CN114316231B - Polycarbonate polyesters - Google Patents
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Abstract
A polycarbonate polyester comprising residues of the following formulas (1), (2) and (3):wherein R is 1 Is C 2 ‑C 15 A hydrocarbon group; r is R 2 Is C 4 ‑C 16 A hydrocarbon group; the molar ratio of residues of formula (2) to residues of formula (1) is in the range of greater than 0.05 to less than 0.8; * Representing a connection key. The molar ratio of the residue of formula (2) to the residue of formula (1) in the range of more than 0.05 to less than 0.8 allows the polycarbonate polyester to have both good heat resistance and mechanical properties.
Description
Technical Field
The present disclosure relates to a polycarbonate polyester, and more particularly, to a polycarbonate polyester including specific residues, i.e., formula (1), formula (2) and formula (3) below.
Background
In general, polycarbonate is poor in heat resistance, chemical resistance and impact resistance. Polycarbonates and polyesters used in combination may increase the chemical resistance of the composition, but may significantly decrease the heat resistance and impact resistance of the composition. Therefore, it is an urgent task in the art how to provide a polycarbonate polyester with both good heat resistance and good mechanical properties.
Disclosure of Invention
One aspect of the present disclosure provides a polycarbonate polyester comprising residues of the following formulas (1), (2) and (3):
wherein R is 1 Is C 2 -C 15 A hydrocarbon group; r is R 2 Is C 4 -C 16 A hydrocarbon group; the molar ratio of residues of formula (2) to residues of formula (1) is in the range of greater than 0.05 to less than 0.8; * Representing a connection key.
In some embodiments of the present disclosure, the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of 0.1 to 0.6.
In some embodiments of the present disclosure, the residue of formula (1) comprises:
in some embodiments of the present disclosure, the residue of formula (1) further comprises C 2 -C 15 Aliphatic straight or branched diol residues of (a)。
In some embodiments of the disclosure, C 2 -C 15 Is selected from the group consisting of: and combinations of the above, wherein x represents a bond.
In some embodiments of the disclosure, C 2 -C 15 Is selected from the group consisting of: and combinations of the above, wherein x represents a bond.
In some embodiments of the disclosure, R 2 Is thatOr a combination of the foregoing, wherein x represents a bond.
In some embodiments of the present disclosure, the residue of formula (3) comprises no more than 50 mole% of the polycarbonate polyester.
Detailed Description
In order that the detailed description of the disclosure may be more complete and thorough, the following illustrative descriptions of embodiments and specific examples of the disclosure are presented; this is not the only form of practicing or applying the specific embodiments of the disclosure. The embodiments disclosed below may be combined with or substituted for each other as desired, and other embodiments may be added to one embodiment without further description or illustration. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments below. However, embodiments of the disclosure may be practiced without these specific details.
One aspect of the present disclosure provides a polycarbonate polyester comprising residues of the following formulas (1), (2) and (3):
wherein R is 1 Is C 2 -C 15 Hydrocarbyl radicals, R 2 Is C 4 -C 16 A hydrocarbon group. * Representing a connection key.
The number of moles of the residue of formula (2) is less than the number of moles of the residue of formula (1), i.e. the number of moles of dialkyl carbonate monomer used is less than the number of moles of diol monomer. It is noted that the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of more than 0.05 to less than 0.8, which results in polycarbonate polyesters having both good heat resistance and mechanical properties. In some embodiments, the molar ratio of the residue of formula (2) to the residue of formula (1) is from 0.1 to 0.6, which may be, for example, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or 0.55.
In some embodiments, the residue of formula (1) is derived from a diol monomer. In some embodiments, the diol monomer comprises a polycycloalkane dialkyl alcohol, such as a dicycloalkane dialkyl alcohol or a tricycloalkane dialkyl alcohol. In some embodiments, R of formula (1) 1 Is C 7 -C 17 Polycycloalkyl groups such as bicycloalkyl or tricycloalkyl. In some embodiments, the residue of formula (1) comprises:R 1 is->In some embodiments, this residue is derived from tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM).
In some embodiments, the diol monomer further comprises an aliphatic linear diol or an aliphatic branched diol. In some embodiments, the residue of formula (1) further comprises C 2 -C 15 Aliphatic linear or branched diol residues of (a).
In some embodiments, the aliphatic linear diol may be, for example, ethylene Glycol (EG), propylene Glycol (PG), butylene glycol (BDO), pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, or decylene glycol. In some embodiments, the residue of formula (1) further comprises C 2 -C 9 Aliphatic linear diol residues, R 1 Is C 2 -C 9 A linear alkyl group. In some embodiments, the residue of formula (1) further comprises C 2 -C 6 Aliphatic linear diol residues, R 1 Is C 2 -C 6 A linear alkyl group. In some embodiments, the residue of formula (1) further comprises C 2 -C 4 Aliphatic linear diol residues, R 1 Is C 2 -C 4 A linear alkyl group.
In some embodiments, the aliphatic branched diol may be, for example, 2-methyl-1,3-propanediol (MPO), 2-methyl-1, 3-pentanediol, 2-ethyl-1, 3-propanediol, 2-ethyl-1, 6-hexanediol, 2-butyl-1, 3-propanediol, 2-methyl-1, 4-butanediol, 2-methyl-1, 5-pentanediol, 2-methyl-1, 8-octanediol, 2-ethyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2, 4-dimethyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, or 2, 2-dimethyl-1, 3-propanediol. In some embodiments, the residue of formula (1) further comprises a C4-C9 aliphatic branched diol residue, R1 is a C4-C9 branched alkyl group.
In some embodiments, C 2 -C 15 Is selected from the group consisting of: and combinations of the above, wherein x represents a bond.
In some embodiments, C 2 -C 15 Is selected from the group consisting of: and combinations of the above, wherein x represents a bond.
In some embodiments, the residue of formula (2) is derived from a dialkyl carbonate monomer. In some embodiments, the dialkyl carbonate monomer is dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (diethyl carbonate, DEC), dipropyl carbonate (dipropyl carbonate), dibutyl carbonate (dibutyl carbonate, DBC), dipentyl carbonate (dipentyl carbonate), diphenyl carbonate (diphenyl carbonate), or a combination thereof. In some embodiments, the residue of formula (2) is derived from dibutyl carbonate.
The residue of formula (3) is derived from a diacid monomer. In some embodiments, the diacid monomer comprises an aromatic dicarboxylic acid, such as terephthalic acid (terephthalic acid, PTA) or 1, 4-naphthalene dicarboxylic acid (2, 6-naphthalenedicarboxylic acid, NDA). In some embodiments, R of formula (3) 2 Is C 6 -C 16 An aromatic group. In some embodiments, R of formula (3) 2 Is thatOr a combination of the foregoing, wherein x represents a bond.
In some embodiments, the residue of formula (3) comprises no more than (i.e., less than or equal to) 50 mole percent of the polycarbonate polyester. In some embodiments, the moles of diacid monomer are less than or equal to 50 mole percent of the sum of the moles of diol monomer, dialkyl carbonate monomer, and diacid monomer.
In some embodiments, the polycarbonate polyester further comprises residues of formula (4) below:
wherein R is 3 Is C 3 -C 20 Hydrocarbyl radicals, R 4 、R 5 R is R 6 Is C 1 -C 6 Hydrocarbon group, n 1 、n 2 、n 3 、n 4 、n 5 N is as follows 6 0 or 1. In some embodiments, R 3 Is C 3 -C 20 Aliphatic hydrocarbon radicals or C 4 -C 20 Aromatic hydrocarbon groups.
In some embodiments, the residue of formula (4) is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
In some embodiments, the residue of formula (4) is derived from a monomer having a group of formula (4), the monomer having a group of formula (4) is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
In some embodiments, the residue of formula (4) comprises less than or equal to 0.4 mole% of the polycarbonate polyester. In some embodiments, the residues of formula (4) comprise 0.05 mole% to 0.2 mole% of the polycarbonate polyester.
The polycarbonate polyester of the present disclosure may be used for a molding material, which may be, for example, food contact (food contact), automotive molds (automatic molds), commercial household items (commercial housewares), composite consumables (compounders consumer), electronic products (electronics), consumer household items (consumer housewares), equipment housings (device housings), displays (displays), interior lighting (in-store lights), electronic product packages (electronic packaging), outdoor signs (outdoor signs), personal care items (personal care), cosmetic packages (cosmetics packaging), sports equipment tools (sporting equipment tools), toys (toys), and sports water bottles (water/sport bottles), etc., but is not limited thereto.
As described above, the polycarbonate polyesters of the present disclosure are formed from the reaction of the monomers described above. In some embodiments, preparing the polycarbonate polyester of the present disclosure comprises the following operations: (a) Uniformly mixing various monomers with a catalyst to form a mixture; (b) Placing the mixture in a proper pressure environment and heating to enable the monomers to react to form oligomers; and (c) heating the mixture comprising the oligomers and evacuating in vacuo to remove unreacted monomers, and then continuously exposing the mixture to the heating temperature to polymerize the oligomers in the mixture to form the polycarbonate polyester.
In some embodiments, operation (a) is performed in an autoclave. In some embodiments, operation (a) is to uniformly mix the various monomers and catalyst by stirring, which may be at a rate between 100rpm and 500 rpm.
In some embodiments, the catalyst of operation (a) is, for example, titanium (IV) butoxide, TBT, antimony trioxide (Sb 2 O 3 ) Antimony triacetate (Sb (OAc)) 3 ) Germanium dioxide (GeO) 2 ) Or titanium (IV) isopropoxide, but not limited thereto.
In some embodiments, in operation (a), a co-catalyst, such as magnesium acetate (Mg (OAc), may be optionally added 2 ) Or zinc acetate (Zn (OAc) 2 ) But is not limited thereto. In some embodiments, in operation (a), a triol, a cross-linking agent, a heat stabilizer, or a combination thereof may be optionally added. Triols are, for example, the monomers described above having groups of formula (4). The crosslinking agent is, for example, trimellitic acid (TMA) or trimethylol propane (TMP). Heat stabilizers are, for example, triphenyl phosphite (triphenyl phosphite), phosphoric acid, phosphorous acid, hypophosphorous acid and salts thereof, trimethyl phosphate (trimethyl phosphate, TMP), triethyl phosphate (triethyl phosphate, TEP), tripropyl phosphate (tripropyl phosphate, TPP), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ]]Undecane (3, 9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3, 9-diphosphofirao [5.5 ]]unredecane), bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Bis (2, 6-di-ter-4-methylphenyl) penta-phosphinite), tris (2, 4-di-tert-butylphenyl) phosphite (Tris (2, 4-di-tert-butylphenyl) 4,4 '-biphenidenedi (2, 4-di-tert-butylphenyl) 4,4' -biphenydi).
In some embodiments, the heating of operation (b) refers to warming from room temperature to 220 ℃ or from room temperature to 260 ℃. In some embodiments, the appropriate pressure for operation (b) is between 1atm and 6 atm. In some embodiments, the suitable pressure for operation (b) is between 1.5atm and 4 atm.
In some embodiments, the reaction condition is judged by observing the amount of water (or alcohol, phenol, or hydrochloric acid gas) produced in operation (b). Specifically, by theoretical calculation, the amount of theoretical water (or alcohol, phenol, or hydrochloric acid gas) produced after all the monomers in the mixture are reacted can be obtained. When the amount of water (or alcohol, phenol or hydrochloric acid gas) produced reaches 80% or more (e.g., 85%, 90% or 95%) of the theoretical amount of water (or alcohol, phenol or hydrochloric acid gas), it means that the reaction is substantially completed and operation (c) can be performed.
In some embodiments, the heating of operation (c) refers to increasing the temperature to 250 ℃ to 300 ℃. In some embodiments, the vacuum pump of operation (c) brings the ambient pressure to below 3 torr. In some embodiments, the vacuum pump of operation (c) brings the ambient pressure to below 1torr. In some embodiments, the vacuum pump of operation (c) is conducted for 30 to 60 minutes, such as 40 minutes or 50 minutes.
In some embodiments, the oligomer is polymerized to remove the diol and the viscosity of the mixture is gradually increased. The product is collected when the viscosity of the mixture reaches a specific value. In some embodiments, the time of operation (c) is from 1.5 hours to 8 hours.
The following examples are presented to describe the particular manner of practicing the invention and to enable one of ordinary skill in the art to practice the invention. However, the following experimental examples are not intended to limit the present invention.
Comparative examples 1to 4 and Experimental examples 1to 4
Tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM), 1, 4-Cyclohexanedimethanol (CHDM), dibutyl carbonate (dibutyl carbonate, DBC), ethylene Glycol (EG), terephthalic acid (terephthalic acid, PTA), trimellitic acid (TMA), trimethylol propane (TMP), titanium (IV) butoxide (TBT), and Mg (OAc) 2 Added to the autoclave in various weight ratios and stirred uniformly to form the mixtures of comparative examples 1to 4 and experimental examples 1to 4. The compositions of the mixtures of comparative examples 1to 4 and experimental examples 1to 4 will be described in detail below.
Comparative example 1 contained 662.5 grams of TCDDM, 153.6 grams of EG, 747.6 grams of PTA, and 0.619 grams of TBT.
Comparative example 2 contained 706.6 grams of TCDDM, 39.2 grams of DBC, 153.6 grams of EG, 747.6 grams of PTA, and 0.619 grams of TBT.
Comparative example 3 included 1369.1 grams of TCDDM, 627.3 grams of DBC, 153.6 grams of EG, 747.6 grams of PTA, 2.4 grams of TMP, and 0.619 grams of TBT.
Comparative example 4 contained 746.3 grams CHDM, 313.6 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 1 contains 750.8 grams TCDDM, 78.4 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 2 contains 927.5 g TCDDM, 235.2 g DBC, 153.6 g EG, 747.6 g PTA, 0.619 g TBT, and 0.21 g Mg (OAc) 2 。
Experimental example 3 contains 1015.8 grams TCDDM, 313.6 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 4 contains 1192.5 grams TCDDM, 470.4 grams DBC, 153.6 grams EG, 747.6 grams PTA, 3.5 grams TMA, and 0.619 grams TBT.
Then performing the above operation (b) placing the mixture in a proper pressure environment and heating to react the monomers to form oligomers; and (c) heating the mixture containing the oligomers and evacuating in vacuo to remove unreacted monomers, and then continuously exposing the mixture to the heating temperature to polymerize the oligomers in the mixture to form the polyesters of comparative example 1 and the polycarbonate polyesters of comparative examples 2 to 4 and experimental examples 1to 4.
The products of comparative examples 1to 4 and experimental examples 1to 4 were subjected to tests of tensile strength, flexural strength, impact resistance, glass transition temperature (glass transition temperature, tg), melting temperature (melting temperature, tm), intrinsic viscosity (intrinsic viscosity, IV), and penetration, etc. The test results are shown in tables 1 and 2.
Tensile strength was measured using a universal material tester (manufactured by Instron Co.) and in accordance with ISO 527.
Flexural strength was tested using a universal material tester and in accordance with ISO 178.
Impact resistance testing was performed using a test bench manufactured by inteltek corporation and in accordance with ISO 180.
Glass transition temperature and melting temperature were measured using a thermal differential scanning calorimeter (differential scanning calorimetry, DSC, TA instruments vendor) and tested in accordance with ISO 3146.
Intrinsic viscosity was tested according to ASTM D4603.
Penetration was measured using a haze meter (NIPPON DENSHOKU NDH-2000) and according to ASTM D1003.
TABLE 1
TABLE 2
| Experimental example 3 | Experimental example 4 | Comparative example 3 | Comparative example 4 | |
| Tensile Strength (MPa) | 53 | 51 | N/A | 45 |
| Flexural Strength (MPa) | 77 | 72 | N/A | 65 |
| Impact resistance (KJ/m) 2 ) | 2.6 | 1.6 | N/A | 2.4 |
| Tg(℃) | 117 | 119 | 108 | 90 |
| Tm(℃) | N/A | N/A | N/A | 274 |
| IV(dl/g) | 0.63 | 0.40 | <0.3 | 0.64 |
| Penetration (%) | 90 | 90 | N/A | N/A |
The molar ratios of formula (2)/formula (1) of comparative example 1, comparative example 2, and comparative example 3 were 0, 0.05, and 0.8, respectively, and the glass transition temperatures were all 110 ℃ or lower as shown in tables 1 and 2. As for the molar ratios of formula (2)/formula (1) of experimental examples 1to 4, 0.1, 0.3, 0.4 and 0.6, respectively, the glass transition temperatures thereof were between 112℃and 119℃as shown in tables 1 and 2. It is clear that the molar ratio of formula (2)/formula (1) in the range of more than 0.05 to less than 0.8 can make the glass transition temperature of the polycarbonate polyester higher, have better heat resistance, and in addition, can provide better tensile strength and bending strength, and have better mechanical properties.
The molar ratio of formula (2)/formula (1) of experimental example 3 and comparative example 4 was 0.4, except that TCDDM and CHDM were used, respectively, and glass transition temperatures thereof were 117℃and 90℃as shown in Table 2, respectively, so that it was found that the use of TCDDM can provide polycarbonate polyester with better heat resistance, and also can provide better tensile strength and flexural strength, and have better mechanical properties.
Comparative example 5 and Experimental example 5
Tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM), dibutyl carbonate (dibutyl carbonate, DBC), butanediol (BDO), terephthalic acid (terephthalic acid, PTA) and titanium (IV) butoxide (TBT) were added to an autoclave in various weight ratios and stirred uniformly to form a mixture of comparative example 5 and experimental example 5. The composition of the mixture of comparative example 5 and experimental example 5 will be described in detail below.
Comparative example 5 contained 662.5 grams of TCDDM, 223.0 grams BDO, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 5 contains 750.8 grams TCDDM, 78.4 grams DBC, 223.0 grams BDO, 747.6 grams PTA, and 0.619 grams TBT.
Then, the above-mentioned operations (b) and (c) were carried out to form the polyester of comparative example 5 and the polycarbonate polyester of experimental example 5.
The products of comparative example 5 and experimental example 5 were subjected to the above-mentioned tests of tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, penetration and the like. The test results are shown in Table 3.
TABLE 3 Table 3
| Comparative example 5 | Experimental example 5 | |
| Tensile Strength (MPa) | 32 | 36 |
| Flexural Strength (MPa) | 61 | 65 |
| Impact resistance (KJ/m) 2 ) | 2.3 | 2.4 |
| Tg(℃) | 103 | 106 |
| Tm(℃) | N/A | N/A |
| IV(dl/g) | 0.63 | 0.68 |
| Penetration (%) | 89 | 89 |
The molar ratio of formula (2)/formula (1) in comparative example 5 and experimental example 5 was 0 and 0.1, respectively. As shown in table 3, the tensile strength, flexural strength, impact resistance and glass transition temperature of experimental example 5 were higher, and had better mechanical properties and heat resistance than those of comparative example 5.
Comparative example 6 and Experimental example 6
Tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM), dibutyl carbonate (dibutyl carbonate, DBC), 2-methyl-1,3-propanediol (MPO), terephthalic acid (terephthalic acid, PTA) and titanium (IV) butoxide (TBT) were added to an autoclave in various weight ratios and stirred uniformly to form a mixture of comparative example 6 and experimental example 6. The composition of the mixture of comparative example 6 and experimental example 6 will be described in detail below.
Comparative example 6 contained 662.5 grams of TCDDM, 39.2 grams of DBC, 223.0 grams of MPO, 747.6 grams of PTA, and 0.619 grams of TBT.
Experimental example 6 contains 1015.8 g TCDDM, 313.6 g DBC, 223.0 g MPO, 747.6 g PTA and 0.619 g TBT.
Then, the above-mentioned operation (b) and operation (c) were carried out to form polycarbonate polyesters of comparative example 6 and experimental example 6.
The products of comparative example 6 and experimental example 6 were subjected to the above-mentioned tests of tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, penetration and the like. The test results are shown in Table 4.
TABLE 4 Table 4
| Comparative example 6 | Experimental example 6 | |
| Tensile Strength (MPa) | 47 | 50 |
| Flexural Strength (MPa) | 73 | 73 |
| Impact resistance (KJ/m) 2 ) | 2.5 | 2.8 |
| Tg(℃) | 104 | 107 |
| Tm(℃) | N/A | N/A |
| IV(dl/g) | 0.60 | 0.55 |
| Penetration (%) | 88 | 89 |
The molar ratio of formula (2)/formula (1) in comparative example 6 and experimental example 6 was 0.05 and 0.4, respectively. As shown in Table 4, the tensile strength, impact resistance and glass transition temperature of Experimental example 6 were higher, and the mechanical properties and heat resistance were better than those of comparative example 6.
Comparative example 7 and Experimental example 7
Tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM), dibutyl carbonate (dibutyl carbonate, DBC), ethylene Glycol (EG), terephthalic acid (terephthalic acid, PTA), 1, 4-naphthalene dicarboxylic acid (2, 6-naphthalenedicarboxylic acid, NDA) and titanium (IV) butoxide (TBT) were added to an autoclave in various weight ratios and stirred uniformly to form a mixture of comparative example 7 and experimental example 7. The composition of the mixture of comparative example 7 and experimental example 7 will be described in detail below.
Comparative example 7 contained 662.5 grams of TCDDM, 153.6 grams of EG, 448.6 grams of PTA, 389.1 grams of NDA, and 0.619 grams of TBT.
Experimental example 7 contains 750.8 grams TCDDM, 78.4 grams DBC, 153.6 grams EG, 448.6 grams PTA, 389.1 grams NDA, and 0.619 grams TBT.
Then, the above-mentioned operations (b) and (c) were carried out to form the polyester of comparative example 7 and the polycarbonate polyester of experimental example 7.
The products of comparative example 7 and experimental example 7 were subjected to the above-mentioned tests of tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, penetration and the like. The test results are shown in Table 5.
TABLE 5
| Comparative example 7 | Experimental example 7 | |
| Tensile Strength (MPa) | 26 | 27 |
| Flexural Strength (MPa) | 56 | 58 |
| Impact resistance (KJ/m) 2 ) | 2.6 | 2.7 |
| Tg(℃) | 124 | 130 |
| Tm(℃) | N/A | N/A |
| IV(dl/g) | 0.63 | 0.61 |
| Penetration (%) | 89 | 90 |
The molar ratio of formula (2)/formula (1) in comparative example 7 and experimental example 7 was 0 and 0.1, respectively. As shown in table 5, the tensile strength, flexural strength, impact resistance and glass transition temperature of experimental example 7 were higher, and had better mechanical properties and heat resistance than those of comparative example 7.
Comparative example 8 and Experimental example 8
Tricyclodecanedimethanol (tricyclodecane dimethanol, TCDDM), dibutyl carbonate (dibutyl carbonate, DBC), terephthalyl alcohol (terephthalyl alcohol, PXG), ethylene Glycol (EG), terephthalic acid (terephthalic acid, PTA) were added to an autoclave in various molar ratios and stirred uniformly to form a mixture of comparative example 8 and experimental example 8. The composition of the mixture of comparative example 8 and experimental example 8 will be described in detail below.
Comparative example 8 contained 932.6 grams PXG, 235.2 grams DBC, 3.5 grams TMA, 0.772 grams TBT, 0.25 grams Mn (OAc) 2, and 747.6 grams PTA.
Experimental example 8 contains 1325 g TCDDM, 235.2 g DBC, 3.5g TMA, 0.772 g TBT, 0.25 g Mn (OAc) 2 and 747.6 g PTA.
Then, the above-mentioned operation (b) and operation (c) were carried out to form polycarbonate polyesters of comparative example 8 and experimental example 8.
The products of comparative example 8 and experimental example 8 were subjected to the above-mentioned tests of tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, penetration and the like.
TABLE 6
| Comparative example 8 | Experimental example 8 | |
| Tg(℃) | 81 | 118 |
| Tm(℃) | N/A | N/A |
| IV(dl/g) | <0.30 | 0.47 |
| Penetration (%) | N/A | 90 |
The molar ratio of formula (2)/formula (1) was 0.3 in comparative example 8 and experimental example 8, except that PXG was used in comparative example 8 and TCDDM was used in experimental example 8. As shown in Table 6, the glass transition temperatures of comparative example 8 and experimental example 8 were 81℃and 118℃respectively, which means that the use of TCDDM provides better heat resistance and also better penetration of polycarbonate polyester.
It will be apparent to those skilled in the art that various modifications and variations can be made in the structure of the present disclosure without departing from the scope or spirit of the invention. In view of the foregoing, this disclosure is intended to cover modifications and variations of the present invention as fall within the scope of the appended claims.
Claims (6)
1. A polycarbonate polyester comprising residues of the following formulas (1), (2) and (3):
wherein R is 1 Is C 2 -C 15 A hydrocarbon group;
R 2 is C 4 -C 16 A hydrocarbon group;
the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of 0.1 to 0.6;
* Representing a connection key
Wherein the residue of formula (1) comprises:
2. the polycarbonate polyester of claim 1, wherein the residues of formula (1) further comprise C 2 -C 15 Aliphatic linear or branched diol residues of (a).
3. The polycarbonate polyester of claim 2, wherein the C 2 -C 15 Is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
4. The polycarbonate polyester of claim 2, wherein the C 2 -C 15 Is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
5. The polycarbonate polyester of claim 1, wherein R 2 Is thatOr a combination of the foregoing, wherein x represents a bond.
6. The polycarbonate polyester of claim 1, wherein the residues of formula (3) comprise no more than 50 mole% of the polycarbonate polyester.
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| CN103265689A (en) * | 2013-06-17 | 2013-08-28 | 中国科学院化学研究所 | Copolymer of aliphatic polycarbonate and aromatic polyester and preparation method thereof |
| JP2014214251A (en) * | 2013-04-26 | 2014-11-17 | 帝人株式会社 | Polyester carbonate copolymer |
| WO2019066292A1 (en) * | 2017-09-28 | 2019-04-04 | 에스케이케미칼 주식회사 | Highly heat-resistant polycarbonate ester and preparation method therefor |
| JP2019151813A (en) * | 2018-03-01 | 2019-09-12 | 三菱ケミカル株式会社 | Polyester polycarbonate diol and method for producing the same, and polyurethane |
| CN111133028A (en) * | 2017-09-28 | 2020-05-08 | Sk化学公司 | Highly heat-resistant polycarbonate and method for producing same |
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| JP4706808B2 (en) * | 2000-04-21 | 2011-06-22 | 三菱瓦斯化学株式会社 | Method for producing aliphatic polyester carbonate |
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| JPH06100675A (en) * | 1992-09-22 | 1994-04-12 | Teijin Ltd | Aromatic polyester carbonate and its production |
| JP2014214251A (en) * | 2013-04-26 | 2014-11-17 | 帝人株式会社 | Polyester carbonate copolymer |
| CN103265689A (en) * | 2013-06-17 | 2013-08-28 | 中国科学院化学研究所 | Copolymer of aliphatic polycarbonate and aromatic polyester and preparation method thereof |
| WO2019066292A1 (en) * | 2017-09-28 | 2019-04-04 | 에스케이케미칼 주식회사 | Highly heat-resistant polycarbonate ester and preparation method therefor |
| CN111133028A (en) * | 2017-09-28 | 2020-05-08 | Sk化学公司 | Highly heat-resistant polycarbonate and method for producing same |
| JP2019151813A (en) * | 2018-03-01 | 2019-09-12 | 三菱ケミカル株式会社 | Polyester polycarbonate diol and method for producing the same, and polyurethane |
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