CN113072691A - Polycarbonate cyclohexene ester copolymer and preparation method thereof - Google Patents
Polycarbonate cyclohexene ester copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polycarbonate cyclohexene ester copolymer and a preparation method thereof, wherein the polycarbonate cyclohexene ester copolymer is B- (AB) consisting of an A chain segment and a B chain segmentnA block copolymer of the type wherein n ═ 1, 3 or 5; the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment; the B chain segment is formed by taking biodegradable aliphatic polyester C with active tail ends at two sides (hydroxyl groups at two sides or carboxyl groups at two sides) as a macromolecular chain transfer agent through copolymerization reaction of carbon dioxide and 1, 2-epoxy cyclohexane; the preparation method adopts a block polymerization mode of adding the macromolecular chain transfer agent K times to synthesize the B chain segment, and the polycarbonate cyclohexene ester copolymer is obtained. The invention effectively solves the problem that the toughness of the polycarbonate cyclohexene ester is improved and the thermal performance of the material is deteriorated in the prior art.
Description
Technical Field
The invention belongs to the technical field of biodegradable high polymer materials, and relates to a polycarbonate cyclohexene ester copolymer and a preparation method thereof.
Background
Carbon dioxide (CO)2) Is a main greenhouse gas and is also a cheap and clean carbon-oxygen resource, and the carbon-oxygen resource is collected, purified and utilized, thereby changing waste into valuable. Among the various utilization approaches, the conversion and fixation of carbon dioxide into high molecular materials has become an important research direction, wherein the ring-opening copolymerization reaction of carbon dioxide and epoxide is particularly attractive, and the polycarbonate polymer prepared by the reaction is a chemical with important economic value, has excellent biodegradability, good transparency, high barrier property and biocompatibility, and is widely applied in the fields of degradable packaging bags, biodegradable agricultural mulching films, carbon dioxide-based polyurethane intermediates and the like. The copolymerization reaction of carbon dioxide and propylene oxide is the focus of most attention in the field, the Prepared Polypropylene Carbonate (PPC) achieves industrial yield and application at the earliest time, but the polypropylene carbonate molecules are in an amorphous state and have weak intermolecular interaction force, so that the thermal property and the mechanical property of the PPC are poor, and particularly the glass transition temperature (T) of the PPC is lowg) The temperature is only 30-50 ℃, and the practical application of the high-temperature-resistant glass fiber reinforced plastic is severely limited in a high-temperature environment. In sharp contrast, based on CO2The polycarbonate cyclohexene ester (PCHC) prepared by copolymerization with cyclohexene oxide (CHO) has good thermal property (T)g>100 ℃) and mechanical property, therefore, the carbon dioxide-based polymer is the first choice material for expanding the class of high-temperature use environment, but has the defect of brittle material, and limits the processing process and the use range. Therefore, the toughening modification of the polycyclohexene carbonate by a chemical method has important scientific value and practical significance.
Block copolymerization is an important method for improving the properties of polymers. At present, it has been reported that polyether such as polyethylene glycol, polypropylene glycol, etc. is bonded to a polycarbonate segment as an initiator, and for example, it has been reported in the known art that an amphiphilic block polymer is prepared by introducing polyethylene glycol into an aliphatic polycarbonate chain. The method generally introduces some soft segment structures, and although the soft segment structures can obviously improve the toughness of the PCHC material, the introduction of the soft segment also destroys the tensile strength and modulus of the PCHC, and more importantly, leads to glass transitionVariable temperature TgA significant drop occurs; that is, the results of the toughening modification are established with the significant loss of thermal properties, the T of the prior art toughening modified PCHCgThe performance is difficult to maintain to be more than 75 ℃, the temperature of the general material with better toughness can be reduced to 40-60 ℃, and the T is optimized along with the toughnessgThe lower; the modified PCHC cannot be applied to a high-temperature use environment, and the advantage of the PCHC as a preferred degradable material in the high-temperature environment is lost.
Therefore, under the condition of keeping the high glass transition temperature of the polycyclohexene carbonate, the method has very important significance for greatly improving the toughness of the material.
Disclosure of Invention
The invention aims to solve the problem that the toughness of the polycyclohexene carbonate is improved and the thermal property of a material is deteriorated in the prior art, and provides a polycyclohexene carbonate copolymer and a preparation method thereof.
It is an object of the present invention to provide a polycyclohexene carbonate copolymer having a biodegradable polyester segment A in the molecular main chain.
The invention also aims to provide a preparation method of the polycarbonate cyclohexene ester copolymer, which adopts biodegradable aliphatic polyester C with active ends at two sides (hydroxyl groups at two sides or carboxyl groups at two sides) as a macromolecular chain transfer agent, and introduces a biodegradable polyester chain segment A onto a polycarbonate cyclohexene ester molecular chain in a block copolymerization mode.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polycarbonate cyclohexenyl ester copolymer is B- (AB) composed of A chain segment and B chain segmentnBlock copolymers of the type wherein n is 1, 3 or 5;
the A chain segment is a biodegradable aliphatic polyester chain segment, the B chain segment is a polycarbonate cyclohexene ester chain segment, and the A chain segment is connected with the B chain segment through ether bonds or ester bonds.
B- (AB)nThe block copolymer is prepared by introducing biodegradable aliphatic polyester A segment with A, ABABA or ABABABABABABA as middle segment and B as end segmentThe purpose is to be incorporated as a soft segment into the B polymer segment. The obtained novel copolymer shows excellent toughness, because the flexibility of the fatty chain effectively improves the toughness of the material, so that the material has good performance in breaking elongation and impact strength; tests show that when the B chain segment is used as the end group at two sides and the A chain segment is used as the end group or the A chain segment and the B chain segment are simultaneously used as the end group, the obtained polymer can better keep the thermal property of the polycarbonate cyclohexene ester copolymer, the negative influence of the reduction of the glass transition temperature of the material caused by introducing the A chain segment is smaller, the problem of obvious thermal property reduction while the toughness is improved is effectively avoided, this is because when the aliphatic polyester segment serves as the intermediate segment, a "sandwich-like hard-to-soft structure" is formed, when the soft segment is connected in the middle, the performance of the PCHC material formed by the original hard segment structure is not greatly damaged, and because the existence of the polyester soft segment enables the polycarbonate cyclohexene ester (PCHC) to present a strong and tough mechanical structure, the rigid hard section is used as a support, and when the rigid hard section is subjected to external impact, the hard section transmits the impact force to the soft section to be absorbed; b- (AB)nThe mobility of the A chain segment (aliphatic polyester chain segment) in the block copolymer is limited by the B chain segments (PCHC chain segments) at two ends, and the high proportion of the B chain segment structure (the B chain segment in the formed final product is a high proportion of the chain segment component relative to the A chain segment) also enables the whole copolymer to keep higher glass transition temperature (more than or equal to 93 ℃).
As a preferred technical scheme:
a polycyclohexene carbonate copolymer as described in any one of the above, having a glass transition temperature (T)g) At a temperature of 93 to 105 ℃ and a decomposition temperature (T)d) 260 to 280 ℃ and an impact strength (without gaps) of 25 to 30KJ/m2The elongation at break is 15-30%, the modulus is 1600-3000 MPa, and the tensile strength is 50-70 MPa.
A polycyclohexene carbonate copolymer as described above, n is 1;
the total number average molecular weight of the polycarbonate cyclohexene ester copolymer is 35-350 kg/mol, and the molecular weight distribution index is 1.5-3.5; wherein, the ratio of the contribution of the A chain segment to the number average molecular weight to the contribution of the B chain segment to the molecular weight is 1: 1.3-14.4, and the contribution of the A chain segment to the number average molecular weight (namely the number average molecular weight of the macromolecular chain transfer agent selected in the synthesis process) is 5-25 kg/mol.
The above definition of molecular weight is for two purposes: (1) the copolymerization reaction for synthesizing the B chain segment under the condition of adding the macromolecular chain transfer agent is ensured to have good copolymerization reaction activity and selectivity; (2) the addition of the macromolecular chain transfer agent introduces a soft segment under the condition of not losing the thermal property of high glass transition temperature, thereby achieving the aim of toughening modification. When the number average molecular weight of the macromolecular chain transfer agent is less than 5kg/mol, the formed A chain segment can not obviously improve brittleness and achieve the aim of toughening, on the other hand, the biodegradable aliphatic polyester C with active ends at two sides is used as the macromolecular chain transfer agent to participate in the copolymerization reaction for synthesizing the B chain segment, the total hydroxyl value contained in the polyester C obviously influences the reactivity and the selectivity of the B copolymerization, and when the number average molecular weight of the polyester C is too low (less than 5kg/mol), the content of hydroxyl active groups under the same adding mass is too high, thus bringing adverse influence to the reaction for synthesizing the B chain segment by copolymerization; when the number average molecular weight of the polyester C is more than 25kg/mol, the molecular weight is too high, the activity of the terminal hydroxyl is reduced, the situation that the polyester C does not completely participate in copolymerization reaction can occur, and a blending product is formed; when the contribution of the chain segment B to the molecular weight is too small, the repeated unit structure of the PCHC is too small, so that the mechanical property of the block-modified PCHC is remarkably deteriorated, the strength is reduced, the brittleness is increased, and the final product has higher performance; when the contribution of the chain segment B to the molecular weight is too large, the proportion of the chain segment A is too low, and the aim of toughening modification cannot be achieved; it is preferable that the B-A-B type polycyclohexene carbonate copolymer has the best hot melt processability within a molecular weight distribution range selected from the molecular weight distributions of the above B-A-B type polycyclohexene carbonate copolymer according to the hot melt processability of the B-A-B type polycyclohexene carbonate copolymer in different molecular weight distribution states obtained at different reaction degrees in the copolymerization process.
A polycyclohexene carbonate copolymer as described above, n is 3 or 5;
the total number average molecular weight of the polycarbonate cyclohexene ester copolymer is 50-500 kg/mol, and the molecular weight distribution index is 1.5-3.5; wherein the ratio of the contribution of the A chain segment to the number average molecular weight to the contribution of the B chain segment to the molecular weight is 1: 1.3-14.4, and the contribution of the A chain segment to the number average molecular weight (namely the sum of the number average molecular weights of the selected macromolecular chain transfer agents added in each time in the synthesis process) is 15-125 kg/mol.
Similarly, for multiblock B- (AB)nPolycyclohexene carbonate copolymers of the type, the above definition of molecular weight is also for two purposes: (1) the copolymerization reaction for synthesizing the copolymer B under the condition of adding the macromolecular chain transfer agent polyester C is ensured to have good copolymerization reaction activity and selectivity; (2) the addition of the macromolecular chain transfer agent polyester C introduces a soft segment under the condition of not losing the thermal property of high glass transition temperature, thereby achieving the aim of toughening modification.
The invention also provides a method for preparing the polycyclohexene carbonate copolymer, which comprises the steps of taking carbon dioxide and 1, 2-epoxycyclohexane as reaction raw materials, and preparing the polycyclohexene carbonate copolymer by adopting a block polymerization mode of adding the macromolecular chain transfer agent for K times;
the macromolecular chain transfer agent is biodegradable aliphatic polyester C with double-side active ends;
the active ends on both sides are all hydroxyl or carboxyl;
the biodegradable aliphatic polyester C with double-side active ends as a macromolecular chain transfer agent shows good copolymerization activity with carbon dioxide and 1, 2-epoxycyclohexane in multiple experimental demonstrations, wherein the biodegradable aliphatic polyester C with double-side active ends has a structure that two sides of an A chain segment are connected with active ends (hydroxyl or carboxyl), the active ends participate in reaction as chain transfer groups, and a B chain segment is formed through copolymerization of the carbon dioxide and the 1, 2-epoxycyclohexane to obtain B- (AB)nA block copolymer of type (II);
wherein the relationship between K and n is as follows: n-2 x K-1;
in the synthesis process, B- (AB)nThe n value of the block copolymer is related to the addition frequency K of the biodegradable aliphatic polyester C with double-side active ends (hydroxyl or carboxyl) as a macromolecular chain transfer agent in the process of synthesizing the B chain segment, and the addition frequency K is too high>3) Will make the utility modelThe copolymerization reaction activity of the synthesized B chain segment is obviously reduced, even is inactivated, the selectivity is poor, and part of polyester C does not serve as an active chain transfer agent to form B- (AB)nRather, the chain structure of (a) is formed into a blended state, so that the glass transition temperature and mechanical properties of the material are greatly reduced.
As described above, the biodegradable aliphatic polyester C having active terminals at both sides (hydroxyl groups at both sides or carboxyl groups at both sides) is a degradable aliphatic polyester having active functional groups at both hydroxyl terminals, and specifically can be polybutylene terephthalate-co-adipate, polybutylene adipate, polyethylene adipate, polybutylene succinate, polybutyl acrylate, poly-DL-lactide, poly-gamma-butyrolactone, poly-beta-butyrolactone, poly-delta-valerolactone, poly-gamma-caprolactone, poly-epsilon-caprolactone, poly-delta-nonalactone, poly-epsilon-decalactone, polypropylene carbonate or polybutylene carbonate, and preferably is a polymer such as polybutylene terephthalate-co-adipate, polybutylene terephthalate, or the like, Polybutylene adipate, poly DL-lactide, poly epsilon-caprolactone or polypropylene carbonate.
As described above, when K ═ 1, the process for preparing the polycyclohexene carbonate copolymer is: in a high-pressure reaction kettle (the pressure of the high-pressure reaction kettle is the pressure after the subsequent carbon dioxide filling), a macromolecular chain transfer agent, 1, 2-epoxycyclohexane, a solvent and a catalyst are added at one time in the initial stage of the reaction, and after the carbon dioxide filling, a chain segment B is synthesized by copolymerization to obtain the polycarbonate cyclohexene ester copolymer.
As described above, when K >1, the preparation process of the polycyclohexene carbonate copolymer is as follows: adding a certain amount of macromolecular chain transfer agent, 1, 2-epoxycyclohexane, solvent and catalyst into a high-pressure reaction kettle at the initial stage of reaction, filling carbon dioxide, and copolymerizing to form a B chain segment to form a B-A-B type prepolymer; then, continuously adding a macromolecular chain transfer agent into the reaction system by K-1 times until the copolymerization reaction is completed to obtain a polycarbonate cyclohexene ester copolymer;
the amount of the macromolecular chain transfer agent added in each time is equal, and the interval time between every two adjacent times of continuously adding the macromolecular chain transfer agent into the reaction system after the B-A-B type prepolymer is formed is equal.
The method as described above, wherein the solvent is tetrahydrofuran, dichloromethane, chloroform, dioxolane, dioxane, ethyl acetate, acetone or butanone, preferably tetrahydrofuran, dichloromethane or dioxolane;
the catalyst is a heterogeneous complex catalyst or a catalytic system which is composed of a homogeneous complex as a main catalyst and a cocatalyst;
the heterogeneous complex catalyst is ZnR2More than one of a catalyst, a zinc dicarboxylate catalyst, a rare earth ternary catalyst and a double metal cyanide catalyst, preferably more than one of a zinc glutarate catalyst and a Zn-Co-DMC catalyst, wherein R is ethyl, butyl, isopropyl, cyclohexyl or phenyl; the zinc dicarboxylate catalyst is zinc succinate, zinc glutarate, zinc adipate or zinc pimelate, and the rare earth ternary catalyst is Y (P)2O4)3-Al(i-Bu)3Glycerol, Re (P)2O4)3-Al(i-Bu)3、Ln(CCl3COO)3-glycerol-ZnEt2Or Nd (CCl)3COO)3-ZnEt2-glycerol, said double metal cyanide catalyst being Zn-Co-DMC, Zn-Fe-DMC, Fe-Co-DMC or Ni-Co-DMC;
in a catalytic system consisting of a homogeneous complex serving as a main catalyst and a cocatalyst, the mass ratio of the main catalyst to the cocatalyst is 1: 0.5-10; the main catalyst is more than one of a zinc phenol catalyst, a porphyrin metal complex catalyst and a Schiff base metal complex catalyst, preferably more than one of a beta-diimine zinc complex, an aluminum porphyrin complex and a cobalt Schiff base complex, and the cocatalyst is more than one of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphine nitroamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene 4-dimethylaminopyridine and gamma-chloropropylmethyldimethoxysilane, preferably more than one of bistriphenylphosphine ammonium chloride and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene 4-dimethylaminopyridine; the zinc-phenol catalyst is a diethyl zinc/ternary phenol complex, a beta-diimine zinc complex or a prolinol zinc complex, the porphyrin metal complex catalyst is an aluminum porphyrin complex, a cobalt porphyrin complex or a chromium porphyrin complex, and the Schiff base metal complex catalyst is an aluminum Schiff base complex, a cobalt Schiff base complex or a chromium Schiff base complex;
the feeding mass ratio of the heterogeneous complex catalyst to the 1, 2-epoxycyclohexane is 1: 1000-10000, preferably 1: 2000-5000;
the mass ratio of the homogeneous complex to the 1, 2-epoxycyclohexane is 1: 2000-500000, preferably 1: 5000-300000;
the mass ratio of the total feeding amount of the macromolecular chain transfer agent to the feeding amount of the 1, 2-epoxycyclohexane is 1: 1-10;
the volume ratio of the 1, 2-epoxycyclohexane to the solvent is 1-5: 1, and the volume ratio of the 1, 2-epoxycyclohexane to the solvent is set as long as the aim of not less than 90% of the monomer conversion rate is achieved.
In the method, the pressure in the high-pressure reaction kettle after the carbon dioxide is filled (before the copolymerization reaction occurs) is 1.0-8.0 MPa, preferably 3.0-6.0 MPa, and the setting can ensure that the carbon dioxide is sufficient in the whole reaction;
the copolymerization reaction temperature is 25-150 ℃, and preferably 30-100 ℃; the copolymerization reaction time is 5-48 h, preferably 10-24 h;
the conversion rate of the 1, 2-epoxy cyclohexane in the copolymerization reaction is more than or equal to 90 percent, preferably more than or equal to 99 percent; the content of cyclocyclohexenyl carbonate by-products is < 5 wt.%, preferably < 1 wt.%; the polycarbonate cyclohexene ester copolymer has a content of carbonate units of the B segment of > 90%, preferably > 99%.
The content of carbonate units in the B segment in the polycyclohexene carbonate copolymer affects the degradability of the polymer, and when the content of carbonate units in the B segment is too low, the degradability of the copolyester is deteriorated because during polymerization, the polymer species contains polyether units formed by cyclohexene oxide, and the polyether component is a non-biodegradable component relative to the carbonate units, so that the limitation of the low content of polyether is to ensure the biodegradability of the material.
The biodegradable polycarbonate cyclohexene ester material with high glass transition temperature and better toughness is synthesized by a chemical modification mode; the invention takes a biodegradable aliphatic polyester chain segment as a soft segment to modify the molecular structure and physical characteristics of the original polycarbonate cyclohexene ester.
Biodegradable aliphatic polyester C with active ends (hydroxyl or carboxyl) at two sides is used as a macromolecular chain transfer agent to participate in copolymerization synthesis of cyclohexene polycarbonate to form a single-block or multi-block cyclohexene carbonate copolymer; the aliphatic polyester of a macromolecular chain is used as an A chain segment of a middle chain segment, so that the problem of high brittleness of the polycarbonate cyclohexene ester material is solved, and the aim of toughening modification is fulfilled; the introduction of soft segments to form block copolymers generally changes the brittleness of the material, but also deteriorates the thermal properties and lowers the glass transition temperature, because soft segments are generally flexible chains whose segment mobility at low temperatures is much higher than that of PCHC, and when incorporated into the PCHC segment, the mobility of the entire segment of the copolymer is reduced; in the invention, the type, position and quantity of the introduced soft segment are optimized, when the aliphatic polyester chain segment is used as the middle chain segment, a hard-packaging soft structure similar to a sandwich is formed, meanwhile, the soft segment does not completely destroy the material performance of the hard segment, the PCHC presents a strong and tough mechanical structure due to the existence of the polyester soft segment, the rigid hard segment is used as a support, and when external impact is applied, the hard segment transmits the impact force to the soft segment to be absorbed; b- (AB)nThe mobility of the A chain segment (aliphatic polyester chain segment) in the block copolymer is limited by the B chain segments (PCHC chain segments) at two ends, and the high proportion of the B chain segment structure also enables the whole copolymer to maintain higher glass transition temperature (more than or equal to 93 ℃).
Has the advantages that:
according to the invention, by embedding a biodegradable aliphatic polyester chain segment in a molecular chain of the polycyclohexene carbonate and controlling the embedding position and the embedding quantity of the chain segment and the unit number ratio of the aliphatic polyester chain segment to the polycyclohexene carbonate chain segment, the obtained novel copolymer shows excellent mechanical property and thermal property, especially in the aspect of improving the toughness, the improvement is obvious, and the elongation at break of the modified polymer can reach 30 percent at most;
more importantly, the invention breaks through the problem that the traditional toughening modification technology causes serious thermal performance reduction (general T)gThe glass transition temperature of the polycyclohexene carbonate copolymer is higher than 93 ℃ and can reach 105 ℃ at most, the glass transition temperature is basically close to that of unmodified PCHC, the design on a chain segment structure can be said, so that the thermal property of the material is well maintained, and the application range of the polycyclohexene carbonate in the high-temperature application field is expanded.
Drawings
FIG. 1 is a schematic view of the reaction process of the biodegradable aliphatic polyester C with active terminal of hydroxyl group at both sides participating in the copolymerization of the polycyclohexene carbonate as a macromolecular chain transfer agent;
FIG. 2 is a schematic view of the reaction process of the biodegradable aliphatic polyester C with double-sided carboxyl active terminals as macromolecular chain transfer agent participating in the copolymerization synthesis of the cyclohexene carbonate.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
According to the invention, carbon dioxide and 1, 2-epoxycyclohexane are subjected to polymerization reaction in a high-pressure reaction kettle, before the polymerization reaction is carried out, water removal and oxygen removal treatment are carried out on the high-pressure reaction kettle, the specific method comprises the steps of carrying out pressure reduction and argon replacement treatment on the high-pressure reaction kettle in a vacuum oven at the temperature of 80 ℃, repeating the operation of reducing pressure and replacing argon once per hour for three times, and then putting the high-pressure reaction kettle into a glove box.
In the invention, the reaction process of the biodegradable aliphatic polyester C with the active terminals of hydroxyl groups at both sides, which is a macromolecular chain transfer agent, participating in the copolymerization synthesis of the cyclohexene carbonate is shown in figure 1, and the reaction process of the biodegradable aliphatic polyester C with the active terminals of carboxyl groups at both sides, which is a macromolecular chain transfer agent, participating in the copolymerization synthesis of the cyclohexene carbonate is shown in figure 2.
In the invention, the contribution of the A chain segment to the number average molecular weight means that biodegradable aliphatic polyester C with active ends at both sides is used as a macromolecular chain transfer agent and CO in the synthesis of the polycyclohexene carbonate copolymer2Copolymerization of 1, 2-epoxycyclohexane, reaction of the two active ends of polyester C, and CO at the end2Polymerizing with 1, 2-epoxycyclohexane to generate a B chain segment (PCHC chain segment), wherein the A chain segment (biodegradable aliphatic polyester chain segment) is connected with the B chain segment (PCHC chain segment) through ester bonds or ether bonds, and the contribution of the A chain segment to the number average molecular weight reflects the whole B- (AB) when the active end of the polyester C is converted into the A chain segment after reactionnThe number average molecular weight of the product of the synthesis of the polycyclohexene carbonate copolymer, the contribution of the A segment to the molecular weight, is equal to the sum of the number average molecular weights of the polyesters C added each time. The contribution of the A segment to the number average molecular weight is B- (AB)nIn the polycarbonate cyclohexene copolymer, the molecular chain of the A chain segment and the B chain segment accounts for the specific level.
The performance test method comprises the following steps:
1. glass transition temperature (T)g): using ISO 11357-1:2016&ISO 11357-2:2020 determines the glass transition temperature of a material; the testing condition is that the temperature rise rate is 10 ℃/min, the temperature rises from 25 ℃ to 150 ℃, the temperature is balanced for 2min at 150 ℃, the temperature is reduced to 25 ℃ at the temperature reduction rate of 10 ℃/min, the temperature is raised to 150 ℃ for the second time at the temperature rise rate of 10 ℃/min, and the glass transition temperature Tg under the second temperature rise is obtained; the measuring instrument is a German relaxation tolerance type scanning calorimeter with the model of DSC204F1 Nevio;
2. decomposition temperature (T)d): the thermal decomposition temperature of the material was determined using ISO 11358-1: 2014; the test condition is a temperature rise rate of 20 ℃/min, the temperature is raised from room temperature (25 ℃) to 500 ℃, and a thermal decomposition temperature Td is obtained; the test instrument is a German relaxation-resistant thermogravimetric analyzer with the model number of TG209F1 Nevio;
3. tensile strength, elongation at break, modulus: the tensile strength and elongation at break of the material were tested using ISO 527-1:2019& ISO 527-2:2012, with a gauge length of 50mm and a tensile speed of 50 mm/min; the testing instrument is a German universal testing machine with the model number of Z1200E;
4. impact strength (unnotched): the unnotched impact strength of the material was tested using ISO 197-1: 2010; the test instrument is a pendulum impact tester of Zwick, Germany, with the model number HIT-5P.
Example 1
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high pressure reaction kettle after water removal and oxygen removal, firstly adding biodegradable aliphatic polyester C (polybutylene terephthalate-Co-adipate) with active ends at two sides (2g, the number average molecular weight is 8000g/mol, the molecular weight distribution index is 1.21), dried 1, 2-epoxycyclohexane (20ml), dried dioxolane (10ml) and a Zn-Co double metal cyanide catalyst (5mg) at one time in the initial reaction stage, then filling carbon dioxide into the high pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function to ensure that the pressure in the high pressure reaction kettle reaches 5.0MPa, carrying out copolymerization reaction, cooling the high pressure reaction kettle to 25 ℃, slowly discharging the carbon dioxide in the high pressure reaction kettle after the copolymerization reaction kettle is opened for the first time, and adopting a method of adopting the steps of1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in a vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer (B-A-B type, wherein A chain segment is biodegradable aliphatic polyester chain segment, and B chain segment is polycyclohexene carbonate chain segment);
wherein the copolymerization reaction temperature is 80 ℃, the copolymerization reaction time is 10h, and the copolymerization reaction pressure is 5.0 MPa.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99.8 percent, the content of the cyclic cyclohexene carbonate by-product is 0.9 percent by weight, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 94 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is measured by GPC and is 96kg/mol, and the molecular weight distribution index is 2.5; copolymerization of polycyclohexyl carbonateThe glass transition temperature of the material is 103 ℃; the decomposition temperature is 270 ℃; the modulus is 1600 MPa; the impact strength (unnotched) was 28KJ/m2(ii) a The tensile strength is 58 MPa; the elongation at break was 15%.
Comparative example 1
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: firstly, adding 1, 2-epoxycyclohexane, solvent and catalyst into a 100ml high-pressure reaction kettle after water removal and oxygen removal at one time in the initial stage of reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function to ensure that the pressure in the high-pressure reaction kettle reaches 5.0MPa, carrying out copolymerization reaction, cooling the high-pressure reaction kettle to 25 ℃ after the copolymerization reaction is finished, slowly discharging the carbon dioxide in the high-pressure reaction kettle, and adopting the method for the first time when the reaction kettle is opened1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in a vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer.
Wherein, the addition amounts of the 1, 2-epoxycyclohexane, the solvent and the catalyst are the same as those in example 1, and the types of the catalyst and the solvent are the same as those in example 1; the copolymerization temperature and the copolymerization time were the same as in example 1.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 1 percent, and the content of carbonate units in the polycyclohexene carbonate copolymer is 93 percent; the number average molecular weight of the prepared polycyclohexene carbonate copolymer is 85kg/mol and the molecular weight distribution index is 2.06 by GPC; the glass transition temperature of the polycarbonate cyclohexene ester copolymer is 109 ℃, the decomposition temperature is 271 ℃, the modulus is 1500MPa, and the impact strength (without gaps) is 14KJ/m2The tensile strength was 65MPa and the elongation at break was only 4.5%.
As can be seen by comparing example 1 with comparative example 1, the elongation at break of the polycyclohexene carbonate copolymer prepared in example 1 is significantly improved, and the glass transition temperature and the mechanical strength are well maintained, because the introduction of a proper amount of polyester soft segment achieves the goal of toughening modification without reducing the strength and the thermal properties of the copolymer.
Comparative example 2
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high pressure reaction kettle after water removal and oxygen removal, firstly, adding single-side end capping poly epsilon-caprolactone (2g, the number average molecular weight is 7000g/mol, the molecular weight distribution index is 1.19), dry 1, 2-epoxycyclohexane (20ml), dry dioxolane (10ml) and Zn-Co double metal cyanide catalyst (5mg) at one time in the initial reaction stage, then filling carbon dioxide into the high pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function to ensure that the pressure in the high pressure reaction kettle reaches 5.0MPa, carrying out copolymerization reaction, cooling the high pressure reaction kettle to 25 ℃ after the copolymerization reaction is finished, slowly discharging the carbon dioxide in the high pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in a vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer (A-B type, wherein A chain segment is biodegradable aliphatic polyester chain segment, and B chain segment is polycyclohexene carbonate chain segment);
wherein the copolymerization reaction temperature is 80 ℃; the copolymerization reaction time is 10 hours; the copolymerization pressure was 5.0 MPa.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 97 percent, the content of the cyclic cyclohexene carbonate by-product is 0.9 percent by weight, and the content of the carbonate unit of the B chain segment in the cyclohexene ester copolymer is 90 percent; the number average molecular weight of the prepared polycyclohexene carbonate copolymer is 45kg/mol and the molecular weight distribution index is 2.23 according to GPC measurement; the glass transition temperature of the polycyclohexene carbonate copolymer is 78 ℃, the decomposition temperature is 256 ℃, the modulus is 1200MPa, and the impact strength (without gaps) is 21KJ/m2The tensile strength was 48MPa, and the elongation at break was 12%.
Comparative example 2 is mainly compared with example 1 in terms of the difference in properties of the polymer obtained by replacing the biodegradable aliphatic polyester C having both active ends with the single-sided end-capped poly-epsilon-caprolactone, and it can be seen from the comparison of example 1 with comparative example 2 that the glass transition temperature of the copolymer in comparative example 2 is significantly reduced and the impact strength is not improved, because the A-B type structure is very easily degraded by heat when external energy is directly applied to the A segment when being heated or subjected to external force, and the strength of the A segment is not as strong as that of the B segment, which lowers the strength of the A-B type polycyclohexene carbonate copolymer, which is applied at a lower energy during impact failure than that of the B-A-B type, can be destroyed, and the ductility of the two is equivalent.
Example 2
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 50ml high-pressure reaction kettle after water removal and oxygen removal, adding biodegradable aliphatic polyester C with active tail ends at two sides, 1, 2-epoxycyclohexane, a solvent and a catalyst for the first time in the initial stage of the reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, enabling the pressure in the high-pressure reaction kettle to reach 5MPa, and carrying out copolymerization reaction to synthesize a B chain segment to form a B-A-B type prepolymer; then continuously adding biodegradable aliphatic polyester C with double-side active ends into the reaction system for the 2 nd time; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer B- (AB)3A type multi-block copolymer, wherein the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment);
the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with the active tail ends at two sides to the feeding amount of the 1, 2-epoxy cyclohexane is 1:10, the volume ratio relation of the 1, 2-epoxy cyclohexane to the solvent is 1:1, the biodegradable aliphatic polyester C with the active tail ends at two sides is polybutylene adipate (the number average molecular weight is 10000g/mol, the molecular weight distribution index is 1.25), the solvent is dioxolane, and the catalyst is a heterogeneous Zn-Co double metal cyanide catalyst; the feeding mass ratio of the catalyst to the 1, 2-epoxycyclohexane is 1: 4000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 60 ℃; the time for synthesizing the B chain segment by copolymerization is 5 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 5 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 0.8 percent by weight, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 93 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is determined by GPC to be 98kg/mol, and the molecular weight distribution index is 2.35; the glass transition temperature of the polycyclohexyl carbonate copolymer is 95 ℃; the decomposition temperature is 278 ℃; modulus is 1670 MPa; the impact strength (unnotched) was 26KJ/m2(ii) a The tensile strength is 62 MPa; the elongation at break was 20%.
Example 3
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high-pressure reaction kettle after water removal and oxygen removal, adding biodegradable aliphatic polyester C with active tail ends at two sides, 1, 2-epoxycyclohexane, a solvent and a catalyst for the first time at the initial stage of the reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, enabling the pressure in the high-pressure reaction kettle to reach 4MPa, and carrying out copolymerization reaction to synthesize a B chain segment to form a B-A-B type prepolymer; then, continuously adding biodegradable aliphatic polyester C with active ends at two sides into the reaction system for 2 times; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer B- (AB)5The A chain segment of the multi-block copolymer is a biodegradable aliphatic polyester chain segment,the B chain segment is a polycyclohexene carbonate chain segment);
the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with the active ends on two sides to 1, 2-epoxycyclohexane is 1:6.6, the volume ratio relation of the 1, 2-epoxycyclohexane to the solvent is 1:1, the biodegradable aliphatic polyester C with the active ends on two sides is polypropylene carbonate (the number average molecular weight is 5000g/mol, the molecular weight distribution index is 1.18), the solvent is dichloromethane, and the catalyst is heterogeneous zinc glutarate; the feeding mass ratio of the catalyst to the 1, 2-epoxycyclohexane is 1: 1000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 65 ℃; the time for synthesizing the B chain segment by copolymerization is 4 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 8 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 1.5 weight percent, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 95 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is 126kg/mol and the molecular weight distribution index is 2.91 through GPC measurement; the glass transition temperature of the polycyclohexyl carbonate copolymer is 93 ℃; the decomposition temperature is 270 ℃; the modulus is 1810 MPa; the impact strength (unnotched) was 27KJ/m2(ii) a The tensile strength is 66 MPa; the elongation at break was 25%.
Comparative example 3
A preparation method of a polycyclohexene carbonate copolymer, which is basically the same as that in example 3, except that the number of times of continuously adding polypropylene carbonate into a reaction system after forming a B-A-B type prepolymer is 5;
by passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 76 percent, the content of the cyclic cyclohexene carbonate by-product is 4.5 weight percent, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer>89 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is 56kg/mol and the molecular weight distribution index is 3.1 by GPC measurement; the glass transition temperature of the polycyclohexyl carbonate copolymer is 62 ℃; decomposition temperature of258 ℃; the modulus is 1500 MPa; the impact strength (unnotched) was 16KJ/m2(ii) a The tensile strength is 45 MPa; the elongation at break was 18%.
As can be seen by comparing example 3 with comparative example 3, the glass transition temperature and mechanical properties of the material of comparative example 3 are significantly reduced because the copolymerization reactivity of the B segment synthesized is significantly reduced and the selectivity is deteriorated due to the excessive addition of the polypropylene carbonate, and a portion of the A segment is formed as B- (AB) without being used as an active chain transfer agentnRather, the chain structure of (a) is formed into a blended state, so that the glass transition temperature and mechanical properties of the material are greatly reduced.
Example 4
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high-pressure reaction kettle after water removal and oxygen removal, adding biodegradable aliphatic polyester C with active tail ends at two sides, 1, 2-epoxycyclohexane, a solvent and a catalyst for the first time at the initial stage of the reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, enabling the pressure in the high-pressure reaction kettle to reach 3MPa, and carrying out copolymerization reaction to synthesize a B chain segment to form a B-A-B type prepolymer; then, continuously adding biodegradable aliphatic polyester C with active ends at two sides into the reaction system for 2 times; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer B- (AB)5A type multi-block copolymer, wherein the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment);
the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with the bilateral active terminals to the feeding amount of the 1, 2-epoxycyclohexane is 1:12, the volume ratio relation of the 1, 2-epoxycyclohexane to the solvent is 1:1.2, the biodegradable aliphatic polyester C with the bilateral active terminals is poly-DL-lactide (the number average molecular weight is 7000g/mol, the molecular weight distribution index is 1.18), the solvent is tetrahydrofuran, the catalyst is a catalytic system taking homogeneous tetraphenylporphyrin aluminum complex (TPPALCl) as a main catalyst and bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) as a cocatalyst, and the mass ratio of the main catalyst to the cocatalyst is 1: 0.5; the mass ratio of the homogeneous tetraphenylporphyrin aluminum complex to the 1, 2-epoxycyclohexane is 1: 5000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 70 ℃; the time for synthesizing the B chain segment by copolymerization is 2 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 7 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 0.8 percent by weight, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 99 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is 112kg/mol and the molecular weight distribution index is 1.98 according to GPC measurement; the glass transition temperature of the polycyclohexyl carbonate copolymer is 96 ℃; the decomposition temperature is 266 ℃; modulus 1950 MPa; the impact strength (unnotched) was 25KJ/m2(ii) a The tensile strength is 65 MPa; the elongation at break was 16%.
Example 5
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high-pressure reaction kettle after water removal and oxygen removal, adding biodegradable aliphatic polyester C with active tail ends at two sides, 1, 2-epoxycyclohexane, a solvent and a catalyst for the first time at the initial stage of the reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, enabling the pressure in the high-pressure reaction kettle to reach 5MPa, and carrying out copolymerization reaction to synthesize a B chain segment to form a B-A-B type prepolymer; then, continuously adding biodegradable aliphatic polyester C with active ends at two sides into the reaction system for 2 times; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. The crude product is dissolved in dichloromethane and then washed withPrecipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycarbonate cyclohexene ester copolymer B- (AB)5A type multi-block copolymer, wherein the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment);
the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with the active ends on two sides to the feeding amount of the 1, 2-epoxycyclohexane is 1:5.5, the volume ratio relation of the 1, 2-epoxycyclohexane to the solvent is 1:1.2, the biodegradable aliphatic polyester C with the active ends on two sides is poly-epsilon-caprolactone (the number average molecular weight is 12000g/mol, the molecular weight distribution index is 1.15), the solvent is tetrahydrofuran, the catalyst is a catalytic system taking homogeneous tetraphenylporphyrin aluminum complex (TPPALCl) as a main catalyst and bis (triphenyl phosphoranylidene) ammonium chloride (PPNCl) as a cocatalyst, and the mass ratio of the main catalyst to the cocatalyst is 1: 1; the mass ratio of the homogeneous tetraphenylporphyrin aluminum complex to the 1, 2-epoxycyclohexane is 1: 6000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 100 ℃; the time for synthesizing the B chain segment by copolymerization is 4 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 8 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 0.9 weight percent, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 99 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is 144kg/mol and the molecular weight distribution index is 1.58 by GPC; the glass transition temperature of the polycyclohexyl carbonate copolymer is 98 ℃; the decomposition temperature is 278 ℃; modulus of 2510 MPa; the impact strength (unnotched) was 26KJ/m2(ii) a The tensile strength is 62 MPa; the elongation at break was 30%.
Example 6
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 100ml high-pressure reaction kettle after water removal and oxygen removal, biodegradable aliphatic polyester C with double-side active ends, 1, 2-epoxy cyclohexane and solvent are added for the first time in the initial stage of the reactionA catalyst and a catalyst, and then carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, so that the pressure in the high-pressure reaction kettle reaches 5MPa, and a copolymerization reaction is carried out to synthesize a B chain segment, thereby forming a B-A-B type prepolymer; then, continuously adding biodegradable aliphatic polyester C with active ends at two sides into the reaction system for 2 times; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer B- (AB)5A type multi-block copolymer, wherein the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment);
wherein the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with bilateral active terminals to the feeding amount of the 1, 2-epoxy cyclohexane is 1:5, the volume ratio relation of the 1, 2-epoxy cyclohexane to the solvent is 1:0.66, the biodegradable aliphatic polyester C with bilateral active terminals is polybutylene terephthalate-co-adipate butanediol (the number average molecular weight is 15000g/mol, the molecular weight distribution index is 1.20), the solvent is dichloromethane, the catalyst is a catalytic system taking homogeneous tetraphenyl porphyrin aluminum complex (TPPALCl) as a main catalyst and bis (triphenyl phosphoranylidene) ammonium chloride (PPNCl) as a cocatalyst, and the mass ratio of the main catalyst to the cocatalyst is 1: 2; the mass ratio of the homogeneous tetraphenylporphyrin aluminum complex to the 1, 2-epoxycyclohexane is 1: 7000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 100 ℃; the time for synthesizing the B chain segment by copolymerization is 5 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 10 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 0.9 weight percent, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 99 percent; the polycyclohexyl carbonate co-produced was determined by GPCThe number average molecular weight of the copolymer was 344kg/mol, and the molecular weight distribution index was 2.48; the glass transition temperature of the polycyclohexyl carbonate copolymer is 105 ℃; the decomposition temperature is 280 ℃; the modulus is 3000 MPa; the impact strength (unnotched) was 30KJ/m2(ii) a The tensile strength is 70 MPa; the elongation at break was 24%.
Example 7
A preparation method of a polycyclohexene carbonate copolymer comprises the following specific preparation processes: in a 50ml high-pressure reaction kettle after water removal and oxygen removal, adding biodegradable aliphatic polyester C with active tail ends at two sides, 1, 2-epoxycyclohexane, a solvent and a catalyst for the first time in the initial stage of the reaction, then filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, enabling the pressure in the high-pressure reaction kettle to reach 5MPa, and carrying out copolymerization reaction to synthesize a B chain segment to form a B-A-B type prepolymer; then continuously adding biodegradable aliphatic polyester C with double-side active ends into the reaction system for the 2 nd time; after the copolymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. Dissolving the crude product in dichloromethane, precipitating with ethanol, separating, and drying in vacuum drying oven at 50 deg.C to obtain polycyclohexene carbonate copolymer B- (AB)3A type multi-block copolymer, wherein the A chain segment is a biodegradable aliphatic polyester chain segment, and the B chain segment is a polycarbonate cyclohexyl chain segment);
the mass ratio of the total feeding amount of the biodegradable aliphatic polyester C with the active ends at two sides to the feeding amount of the 1, 2-epoxy cyclohexane is 1:4, the volume ratio relation of the 1, 2-epoxy cyclohexane to the solvent is 1:0.5, the biodegradable aliphatic polyester C with the active ends at two sides is polybutylene adipate (the number average molecular weight is 10000g/mol, the molecular weight distribution index is 1.15), the solvent is dichloromethane, the catalyst is a catalytic system taking a homogeneous Schiff base cobalt complex (salenccl) as a main catalyst and bis (triphenyl phosphorane) ammonium chloride (PPNCl) as an auxiliary catalyst, and the mass ratio of the main catalyst to the auxiliary catalyst is 1: 2; the mass ratio of the homogeneous Schiff base cobalt complex to the 1, 2-epoxycyclohexane is 1: 3000; the amount of biodegradable aliphatic polyester C having double-sided active ends added each time was equal; the copolymerization reaction temperature is 100 ℃; the time for synthesizing the B chain segment by copolymerization is 5 hours, and the time for copolymerization after forming the B-A-B type prepolymer is 5 hours.
By passing1H-NMR nuclear magnetic resonance detection shows that the conversion rate of the 1, 2-epoxycyclohexane is 99 percent, the content of the cyclic cyclohexene carbonate by-product is 0.9 weight percent, and the content of the carbonate unit of the B chain segment in the polycyclohexene carbonate copolymer is 99 percent; the number average molecular weight of the prepared polycyclohexyl carbonate copolymer is 109kg/mol and the molecular weight distribution index is 1.88 according to GPC measurement; the glass transition temperature of the polycyclohexyl carbonate copolymer is 102 ℃; the decomposition temperature is 264 ℃; the modulus is 2100 MPa; the impact strength (unnotched) was 26KJ/m2(ii) a The tensile strength is 64 MPa; the elongation at break was 19%.
Claims (10)
1. A polycyclohexene carbonate copolymer characterized by: is B- (AB) composed of an A chain segment and a B chain segmentnBlock copolymers of the type wherein n is 1, 3 or 5;
the A chain segment is a biodegradable aliphatic polyester chain segment, the B chain segment is a polycarbonate cyclohexene ester chain segment, and the A chain segment is connected with the B chain segment through ether bonds or ester bonds.
2. The polycyclohexene carbonate copolymer according to claim 1, wherein the glass transition temperature of the polycyclohexene carbonate copolymer is 93-105 ℃, and the impact strength is 25-30 KJ/m2The elongation at break is 15 to 30%.
3. The polycyclohexene carbonate copolymer according to claim 1, wherein n is 1;
the number average molecular weight of the polycarbonate cyclohexene ester copolymer is 35-350 kg/mol, and the molecular weight distribution index is 1.5-3.5; wherein the ratio of the contribution of the A chain segment to the number average molecular weight to the contribution of the B chain segment to the molecular weight is 1: 1.3-14.4, and the contribution of the A chain segment to the number average molecular weight is 5-25 kg/mol.
4. The polycyclohexene carbonate copolymer according to claim 1, wherein n is 3 or 5;
the number average molecular weight of the polycarbonate cyclohexene ester copolymer is 50-500 kg/mol, and the molecular weight distribution index is 1.5-3.5; wherein the ratio of the contribution of the A chain segment to the number average molecular weight to the contribution of the B chain segment to the molecular weight is 1: 1.3-14.4, and the contribution of the A chain segment to the number average molecular weight is 15-125 kg/mol.
5. A method for preparing the polycyclohexene carbonate copolymer according to any of claims 1 to 4, wherein: preparing a polycarbonate cyclohexene ester copolymer by taking carbon dioxide and 1, 2-epoxy cyclohexane as reaction raw materials and adopting a block polymerization mode of adding a macromolecular chain transfer agent for K times;
the macromolecular chain transfer agent is biodegradable aliphatic polyester C with double-side active ends;
the active ends on both sides are all hydroxyl or carboxyl;
wherein the relationship between K and n is as follows: n-2 × K-1.
6. The method according to claim 5, wherein the biodegradable aliphatic polyester C having double-sided reactive ends is polybutylene terephthalate-co-adipate, polybutylene adipate, poly DL-lactide, poly epsilon-caprolactone or polypropylene carbonate.
7. The method according to claim 5, wherein when K ═ 1, the polycyclohexene carbonate copolymer is prepared by: in a high-pressure reaction kettle, a macromolecular chain transfer agent, 1, 2-epoxycyclohexane, a solvent and a catalyst are added at one time at the initial stage of the reaction, and after carbon dioxide is filled, a B chain segment is copolymerized to obtain the polycarbonate cyclohexene ester copolymer.
8. The method of claim 5, wherein when K >1, the polycyclohexene carbonate copolymer is prepared by: adding a certain amount of macromolecular chain transfer agent, 1, 2-epoxycyclohexane, solvent and catalyst into a high-pressure reaction kettle at the initial stage of the reaction, filling carbon dioxide, and copolymerizing to form a B chain segment to form a B-A-B type prepolymer; then, continuously adding a macromolecular chain transfer agent into the reaction system by K-1 times until the copolymerization reaction is completed to obtain a polycarbonate cyclohexene ester copolymer;
the amount of the macromolecular chain transfer agent added in each time is equal, and the interval time between every two adjacent times of continuously adding the macromolecular chain transfer agent into the reaction system after the B-A-B type prepolymer is formed is equal.
9. The method according to claim 7 or 8, wherein the solvent is tetrahydrofuran, dichloromethane, chloroform, dioxolane, dioxane, ethyl acetate, acetone, or butanone;
the catalyst is a heterogeneous complex catalyst or a catalytic system which is composed of a homogeneous complex as a main catalyst and a cocatalyst;
the heterogeneous complex catalyst is ZnR2More than one of a catalyst, a zinc dicarboxylate catalyst, a rare earth ternary catalyst and a double metal cyanide catalyst, wherein R is ethyl, butyl, isopropyl, cyclohexyl or phenyl; the zinc dicarboxylate catalyst is zinc succinate, zinc glutarate, zinc adipate or zinc pimelate, and the rare earth ternary catalyst is Y (P)2O4)3-Al(i-Bu)3Glycerol, Re (P)2O4)3-Al(i-Bu)3、Ln(CCl3COO)3-glycerol-ZnEt2Or Nd (CCl)3COO)3-ZnEt2-glycerol, said double metal cyanide catalyst being Zn-Co-DMC, Zn-Fe-DMC, Fe-Co-DMC or Ni-Co-DMC;
in a catalytic system consisting of a homogeneous complex serving as a main catalyst and a cocatalyst, the mass ratio of the main catalyst to the cocatalyst is 1: 0.5-10; the main catalyst is more than one of a zinc phenol catalyst, a porphyrin metal complex catalyst and a Schiff base metal complex catalyst, and the cocatalyst is more than one of tetraethyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium hydrogen sulfate, bis-triphenylphosphine ammonium chloride, bis-triphenylphosphine ammonium bromide, bis-triphenylphosphine nitramine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene 4-dimethylamino pyridine and gamma-chloropropyl methyl dimethoxy silane; the zinc-phenol catalyst is a diethyl zinc/ternary phenol complex, a beta-diimine zinc complex or a prolinol zinc complex, the porphyrin metal complex catalyst is an aluminum porphyrin complex, a cobalt porphyrin complex or a chromium porphyrin complex, and the Schiff base metal complex catalyst is an aluminum Schiff base complex, a cobalt Schiff base complex or a chromium Schiff base complex;
the feeding mass ratio of the heterogeneous complex catalyst to the 1, 2-epoxycyclohexane is 1: 1000-10000;
the mass ratio of the homogeneous phase complex to the 1, 2-epoxycyclohexane is 1: 2000-500000;
the mass ratio of the total feeding amount of the macromolecular chain transfer agent to the feeding amount of the 1, 2-epoxycyclohexane is 1: 1-10;
the volume ratio of the 1, 2-epoxycyclohexane to the solvent is 1-5: 1.
10. The method according to claim 7 or 8, wherein the pressure in the autoclave after the carbon dioxide filling is 1.0 to 8.0 MPa;
the copolymerization reaction temperature is 25-150 ℃, and the copolymerization reaction time is 5-48 h;
the conversion rate of the 1, 2-epoxy cyclohexane in the copolymerization reaction is more than or equal to 90 percent; the content of the cyclic cyclohexene carbonate by-product is less than 5 wt%; the polycarbonate cyclohexene ester copolymer has a content of carbonate units of the B segment of > 90%.
Priority Applications (1)
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