addition polymerization reaction of ethyl sorbate at room temperature, and the initiation efficiency is 131-142%.
The invention provides a preparation method of a sorbate polymer. In the Lewis base adopted by the invention, the nucleophilicity of the azacycloolefine is strong, and the initiation efficiency and the polymerization activity of the polymerization of the (E, E) -sorbate monomer can be improved; the organic aluminum compound and/or the organic boron compound has proper steric hindrance and acidity, chain back biting and inactivation in the polymerization process of the (E, E) -sorbate monomer are avoided, and 100 percent of the (E, E) -sorbate is subjected to 1, 4-selective addition polymerization reaction at room temperature; in the present invention, the azacycloolefine and the organoaluminum compound are used in combination as a polymerization catalyst for (E, E) -sorbate, and a 100% 1, 4-selective addition polymerization reaction can be achieved at room temperature, resulting in high initiation efficiency. Moreover, the polymers prepared by the preparation method provided by the invention are all 1, 4-addition polymerization products, and the yield is high; and the preparation method is simple to operate and suitable for industrial production.
The invention provides a sorbate polymer obtained by the preparation method in the technical scheme, wherein the number average molecular weight of the sorbate polymer is 20-300 kg/mol, the weight average molecular weight is 22-350 kg/mol, and the molecular weight distribution is 1.06-1.32. The sorbate polymer provided by the invention has a large molecular weight and a narrow molecular weight distribution.
The invention provides a sorbate polymer derivative. The invention provides a sorbate polymer derivative having (AB)nThe sequences can not be obtained by traditional monomer copolymerization, and have potential application value in the field of preparing elastomers or adhesives.
The invention also provides a preparation method of the sorbate polymer derivative in the technical scheme. The preparation method provided by the invention is simple to operate and suitable for industrial production.
Drawings
FIG. 1 is a scheme for the preparation of sorbate polymer derivatives;
FIG. 2 is a hydrogen spectrum of PMS prepared in example 5;
FIG. 3 is a carbon spectrum of PMS prepared in example 5;
FIG. 4 is a hydrogen spectrum of PES prepared in example 9;
FIG. 5 is a carbon spectrum of PES prepared in example 9;
FIG. 6 is a GPC curve of PMS prepared in examples 1 to 5;
FIG. 7 shows M of PMS prepared in examples 1 to 5n、MwAnd D results;
FIG. 8 is a GPC curve of PES prepared in examples 6 to 8;
FIG. 9 is a DSC analysis curve of PMS prepared in example 5 and PMS derivatives prepared in examples 16 to 19;
FIG. 10 is a TGA analysis curve of PMS prepared in example 5 and PMS derivatives prepared in examples 16 to 19;
FIG. 11 is a graph showing the results of the adhesive strength between the stainless steel surface and the PMMA surface of PMS prepared in example 5, Poly (propylene-al-methyl acrylate) prepared in example 17, and Poly (propylene-al-acrylic acid) prepared in example 18.
Detailed Description
The invention provides an application of Lewis base in catalyzing 1, 4-selective addition polymerization of sorbate, wherein the Lewis Base (LB) is azacycloolefine which has a structure shown in a formula I or a formula II:
in the invention, in the formula I, R1～R4Independently hydrogen (H), methyl (Me), isopropyl (i-Pr), t-butyl (t-Bu), phenyl (Ph), 2,4, 6-trimethylphenyl (Mes), or diisodecyl phthalate (Dipp); in the formula II, R1～R6Independently include hydrogen (H), methyl (Me), isopropyl (i-Pr), tert-butyl (t-Bu), phenyl (Ph), 2,4, 6-trimethylphenyl (Mes) or orthophthalic bisDiisodecyl formate (Dipp).
In the present invention, the lewis base preferably has a structure represented by the formulae NHO1 to NHO 4:
the invention provides a preparation method of a sorbate polymer, which comprises the following steps:
mixing (E, E) -sorbate, Lewis acid, Lewis base and an organic solvent, and carrying out 1, 4-selective addition polymerization reaction to obtain a sorbate polymer; the temperature of the 1, 4-selective addition polymerization reaction is-50-100 ℃;
the Lewis base is the Lewis base described in the technical scheme.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the (E, E) -sorbate monomer preferably has the structure shown in formula III:
in the formula III, R preferably comprises methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triphenylmethyl or methyl ethyl ether; the (E, E) -sorbate monomer preferably includes Methyl Sorbate (MS), Ethyl Sorbate (ES), isopropyl sorbate, n-butyl sorbate, isobutyl sorbate, tert-butyl sorbate, phenyl sorbate, benzyl sorbate, trimethylsilyl sorbate, triethylsilyl sorbate, trimethoxysilyl sorbate, phenylalkyl trissorbate or ethyl methyl sorbate. In the present invention, the molar ratio of the (E, E) -sorbate monomer to the Lewis base is preferably (10-1600): 1, more preferably (150-1500): 1, and still more preferably (400-1200): 1.
In bookIn the invention, the Lewis Acid (LA) is an organoaluminum compound and/or an organoboron compound, and the organoaluminum compound preferably includes trimethylaluminum (AlMe)3) Tri-tert-butylaluminum (Al)tBu3) Tris (pentafluorophenyl) aluminum (Al (C)6F5)3) Bis (2, 6-di-tert-butyl-4-methylphenoxy) (methyl) aluminum ((BHT)2AlMe), bis (2, 6-di-tert-butyl-4-methylphenoxy) (isobutyl) aluminum ((BHT)2AliBu) or bis (2, 6-di-tert-butyl-4-methylphenoxy) (phenyl) aluminum ((BHT)2AlPh); the organoboron compound preferably comprises tris (pentafluorophenyl) boron. The organic aluminum compound and/or the organic boron compound adopted by the invention has proper steric hindrance and acidity, avoids chain back biting and inactivation in the polymerization process of the (E, E) -sorbate monomer, and realizes 100 percent of 1, 4-selective addition polymerization reaction of the (E, E) -sorbate at room temperature. In the present invention, the molar ratio of the Lewis base to the Lewis acid is preferably 1 (1 to 10), more preferably 1 (2 to 8), and most preferably 1 (4 to 5).
In the present invention, the organic solvent preferably includes toluene, tetrahydrofuran, N-dimethylformamide, fluorobenzene or chlorobenzene. In the present invention, the ratio of the amount of the (E, E) -sorbate monomer to the volume of the organic solvent is preferably (0.5 to 4) mol:1L, more preferably (1 to 3) mol:1L, and most preferably 2mol: 1L.
In the present invention, the mode of mixing the (E, E) -sorbate monomer, the lewis acid, the lewis base and the organic solvent is preferably stirring and mixing, and the speed of stirring and mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed. In the present invention, the order of mixing the (E, E) -sorbate monomer, lewis acid, lewis base and organic solvent is preferably such that the (E, E) -sorbate monomer is dissolved in the organic solvent to give a sorbate solution, and the sorbate solution and lewis base are mixed. In the present invention, the mixing of the sorbate solution and the lewis base preferably includes mixing the sorbate solution and the lewis base, and mixing the resulting mixture with the lewis acid. In the invention, the concentration of the sorbate solution is preferably 0.4-5 mol/L, more preferably 1-4 mol/L, and most preferably 1 mol/L. In the invention, the mixing time of the sorbate solution and the Lewis base is preferably 1-2 min, and more preferably 1.5 min; the mixing time of the mixed solution and the Lewis acid is preferably 1-2 min, and more preferably 1.5 min. In the invention, the Lewis base is preferably used in the form of Lewis base solution, and the concentration of the Lewis base solution is preferably 0.05-10 mg/mL, and more preferably 0.1-4.32 mg/mL; the Lewis acid is preferably used in the form of a Lewis acid solution, and the concentration of the Lewis acid solution is preferably 0.1-25 mg/mL, and more preferably 0.2-15 mg/mL; the solvent in the lewis base solution and lewis acid solution independently comprises toluene, tetrahydrofuran, N-dimethylformamide, fluorobenzene or chlorobenzene.
In the invention, the temperature of the 1, 4-selective addition polymerization reaction is-50-100 ℃, more preferably 20-80 ℃, and most preferably 25-50 ℃; the time of the 1, 4-selective addition polymerization reaction is preferably 0.5 to 120 hours, more preferably 0.5 to 100 hours, and most preferably 1 to 72 hours.
The invention provides a sorbate polymer prepared by the preparation method in the technical scheme. In the invention, the number average molecular weight of the sorbate polymer is preferably 9.8 to 300kg/mol, more preferably 20 to 290kg/mol, and most preferably 27 to 287 kg/mol; the weight average molecular weight of the sorbate polymer is preferably 22-350 kg/mol, more preferably 24-340 kg/mol, and most preferably 29-333 kg/mol; the molecular weight distribution of the sorbate polymer is 1.06-1.32, preferably 1.10-1.32, and more preferably 1.15-1.25.
The invention provides a sorbate polymer derivative, which comprises a derivative A, a derivative B, a derivative C and a derivative D.
In the present invention, the derivative A (polysorbate) has (AB)nThe number average molecular weight of the derivative A is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the weight average molecular weight of the derivative A is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the molecular weight distribution of the derivative A is preferably 1.01-1.5, and more preferably 1.05-1.40; the derivative A has a structure shown as a formula IV：
In the present invention, the derivative B (alternating copolymer of propylene and acrylic ester) has (AB)nThe data molecular weight of the derivative B is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the weight average molecular weight of the derivative B is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the molecular weight distribution of the derivative B is preferably 1.01-1.5, and more preferably 1.05-1.40; the derivative B has a structure shown as a formula V:
in the present invention, the derivative C (alternating copolymer of propylene and acrylic acid) has (AB)nThe data molecular weight of the derivative C is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the weight average molecular weight of the derivative C is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the molecular weight distribution of the derivative C is preferably 1.01-1.5, and more preferably 1.05-1.40; the derivative C has a structure shown in formula VI:
in the present invention, the derivative D (alternating copolymer of propylene and ethylene) has (AB)nThe data molecular weight of the derivative D is preferably 12-300 kg/mol, more preferably 24-150 kg/mol; the weight average molecular weight of the derivative D is preferably 12-300 kg/mol, and more preferably 24-150 kg/mol; the molecular weight distribution of the derivative D is preferably 1.01-1.5, and more preferably 1.05-1.40; the derivative D has a structure shown in a formula VII:
the invention provides a preparation method of the sorbic acid ester polymer derivative in the technical scheme,
the preparation method of the derivative A comprises the following steps: mixing a sorbate polymer, an alkaline reagent and an organic solvent, carrying out a first hydrolysis reaction, and then acidifying to obtain a derivative A;
the preparation method of the derivative B comprises the following steps: mixing a sorbate polymer, a catalyst and an organic solvent, introducing hydrogen, and carrying out hydrogenation reduction reaction to obtain a derivative B;
the preparation method of the derivative C comprises the following steps: mixing the derivative B, an alkaline reagent and an organic solvent, carrying out a second hydrolysis reaction, and then acidifying to obtain a derivative C;
the preparation method of the derivative D comprises the following steps: mixing a sorbate polymer, a catalyst, a reducing agent and an organic solvent, and carrying out a deoxidation reaction to obtain a derivative D;
the sorbate polymer is the sorbate polymer in the technical scheme.
The preparation method of the derivative A comprises the following steps: mixing a sorbate polymer, an alkaline reagent and an organic solvent, carrying out a first hydrolysis reaction, and then acidifying to obtain a derivative A; the sorbate polymer is the sorbate polymer in the technical scheme.
In the present invention, the alkaline agent preferably includes sodium hydroxide, potassium hydroxide; the alkaline reagent is preferably used in the form of an alkaline reagent aqueous solution, and the mass percentage concentration of the alkaline reagent aqueous solution is preferably 10-40%, and more preferably 20%; the ratio of the mass of the sorbate polymer to the volume of the aqueous alkaline reagent solution is preferably 1g (10-40) mL, more preferably 1g: (19-20) mL. In the present invention, the organic solvent preferably includes 1, 4-dioxane, tetrahydrofuran; the mass to volume ratio of the sorbate polymer to the organic solvent is preferably 1g (10 to 40) mL, more preferably 1g: (15-16) mL.
In the invention, the mixing mode is preferably stirring mixing, the speed and time of stirring mixing are not particularly limited, and the raw materials can be uniformly mixed; the order of mixing is preferably such that the sorbate polymer is dissolved in the organic solvent and then mixed by adding an alkaline agent. In the invention, the temperature of the hydrolysis reaction is preferably 30-100 ℃, and more preferably 70 ℃; the time of the hydrolysis reaction is preferably 4-24 hours, and more preferably 8 hours. In the invention, the system of the hydrolysis reaction is preferably cooled to room temperature and then acidified, and the pH value of the system during acidification is preferably 4-7, more preferably 6; the acid adopted for acidification is preferably a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 2-6 mol/L, and more preferably 4 mol/L. Taking the methyl sorbate polymer as an example, the reactions that occur during the first hydrolysis and acidification are shown in scheme (a) in fig. 1. After the acidification, the invention preferably also comprises the steps of adding water into the acidification system for precipitation, and drying the obtained precipitate to obtain a derivative A; the ratio of the mass of the sorbate polymer to the volume of water is preferably 1g (30 to 80) mL, more preferably 1g: (47-48) mL; the drying method is preferably vacuum drying, and the temperature and time of the vacuum drying are not particularly limited in the present invention, and the drying may be carried out to a constant weight.
The preparation method of the derivative B comprises the following steps: mixing a sorbate polymer, a catalyst and an organic solvent, introducing hydrogen, and carrying out hydrogenation reduction reaction to obtain a derivative B; the sorbate polymer is the sorbate polymer in the technical scheme. In the present invention, the catalyst preferably comprises Pd/C or p-toluenesulfonyl hydrazide, more preferably Pd/C; the mass ratio of the sorbate polymer to the catalyst is preferably 1: (0.01 to 0.05), more preferably 1: (0.02-0.03). In the present invention, the organic solvent preferably includes tetrahydrofuran, toluene or chloroform; the mass to volume ratio of the sorbate polymer to the organic solvent is preferably 1g (5 to 20) mL, more preferably 1g: (9-10) mL. In the invention, the pressure of the hydrogen is preferably 0.1-1 MPa, and more preferably 0.2-0.3 MPa; in the embodiment of the invention, the hydrogen is preferably introduced by connecting the reaction device with a balloon filled with hydrogen; the hydrogen pressure is preferably kept constant by replacing the balloon containing hydrogen. In the invention, the mixing mode is preferably stirring mixing, the speed and time of stirring mixing are not particularly limited, and the raw materials can be uniformly mixed; the order of mixing is preferably such that the sorbate polymer is dissolved in the organic solvent and then mixed by adding the catalyst. In the invention, the temperature of the hydrogenation reduction reaction is preferably 50-100 ℃, and more preferably 70 ℃; the time of the hydrogenation reduction reaction is preferably 24-100 h, and more preferably 72 h; taking the methyl sorbate polymer as an example, the reactions that occur during the hydrogenation reduction reaction are shown in scheme (B) in fig. 1. After the hydrogenation reduction reaction, the invention preferably performs solid-liquid separation on the hydrogenation reduction reaction system, and the obtained filtrate is concentrated and then dried to obtain a derivative B; the solid-liquid separation mode is not particularly limited, and the solid-liquid separation mode known to those skilled in the art can be adopted, such as filtration; the purpose of the filtration is to remove the catalyst; the concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be adopted; in the present invention, the drying temperature and time are not particularly limited, and the drying may be carried out to a constant weight.
The preparation method of the derivative C comprises the following steps: and mixing the derivative B, an alkaline reagent and an organic solvent, carrying out a second hydrolysis reaction, and then acidifying to obtain a derivative C. In the present invention, the alkaline agent preferably includes sodium hydroxide or potassium hydroxide; the alkaline reagent is preferably used in the form of an alkaline reagent aqueous solution, and the mass percentage concentration of the alkaline reagent aqueous solution is preferably 10-40%, and more preferably 20%; the ratio of the mass of the derivative B to the volume of the alkaline reagent aqueous solution is preferably 1g (10-40) mL, more preferably 1g: (19-20) mL. In the present invention, the organic solvent preferably includes 1, 4-dioxane or tetrahydrofuran; the mass to volume ratio of the sorbate polymer to the organic solvent is preferably 1g (10 to 40) mL, more preferably 1g: (15-16) mL. In the invention, the mixing mode is preferably stirring mixing, the speed and time of stirring mixing are not particularly limited, and the raw materials can be uniformly mixed; the mixing order is preferably that the derivative B is dissolved in an organic solvent and then mixed with an alkaline reagent. In the invention, the temperature of the second hydrolysis reaction is preferably 30-100 ℃, and more preferably 70 ℃; the time of the second hydrolysis reaction is preferably 4-24 hours, and more preferably 8 hours. Preferably, the system of the second hydrolysis reaction is cooled to room temperature and then acidified, and the pH value of the system during acidification is preferably 4-6, and more preferably 5-6; the acid used for acidification is preferably hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 3-5 mol/L, and more preferably 4 mol/L. Taking the methyl sorbate polymer as an example, the reactions that occur during the second hydrolysis reaction and acidification are shown in scheme (C) in fig. 1. After the acidification, the invention preferably further comprises adding water into the acidification system for precipitation, and drying the obtained precipitate to obtain a derivative C; the ratio of the mass of the derivative B to the volume of water is preferably 1g (4-7) mL, more preferably 1g: (47-48) mL; the drying method is preferably vacuum drying, and the temperature and time of the vacuum drying are not particularly limited in the present invention, and the drying may be carried out to a constant weight.
The preparation method of the derivative D comprises the following steps: mixing a sorbate polymer, a catalyst, a reducing agent and an organic solvent, and carrying out a deoxidation reaction to obtain a derivative D; the sorbate polymer is the sorbate polymer in the technical scheme. In the present invention, the catalyst preferably comprises B (C)6F5)3(ii) a The mass ratio of the sorbate polymer to the catalyst is preferably 1: (0.01 to 0.05), more preferably 1: (0.02-0.03). In the present invention, the reducing agent preferably includes tetramethyldisiloxane ((Me)2SiH)2O) or Me3SiH; the mass ratio of the sorbate polymer to the reducing agent is preferably 1: (3.0 to 6.0), more preferably 1: (4.2-4.3). In the present invention, the organic solvent preferably includes toluene, dichloromethane or chloroform; the mass to volume ratio of the sorbate polymer to the organic solvent is preferably 1g (10 to 40) mL, more preferably 1g: 20 mL. In the present invention, the mixing is carried outThe mixing mode is preferably stirring and mixing, the speed and time of stirring and mixing are not particularly limited, and the raw materials can be uniformly mixed; the order of mixing is preferably such that the sorbate polymer is dissolved in the organic solvent, and then the catalyst and the reducing agent are added and mixed. In the invention, the temperature of the deoxidation reaction is preferably 20-40 ℃, and more preferably 25-30 ℃; the time of the deoxidation reaction is preferably 8-24 h, and more preferably 12 h; taking the methyl sorbate polymer as an example, the reactions that occur during the deoxygenation reaction are shown in scheme (D) in FIG. 1. After the deoxidation reaction, the deoxidation reaction system is preferably subjected to concentration, precipitation and drying in sequence to obtain a derivative D; the concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be adopted; the precipitating agent used for precipitation preferably comprises methanol or ethanol; the dosage of the precipitant is not specially limited, and the precipitant is added until the precipitation amount of the derivative is not increased; in the present invention, the drying temperature and time are not particularly limited, and the drying may be carried out to a constant weight.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 2.0mmol of Methyl Sorbate (MS) in 500 mu L of toluene, adding 0.5mL of a toluene solution of LA with the concentration of 0.08mol/L (the amount of LA is 0.04mmol), stirring for 1min, adding 500mL of a toluene solution of NHO1 with the concentration of 0.04mol/L (the amount of LB is 0.02mmol), supplementing toluene until the total volume of toluene is 2.0mL, and carrying out 1, 4-selective addition polymerization at 25 ℃ for 1h to obtain a sorbate Polymer (PMS);
wherein LA is (BHT)2AlPh; LB is NHO 1; LB: LA: MS molar ratio 1:2: 100;
examples 2 to 15
A sorbate polymer was produced by the method of example 1, and the production conditions of examples 2 to 15 are shown in Table 1, and other conditions not shown in Table 1 were the same as those of example 1.
TABLE 1 preparation conditions for examples 1 to 15
(1) Structural characterization of sorbate polymers
Process for preparing the sorbate Polymer of example 51H NMR Spectrum (500MHz, CDCl)3) As shown in fig. 2, it can be seen from fig. 2 that no H signal was observed at 1.2ppm on the spectrum, indicating that the sorbate polymer prepared in example 1 has 100% of 1, 4-addition structure. Preparation of Pear acid ester Polymer prepared in examples 1 to 41The results of the H NMR spectrum are in agreement with those of FIG. 2.
Process for preparing the sorbate Polymer of example 513C NMR spectrum (126MHz, CDCl)3) As shown in fig. 3, no CH ═ CH-CH was observed in the spectrum3Indicating that the sorbate polymer prepared in example 1 has 100% 1, 4-addition structure. Preparation of Pear acid ester Polymer prepared in examples 1 to 413The C NMR spectrum results are in agreement with those of FIG. 3.
Preparation of the sorbate Polymer of example 91H NMR Spectrum (500MHz, CDCl)3) As shown in fig. 4, it can be seen from fig. 4 that no H signal was observed at 1.2ppm on the spectrum, indicating that the sorbate polymer prepared in example 1 has 100% of 1, 4-addition structure. Preparation of Pear acid ester Polymer prepared in examples 6 to 81The results of the H NMR spectrum are in agreement with those of FIG. 4.
Preparation of the sorbate Polymer of example 913C NMR spectrum (126MHz, CDCl)3) As shown in fig. 5, no CH ═ CH-CH was observed in the spectrum3Indicating the sorbate prepared in example 1The polymer had 100% 1, 4-addition structure. Preparation of Pear acid ester Polymer prepared in examples 6 to 813The C NMR spectrum results are in agreement with those of FIG. 5.
(2) Polymerization results
Examples 1 to 5 (BHT)2Results of MS polymerization catalyzed by AlPh/NHO1 catalyst and examples 6 to 9 (BHT)2AliResults of ES polymerization catalyzed by Bu/NHO1 catalyst;
wherein the number average molecular weight MnWeight average molecular weight MwAnd molecular weight distribution
Number average molecular weight M measured by gel permeation chromatography and laser light scattering detectornWeight average molecular weight MwAnd molecular weight distribution
The results are shown in FIGS. 6 to 7 and Table 2; FIG. 6 is a GPC curve of PMS prepared in examples 1 to 5, and FIG. 7 is M of PMS prepared in examples 1 to 5n、MwAnd
the result is; FIG. 8 is a GPC curve of PES prepared in examples 6 to 8.
Initiation efficiency of the catalyst I ═ Mn(calcd)/Mn(exptl)，
Mn(calcd)＝[MW(MS)]×([MS]0/[I]0)×(conversion％)+MW(end groups);
wherein [ MS]0As the initial concentration of MS in the reaction system, [ MS]0＝1mmol/mL；
Initial concentration of Lewis base [ I]0＝0.01～0.0001mmol/mL；
conversion% is monomer conversion;
MW(end groups) are end group molecular weights (i.e.the molecular weight of the Lewis base used).
Table 2 results of MS and ES polymerization catalyzed by the catalysts of examples 1 to 9
As can be seen from FIGS. 6 to 8 and Table 2, the molecular weight of the polymer increases linearly with increasing proportions of the MS and ES monomers; the initiation efficiency of the Lewis base is 61-142%. The prepared pear ester polymer has the advantages of large molecular weight, narrow molecular weight distribution and high initiation efficiency.
Example 16
According to the scheme (A) in FIG. 1, 2.52g of PMS prepared in example 5 is dissolved in 40mL of 1, 4-dioxane, 50mL of 20 wt% aqueous NaOH solution is added and mixed uniformly, hydrolysis reaction is carried out at 70 ℃ for 8h, after cooling to room temperature, 4mol/L aqueous HCl solution is added to adjust the pH value to 6, 120mL of water is added for precipitation, filtration is carried out, and the obtained solid product is dried in vacuum to constant weight to obtain polysorbates (Poly (sorbic acid), 2.05g and 91% yield).
Poly (sorbic acid) has the following structural characterization data of hydrogen spectrum and carbon spectrum:1H NMR(500MHz,DMSO-d6)δ12.20(s,1H,COOH),5.43-5.25(m,2H,CH＝CH),2.73～2.60(m,1H,CHCOOH),2.45-2.38(m,1H,CH3CH),1.01～0.85(m,3H,CH3)；13C NMR(126MHz,DMSO-d6)δ174.7,136.1,126.7,55.9,55.0,18.6。
example 17
According to the scheme (B) in FIG. 1, 7.56g of PMS prepared in example 5 was dissolved in 70mL of tetrahydrofuran, 200mg of Pd/C catalyst was added, a balloon containing hydrogen was attached, hydrogenation reduction was carried out at 70 ℃ for 72 hours while maintaining the hydrogen pressure constant at 0.3MPa by replacing the balloon, after the reaction was completed, Pd/C was removed by filtration, and after concentration and drying to constant weight, acrylic acid-methyl acrylate copolymer (Poly (propylene-alt-methyl acrylate), 6.12g, yield 79%) was obtained.
The hydrogen and carbon spectrum structure characterization data of Poly (propylene-alt-methyl acrylate) are as follows:1HNMR(500MHz,CDCl3)δ3.66(s,3H,COOCH3),2.27～2.13(m,1H,CHCOOCH3),1.74～1.28(m,4H,CH2CH2),1.12～1.00(m,1H,CH3CH),0.89(s,3H,CH3)；13C NMR(126MHz,CDCl3)δ16.9.16.4～16.8(-CH-CH3),26.0,26.5(erythro),26.8,27.1,27.3,27.5(threo)(-CH2-CH-CO-),32.2,32.8,32.9(-CH2-CH-CH3)35.4,35.5,35.8,36.0(-CH-CH3),50.6～51.0(-COOCH3),51.1,51.2(threo)(-CH-CO-),175.5,175.7(threo),175.9,176.0(erythro)(-COOCH3)。
example 18
According to the scheme (C) in FIG. 1, 2.52g of Poly (propylene-al-methyl acrylate) prepared in example 11 was dissolved in 40mL of 1, 4-dioxane, added with 50mL of 20 wt% aqueous NaOH solution, mixed well, subjected to hydro-hydrolysis at 70 ℃ for 8 hours, cooled to room temperature, added with 4mol/L aqueous HCl solution to adjust the pH to 6, then added with 120mL of water for precipitation, filtered, and the resulting solid product was vacuum-dried to constant weight to obtain propylene-acrylic acid copolymer (Poly (propylene-al-acrylic acid), 1.97g, yield 88%).
The hydrogen spectrum and carbon spectrum structure characterization data of Poly (propylene-alt-acrylic acid) are as follows:1HNMR(500MHz,DMSO-d6)δ12.41(s,1H,COOH),2.16～2.03(m,1H,CHCOOH),1.60～1.18(m,4H,CH2),1.06～1.10(m,1H,CH3CH),0.86～0.79(m,3H,CH3)；13C NMR(126MHz,DMSO-d6)δ175.2,51.3,35.3,32.4,27.0,16.9。
example 19
According to the scheme (D) in FIG. 1, 2.5g of PMS prepared in example 5 was dissolved in 50mL of toluene, and 52mgB (C) was added6F5)3And 10.7g (Me)2SiH)2Mixing O, deoxidizing at 25 deg.C for 12h, concentrating, adding methanol for precipitation, drying the obtained precipitate to constant weight to obtain propylene-ethylene copolymer (Poly (ethylene-alt-2-butylene),0.98g, yield 60%)
The structural characterization data of hydrogen spectrum and carbon spectrum of Poly (ethylene-alt-2-butyl) are as follows:1H NMR(400MHz,1,2-Dichlorobenzene-d4)δ1.80～0.30(m,12H)；13C NMR(100MHz,1,2-Dichlorobenzene-d4)δ42.9,38.2,26.5,19.5,16.8,11.0。
DSC analysis curves of PMS prepared in example 5 and PMS derivatives prepared in examples 16 to 19 are shown in FIG. 9 and Table 3, and TGA analysis curves are shown in FIG. 10 and Table 3.
TABLE 3 thermal stability Properties of PMS prepared in example 5 and PMS derivatives prepared in examples 16 to 19
In Table 3, TgDenotes the glass transition temperature, Td,5Indicating a temperature of 5% weight loss.
As can be seen from fig. 9 to 10 and table 3, PMS and PMS derivatives prepared by the present invention are excellent in thermal stability.
The adhesion strength of PMS prepared in example 5, Poly (propylene-al-methyl acrylate) prepared in example 17 and Poly (propylene-al-acrylic acid) prepared in example 18 on the surface of stainless steel and PMMA (polymethyl methacrylate) is shown in fig. 11, in which the adhesion strength of PMS, Poly (propylene-al-methyl acrylate) and Poly (propylene-al-acrylic acid) on the surface of stainless steel is 1.89MPa, 1.66MPa and 1.39MPa, respectively, and the adhesion strength on the surface of PMMA is 0.48MPa, 0.74MPa and 3.22MPa, respectively, indicating that the adhesion strength of the sorbate polymer and the sorbate polymer derivative prepared in the present invention is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Use of a lewis base to catalyze the 1, 4-selective addition polymerization of a sorbate ester, the lewis base being an azacycloalkene having a structure represented by formula I or formula II:
in the formula I, R1～R4Independently comprises hydrogen, methyl, isopropyl, tert-butyl, phenyl, 2,4, 6-trimethylphenyl or diisodecyl phthalate;
in the formula II, R1～R6Independently include hydrogen, methyl, isopropyl, t-butyl, phenyl, 2,4, 6-trimethylphenyl, or diisodecyl phthalate.
2. A method of making a sorbate polymer comprising the steps of:
mixing (E, E) -sorbate, Lewis acid, Lewis base and an organic solvent, and carrying out 1, 4-selective addition polymerization reaction to obtain a sorbate polymer; the temperature of the 1, 4-selective addition polymerization reaction is-50-100 ℃;
the Lewis base is the Lewis base described in claim 1, and the Lewis acid is an organoaluminum compound and/or an organoboron compound.
3. The production method according to claim 2, wherein the organoaluminum compound comprises trimethylaluminum, tri-tert-butylaluminum, tris (pentafluorophenyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (methyl) aluminum, bis (2, 6-di-tert-butyl-4-methylphenoxy) (isobutyl) aluminum or bis (2, 6-di-tert-butyl-4-methylphenoxy) (phenyl) aluminum;
the organoboron compound comprises tris (pentafluorophenyl) boron;
the molar ratio of the Lewis base to the Lewis acid is 1 (1-10).
4. The method of claim 2, wherein the (E, E) -sorbate monomer has the structure of formula III:
in the formula III, R comprises methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triphenylmethyl or methyl ethyl ether.
5. The method according to claim 2 or 4, wherein the molar ratio of the (E, E) -sorbate monomer to the Lewis base is (10-1600): 1.
6. The method of claim 2, wherein the organic solvent comprises toluene, tetrahydrofuran, N-dimethylformamide, fluorobenzene, or chlorobenzene.
7. The sorbate polymer produced by the production method according to any one of claims 3 to 6, which has a number average molecular weight of 20 to 300kg/mol, a weight average molecular weight of 22 to 350kg/mol, and a molecular weight distribution of 1.06 to 1.32.
8. A sorbate polymer derivative is characterized by comprising a derivative A, a derivative B, a derivative C and a derivative D; the derivatives A, B, C and D have (AB)nA sequence;
the derivative A has a structure shown in a formula IV:
the derivative B has a structure shown as a formula V:
the derivative C has a structure shown in formula VI:
the derivative D has a structure shown in a formula VII:
9. the process for producing a sorbate polymer derivative of claim 8,
the preparation method of the derivative A comprises the following steps: mixing a sorbate polymer, an alkaline reagent and an organic solvent, carrying out a first hydrolysis reaction, and then acidifying to obtain a derivative A;
the preparation method of the derivative B comprises the following steps: mixing a sorbate polymer, a catalyst and an organic solvent, introducing hydrogen, and carrying out hydrogenation reduction reaction to obtain a derivative B;
the preparation method of the derivative C comprises the following steps: mixing the derivative B, an alkaline reagent and an organic solvent, carrying out a second hydrolysis reaction, and then acidifying to obtain a derivative C;
the preparation method of the derivative D comprises the following steps: mixing a sorbate polymer, a catalyst, a reducing agent and an organic solvent, and carrying out a deoxidation reaction to obtain a derivative D;
the sorbate polymer of claim 7.
10. Use of the sorbate polymer of claim 7, the sorbate polymer derivative of claim 9 or the sorbate polymer obtained by the process of claim 9 for the preparation of elastomers or adhesives.
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