A polycarbonate modifier, a polycarbonate composite material and a preparation method thereof

Abstract

The application discloses a polybutylene carbonate modifier, a polybutylene carbonate composite material and a preparation method thereof. The polybutylene carbonate modifier is an aliphatic polyester-polycarbonate copolymer ionomer. The application further discloses a polybutylene carbonate modifier, a polybutylene carbonate composite material and a preparation method thereof. The polybutylene carbonate modifier, the polybutylene carbonate composite material and the preparation method thereof can improve the compatibility of PBC and other biodegradable polyester materials by adding the ionomer, and a series of composite materials with excellent comprehensive performance are obtained.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a polybutylene carbonate modifier, a polybutylene carbonate composite material, and a method for preparing the same. Background Technology

[0002] Microplastic pollution caused by the use of traditional petroleum-based polymers has become a major ecological disaster facing human society. Replacing traditional petroleum-based polymers with fully biodegradable polymers in the plastics industry can effectively solve the plastic pollution problem and has become a hot topic of global concern.

[0003] Currently, aliphatic polyesters and polycarbonate polymers with biodegradable properties, such as PLA, PBS, PHA, PPC, and PBC, have been industrialized as basic materials for plastic products. Unfortunately, due to performance limitations, none of these polymers can be used alone; they must be blended to achieve functional complementarity to meet product processing requirements. Among these, selecting suitable compatibilizers to improve the compatibility between blend components is key to obtaining composite materials with excellent overall performance.

[0004] High molecular weight polybutylene carbonate (PBC) possesses excellent biodegradability, mechanical properties, and ductility, making it a promising candidate for application in the field of environmentally friendly, fully biodegradable polymers. However, the presence of a symmetrical carbonate structure in the PBC molecular chain results in relatively low molecular chain polarity, leading to drawbacks such as low thermal deformation temperature and slow crystallization rate, which limits the expansion of PBC's application range. Therefore, other fully biodegradable polymers are often blended or copolymerized with PBC to improve its performance. Patents CN 102875998 A, CN 102153838 A, and CN114702810 A add aliphatic polyesters to the PBC matrix, resulting in composite materials with excellent mechanical properties. Patents CN 115232315 A and CN 115232297 A further employ a copolymerization strategy to introduce polyglycolic acid segments into the PBC molecular chain to improve the mechanical and degradation properties of PBC. Although the introduction of aliphatic polyesters can improve the mechanical properties of PBC, the poor compatibility between PBC and aliphatic polyesters has resulted in low heat deformation temperature and poor overall performance, which has not been effectively solved.

[0005] In view of this, the present invention proposes a new polybutylene carbonate modifier, a polybutylene carbonate composite material and its preparation method. The aliphatic polycarbonate-polyester copolymer ionomer (PBSC) is used as a compatibilizer and added to the PBC and aliphatic polyester copolymer system to improve the compatibility between PBC and aliphatic polyester, thereby obtaining a PBC-based composite material with excellent comprehensive performance. Summary of the Invention

[0006] The purpose of this invention is to provide a polybutylene carbonate (PBSC) modifier. In this PBSC modifier, the PBC segments and aliphatic polyester segments can generate strong interfacial adhesion with the PBC and aliphatic polyester in the matrix, respectively. The sulfonate groups present in the segments can generate strong interactions with the matrix through hydrogen bonding, which significantly improves the compatibility between PBC and aliphatic polyester.

[0007] To achieve the above objectives, the technical solution adopted is as follows:

[0008] A polybutylene carbonate modifier is an aliphatic polyester-polycarbonate copolymer ionomer.

[0009] Furthermore, the structural formula of the polybutylene carbonate modifier is as follows:

[0010]

[0011] In the formula, R is an alkyl or cyclic alkyl group with 2-10 carbon atoms, and m and n are the degrees of polymerization.

[0012] The second objective of this invention is to provide a method for preparing the above-mentioned polybutylene carbonate modifier, which synthesizes an aliphatic polycarbonate-polyester copolymer ionic polymer (PBSC) by melt polycondensation. The process is simple and the polymer structure is easy to control.

[0013] To achieve the above objectives, the technical solution adopted is as follows:

[0014] The above-mentioned method for preparing polybutylene carbonate modifier is a melt polycondensation method, which includes the following steps:

[0015] (1) 1,4-Butanediol and organic carbonate are reacted at 70-200℃ under catalyst 1 and N2 atmosphere for 0.5-6h to obtain polycarbonate prepolymer;

[0016] Dimethyl fumarate and aliphatic diol are reacted in catalyst 2, N2 atmosphere, 150-200℃ for 1-8h to obtain polyfumarate diol prepolymer.

[0017] (2) The polyfumarate prepolymer and polycarbonate prepolymer are subjected to polycondensation reaction for 1-10 h under the conditions of catalyst 3, below 200 Pa and 200-230 °C to obtain an aliphatic polyester-polycarbonate copolymer with double bonds.

[0018] (3) After dissolving the aliphatic polyester-polycarbonate copolymer in an organic solvent, sodium bisulfite is added and reacted at 100-130℃ for 7-24h to obtain an aliphatic polyester-polycarbonate copolymer ionomer, namely the polybutylene carbonate modifier.

[0019] Furthermore, the molar ratio of the 1,4-butanediol to the organic carbonate is 0.5-5:1;

[0020] The molar ratio of the aliphatic diol to dimethyl fumarate is 1-4:1;

[0021] The mass ratio of carbonate to ester segments in the polybutylene carbonate modifier is 1-5:5-1.

[0022] Furthermore, catalyst 1, catalyst 2, and catalyst 3 are at least one of sodium methoxide, sodium hydroxide, sodium acetate, potassium hydroxide, antimony acetate, potassium bicarbonate, sodium ethoxide, antimony glycolate, sodium acetylacetonate, zinc acetate, magnesium oxide, zirconium dichlorocerocene, zinc nitrate, magnesium acetate, tetrabutyl titanate, dibutyltin dilaurate, zirconium chloride, calcium acetate, barium acetate, zinc chloride, tetraisopropyl titanate, potassium carbonate, manganese acetate, basic magnesium carbonate, potassium acetate, tetraethyl titanate, tin chloride, stannous octoate, 4-dimethylaminopyridine, and antimony oxide.

[0023] Furthermore, in step (1), the organic carbonate is one of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate;

[0024] The aliphatic diol is one of the following: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,4-cyclohexanediol, 1,8-octanediol, 3,6-octanediol, and 1,0-decanediol;

[0025] In step (3), the organic solvent is one of N,N-dimethylformamide, ethylene glycol monomethyl ether, and dimethyl sulfoxide.

[0026] The third objective of this invention is to provide a polybutylene carbonate composite material in which an aliphatic polycarbonate-polyester copolymer ionomer (PBSC) is added to PBC and its composite material as a compatibilizer, which significantly improves the compatibility between PBC and aliphatic polyester, resulting in a PBC-based composite material with excellent comprehensive performance, which is of great significance for expanding the application range of PBC.

[0027] To achieve the above objectives, the technical solution adopted is as follows:

[0028] A polybutylene carbonate composite material includes: polybutylene carbonate, an aliphatic polybutylene carbonate modifier, and an aliphatic polyester;

[0029] The polybutylene carbonate content is 5-90% by mass.

[0030] The mass content of the aliphatic polybutylene carbonate modifier is 0.5-50%;

[0031] The aliphatic polyester has a mass content of 0-70%;

[0032] The aliphatic polybutylene carbonate modifier is the aliphatic polybutylene carbonate modifier described above or prepared using the above preparation method.

[0033] Furthermore, the aliphatic polyester is at least one of polylactic acid (PLA), polybutylene succinate (PBS), polyethylene succinate (PES), polyglycolic acid (PGA), and polybutylene adipate (PBSA).

[0034] The fourth objective of this invention is to provide a method for preparing the above-mentioned polybutylene carbonate composite material, which is a simple filler blending process.

[0035] To achieve the above objectives, the technical solution adopted is as follows:

[0036] The preparation method of the above-mentioned polybutylene carbonate composite material is as follows: after stirring and mixing polybutylene carbonate, aliphatic polybutylene carbonate modifier and aliphatic polyester, the mixture is extruded and granulated at 60-230℃ to obtain the polybutylene carbonate composite material.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] 1. In the technical solution of the present invention, the aliphatic polycarbonate-polyester copolymer ionic polymer is synthesized by melt polycondensation, which has the advantages of simple process and easy structure control.

[0039] 2. In the technical solution of the present invention, PBSC is used as a compatibilizer. The PBC segments and aliphatic polyester segments in the PBSC structure can generate strong interfacial adhesion with the PBC and aliphatic polyester in the matrix, respectively. The sulfonate groups present in the segments can generate strong interactions with the matrix through hydrogen bonding, which significantly improves the compatibility between PBC and aliphatic polyester, and obtains a PBC-based composite material with excellent comprehensive performance.

[0040] 3. In the technical solution of the present invention, PBSC is used as a compatibilizer for PBC and aliphatic polyester to prepare high-performance PBC-based composite materials. The comprehensive performance of PBC-based composite materials can be significantly improved through a simple filling and blending process without affecting the degradation performance of the composite materials. It has the advantages of simple process and good modification effect. Attached Figure Description

[0041] Figure 1 The PBSC-X synthesized in Example 61 H-NMR;

[0042] Figure 2 DSC curves of PBC / PBS composite materials were obtained for comparative examples 1, 2, 3 and example 6. Detailed Implementation

[0043] To further illustrate the polybutylene carbonate modifier, polybutylene carbonate composite material, and their preparation method according to the present invention, and to achieve the intended purpose of the invention, the following, in conjunction with preferred embodiments, details the specific implementation methods, structures, features, and effects of the polybutylene carbonate modifier, polybutylene carbonate composite material, and their preparation method proposed according to the present invention. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0044] The following will provide a more detailed description of the polybutylene carbonate modifier, polybutylene carbonate composite material, and their preparation method according to specific embodiments of the present invention:

[0045] In view of the shortcomings of existing PBC and aliphatic polyester blend systems, namely poor compatibility and poor overall performance, this invention proposes a polybutylene carbonate modifier, a polybutylene carbonate composite material, and a method for preparing the same. To address the problems of poor compatibility and overall performance between PBC and aliphatic polyester, this invention adds the aliphatic polyester ionomer PBSC to the blend of PBC and aliphatic biodegradable polyester to enhance the interfacial adhesion and interaction between PBC and aliphatic polyester, thereby improving the compatibility of the composite material and obtaining a series of biodegradable PBC-based composite materials with excellent overall performance.

[0046] This invention relates to the field of biodegradable polymer materials, specifically to a biodegradable polybutylene carbonate (PBC) composite material and its preparation method. The composite material consists of PBC, an aliphatic polyester-polycarbonate copolymer ionomer, and other biodegradable polyesters. The polyester-polycarbonate copolymer ionomer is prepared by melt polycondensation and accounts for 0.5-50 wt% of the total mass of the composite material. The composite material is prepared by twin-screw extrusion granulation. The addition of the ionomer improves the compatibility of PBC with other biodegradable polyester materials, resulting in a series of composite materials with excellent comprehensive properties. The specific technical solution of this invention is as follows:

[0047] A polybutylene carbonate modifier is an aliphatic polyester-polycarbonate copolymer ionomer.

[0048] Preferably, the polybutylene carbonate modifier has the following structural formula:

[0049]

[0050] In the formula, R is an alkyl or cyclic alkyl group with 2-10 carbon atoms, and m and n are the degrees of polymerization.

[0051] In the above technical solution, the PBC segment and aliphatic polyester segment in the PBSC modifier structure can generate strong interfacial adhesion with PBC and aliphatic polyester in the matrix, respectively. The sulfonate group present in the segment can generate strong interaction with the matrix through hydrogen bonding, which significantly improves the compatibility between PBC and aliphatic polyester.

[0052] The above-mentioned method for preparing polybutylene carbonate modifier is a melt polycondensation method, which includes the following steps:

[0053] (1) 1,4-Butanediol and organic carbonate are reacted at 70-200℃ under catalyst 1 and N2 atmosphere for 0.5-6h to obtain polycarbonate prepolymer;

[0054] Dimethyl fumarate and aliphatic diol are reacted in catalyst 2, N2 atmosphere, 150-200℃ for 1-8h to obtain polyfumarate diol prepolymer.

[0055] (2) The polyfumarate prepolymer and polycarbonate prepolymer are subjected to polycondensation reaction for 1-10 h under the conditions of catalyst 3, below 200 Pa and 200-230 °C to obtain an aliphatic polyester-polycarbonate copolymer with double bonds.

[0056] (3) After dissolving the aliphatic polyester-polycarbonate copolymer in an organic solvent, sodium bisulfite is added and reacted at 100-130℃ for 7-24h to obtain an aliphatic polyester-polycarbonate copolymer ionomer, namely the polybutylene carbonate modifier.

[0057] Preferably, the molar ratio of 1,4-butanediol to organic carbonate is 0.5-5:1;

[0058] The molar ratio of the aliphatic diol to dimethyl fumarate is 1-4:1;

[0059] The mass ratio of carbonate to ester segments in the polybutylene carbonate modifier is 1-5:5-1.

[0060] Preferably, catalyst 1, catalyst 2, and catalyst 3 are at least one of sodium methoxide, sodium hydroxide, sodium acetate, potassium hydroxide, antimony acetate, potassium bicarbonate, sodium ethoxide, antimony glycolate, sodium acetylacetonate, zinc acetate, magnesium oxide, zirconium dichlorocerocene, zinc nitrate, magnesium acetate, tetrabutyl titanate, dibutyltin dilaurate, zirconium chloride, calcium acetate, barium acetate, zinc chloride, tetraisopropyl titanate, potassium carbonate, manganese acetate, basic magnesium carbonate, potassium acetate, tetraethyl titanate, stannous chloride, stannous octoate, 4-dimethylaminopyridine, and antimony oxide.

[0061] Preferably, in step (1), the organic carbonate is one of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate;

[0062] The aliphatic diol is one of the following: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,4-cyclohexanediol, 1,8-octanediol, 3,6-octanediol, and 1,0-decanediol;

[0063] In step (3), the organic solvent is one of N,N-dimethylformamide, ethylene glycol monomethyl ether, and dimethyl sulfoxide.

[0064] A polybutylene carbonate composite material includes: polybutylene carbonate, an aliphatic polybutylene carbonate modifier, and an aliphatic polyester;

[0065] The polybutylene carbonate content is 5-90% by mass.

[0066] The mass content of the aliphatic polybutylene carbonate modifier is 0.5-50%;

[0067] The aliphatic polyester has a mass content of 0-70%;

[0068] The aliphatic polybutylene carbonate modifier is the aliphatic polybutylene carbonate modifier described above or prepared using the above preparation method.

[0069] Preferably, the aliphatic polyester is at least one selected from polylactic acid, polybutylene succinate, polyethylene succinate, polyglycolic acid, and polybutylene adipate.

[0070] The preparation method of the above-mentioned polybutylene carbonate composite material is as follows: after stirring and mixing polybutylene carbonate, aliphatic polybutylene carbonate modifier and aliphatic polyester, the mixture is extruded and granulated at 60-230℃ to obtain the polybutylene carbonate composite material.

[0071] The mechanical properties of composite materials were tested according to GB / T 1040.2-2022 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics".

[0072] Thermal performance testing (DSC) of composite materials was performed in accordance with the Journal of Polymer Science, 53(2022)1041.

[0073] In the embodiments, "parts" refers to "parts by weight".

[0074] Example 1.

[0075] The specific steps are as follows:

[0076] (1) Preparation of PBSC ionomer

[0077] ① Add 1,4-butanediol and organic carbonate to the reactor, stir until homogeneous, and then add the catalyst. React at N2 atmosphere and 70-200℃ for 0.5-6 h to obtain polybutylene carbonate (PBC) prepolymer.

[0078] The molar ratio of 1,4-butanediol to organic carbonate is 0.5-5:1.

[0079] Organic carbonates are one of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate.

[0080] ② Dimethyl fumarate and aliphatic diols are added to the reactor and stirred until homogeneous, then the catalyst is added. The reaction is carried out under N2 atmosphere and at 150-200℃ for 1-8 hours to obtain polybutylene fumarate (PBF) prepolymer.

[0081] The molar ratio of aliphatic diols to dimethyl fumarate is 1-4:1.

[0082] Aliphatic diols are one of the following: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,4-cyclohexanediol, 1,8-octanediol, 3,6-octanediol, and 1,0-decanediol.

[0083] ③ Add PBC, PBF prepolymer and catalyst to the polymerization reactor, reduce the pressure of the reaction system to below 200Pa, and perform polycondensation reaction at 200-230℃ for 1-10h to obtain poly(butylene carbonate-co-butylene fumarate) (PBCF).

[0084] In steps ①-③, the catalyst is at least one of the following: sodium methoxide, sodium hydroxide, sodium acetate, potassium hydroxide, antimony acetate, potassium bicarbonate, sodium ethoxide, antimony glycolate, sodium acetylacetonate, zinc acetate, magnesium oxide, zirconium dichlorocerocene, zinc nitrate, magnesium acetate, tetrabutyl titanate, dibutyltin dilaurate, zirconium chloride, calcium acetate, barium acetate, zinc chloride, tetraisopropyl titanate, potassium carbonate, manganese acetate, basic magnesium carbonate, potassium acetate, tetraethyl titanate, stannous chloride, octoate, 4-dimethylaminopyridine, and antimony oxide.

[0085] ④ After dissolving the obtained PBCF in an organic solvent, a certain amount of sodium bisulfite is added, and the mixture is reacted at 100-130℃ for 7-24 hours to obtain an aliphatic polyester-polycarbonate copolymer (PBSC), namely the polybutylene carbonate modifier, whose structural formula is as follows:

[0086]

[0087] In the formula, R is an alkyl or cyclic alkyl group with 2-10 carbon atoms, and m and n are the degrees of polymerization.

[0088] The mass ratio of carbonate to ester segments in this polybutylene carbonate modifier is 1-5:5-1.

[0089] (2) Preparation of PBC / PBS composite material

[0090] Polybutylene carbonate, aliphatic polybutylene carbonate modifier, and aliphatic polyester are placed in a high-speed mixer and stirred rapidly for 5-10 minutes until uniformly mixed. The mixture is then extruded and granulated using a twin-screw extruder at 60-230℃ to obtain the PBC / PBS composite material.

[0091] The mass content of polybutylene carbonate is 5-90%;

[0092] The mass content of the aliphatic polybutylene carbonate modifier is 0.5-50%;

[0093] The mass content of aliphatic polyester is 0-70%;

[0094] The aliphatic polyester is at least one of polylactic acid, polybutylene succinate, polyethylene succinate, polyglycolic acid, and polybutylene adipate.

[0095] Example 2: PBC / PBS composite material

[0096] (1) Preparation of PBSC ionomer

[0097] ① Add 1,4-butanediol and dimethyl carbonate in a molar ratio of 1:2 to a reactor, stir until homogeneous, and then add tetrabutyl titanate catalyst, with the catalyst accounting for 1% of the mass of the reactants. React at 80℃ for 1 hour under N2 atmosphere, and then slowly raise the temperature to 200℃ over 3 hours, continuing the reaction for another hour to obtain polybutylene carbonate (PBC) prepolymer.

[0098] ② Add 1,4-butanediol and dimethyl fumarate in a molar ratio of 1:1 to the reactor, stir until homogeneous, and then add antimony acetate catalyst, with the catalyst accounting for 0.5% of the mass of the reactants. React at 160℃ for 4 hours under N2 atmosphere to obtain polybutylene fumarate (PBF) prepolymer.

[0099] ③ Add two prepolymers, PBC and PBF, and antimony oxide catalyst in a mass ratio of 1:1 to the polymerization reactor, wherein the catalyst accounts for 0.5% of the total mass of the reactants. Reduce the pressure of the reaction system to below 200 Pa and perform polycondensation reaction at 210℃ for 3 hours to obtain poly(butylene carbonate-co-butylene fumarate) (PBCF).

[0100] ④ Dissolve the obtained PBCF in ethylene glycol monomethyl ether, add 10% NaHSO3, and react at 120℃ for 24h to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0101] (2) Preparation of PBC / PBS composite material

[0102] 60 parts of PBC, 35 parts of PBS and 5 parts of ion-based polymer were placed in a mixer and stirred for 5 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 160°C to obtain the PBC / PBS composite material.

[0103] Example 3: PBC / PES composite material

[0104] (1) Preparation of PBSC ionomer

[0105] ① Add 1,4-butanediol and diphenyl carbonate in a molar ratio of 1.5:1 to a reactor, stir until homogeneous, and then add magnesium acetate catalyst, with the catalyst accounting for 1% of the mass of the reactants. React at 80℃ for 1 hour under N2 atmosphere, then slowly raise the temperature to 200℃ over 3 hours and continue the reaction for 1 hour to obtain polybutylene carbonate (PBC) prepolymer.

[0106] ② Ethylene glycol and dimethyl fumarate in a molar ratio of 2:1 were added to the reactor and stirred until homogeneous. Then, antimony acetate catalyst was added, with the catalyst accounting for 1% of the mass of the reactants. The reaction was carried out at 120°C for 1 hour under a N2 atmosphere. The temperature was then slowly increased to 180°C over 3 hours, and the reaction was continued for another hour to obtain polyethylene fumarate (PGF) prepolymer.

[0107] ③ Add two prepolymers, PBC and PGF, and antimony oxide catalyst in a mass ratio of 4:1 to the polymerization reactor, wherein the catalyst accounts for 1.5% of the total mass of the reactants. Reduce the pressure of the reaction system to below 200 Pa and perform polycondensation reaction at 210℃ for 3 hours to obtain poly(butylene carbonate-co-fumarate) (PBGF).

[0108] ④ Dissolve the obtained PBGF in ethylene glycol monomethyl ether, add 10% NaHSO3, and react at 120℃ for 24h to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0109] (2) Preparation of PBC / PES composite material

[0110] 50 parts of PBC, 47 parts of PES, and 3 parts of ion-based polymer were placed in a mixer and stirred for 6 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 135°C to obtain the PBC / PES composite material.

[0111] Example 4: PBC / PGA composite material

[0112] (1) Preparation of PBSC ionomer

[0113] ① Add 1,4-butanediol and dimethyl carbonate in a molar ratio of 1:1.5 to a reactor, stir until homogeneous, and then add sodium acetylacetonate catalyst, with the catalyst accounting for 1% of the mass of the reactants. React at 80℃ for 1 hour under N2 atmosphere, then slowly raise the temperature to 200℃ over 3 hours and continue the reaction for 1 hour to obtain polybutylene carbonate (PBC) prepolymer.

[0114] ② Add 1,6-hexanediol and dimethyl fumarate in a molar ratio of 1.5:1 to the reactor, stir until homogeneous, and then add antimony acetate catalyst, with the catalyst accounting for 1% of the mass of the reactants. React at 120℃ for 1.0 h under N2 atmosphere, then slowly raise the temperature to 200℃ over 2.0 h and continue the reaction for another 1.0 h to obtain polyhexanediol fumarate (PHF) prepolymer.

[0115] ③ Add two prepolymers, PBC and PHF, and antimony oxide catalyst in a mass ratio of 1:3 to the polymerization reactor, wherein the catalyst accounts for 0.5% of the total mass of the reactants. Reduce the pressure of the reaction system to below 200 Pa and perform polycondensation reaction at 210℃ for 3 hours to obtain poly(butylene carbonate-co-hexanediol fumarate) (PBHF).

[0116] ④ Dissolve the obtained PBHF in dimethyl sulfoxide, add 10% NaHSO3, and react at 120℃ for 24h to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0117] (2) Preparation of PBC / PGA composite material

[0118] 60 parts of PBC, 30 parts of PGA and 10 parts of ion-based polymer were placed in a mixer and stirred for 5 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 210°C to obtain the PBC / PGA composite material.

[0119] Example 5: PBC / PLA composite material

[0120] (1) Preparation of ionomers

[0121] ① Add 1,4-butanediol and dimethyl carbonate in a molar ratio of 1:2 to the transesterification reactor, stir evenly, and then add potassium acetate catalyst, with the catalyst accounting for 0.5% of the mass of the reactants.

[0122] After reacting at 80°C under N2 atmosphere and normal pressure for 1 hour, the temperature was slowly increased to 200°C over 3 hours, and the reaction was continued for another hour to obtain polybutylene carbonate (PBC) prepolymer.

[0123] ② 1,3-propanediol and dimethyl fumarate in a molar ratio of 2.5:1 were added to the transesterification reactor, mixed and stirred until homogeneous, and then zinc acetate catalyst was added, with the catalyst accounting for 2.0% of the mass of the reactants. The reaction was carried out at 150℃ for 2 hours under a N2 atmosphere, and then the temperature was slowly increased to 180℃ over 3 hours, and the reaction was continued for 1 hour to obtain polypropylene fumarate (PPF) prepolymer.

[0124] ③ Add PBC and PPF prepolymers in a mass ratio of 2:1 and manganese acetate to the polymerization reactor, wherein the manganese acetate catalyst accounts for 1.0% of the total mass of the reactants. Reduce the pressure of the reaction system to below 200 Pa and perform polycondensation reaction at 210℃ for 3 hours to obtain poly(butylene carbonate-co-propylene fumarate) (PBPF).

[0125] ④ Dissolve the obtained PBPF in N,N-dimethylformamide, add 10% NaHSO3, and react at 120℃ for 24h to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0126] (2) Preparation of PBC / PLA composite material

[0127] 30 parts of PBC, 60 parts of PLA and 10 parts of ion-based polymer were put into a mixer and stirred for 10 minutes. The mixture was then extruded and granulated at 180°C using a twin-screw extruder to obtain the PBC / PLA composite material.

[0128] Example 6: PBC / PBS composite material

[0129] (1) Preparation of ionomers

[0130] ① Add 1,4-butanediol and dimethyl carbonate in a molar ratio of 3:1 to a transesterification reactor and stir until homogeneous. After homogeneity, add barium acetate catalyst, with the catalyst accounting for 0.7% of the mass of the reactants. React at 80°C under a nitrogen atmosphere for 2 hours, then slowly raise the temperature to 210°C over 3 hours and continue the reaction for 1 hour to obtain polybutylene carbonate (PBC) prepolymer.

[0131] ② Add 1,4-butanediol and dimethyl fumarate and basic magnesium carbonate catalyst in a molar ratio of 2:1 to a reaction flask. The catalyst accounts for 1.0% of the mass of the reactants. React at 150°C under a nitrogen atmosphere for 2 hours. Slowly raise the temperature to 180°C within 3 hours and continue the reaction for 1 hour to obtain polyhexyl fumarate (PBF) prepolymer.

[0132] ③ The two prepolymers mentioned above are mixed in different mass ratios, and then sodium acetate is added as a catalyst. The polycondensation reaction is carried out at 210°C for 3 hours under a pressure of less than 200 Pa to obtain poly(butylene carbonate-co-butylene fumarate) (PBCF-X, where X is the mass ratio of polybutylene fumarate segments to block copolymers) block copolymers.

[0133] ④ Dissolve 5g of PBCF in 20ml of dimethyl sulfoxide, add 20ml of 10% NaSO3 for sulfonation, and react at 120℃ for 24h. This yields an aliphatic polycarbonate ionomer (PBSC-X).

[0134] (2) Preparation of PBC / PBS composite material

[0135] 70 parts of PBC, 25 parts of PBS and 5 parts of ion-based polymer were placed in a mixer and stirred for 8 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 140°C to obtain the PBC / PBS composite material.

[0136] Figure 1 The PBSC-X synthesized in Example 6 1 H-NMR confirmed the formation of this structure.

[0137] Example 7. PBC composite material

[0138] (1) Preparation of ionomers

[0139] ① Add 1,4-butanediol and dibutyl carbonate in a molar ratio of 5:1 to the transesterification reactor, stir evenly, and then add potassium hydroxide catalyst, with the catalyst accounting for 0.5% of the mass of the reactants.

[0140] After reacting at 70°C under N2 atmosphere and normal pressure for 1 hour, the temperature was slowly increased to 200°C over 4 hours, and the reaction was continued for another hour to obtain polybutylene carbonate (PBC) prepolymer.

[0141] ② Add 1,4-pentanediol and dimethyl fumarate in a molar ratio of 4:1 to the transesterification reactor, mix and stir evenly, then add potassium bicarbonate catalyst, with the catalyst accounting for 1.5% of the mass of the reactants. React at 150℃ for 2 hours under N2 atmosphere, then slowly raise the temperature to 200℃ within 4 hours and continue the reaction for 2 hours to obtain polypropylene fumarate (PPF) prepolymer.

[0142] ③ Add PBC and PPF prepolymers in a mass ratio of 3:1 and manganese acetate to the polymerization reactor, wherein the manganese acetate catalyst accounts for 1.5% of the total mass of the reactants. Reduce the pressure of the reaction system to below 100 Pa and perform polycondensation reaction at 200℃ for 10 h to obtain poly(butylene carbonate-co-propylene fumarate) (PBPF).

[0143] ④ Dissolve the obtained PBPF in N,N-dimethylformamide, add 10% NaHSO3, and react at 130℃ for 7 hours to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0144] (2) Preparation of PBC composite material

[0145] 90 parts of PBC and 10 parts of ion-based polymer were placed in a mixer and stirred for 10 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 230°C to obtain the PBC composite material.

[0146] Example 8. PBC / PLA composite material

[0147] (1) Preparation of ionomers

[0148] ① Add 1,4-butanediol and diethyl carbonate in a molar ratio of 1:2 to the transesterification reactor, stir evenly, and then add sodium ethoxide catalyst, with the catalyst accounting for 1.0% of the mass of the reactants.

[0149] After reacting at 80°C under N2 atmosphere and normal pressure for 1 hour, the temperature was slowly increased to 180°C over 2.5 hours, and the reaction was continued for another hour to obtain polybutylene carbonate (PBC) prepolymer.

[0150] ② Add 1,5-pentanediol and dimethyl fumarate in a molar ratio of 3.0:1 to the transesterification reactor, mix thoroughly, and then add zinc chloride catalyst, with the catalyst accounting for 1.5% of the mass of the reactants. React at 150℃ for 2 hours under a N2 atmosphere, then slowly raise the temperature to 160℃ over 3 hours and continue the reaction for 1 hour to obtain polypropylene fumarate (PPF) prepolymer.

[0151] ③ Add PBC and PPF prepolymers in a mass ratio of 2:1 and manganese acetate to the polymerization reactor, wherein the zinc nitrate catalyst accounts for 1.0% of the total mass of the reactants. Reduce the pressure of the reaction system to below 150 Pa and perform polycondensation reaction at 230℃ for 1 hour to obtain poly(butylene carbonate-co-propylene fumarate) (PBPF).

[0152] ④ Dissolve the obtained PBPF in N,N-dimethylformamide, add 10% NaHSO3, and react at 100℃ for 22h to obtain aliphatic polycarbonate ion-based polymer (PBSC).

[0153] (2) Preparation of PBC / PBSA composite material

[0154] Five parts of PBC, 45 parts of PBSA, and 50 parts of ion-based polymer were placed in a mixer and stirred for 10 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 60°C to obtain the PBC / PBSA composite material.

[0155] Example 9. PBC / PBSA composite material

[0156] 29.5 parts of PBC, 70 parts of PBSA, and 0.5 parts of ion-based polymer from Example 8 were placed in a mixer and stirred for 10 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 60°C to obtain the PBC / PBSA composite material.

[0157] Experimental test:

[0158] Comparative Example 1: Referring to RSC Advances, 5(2015)87311, PBC polymers were synthesized by transesterification polycondensation, and their mechanical properties and T were tested. m value.

[0159] Comparative Example 2: Testing commercial PBS, including its mechanical properties and T0. m value.

[0160] Comparative Example 3: 70 parts of PBC and 30 parts of PBS were added to a mixer and stirred for 8 minutes. The mixture was then extruded and granulated using a twin-screw extruder at 140°C to obtain a PBC / PBS composite material.

[0161] (1) The products of Examples 2-6 and Comparative Examples 1-3 were subjected to performance tests, and the results are shown in Table 1.

[0162] Table 1 Mechanical properties and melting point of PBC / composite materials

[0163] Example 2 32 564 89 Example 3 42 631 85 Example 4 52 197 122 Example 5 39 299 101 Example 6 35 497 97 Comparative Example 1 28 686 59 Comparative Example 2 42 152 115 Comparative Example 3 30 360 59、113

[0164] Comparing Example 6 and Comparative Example 3 in Table 1, it can be found that the tensile strength and elongation at break of the PBC / PBS composite materials obtained after adding ionomers in Examples 2 and 6 are significantly improved compared with those in Comparative Example 3. This is because the ion-dipole interaction between the PBSC ionomer and the composite material increases the interfacial adhesion of the material and improves the compatibility of the material.

[0165] (2) Measure the DSC curves of Comparative Examples 1, 2, 3 and Example 6.

[0166] Figure 2 The figures show the DSC curves for Comparative Examples 1, 2, 3, and Example 6. As can be seen from the figures, the composite material without PBSC exhibits two melting points, located near the respective melting points of each material, indicating that PBC and PBS are completely incompatible without PBSC. With the addition of PBSC, the composite material shows a single melting point, situated between the melting points of PBC and PBS, demonstrating complete material compatibility. This proves that the addition of the ionomer PBSC makes the composite material completely compatible. Using this technique, the application performance of PBC-based composite materials can be precisely controlled by altering the structure of PBSC, the concentration of sulfonate groups, and the type and content of aliphatic polyesters.

[0167] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A polybutylene carbonate modifier, characterized in that, The polybutylene carbonate modifier is an aliphatic polyester-polycarbonate copolymer ionomer; The structural formula of the polybutylene carbonate modifier is as follows: ； In the formula, R is a divalent alkyl group or a divalent cyclic alkyl group with 2-10 carbon atoms, and m and n are the degrees of polymerization.

2. The method for preparing the polybutylene carbonate modifier according to claim 1, characterized in that, The preparation method is a melt polycondensation method, which includes the following steps: (1) 1,4-Butanediol and organic carbonate are reacted at 70-200℃ under catalyst 1 and N2 atmosphere for 0.5-6h to obtain polybutylene carbonate prepolymer; Dimethyl fumarate and aliphatic diol are reacted in catalyst 2, N2 atmosphere, 150-200℃ for 1-8h to obtain polyfumarate diol prepolymer. (2) The polyfuric acid glycol ester prepolymer and polybutylene carbonate prepolymer are subjected to polycondensation reaction under the conditions of catalyst 3, below 200 Pa, and 200-230℃ for 1-10h to obtain an aliphatic polyester-polycarbonate copolymer with double bonds. (3) After dissolving the aliphatic polyester-polycarbonate copolymer in an organic solvent, sodium bisulfite is added and reacted at 100-130℃ for 7-24h to obtain an aliphatic polyester-polycarbonate copolymer ionomer, namely the polybutylene carbonate modifier.

3. The preparation method according to claim 2, characterized in that, The molar ratio of 1,4-butanediol to organic carbonate is 0.5-5:1; The molar ratio of the aliphatic diol to dimethyl fumarate is 1-4:1; The mass ratio of carbonate to ester segments in the polybutylene carbonate modifier is 1-5:5-1.

4. The preparation method according to claim 2, characterized in that, Catalyst 1, Catalyst 2, and Catalyst 3 are respectively at least one of sodium methoxide, sodium hydroxide, sodium acetate, potassium hydroxide, antimony acetate, potassium bicarbonate, sodium ethoxide, antimony glycolate, sodium acetylacetonate, zinc acetate, magnesium oxide, zirconium dichlorocerocene, zinc nitrate, magnesium acetate, tetrabutyl titanate, dibutyltin dilaurate, zirconium chloride, calcium acetate, barium acetate, zinc chloride, tetraisopropyl titanate, potassium carbonate, manganese acetate, basic magnesium carbonate, potassium acetate, tetraethyl titanate, tin chloride, stannous octoate, 4-dimethylaminopyridine, and antimony oxide.

5. The preparation method according to claim 2, characterized in that, In step (1), the organic carbonate is one of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate. The aliphatic diol is one of the following: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,4-cyclohexanediol, 1,8-octanediol, 3,6-octanediol, and 1,10-decanediol; In step (3), the organic solvent is one of N,N-dimethylformamide, ethylene glycol monomethyl ether, and dimethyl sulfoxide.

6. A polybutylene carbonate composite material, characterized in that, include: Polybutylene carbonate, aliphatic polybutylene carbonate modifiers, and aliphatic polyesters; The polybutylene carbonate content is 5-90% by mass. The mass content of the aliphatic polybutylene carbonate modifier is 0.5-50%; The aliphatic polyester content is 0-70% by mass, excluding 0. The aliphatic polybutylene carbonate modifier is the polybutylene carbonate modifier according to claim 1 or the polybutylene carbonate modifier prepared by any one of claims 2-5.

7. The polybutylene carbonate composite material according to claim 6, characterized in that, The aliphatic polyester is at least one of polylactic acid, polybutylene succinate, polyethylene succinate, polyglycolic acid, and polybutylene adipate.

8. The method for preparing the polybutylene carbonate composite material according to any one of claims 6-7, characterized in that, The preparation method is as follows: polybutylene carbonate, aliphatic polybutylene carbonate modifier and aliphatic polyester are stirred and mixed, and then extruded and granulated at 60-230℃ to obtain the polybutylene carbonate composite material.

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