CN114316231A - Polycarbonate polyester - Google Patents
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- CN114316231A CN114316231A CN202011047631.0A CN202011047631A CN114316231A CN 114316231 A CN114316231 A CN 114316231A CN 202011047631 A CN202011047631 A CN 202011047631A CN 114316231 A CN114316231 A CN 114316231A
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Abstract
A polycarbonate polyester comprising residues of the following formulae (1), (2), and (3):
wherein R is1Is C2‑C15A hydrocarbyl group; r2Is C4‑C16A hydrocarbyl group; the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of greater than 0.05 to less than 0.8; denotes a bond. A 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 provides the polycarbonate polyester with 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 comprising specific residues, i.e., the following formulae (1), (2), and (3).
Background
Generally, polycarbonates are poor in heat resistance, chemical resistance, and impact resistance. The use of a polyester in combination with a polycarbonate improves the chemical resistance of the composition, but significantly reduces the heat resistance and impact resistance of the composition. Therefore, how to make polycarbonate polyester have good heat resistance and good mechanical properties at the same time is a problem to be solved in the field.
Disclosure of Invention
One aspect of the present disclosure provides a polycarbonate polyester comprising residues of the following formulae (1), (2), and (3):
wherein R is1Is C2-C15A hydrocarbyl group; r2Is C4-C16A hydrocarbyl group; the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of greater than 0.05 to less than 0.8; denotes a bond.
In some embodiments of the 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 disclosure, the residue of formula (1) comprises:
in some embodiments of the disclosure, the residue of formula (1) further comprises C2-C15Aliphatic linear or branched diol residues of (2).
In some embodiments of the disclosure, C2-C15Is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
In some embodiments of the disclosure, C2-C15Is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
In some embodiments of the disclosure, R2Is composed of
Or 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 to make the description of the present disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and specific examples of the present disclosure; it is not intended to be the only form in which a particular embodiment of the disclosure may be practiced or utilized. The various embodiments disclosed below may be combined with or substituted for one another where appropriate, and additional embodiments may be added to one embodiment without further recitation or description. In the following description, numerous specific details are set forth to provide a thorough understanding of the following embodiments. However, embodiments of the present disclosure may be practiced without these specific details.
One aspect of the present disclosure provides a polycarbonate polyester comprising residues of the following formulae (1), (2), and (3):
wherein R is1Is C2-C15Hydrocarbyl radical, R2Is C4-C16A hydrocarbyl group. Denotes a bond.
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 the dialkyl carbonate monomer used is less than the number of moles of the diol monomer. It is noted that a 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 provides the polycarbonate polyester with 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 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 polycycloalkanediol, such as bicycloalkane diol or tricycloalkane diol. In some embodiments, R of formula (1)1Is C7-C17Polycycloalkyl groups, such as bicycloalkyl or tricycloalkyl. In some embodiments, the residue of formula (1) comprises:
R1is composed of
In some embodiments, this residue is derived from tricyclodecane dimethanol (TCDDM).
In some embodiments, the diol monomers further comprise an aliphatic linear diol or an aliphatic branched diol. In some embodiments, the residue of formula (1) further comprises C2-C15Aliphatic linear or branched diol residues of (2).
In some embodiments, the aliphatic linear diol can 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 C2-C9Of an aliphatic linear diol residue of (2), R1Is C2-C9A linear alkyl group. In some embodiments, the residue of formula (1) further comprises C2-C6Of an aliphatic linear diol residue of (2), R1Is C2-C6A linear alkyl group. In some embodiments, the residue of formula (1) further comprises C2-C4Of an aliphatic linear diol residue of (2), R1Is C2-C4A linear alkyl group.
In some embodiments, the aliphatic branched diol may be, for example, 2-methyl-1,3-propanediol (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, and R1 is a C4-C9 branched alkyl group.
In some embodiments, C2-C15Is selected from the group consisting of:
and combinations of the above, wherein x represents a bond.
In some embodiments, C2-C15Is 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 (DMC), diethyl carbonate (DEC), dipropyl carbonate (dipropyl carbonate), dibutyl carbonate (DBC), diamyl 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 (PTA) or 1, 4-naphthalenedicarboxylic acid (NDA). In some embodiments, R of formula (3)2Is C6-C16An aromatic group. In some embodiments, R of formula (3)2Is composed of
Or 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% of the polycarbonate polyester. In some embodiments, the moles of diacid monomer comprise 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 the following formula (4):
wherein R is3Is C3-C20Hydrocarbyl radical, R4、R5And R6Is C1-C6Hydrocarbyl radical, n1、n2、n3、n4、n5And n6Is 0 or 1. In some embodiments, R3Is C3-C20Aliphatic hydrocarbon radical or C4-C20An aromatic hydrocarbon group.
In some embodiments, the residue of formula (4) is selected from the group consisting of:
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) being 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 residue of formula (4) comprises 0.05 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), automobile molds (automatic molds), commercial household goods (commercial household goods), composite consumer goods (electronic products), electronic products (electronics), consumer household goods (consumer household goods), equipment housings (device housings), displays (displays), indoor lamps (in-store fixtures), electronic product packaging (electronic packaging), outdoor signs (outdoor signs), personal care products (personal care products), cosmetic packaging (cosmetics packaging), sports equipment tools (sports equipment packaging), toys (toys), and sports water bottles (sports/sports bottles), etc., but is not limited thereto.
As noted above, the polycarbonate polyesters of the present disclosure are formed from the reaction of the above-mentioned monomers. In some embodiments, preparing the polycarbonate polyesters of the present disclosure comprises the following operations: (a) uniformly mixing various monomers and a catalyst to form a mixture; (b) placing the mixture in a proper pressure environment and heating to react the monomers to generate oligomers; and (c) heating the mixture containing the oligomer, and performing vacuum pumping to remove unreacted monomers, and then continuously placing the mixture at the heating temperature to perform polymerization reaction on the oligomer in the mixture to generate the polycarbonate polyester.
In some embodiments, operation (a) is performed in an autoclave. In some embodiments, operation (a) is performed by uniformly mixing the monomers and the catalyst by stirring at a speed of between 100rpm and 500 rpm.
In some embodiments, the catalyst of operation (a) is, for example, titanium (IV) butoxide (TBT), antimony trioxide (Sb)2O3) 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)2) Or zinc acetate (Zn (OAc)2) But not limited thereto. In some embodiments, in operation (a), a triol, a crosslinking agent, a thermal stabilizer, or a combination thereof may be optionally added. Triols are, for example, the monomers described above having a radical of formula (4). The crosslinking agent is, for example, trimellitic acid (TMA) or Trimethylolpropane (TMP). Examples of heat stabilizers are triphenyl phosphite (triphenyl phosphate), phosphoric acid, phosphorous acid, hypophosphorous acid and its salts, trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPP), 3,9-bis (octadecyloxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5 ]]Undecane (3,9-Bis (o)ctadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane), Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite), Tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-di-tert-butylphenyl) phosphite), tetrakis (2,4-di-tert-butylphenyl)4,4 '-biphenylbis (tetrapkis (2,4-di-tert-butylphenyl)4, 4' -biphenyldi (biphenyldi).
In some embodiments, the heating of operation (b) refers to warming from room temperature to 220 ℃ or warming from room temperature to 260 ℃. In some embodiments, a suitable pressure for operation (b) is between 1atm and 6 atm. In some embodiments, a suitable pressure for operation (b) is between 1.5atm and 4 atm.
In some embodiments, the reaction is judged by observing the amount of water (or alcohol, phenol, or hydrochloric acid gas) produced in operation (b). Specifically, the theoretical amount of water (or alcohol, phenol, or hydrochloric acid gas) generated after the reaction of all monomers in the mixture can be obtained by theoretical calculation. When the amount of water (or alcohol, phenol, or hydrochloric acid gas) produced reaches 80% or more (for example, 85%, 90%, or 95%) of the theoretical amount of water (or alcohol, phenol, or hydrochloric acid gas), the reaction is substantially completed and operation (c) can be performed.
In some embodiments, the heating of operation (c) is to raise the temperature to 250 ℃ to 300 ℃. In some embodiments, the vacuum pumping of operation (c) achieves an ambient pressure below 3 torr. In some embodiments, the vacuum pumping of operation (c) achieves an ambient pressure below 1 torr. In some embodiments, the vacuum pumping of operation (c) is performed for 30 to 60 minutes, such as 40 minutes or 50 minutes.
In some embodiments, the oligomer will evolve diol upon polymerization, and the viscosity of the mixture will gradually rise. The product is collected when the viscosity of the mixture reaches a certain value. In some embodiments, the time of operation (c) is 1.5 hours to 8 hours.
The following examples are presented to illustrate specific embodiments of the present invention and to enable those skilled in the art to practice the invention. However, the following examples are not intended to limit the present invention.
Comparative examples 1to 4 and Experimental examples 1to 4
Tricyclodecane dimethanol (TCDDM), 1, 4-cyclohexane dimethanol (CHDM), dibutyl carbonate (DBC), Ethylene Glycol (EG), terephthalic acid (PTA), trimellitic acid (TMA), Trimethylolpropane (TMP), titanium (IV) butoxide (TBT) and Mg (OAc)2Added to the autoclave in various weight ratios and stirred uniformly to form mixtures of comparative examples 1to 4 and experimental examples 1to 4. The composition of the mixture 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 TCDDM, 39.2 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Comparative example 3 contained 1369.1 grams TCDDM, 627.3 grams DBC, 153.6 grams EG, 747.6 grams PTA, 2.4 grams TMP, and 0.619 grams TBT.
Comparative example 4 contained 746.3 g of CHDM, 313.6 g of DBC, 153.6 g of EG, 747.6 g of PTA, and 0.619 g of TBT.
Experimental example 1 contained 750.8 grams TCDDM, 78.4 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 2 contained 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 contained 1015.8 grams TCDDM, 313.6 grams DBC, 153.6 grams EG, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 4 contained 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, the mixture is put into a proper pressure environment and heated, so that the monomers react to generate oligomer; and operation (c) heating the mixture including the oligomer and performing vacuum pumping to remove unreacted monomers, and then continuously subjecting the mixture to the heating temperature to perform polymerization of the oligomer in the mixture to form the polyester 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 tensile strength, flexural strength, impact resistance, glass transition temperature (Tg), melting temperature (Tm), Intrinsic Viscosity (IV), and penetration test. The test results are shown in tables 1 and 2.
Tensile strength was measured using a universal material tester (manufactured by Instron corporation) in accordance with ISO 527.
Flexural strength was tested using a universal material testing machine and according to ISO 178.
Impact resistance test was performed according to ISO 180 using a test machine manufactured by Intertek.
The glass transition temperature and melting temperature were measured using a differential scanning calorimeter (DSC, TA instruments) and tested in accordance with ISO 3146.
Intrinsic viscosity was tested according to ASTM D4603.
The penetration was measured using a haze meter (NIPPON DENSHOKU NDH-2000) and in accordance with 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 as shown in tables 1 and 2, the glass transition temperatures were all below 110 ℃. As for the molar ratios of formula (2)/formula (1) of experimental examples 1to 4, which were 0.1, 0.3, 0.4 and 0.6, respectively, the glass transition temperatures were between 112 ℃ and 119 ℃ as shown in tables 1 and 2. It is understood that the molar ratio of formula (2)/formula (1) in the range of more than 0.05 to less than 0.8 can increase the glass transition temperature of the polycarbonate polyester, and provide better heat resistance, and in addition, can provide better tensile strength and flexural strength, and have better mechanical properties.
The molar ratio of formula (2)/formula (1) in experimental example 3 and comparative example 4 was 0.4, except that TCDDM and CHDM were used, respectively, and the glass transition temperatures were 117 ℃ and 90 ℃ as shown in Table 2, respectively, whereby it was found that the polycarbonate polyester had better heat resistance, better tensile strength and flexural strength, and better mechanical properties.
Comparative example 5 and Experimental example 5
Tricyclodecane dimethanol (TCDDM), dibutyl carbonate (DBC), Butanediol (BDO), terephthalic acid (PTA), and titanium (IV) butoxide (TBT) were added to the autoclave in various weight ratios and stirred uniformly to form the mixtures 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 of BDO, 747.6 grams of PTA, and 0.619 grams of TBT.
Experimental example 5 contained 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 tests for tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, and penetration degree. The test results are listed in 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 ratios of formula (2)/formula (1) in comparative example 5 and experimental example 5 were 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 the mechanical properties and heat resistance were better than those of comparative example 5.
Comparative example 6 and Experimental example 6
Tricyclodecane dimethanol (TCDDM), dibutyl carbonate (DBC), 2-methyl-1,3-propanediol (2-methyl-1,3-propanediol, MPO), terephthalic acid (PTA), and titanium (IV) butoxide (TBT) were added to the autoclave in various weight ratios and stirred uniformly to form the 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 TCDDM, 39.2 grams DBC, 223.0 grams MPO, 747.6 grams PTA, and 0.619 grams TBT.
Experimental example 6 contained 1015.8 grams TCDDM, 313.6 grams DBC, 223.0 grams MPO, 747.6 grams PTA, and 0.619 grams TBT.
Then, the above operations (b) and (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 tests for tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, and penetration degree. The test results are listed in 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 ratios of formula (2)/formula (1) in comparative example 6 and experimental example 6 were 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
Tricyclodecane dimethanol (TCDDM), dibutyl carbonate (DBC), Ethylene Glycol (EG), terephthalic acid (PTA), 1, 4-naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, NDA) and titanium (IV) butoxide (TBT) were added to the 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 g of TCDDM, 153.6 g of EG, 448.6 g of PTA, 389.1 g of NDA and 0.619 g of TBT.
Experimental example 7 contained 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 tests for tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, and penetration degree. The test results are listed 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 ratios of formula (2)/formula (1) in comparative example 7 and experimental example 7 were 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 than those of comparative example 7, and the mechanical properties and heat resistance were better.
Comparative example 8 and Experimental example 8
Tricyclodecane dimethanol (TCDDM), dibutyl carbonate (DBC), terephthalyl alcohol (PXG), Ethylene Glycol (EG), and terephthalic acid (PTA) were added to the 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 contained 1325 grams TCDDM, 235.2 grams DBC, 3.5 grams TMA, 0.772 grams TBT, 0.25 grams Mn (OAc)2, and 747.6 grams PTA.
Then, the above operations (b) and (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 for tensile strength, flexural strength, impact resistance, glass transition temperature, melting temperature, intrinsic viscosity, and penetration degree.
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) in comparative example 8 and experimental example 8 was 0.3, 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 are 81 ℃ and 118 ℃, respectively, which means that the use of TCDDM can provide polycarbonate polyester with better heat resistance and better transmittance.
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, it is intended that the present disclosure cover modifications and variations of this invention provided they come within the scope of the appended claims.
Claims (8)
1. A polycarbonate polyester comprising residues of the following formulae (1), (2), and (3):
wherein R is1Is C2-C15A hydrocarbyl group;
R2is C4-C16A hydrocarbyl group;
the molar ratio of the residue of formula (2) to the residue of formula (1) is in the range of greater than 0.05 to less than 0.8;
denotes a bond.
2. The polycarbonate polyester of claim 1, wherein 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.
3. The polycarbonate polyester of claim 1, wherein the residue of formula (1) comprises:
4. the polycarbonate polyester of claim 3, wherein the residue of formula (1) further comprises C2-C15Aliphatic linear or branched diol residues of (2).
5. The polycarbonate polyester of claim 4, wherein the C is2-C15Is selected from the group consisting of:
6. The polycarbonate polyester of claim 4, wherein the C is2-C15Is selected from the group consisting of:
7. The polycarbonate polyester of claim 1, wherein R2Is composed of
Or a combination of the foregoing, wherein x represents a bond.
8. The polycarbonate polyester of claim 1, wherein the residues of formula (3) comprise not greater than 50 mole% of the polycarbonate polyester.
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| 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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