CN113321796A - High-transparency high-heat-resistance copolyester resin and preparation method thereof - Google Patents
High-transparency high-heat-resistance copolyester resin and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention relates to a polyester high molecular material, and discloses a high-transparency high-heat-resistance copolyester resin and a preparation method thereof, wherein the copolyester resin comprises the following components: (1) the dibasic acid component comprises: (a)80 to 100 mole% of terephthalic acid residues; and (b)0 to 20 mol% of aromatic dibasic acid residue; and (2) the glycol component comprises: (a)20 to 85 mole% of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol residues; and (b)15 to 80 mole% of a first diol residue; and (c)0 to 30 mole% of a second diol residue; the copolyester resin disclosed by the invention is beneficial to avoiding blockage, improving the characteristic viscosity and inhibiting the loss of CBDO monomers in the preparation process by introducing the pentanediol-containing residue or the propylene glycol residue, and the obtained copolyester has high glass transition temperature, excellent strength, toughness and thermal stability and can effectively inhibit foaming, foaming and expansion phenomena caused by thermal decomposition in the melt processing process.
Description
Technical Field
The invention relates to a polyester high polymer material, in particular to a high-transparency high-heat-resistance copolyester resin and a preparation method thereof.
Background
Polycarbonate (PC) based on bisphenol a is the most commonly used high-transparency high-heat-resistant polymer material. PC has excellent transparency, heat resistance and toughness, the light transmittance of the PC is more than 90 percent, the glass transition temperature of the PC is about 150 ℃, the PC can be used for a long time at 120 ℃, and the PC is an important engineering plastic and is also commonly used for water cups, feeding bottles and household utensils. Since PC releases bisphenol a (BPA) at high temperatures and BPA is absorbed by the human body to cause endocrine disorders, PC is concerned about safety and is prohibited from being used in food contact products such as milk bottles.
In 2007, eastman corporation, usa developed 2,2,4, 4-tetramethyl-1, 3-Cyclobutanediol (CBDO) which is a high steric hindrance diol monomer, and the high transparency and high heat resistance copolyester is prepared by copolycondensating CBDO with 1, 4-Cyclohexanedimethanol (CHDM) and dimethyl terephthalate, and is also called as Tritan (PCcBT) copolyester in the invention) and is used as a substitute for PC. The Tritan copolyester has the glass transition temperature of about 120 ℃ at most, has the characteristics of high transparency, high heat resistance, high toughness, no BPA release and high temperature resistance of 100 ℃ in part of brands, and can be used as a baby feeding bottle.
However, as safe high-transparency high-heat-resistant polymer materials, Tritan copolyester resin and other high-transparency high-heat-resistant copolyesters using CBDO as a high-steric hindrance monomer still have the following technical problems in their manufacture, processing and application.
(1) The heat resistance is low. Currently, the Tg of Tritan copolyester products is up to about 120 ℃ which is significantly lower than 150 ℃ for PC; the heat distortion temperature is only 109 ℃ at the most.
(2) The thermal stability is insufficient, and the copolyester is easy to decompose in high-temperature processes such as melt polycondensation, melt processing and the like, generates gas, expands and influences the normal running of reaction and processing. For example, chinese patent publication CN101300285A mentions that the melt level is very unstable without adding a stabilizer, excessive foaming and foaming result in high porosity of the melt, and the melt interface rises rapidly and easily overflows from the flask without stirring or at a low stirring speed. Even with the addition of stabilizers, a stable melt level and limited gas evolution are maintained only at the proper catalyst/stabilizer ratio; chinese patent publication CN104736600A mentions that CHDM residues and CBDO residues decompose to generate volatile components of carbon monoxide and carbon dioxide during high temperature film extrusion, which makes venting difficult and processing difficult, and the resulting sheet has trumpet-shaped defects.
(3) Both the CHDM and the CBDO are solid at room temperature, wherein the CBDO has high melting point and boiling point, is easy to sublimate, has low solubility in CHDM melt, is easy to block pipelines and equipment in the polymerization and recovery processes, and has potential safety hazard; the industry needs additional insulation of the pipes and equipment to prevent clogging, resulting in increased production costs and energy consumption.
(4) CBDO is easy to lose due to sublimation or side reaction in the polymerization process, and CBDO, particularly trans-CBDO cannot enter the copolyester structure completely, so that the content of CBDO residues in the copolyester (namely the composition of the copolymer) is obviously lower than that in a dihydric alcohol monomer (namely the composition of the monomer). For example, in chinese patent publication CN101193938A, when the amount of CBDO charged was 30 mol% of the total amount of diol, the CBDO residues in the final polymer accounted for only 20 mol% of the total amount of diol residues, or even lower. In chinese patent publication CN104736600A, the cis-trans ratio of the added CBDO monomer is 53/47 at high polycondensation temperature, while the cis-trans ratio of the CBDO residue in the resulting copolyester becomes 70/30, which deviates to 60/40 even at lower temperatures. In the chinese patent publication CN104736600A, the cis-trans ratio of CBDO residues of the obtained copolyester is deviated from the cis-trans ratio of CBDO of the monomer to positive extent to a different extent, for example, when the cis-trans ratio of CBDO monomer is 50/50, the cis-trans ratio of CBDO residues of the obtained copolyester is 51.4/48.6 to 54.0/46.0.
(5) Copolymers rich in poly (1, 4-cyclohexylenedimethylene terephthalate) (PCT) chain segments and even PCT homopolymers which have high melting points and are easy to crystallize and precipitate are easy to generate in the reaction process, so that the molecular weight and the transparency of the product are obviously reduced, and the precipitated PCT pollutes equipment. To avoid precipitation, chinese patent publication CN103755930A uses a reaction temperature of 280 ℃ or higher, but high temperature will intensify the thermal decomposition of CBDO and CHDM monomers and products, generating chromophoric groups, and producing colored and low molecular weight products. Chinese patent publication CN101379619A proposes a method of fractional transesterification to solve the above problems, i.e. after dimethyl terephthalate reacts with all or part of CBDO to form polyester oligomer, it reacts with all or part of CHDM to obtain oligomer, which is further polymerized to obtain polymer with high molecular weight. This staged addition reaction process can reduce PCT precipitation but still cannot be completely avoided and increases process costs.
(6) Copolyesters are prone to discoloration during polycondensation and processing. Chinese patent publication CN101300285A mentions that Tritan copolyester is liable to have a yellow color, and even if a stabilizer is added, a yellowish product may be obtained.
Therefore, how to obtain the high-transparency high-heat-resistance copolyester with higher heat resistance and thermal stability based on CBDO, how to obtain a polymerization method and a process which can avoid CBDO blockage, improve controllability of copolymer composition and cis-inverse ratio, inhibit color change and avoid generation of precipitates at lower reaction temperature, and still remain the technical problems to be solved in the fields of high-transparency high-heat-resistance copolyester products and preparation methods thereof.
Disclosure of Invention
The invention aims to solve the problems that the copolyester based on CBDO has poor thermal stability, is easy to sublimate to generate gas and block pipeline equipment, has poor transparency and is easy to discolor in the prior art, and provides the copolyester based on terephthalic acid, dimethyl terephthalate and CBDO monomers, which has excellent thermal stability and mechanical strength, high transparency and difficult discoloration.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-transparency high-heat-resistance copolyester resin comprises the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)80 to 100 mol% of terephthalic acid residues; and
(b)0 to 20 mol% of an aromatic dibasic acid residue;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)20 to 85 mole% of 2,2,4, 4-tetramethyl-1, 3-Cyclobutanediol (CBDO) residues; and
(b)15-80 mol% of a first diol residue; and
(c)0 to 30 mol% of a second glycol residue;
the aromatic dibasic acid residue comprises at least one of isophthalic acid residue, phthalic acid residue, diphenic acid residue, naphthalenedicarboxylic acid residue, furandicarboxylic acid residue and thiophenedicarboxylic acid residue;
the first dihydric alcohol residue includes at least one of a 1, 5-pentanediol residue, a 2-methyl-1, 5-pentanediol residue, a 3-methyl-1, 5-pentanediol residue, a 2-ethyl-1, 5-pentanediol residue, a 3, 3-dimethyl-1, 5-pentanediol residue, a 3, 3-diethyl-1, 5-pentanediol residue, a 2-methyl-1, 3-propanediol residue, a 2-ethyl-1, 3-propanediol residue;
the second diol residue comprises at least one of aliphatic diol residue with the main chain carbon atom number less than or equal to 4 or alicyclic or heterocyclic diol residue with the carbon atom number less than or equal to 12.
Because the 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol residue chain segment has stronger rigidity, higher glass transition temperature and poorer toughness, the toughness of the copolyester is improved by introducing the chain segment containing pentanediol residue or propylene glycol residue into the copolyester, and the copolyester with better glass transition temperature and toughness is obtained by regulating the proportion of the chain segment.
The copolymer composition and CBDO residue of the copolyester are high in sequential and inverse controllability, pipelines and equipment blockage caused by volatilization and condensation of CBDO monomers can be avoided in the preparation process, and foaming, foaming and expansion phenomena of the obtained copolyester resin in the melt processing process are effectively inhibited.
When the content of CBDO residues is too high, the characteristic viscosity of the copolyester is difficult to improve due to too much rigid structure, and the thermal property and the mechanical property of the copolyester are further influenced; and the content of the residue chain segment of the pentanediol or the propanediol is too high, the glass transition temperature of the copolyester can be greatly reduced, and the application of the copolyester is limited.
Preferably, the diol component, in a total of 100 mol%, comprises:
(a)50-80 mol% of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol residues; and
(b)20 to 50 mol% of a first dihydric alcohol residue; and
(c)0 to 30 mol% of a second glycol residue.
Further preferably, the copolyester resin comprises the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)100 mole% of terephthalic acid residues;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)50-80 mol% of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol residues; and
(b)20 to 50 mol% of a first dihydric alcohol residue.
The molar ratio of the dibasic acid component to the glycol component is 1:1-1:3, preferably 1: 1.1-1: 2, and more preferably 1: 1.1-1: 1.5.
Further preferably, the aromatic dibasic acid residue comprises an isophthalic acid residue and/or a phthalic acid residue.
Further preferably, the first dihydric alcohol residue comprises at least one of a 1, 5-pentanediol residue, a 3-methyl-1, 5-pentanediol residue, a 2-methyl-1, 3-propanediol residue, a 2-ethyl-1, 5-pentanediol residue, a 3-ethyl-1, 5-pentanediol residue;
further preferably, the first dihydric alcohol residue comprises at least one of a 1, 5-pentanediol residue, a 3-methyl-1, 5-pentanediol residue, a 2-methyl-1, 3-propanediol residue;
most preferably, the first dihydric alcohol residue is a 2-methyl-1, 3-propanediol residue;
the aliphatic diol residue with the main chain carbon atom number less than or equal to 4 comprises at least one of ethylene glycol residue, 1, 3-propylene glycol residue, 1, 4-butanediol residue, 2, 3-butanediol residue and 1, 2-propylene glycol residue;
the alicyclic or heterocyclic diol residue with the carbon number less than or equal to 12 comprises at least one of 1, 4-cyclohexanedimethanol residue and cyclohexanediol residue.
The intrinsic viscosity of the copolyester resin is 0.53-0.90dL/g, and the intrinsic viscosity is measured at 25 ℃ by using 3/2wt/wt phenol/tetrachloroethane as a solvent. The copolyester provided by the invention has high intrinsic viscosity which is more than or equal to 0.60dL/g and up to 0.90dL/g in most cases, and can effectively inhibit the thermal degradation of raw materials and intermediate products, so that the obtained copolyester has light color.
The intrinsic viscosity of the copolyester resin is preferably 0.59-0.80 dL/g, and more preferably 0.60-0.75 dL/g.
The glass transition temperature (Tg) of the copolyester resin can be adjusted in a wide range (60-150 ℃), and even if the glass transition temperature is lower under the same CBDO content, the copolyester with high Tg can be prepared by increasing the content of CBDO chain links. The glass transition temperature of the copolyester resin is similar to or higher than that of the conventional copolyester in the prior art (110 ℃), so that the copolyester resin has higher Young modulus, tensile strength and ductility and better mechanical property.
The glass transition temperature of the copolyester resin is preferably 80-140 ℃, and more preferably 100-136 ℃.
In the prior art, because CBDO has a cyclic large steric hindrance structure and the hydroxyl group of CBDO is connected with secondary carbon, the reactivity of CBDO with acid or ester is obviously lower than that of the first dihydric alcohol. With increasing CBDO content, the molecular weight of the copolyester is more difficult to increase. In order to obtain high intrinsic viscosity, the prior art often adopts high (more than or equal to 280 ℃) polycondensation reaction temperature. However, higher polymerization temperatures further exacerbate the sublimation of CBDO and copolyester products, resulting in further aggravated line plugging.
The invention also provides a preparation method of the high-transparency high-heat-resistance copolyester resin, which can achieve high characteristic viscosity at the reaction temperature of lower than 280 ℃, can efficiently avoid CBDO blockage, efficiently reduce the composition difference and the cis-inverse ratio difference of the copolymer composition and the monomer, efficiently avoid the generation of opaque products and efficiently inhibit the discoloration of products, and comprises the following steps:
(1) carrying out esterification or ester exchange reaction on a mixture containing a dibasic acid component and a dihydric alcohol component at 200-250 ℃ to obtain an intermediate product;
(2) polycondensing the intermediate product at a pressure of 10-200Pa and a temperature of 250-270 ℃ to obtain the copolyester resin;
the mixture comprises the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)80 to 100 mol% of terephthalic acid or dimethyl ester thereof; and
(b)0 to 20 mol% of an aromatic dibasic acid or its dimethyl ester;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)20-85 mol% of 2,2,4, 4-tetramethyl-1, 3-Cyclobutanediol (CBDO); and
(b)15-80 mol% of a first glycol; and
(c)0-30 mol% of a second glycol;
the aromatic dibasic acid or the dimethyl ester thereof comprises at least one of isophthalic acid or the dimethyl ester thereof, phthalic acid or the dimethyl ester thereof, biphenyl dicarboxylic acid or the dimethyl ester thereof, naphthalene dicarboxylic acid or the dimethyl ester thereof, furan dicarboxylic acid or the dimethyl ester thereof, and thiophene dicarboxylic acid or the dimethyl ester thereof;
the first dihydric alcohol comprises at least one of 1, 5-pentanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 5-pentanediol, 3-dimethyl-1, 5-pentanediol, 3-diethyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-propanediol;
the second dihydric alcohol comprises at least one of aliphatic dihydric alcohol with the carbon atom number of the main chain less than or equal to 4 or alicyclic or heterocyclic dihydric alcohol with the carbon atom number less than or equal to 12.
Preferably, the diol component, in a total of 100 mol%, comprises:
(a)50-80 mol% of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol; and
(b)20 to 50 mol% of a first dihydric alcohol; and
(c)0 to 30 mol% of a second glycol.
Further preferably, the copolyester resin comprises the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)100 mol% of terephthalic acid or its dimethyl ester;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)50-80 mol% of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol; and
(b)20 to 50 mol% of a first dihydric alcohol.
Further preferably, the aromatic dibasic acid or its dimethyl ester comprises isophthalic acid or its dimethyl ester and/or phthalic acid or its dimethyl ester.
Further preferably, the first dihydric alcohol comprises at least one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 5-pentanediol, 3-ethyl-1, 5-pentanediol;
further preferably, the first dihydric alcohol comprises at least one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol;
most preferably, the first dihydric alcohol is 2-methyl-1, 3-propanediol;
preferably, the aliphatic diol with the main chain carbon atom number less than or equal to 4 comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol and 1, 4-pentanediol;
the alicyclic or heterocyclic diol with the carbon number less than or equal to 12 comprises at least one of 1, 4-cyclohexanedimethanol and cyclohexanediol.
CBDO is a key monomer of the high-transparency high-heat-resistance copolyester and is also key to controlling the cost of the copolyester, so that the CBDO monomer which is input is expected to be completely or possibly introduced into the structure of the copolyester chain, and the loss and the recovery load of the CBDO monomer are reduced. However, in practice, because of losses caused by side reactions (especially, the trans-form CBDO is more susceptible to side reactions), volatilization, sublimation, etc., the content of CBDO residues in the copolyester is often significantly lower than the content of CBDO added to the diol monomer, and the content of cis-CBDO residues in the copolyester is significantly higher than the cis-CBDO content in the monomer, and there are deviations between them. These deviations are desired to be minimized in the industry, which reduces CBDO monomer loss and recovery load, and also improves the overall properties of the resulting copolyester.
The composition deviation, relative composition deviation, cis deviation and cis relative deviation of the copolyester are obviously lower than those of the copolyester in the market, and the copolyester has obvious advantages in the aspect of avoiding CBDO side reaction and loss and introducing the input CBDO into the copolyester as much as possible.
In the case of the copolyester resin, it is preferable that,
the difference between the molar percentage of the CBDO residue in the diol residue and the molar percentage of the CBDO monomer in the diol monomer is less than or equal to 8 mol%; preferably, the difference is 6 mol% or less, more preferably 3 mol% or less;
the difference between the ratio of the cis-CBDO residue in the CBDO residue and the ratio of the cis-CBDO monomer in the CBDO monomer is less than or equal to 8%, preferably, the difference between the two is less than or equal to 3%, more preferably, less than or equal to 2%.
The mixture also comprises a catalyst, a heat stabilizer and a light stabilizer;
the dosage of the catalyst is less than 1 wt% of the mass of the dibasic acid component;
the using amount of the heat stabilizer is 0.1-1 wt% of the weight of the dibasic acid component;
the using amount of the light stabilizer is less than 1 wt% of the mass of the dibasic acid component.
The catalyst comprises a tin-based catalyst; or comprises tin catalyst and one or more of tetrabutyl titanate, isopropyl titanate, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate and manganese acetate;
the tin catalyst is one or more selected from dibutyltin oxide, stannous octoate, stannous oxalate, dibutyltin diacetate and dibutyltin dilaurate.
The heat stabilizer is selected from heat stabilizer 1010, heat stabilizer 1500, heat stabilizer 1076, heat stabilizer 425, heat stabilizer 330, heat stabilizer 1178, heat stabilizer 501, heat stabilizer 618, heat stabilizer 626, heat stabilizer 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol bis (2, 4-tert-butylphenyl) diphosphite, bis (2, 4-di-p-isopropylphenyl) pentaerythritol diphosphite phosphoric acid, pentaerythritol tetraphenyl tridecyl phosphite, pentaerythritol diphosphodecyl phosphite, pentaerythritol diisodecyl phosphite, pentaerythritol tetradecyl phosphite, heat stabilizer 1178, heat stabilizer 626, heat stabilizer 168, heat stabilizer 626, heat stabilizer TDD heat stabilizer, heat stabilizer phosphate, heat stabilizer active agent, heat active agent, and heat active agent, and heat active agent, and heat active agent, Pentaerythritol dioctadecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate.
The light stabilizer is selected from one or more of light stabilizer 791, light stabilizer 700, light stabilizer 783, light stabilizer 119, light stabilizer 770, light stabilizer 622, light stabilizer 944, light stabilizer 1164, 2,2,6, 6-tetramethyl-4-piperidine stearate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, 2-hydroxy-4-n-octoxybenzophenone, (3, 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and poly (1-hydroxyethyl, 2,2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.
Preferably, the heat stabilizer comprises at least one of heat stabilizer 1010, heat stabilizer 1500 and heat stabilizer 626;
preferably, the light stabilizer includes at least one of light stabilizer 700, light stabilizer 783, and light stabilizer 119.
Compared with the prior art, the invention has the following beneficial effects:
(1) the copolyester resin of the invention improves the toughness of copolyester by introducing chain segments containing pentanediol residues or propanediol residues to obtain the copolyester resin with excellent comprehensive performance, the glass transition temperature of the copolyester resin can be adjusted within the range of 85-150 ℃, and the copolyester resin has good heat resistance; meanwhile, the high-temperature melt polycondensation foaming agent has excellent thermal stability, is beneficial to improving the characteristic viscosity number in the high-temperature polycondensation process, can effectively avoid foaming, foaming and expansion phenomena caused by thermal decomposition in the melt processing process, and obviously improves the processability; the product also has excellent strength and toughness, the tensile strength is not lower than 37MPa, and the elongation at break is not lower than 25%.
(2) The copolyester resin CBDO can be dissolved in a monomer containing pentanediol or propanediol, and can prepare copolyester with high characteristic viscosity number at a lower temperature, and simultaneously, the thermal degradation of raw materials and intermediate products is effectively inhibited, and the obtained copolyester is light in color; meanwhile, pipeline and equipment blockage caused by volatilization and condensation of the CBDO monomer in the preparation process is avoided, and foaming, foaming and expansion phenomena of the obtained copolyester resin in the melt processing process are effectively inhibited.
(3) According to the preparation method of the copolyester resin, the input CBDO monomer is introduced into the copolyester chain structure as much as possible, and the cis-inverse ratio of the CBDO residue in the polyester is closer to the cis-inverse ratio of the CBDO monomer, so that the consumption and the recovery load of the CBDO monomer can be reduced, and the cost is further reduced.
In conclusion, the high-transparency high-heat-resistance copolyester provided by the invention has excellent comprehensive performance, and the preparation process can effectively solve the technical problems of blockage, thermal decomposition, color change, composition, forward and reverse ratio regulation and control and the like, and is favorable for realizing large-scale production.
Drawings
FIG. 1 is a graph showing the occurrence of clogging of piping and receiver bottles in the synthesis process of comparative example 2.
FIG. 2 is a graph showing that the piping and receiver flask were not clogged during the synthesis of example 2.
FIG. 3 is a diagram showing how the copolyesters prepared in comparative example 1, example 1 and example 2 are foamed by heating at 240 ℃ for 5 hours in a flask and then cooling to room temperature, (a) is comparative example 1, (b) is example 1, and (c) is example 2.
FIG. 4 shows the samples of the sheet obtained by molding comparative example 1 and example 5, wherein (a) is comparative example 1 and (b) is example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available.
In the following embodiments, the names, acronyms, and abbreviations for the monomer residues of the diacids and diols used are shown in table 1. Is composed of monomers
Expressed in physical terms as the percentage of the amount of material of monomer x to the sum of the amounts of material of all glycol or diacid monomers. If cis-trans isomerism exists, the cis content of the monomer is as follows
Expressed in terms of its physical meaning as a molar percentage of cis monomer x relative to the total amount of the monomer (including cis and trans). For example, for the diol monomer CBDO,
representing the mole percent of CBDO to all diol monomers,
represents the molar percentage of cis-CBDO to the total amount of CBDO, including cis-CBDO and trans-CBDO.
TABLE 1 summary of the names and abbreviations of the monomers used in the examples
| Name of monomer | Abbreviation for monomer | Abbreviation for monomer residue |
| Terephthalic acid, dimethyl terephthalate | TPA，DMT | T |
| 2,2,2, 4-tetramethyl-1, 3-cyclobutanediol | CBDO | cB |
| 1, 5-pentanediol | PeDO | Pe |
| 3-methyl-1, 5-pentanediol | mPeDO | mPe |
| 2-methyl-1, 3-propanediol | mPDO | mP |
| Ethylene glycol | EG | E |
| 1, 4-cyclohexanedimethanol | CHDM | C |
In the following embodiments, the copolyesters produced are represented by PXY, where X is an abbreviation for all diol residues and Y is an abbreviation for all diacid residues. Subscripts to residues indicate copolymer composition, i.e., the amount of material of the residue is binaryThe percentage of the sum of the amounts of substances of alcohol residues or diacid residues; the presence of residues X in the copolyester indicates cis-trans isomerism of the residues, and the superscript indicates the molar percentage of cis-residues φcis,XI.e., the percentage of the amount of material of the cis residue to the sum of the amounts of material of the residue (including cis and trans). For example,
showing a copolyester comprising ethylene glycol residues (E), 1, 5-pentanediol residues (Pe), 2,4, 4-tetramethyl-1, 3-cyclobutanediol residues (cB) and terephthalic acid residues (T), wherein the contents of E residues, Pe residues and cB residues in the diol residues (phi)E、φPe、φcB) 9 mol%, 27 mol% and 64 mol%, respectively, of the cB residues, the cis cB residues account for 62 mol% of the total cB residues (including cis and trans). To the copolyester with phicB64 mol% denotes the copolymer composition,. phi.cis,cB62 mol% indicates the content (molar percentage) of cis-cB residues. In addition, for the sake of simplicity, for the copolymerization in which two alcohols are involved, only the content of one of the alcohol residues is indicated, and the content of the other alcohol residue is apparently obtained, and therefore, redundant notation is not given. For example,
the content of cB residues was 34%, and the content of mPe residues was 66% to 100%.
In the following embodiments, the apparent esterification ratio or the apparent ester exchange ratio is described as follows: in the production of polyesters by the esterification-polycondensation or transesterification-polycondensation process, the esterification rate or transesterification rate is generally determined as the percentage of the amount of by-product water or methanol collected as a theoretical yield of water or methanol. However, during the esterification-polycondensation or transesterification-polycondensation reaction in which CBDO participates, low-boiling by-products (e.g., aldehydes) formed can enter the distillate collection bottle with water or methanol due to the presence of undesirable side reactions. The esterification rate or ester exchange rate calculated by using all fractions as water or methanol is referred to as an apparent esterification rate or an apparent ester exchange rate. They are numerically larger than the true esterification or transesterification rate, but the extent to which the esterification or transesterification reaction proceeds can still be roughly estimated from their size.
In the following specific embodiments, the test assays used are as follows:
characteristic viscosity number: the Intrinsic Viscosity (IV) of the copolyester sample was measured by a zhongzhou zhongwang automatic viscometer at 25 ℃ in a solvent of phenol/tetrachloroethane (w/w: 3/2);
and (3) characterizing a chemical structure: the chemical structure of the copolyester is characterized by adopting a Bruker AC-80400M nuclear magnetic resonance instrument, deuterated chloroform is used as a solvent, and tetramethylsilane is used as an internal standard;
thermal properties: adopting Q200 of American TA company to measure a DSC curve of a sample, adopting a temperature program of primary heating-cooling-secondary heating, and measuring the temperature range of room temperature to 250 ℃, the heating and cooling rate of 10 ℃/min and the isothermal time of 3 min;
tensile property: a dumbbell-shaped sample bar with the width of 4mm and the thickness of 2mm is prepared by a HaakeMidijet 11 micro injection molding machine, and is measured after being placed for 1 week at room temperature. Tensile testing was carried out at 25 ℃ and a tensile rate of 10mm/min according to ASTM D638 using a Roell 2020 Universal Material tester from Zwick, Germany. Each sample is tested with 5 splines, and the average value is taken as the test result;
comparative example 1
Synthesis of (2)
(1) To N2An atmospheric reactor was charged with 67.96g (0.35mol) of dimethyl terephthalate, 29.53g (0.20mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content 45%), 36.09g (0.25mol, cis content 26%) of 1, 4-cyclohexanedimethanol, and 0.2039g of dibutyltin oxide, and 10100.068g of a main stabilizer and 6260.034 g of an auxiliary stabilizer were added to react at 220 ℃ for 2.5 hours to obtain an ester exchange product. During the reaction, a small amount of solid sublimated and remained in the subsequent pipeline, but the pipeline was not blocked.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 2.5h to obtain product with intrinsic viscosity of 0.69dL/g and phicBIs 35.4mol％、φcis,cB50.4 mol%, phiC64.6 mol%, phicis,C29.7 mol% of copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 4-cyclohexanedimethanol terephthalate), described
In the reaction process, a large amount of solid is pumped out of the reactor, a pipeline is seriously blocked, and the system is difficult to maintain at a high vacuum degree; the temperature of the pipeline is increased by heating the pipeline, so that the pipeline is dredged, and the reaction is continued under high vacuum degree. Furthermore, after 0.5h of reaction, the melt level in the reaction began to be unable to maintain a steady state, unstable evolution of gas, severe foaming and foaming resulted in high void volumes, and it was necessary to break the foam and bubble by stirring to prevent the melt from overflowing from the flask.
Comparative example 2
Synthesis of (2)
(1) To N258.15g (0.35mol) of terephthalic acid, 39.37g (0.273mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content 45%), 26.25g (0.182mol) of 1, 4-cyclohexanedimethanol (cis content 26%) and 0.2039g of dibutyltin oxide are added into an atmosphere reactor, and reacted at 210 ℃ for 1h and 220 ℃ for 3h to obtain an esterified product. During the reaction, a small amount of solid sublimated and remained in the subsequent pipeline, but the pipeline was not blocked.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 2h to obtain product with intrinsic viscosity of 0.62dL/g and phicB50.1 mol%, phicis,cB53.9 mol%, phiC49.9 mol%, phicis,C31.2 mol% of the copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 4-cyclohexanedimethanol terephthalate), described
During the reaction, a large amount of solid was withdrawn from the reactor, the piping was severely blocked (as shown in FIG. 1), and it was difficult to maintain the system at a high vacuum, by heatingThe pipeline is dredged by removing the solid remained in the pipeline in time, so that the reaction can be continuously carried out under high vacuum degree. Furthermore, after 0.3h of reaction, the melt level in the reaction began to be unable to maintain a steady state, unstable evolution of gas, severe foaming and foaming resulted in high void volumes, and it was necessary to break the foam and bubble by stirring to prevent the melt from overflowing from the flask.
Comparative example 3 commercial copolyester having the designation EX401 was made up by nuclear magnetic analysis, phicB36.6 mol%, phicis,cBIs 55.4 mol%, phiC63.4 mol%, phicis,CIt was 29.6 mol%. The intrinsic viscosity was 0.66 dL/g.
Example 1
Synthesis of (2)
(1) To N2An atmosphere reactor is added with 67.96g (0.35mol) of dimethyl terephthalate, 30.28g (0.21mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 37.22g (0.315mol) of 3-methyl-1, 5-pentanediol and 0.2039g of dibutyltin oxide, 10100.068g of a main stabilizer and 6260.034 g of an auxiliary stabilizer are added, and the mixture is reacted for 3 hours at 220 ℃ to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of 200Pa for 2.7h to obtain product with intrinsic viscosity of 0.75dL/g and phicB34.3 mol%, phicis,cBThe copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-3-methyl-1, 5-pentanediol terephthalate), at 63.8 mol%, is described
During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 2
Synthesis of (2)
(1) To N267.96g (0.35mol) of dimethyl terephthalate, 37.86g (0.2625mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 23.66g (0.2625mol) of 2-methyl-1, 3-propanediol and 0.2039g of dibutyltin oxide are added into an atmosphere reactor, 10100.068g of a main stabilizer and 6260.034 g of an auxiliary stabilizer are added into the atmosphere reactor, and the mixture is reacted for 2.5 hours at 220 ℃ to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 1.5h to obtain product with intrinsic viscosity of 0.70dL/g and phicB46.5 mol%, phicis,cBCopolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-2-methyl-1, 3-propanediol terephthalate) at 64.0 mole%, reported
During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and eventually into the collection vial, unblocking the line (as shown in fig. 2). The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 3
Synthesis of (2)
(1) To N258.15g (0.35mol) of terephthalic acid, 45.43g (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 60%), 21.87g (0.21mol) of 1, 5-pentanediol and 0.1744g of dibutyltin oxide are added into an atmosphere reactor, and the mixture is reacted at 210 ℃ for 1h, 220 ℃ for 1h and 230 ℃ for 5h to obtain an esterified product. During the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 3h to obtain product with intrinsic viscosity of 0.67dL/g and phicB54.6 mol%, phicis,cB62.8 mol% copolyester-poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-terephthalate1, 5-pentanediol ester) and
during the reaction, a viscous clear liquid with a small amount of white solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 4
Synthesis of (2)
(1) To N267.96g (0.35mol) of dimethyl terephthalate, 45.43g (cis content is 62%) (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 24.82g (0.21mol) of 3-methyl-1, 5-pentanediol and 0.2039g of dibutyltin oxide are added into an atmosphere reactor, and the mixture is reacted at 210 ℃ for 1h and at 220 ℃ for 2h to obtain a transesterification product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of 200Pa for 2h to obtain product with intrinsic viscosity of 0.63dL/g and phicBIs 54.7 mol%, phicis,cBCopolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-3-methyl-1, 5-pentanediol terephthalate), at 64.0 mol%, reported
During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 5
Synthesis of (2)
(1) To N2An atmospheric reactor was charged with 67.96g (0.35mol) of dimethyl terephthalate, 45.43g (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content 62%), 18.93g (0.21mol) of 2-methyl-1, 3-propanediol and 0.2039g of dibutyltin oxide, and 10100.0 as a main stabilizer68g and 6260.034 g of auxiliary stabilizer to react for 3.5 hours at 220 ℃ to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 1.5h to obtain product with intrinsic viscosity of 0.60dL/g and phicBIs 54.9 mol%, phicis,cBCopolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-2-methyl-1, 3-propanediol terephthalate) at 64.3 mole%, reported
The properties are shown in Table 4. During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 6
Synthesis of (2)
(1) To N258.15g (0.35mol) of terephthalic acid, 53.00g (0.3675mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 60%), 16.40g (0.1575mol) of 1, 5-pentanediol and 0.1744g of dibutyltin oxide are added into an atmosphere reactor, and the mixture is reacted at 210 ℃ for 1h, 220 ℃ for 1h and 230 ℃ for 5h to obtain an esterification product; during the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 3h to obtain product with intrinsic viscosity of 0.59dL/g and phicB65.2 mol%, phicis,cB61.9 mol% of copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 5-pentanediol terephthalate), described
During the reaction, a viscous clear liquid with a small amount of white solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 7
Synthesis of (2)
(1) To N267.96g (0.35mol) of dimethyl terephthalate, 53.00g (0.3675mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 18.61g (0.1575mol) of 3-methyl-1, 5-pentanediol and 0.2039g of dibutyltin oxide are added into an atmosphere reactor and reacted for 3 hours at 220 ℃ to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 2.7h to obtain product with intrinsic viscosity of 0.53dL/g and phicBIs 64.3 mol%, phicis,cBThe copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-3-methyl-1, 5-pentanediol terephthalate), recorded as 63.9 mol%
During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 8
Synthesis of (2)
(1) 67.96g (0.35mol) of dimethyl terephthalate, 45.43g (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (with a cis content of 60 percent), 21.87g (0.21mol) of 1, 5-pentanediol and 0.2039g of dibutyltin oxide are added into a reactor with an atmosphere of N2 and reacted for 2.2 hours at 220 ℃ to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Polycondensing the ester exchange product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 1.7h to obtain product with intrinsic viscosity of 0.90dL/g and phicB52.6 mol%, phicis,cB59.2 mol% of copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclo-terephthalic acid)Butanediol-co-1, 5-pentanediol ester) and
the properties are shown in Table 4. During the reaction, a viscous clear liquid with a small amount of solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 9
Synthesis of (2)
(1) 58.15g (0.35mol) of terephthalic acid, 53.00g (0.3675mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 60%), 16.40g (0.1575mol) of 1, 5-pentanediol and 0.58g of dibutyltin oxide are added into a reactor with an atmosphere of N2, and the mixture is reacted at 210 ℃ for 1h, at 220 ℃ for 1h and at 230 ℃ for 4h to obtain an esterified product; during the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 1.5h to obtain product with intrinsic viscosity of 0.69dL/g and phicB65.7 mol%, phicis,cB61.1 mol% of copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 5-pentanediol terephthalate), described as
The properties are shown in Table 4. During the reaction, a viscous clear liquid with a small amount of white solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 10
Synthesis of (2)
(1) 58.15g (0.35mol) of terephthalic acid, 53.00g (0.3675mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 60%), 16.40g (0.1575mol) of 1, 5-pentanediol and 0.58g of dibutyltin oxide are added into a reactor with an atmosphere of N2, and the mixture is reacted at 210 ℃ for 1h, 220 ℃ for 1h and 230 ℃ for 4.5h to obtain an esterified product; during the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 2h to obtain product with intrinsic viscosity of 0.68dL/g and phicB64.5 mol%, phicis,cB61.5 mol% of copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 5-pentanediol terephthalate), described as
The properties are shown in Table 4. During the reaction, a viscous clear liquid with a small amount of white solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 11
Synthesis of (2)
(1) 58.15g (0.35mol) of terephthalic acid, 60.57g (0.42mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 60%), 10.94g (0.105mol) of 1, 5-pentanediol and 0.58g of dibutyltin oxide are added into a reactor with an atmosphere of N2, and the mixture is reacted at 210 ℃ for 1h, at 220 ℃ for 1h and at 230 ℃ for 5.3h to obtain an esterified product; during the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 260 deg.C under absolute pressure of less than or equal to 200Pa for 2h to obtain product with intrinsic viscosity of 0.59dL/g and phicB75.6 mol%, phicis,cBCopolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 5-pentanediol terephthalate) at 62.0 mol%, reported
The properties are shown in Table 4. During the reaction, a viscous clear liquid with a small amount of white solid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 12
Synthesis of (2)
(1) Adding 67.96g (0.35mol) of dimethyl terephthalate, 37.86g (0.26mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 31.02g (0.26mol) of 3-methyl-1, 5-pentanediol, 0.10g of TBT and 0.10g of dibutyltin oxide into a reactor with an atmosphere of N2, and reacting at 210 ℃ for 1h, 220 ℃ for 1.5h and 230 ℃ for 0.5h to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Adding 0.10g of TBT, polycondensing the ester exchange product for 2h at 260 ℃ under the absolute pressure of less than or equal to 200Pa to obtain the product with the intrinsic viscosity of 0.69dL/g and phicB43.0 mol%, phicis,cBThe copolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-3-methyl-1, 5-pentanediol terephthalate), at 63.4 mol%, is described
The properties are shown in Table 4. During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 13
Synthesis of (2)
(1) 67.96g (0.35mol) of dimethyl terephthalate, 45.43g (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 24.82g (0.21mol) of 3-methyl-1, 5-pentanediol, 0.10g of TBT and 0.10g of dibutyltin oxide are added into a reactor with an atmosphere of N2, and the mixture is reacted at 210 ℃ for 1h and at 220 ℃ for 2h to obtain an ester exchange product; during the reaction, no solids were observed in the line.
(2) Adding 0.10g of TBT, polycondensing the ester exchange product for 2h at 260 ℃ under the absolute pressure of less than or equal to 200Pa to obtain the product with the intrinsic viscosity of 0.63dL/g and phicBIs 54.7 mol%, phicis,cB64.0 mol% copolyester-poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-3-methyl-)1, 5-pentanediol ester), described as
The properties are shown in Table 4. During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Example 14
Synthesis of (2)
(1) Adding 58.15g (0.35mol) of terephthalic acid, 45.42g (0.315mol) of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol (cis content is 62%), 10.94g (0.105mol) of 1, 5-pentanediol, 6.517g (0.105mol) of ethylene glycol and 0.1745g of dibutyltin oxide into a reactor with an atmosphere of N2, and reacting at 210 ℃ for 1h, 220 ℃ for 1h and 230 ℃ for 4h to obtain an esterified product; during the reaction, no solids were observed in the line.
(2) Polycondensing the esterification product at 270 deg.C under absolute pressure of less than or equal to 200Pa for 1.3h to obtain product with intrinsic viscosity of 0.62dL/g and phicB63.6 mol%, phicis,cB62.0 mol%, phiPe27.5 mol%, phiECopolyester poly (2,2, 4, 4-tetramethyl-1, 3-cyclobutanediol-co-1, 5-pentanediol-co-ethylene terephthalate) at 8.9 mol%, reported
The properties are shown in Table 4. During the reaction, a viscous clear liquid was observed to be drawn out of the reactor and finally into a collection bottle without blocking the line. The melt liquid level is kept stable all the time in the reaction process, and a small amount of bubbles are generated.
Performance analysis
Firstly, about the blockage situation of the pipeline and the equipment
In the synthesis of PCcBT of comparative examples 1-2, CBDO and CHDM monomers are solid at room temperature, volatile and easy to sublimate, which easily causes the pipeline to be blocked in the polycondensation stage, especially serious for the synthesis of copolyester with high CBDO content, and even causes the pipeline to be blocked in the esterification/transesterification stage, thus causing the reaction to be difficult to continue, and the results of comparative example 1 are shown in fig. 1. Increasing the temperature of the piping avoids the above problems, but increases the process cost and energy consumption.
In the synthesis of the copolyesters of the present invention, as in examples 1-14, the fractions obtained during the synthesis were free or very low in visible solids, viscous but liquid with good flow properties, and the lines were not blocked, especially when the first diol was 3-methyl-1, 5-pentanediol or 2-methyl-1, 3-propanediol, the results of example 2 being shown in fig. 2. This is associated with the first diol being liquid at ambient temperature and the CBDO having good solubility in the first diol. The results show that the method has no pipeline blockage in the synthesis process, higher safety and lower operation energy consumption.
Two, composition deviation and cis-trans ratio deviation of copolymer
CBDO is a key monomer of the high-transparency high-heat-resistance copolyester and is also key to controlling the cost of the copolyester, so that the CBDO monomer which is input is expected to be completely or possibly introduced into the structure of the copolyester chain, and the loss and the recovery load of the CBDO monomer are reduced. However, in practice, the content of CBDO residue (. phi.) in the copolyester is lost due to side reactions (especially, trans-CBDO is more susceptible to side reactions), volatilization, sublimation, etc. of CBDOcB) Often significantly lower than the CBDO level of the glycol monomer
Cis cB content (. phi.) in the copolyestercis,cB) Is obviously higher than the cis-CBDO content in the monomer
There is a deviation between them.
The compositional deviation, the relative compositional deviation, the cis deviation, and the cis relative deviation of the copolyesters obtained in comparative examples 1-2 and examples 1-14 are shown in Table 2. Wherein
The results show that the composition deviation, relative composition deviation, cis deviation and cis relative deviation of the copolyesters obtained in examples 1-14 are significantly lower than those of comparative examples 1-2, indicating that the present invention has significant advantages in avoiding the side reactions and losses of CBDO and thus introducing the input CBDO into the copolyester as much as possible.
TABLE 2 comparison of monomer and copolyester compositions, cis content
Third, regarding polycondensation temperature and intrinsic viscosity
Because CBDO has a cyclic large steric hindrance structure and the hydroxyl group is connected with a secondary carbon, the reaction activity of CBDO with acid or ester is obviously lower than that of the first dihydric alcohol. With increasing CBDO content, the molecular weight of the copolyester is more difficult to increase. In order to obtain high intrinsic viscosity, the prior art often adopts high (more than or equal to 280 ℃) polycondensation reaction temperature. Although the PCcBT copolyester with higher intrinsic viscosity can be prepared under the reaction conditions of the comparative example of the invention, the pipeline is seriously blocked. The preparation method of the copolyester provided by the invention can prepare the copolyester with high intrinsic viscosity at a lower polycondensation reaction temperature (about 260 ℃), wherein the intrinsic viscosity is at least 0.53dL/g, is more than or equal to 0.60dL/g and can reach 0.90dL/g in most cases, and even when the cB content is 76%, the intrinsic viscosity still reaches 0.59dL/g (example 11). The above results show that the present invention can successfully synthesize high molecular weight CBDO-based copolyesters at polycondensation temperatures below 280 ℃.
Fourthly, regarding the thermal stability of copolyester melt
The PCcBT copolyester of comparative example 1 had a very unstable melt level during vacuum polycondensation, the level was very sluggish and faster stirring was required to prevent melt overflow from the flask. The polyesters synthesized in examples 1 to 14, however, were able to maintain a stable melt level during the vacuum polycondensation, similar to the phenomenon that the excess diol was slowly removed during the conventional polyester synthesis. This result demonstrates that the CBDO-based copolyesters provided by the present invention have superior melt stability.
To further evaluate the melt stability of the copolyesters, 1 gram of each of the copolyester samples synthesized in comparative example 1, and example 2 was re-introduced into a 50mL flask under N2Heating to 240 deg.C under atmosphere without stirring, maintaining at 240 deg.C for 5 hr, naturally cooling to room temperature, and observing the final state, as shown in FIG. 3. It can be seen that the copolyester of comparative example 1 (fig. 3 (a)) produced a large amount of intensive foaming, and the copolyesters of examples 1 and 2 (fig. 3 (b) and (c)) produced significantly less bubbles. The copolyesters of comparative examples 1-2 were also found to expand very significantly when injection molded using a MiniJet microinjection molding machine, and the copolyesters of examples 1-14, although still showing some expansion, were much less extensive, especially the copolyesters synthesized with 2-methyl-1, 3-propanediol as the first diol. The above results show that the copolyester of the present invention has significantly improved melt stability, and is more favorable for smooth polymerization and processing.
V, regarding thermal stability and mechanical property
The Tg and mechanical properties of the copolyester were measured, and the results are shown in tables 3 and 4. It can be seen that the Tg of the copolyesters of the invention can be adjusted over a wide range (49-136 ℃), and that by increasing the content of cB units, high Tg copolyesters, especially copolyesters with 2-methyl-1, 3-propanediol as the first diol monomer, can be produced with Tg as high as 136 ℃, although at the same cB content the glass transition temperature is lower than PCcBT. The copolyesters of the invention have higher Young's modulus, tensile strength and ductility when their glass transition temperature is similar to or higher (>110 ℃ C.) than comparative examples 1 and EX401, as in examples 5, 10, 14 and 11. When its Tg is lower than that of comparative example 1 and EX401, it also has higher rigidity, strength and ductility as in example 12.
TABLE 3 glass transition temperature of copolyesters
TABLE 4 mechanical Properties of copolyesters in the examples and comparative examples
Sixthly, regarding color and luster and transparency
The color and transparency of the sheets obtained by co-polyester molding of comparative example 1 and example 5 were observed, and the results are shown in FIG. 4, in which (a) is comparative example 1 and (b) is example 5. It can be seen from the figure that the copolyester prepared in example 5 is nearly colorless and transparent, and the inventors have also made copolyesters of other examples, which have transparency similar to that of example 5, good transparency, and color and transparency comparable to PCcBT.
Claims (10)
1. A high-transparency high-heat-resistance copolyester resin is characterized by comprising the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)80 to 100 mole% of terephthalic acid residues; and
(b)0 to 20 mol% of aromatic dibasic acid residue;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)20-85 mol% CBDO residues; and
(b)15-80 mol% of a first diol residue; and
(c)0-30 mol% of a second glycol residue;
the aromatic dibasic acid residue comprises at least one of isophthalic acid residue, phthalic acid residue, diphenic acid residue, naphthalenedicarboxylic acid residue, furandicarboxylic acid residue and thiophenedicarboxylic acid residue;
the first dihydric alcohol residue includes at least one of a 1, 5-pentanediol residue, a 2-methyl-1, 5-pentanediol residue, a 3-methyl-1, 5-pentanediol residue, a 2-ethyl-1, 5-pentanediol residue, a 3, 3-dimethyl-1, 5-pentanediol residue, a 3, 3-diethyl-1, 5-pentanediol residue, a 2-methyl-1, 3-propanediol residue, a 2-ethyl-1, 3-propanediol residue;
the second diol residue comprises at least one of aliphatic diol residue with the main chain carbon atom number less than or equal to 4 or alicyclic or heterocyclic diol residue with the carbon atom number less than or equal to 12.
2. The high transparent and high heat resistant copolyester resin according to claim 1, wherein the glycol component comprises, in a total amount of 100 mol%:
(a)50-80 mol% CBDO residues; and
(b)20 to 50 mol% of a first dihydric alcohol residue; and
(c)0-30 mol% of a second glycol residue.
3. The high-transparency high-heat-resistance copolyester resin according to claim 1, wherein the aliphatic diol residue having a carbon number of the main chain of 4 or less comprises at least one of ethylene glycol residue, 1, 3-propylene glycol residue, 1, 4-butylene glycol residue, 2, 3-butylene glycol residue and 1, 2-propylene glycol residue;
the alicyclic or heterocyclic diol residue with the carbon number less than or equal to 12 comprises at least one of 1, 4-cyclohexanedimethanol residue and cyclohexanediol residue.
4. The highly transparent and heat-resistant copolyester resin according to claim 1, wherein the intrinsic viscosity of the copolyester resin is 0.53 to 0.90 dL/g.
5. The highly transparent and heat-resistant copolyester resin according to claim 1, wherein the glass transition temperature of the copolyester resin is 60 to 150 ℃.
6. The method for preparing a highly transparent and highly heat resistant copolyester resin according to any one of claims 1 to 5, comprising the steps of:
(1) carrying out esterification or ester exchange reaction on a mixture containing a dibasic acid component and a dibasic alcohol component at the temperature of 200 ℃ and 250 ℃ to obtain an intermediate product;
(2) the intermediate product is condensed under the pressure of 10-200Pa and the temperature of 250-270 ℃ to obtain the copolyester resin;
the mixture comprises the following components:
(1) a dibasic acid component comprising, in a total amount of 100 mol%:
(a)80 to 100 mole% of terephthalic acid or its dimethyl ester; and
(b)0 to 20 mol% of an aromatic dibasic acid or its dimethyl ester;
and
(2) a glycol component comprising, based on 100 mol% of the total:
(a)20-85 mol% CBDO; and
(b)15-80 mol% of a first glycol; and
(c)0 to 30 mol% of a second glycol;
the molar ratio of the dibasic acid component to the dibasic alcohol component is 1:1-1: 3;
the aromatic dibasic acid or the dimethyl ester thereof comprises at least one of isophthalic acid or the dimethyl ester thereof, phthalic acid or the dimethyl ester thereof, biphenyl dicarboxylic acid or the dimethyl ester thereof, naphthalene dicarboxylic acid or the dimethyl ester thereof, furan dicarboxylic acid or the dimethyl ester thereof, and thiophene dicarboxylic acid or the dimethyl ester thereof;
the first dihydric alcohol comprises at least one of 1, 5-pentanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 5-pentanediol, 3-dimethyl-1, 5-pentanediol, 3-diethyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-propanediol;
the second dihydric alcohol comprises at least one of aliphatic dihydric alcohol with the carbon atom number of the main chain less than or equal to 4 or alicyclic or heterocyclic dihydric alcohol with the carbon atom number less than or equal to 12.
7. The method for preparing a highly transparent and heat resistant copolyester resin according to claim 6, wherein the aliphatic diol having a carbon number of the main chain of 4 or less comprises at least one of ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol, and 1, 4-pentanediol;
the alicyclic or heterocyclic diol with the carbon number less than or equal to 12 comprises at least one of 1, 4-cyclohexanedimethanol and cyclohexanediol.
8. The method for preparing a highly transparent and highly heat resistant copolyester resin according to claim 6, wherein in the copolyester resin,
the difference between the molar percentage of the CBDO residue in the diol residue and the molar percentage of the CBDO monomer in the diol monomer is less than or equal to 8 mol%;
the difference between the ratio of the cis-CBDO residue in the CBDO residue and the ratio of the cis-CBDO monomer in the CBDO monomer is less than or equal to 8 percent.
9. The method for preparing a highly transparent and heat resistant copolyester resin according to claim 6, wherein the mixture further comprises a catalyst, a heat stabilizer, a light stabilizer;
the dosage of the catalyst is less than 1 wt% of the mass of the dibasic acid component;
the using amount of the heat stabilizer is 0.1-1 wt% of the weight of the dibasic acid component;
the using amount of the light stabilizer is less than 1 wt% of the mass of the dibasic acid component.
10. The method for preparing a highly transparent and highly heat resistant copolyester resin according to claim 6, wherein the catalyst comprises a tin-based catalyst; or comprises tin catalyst and one or more of tetrabutyl titanate, isopropyl titanate, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate and manganese acetate;
the tin catalyst is one or more selected from dibutyltin oxide, stannous octoate, stannous oxalate, dibutyltin diacetate and dibutyltin dilaurate;
the heat stabilizer is selected from heat stabilizer 1010, heat stabilizer 1500, heat stabilizer 1076, heat stabilizer 425, heat stabilizer 330, heat stabilizer 1178, heat stabilizer 501, heat stabilizer 618, heat stabilizer 626, heat stabilizer 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol bis (2, 4-tert-butylphenyl) diphosphite, bis (2, 4-di-p-isopropylphenyl) pentaerythritol diphosphite phosphoric acid, pentaerythritol tetraphenyl tridecyl phosphite, pentaerythritol diphosphodecyl phosphite, pentaerythritol diisodecyl phosphite, pentaerythritol tetradecyl phosphite, heat stabilizer 1178, heat stabilizer 626, heat stabilizer 168, heat stabilizer 626, heat stabilizer TDD heat stabilizer, heat stabilizer phosphate, heat stabilizer active agent, heat active agent, and heat active agent, and heat active agent, and heat active agent, One or more of pentaerythritol dioctadecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate;
the light stabilizer is selected from one or more of light stabilizer 791, light stabilizer 700, light stabilizer 783, light stabilizer 119, light stabilizer 770, light stabilizer 622, light stabilizer 944, light stabilizer 1164, 2,2,6, 6-tetramethyl-4-piperidine stearate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, 2-hydroxy-4-n-octoxybenzophenone, (3, 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and poly (1-hydroxyethyl, 2,2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.
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| CN115572375A (en) * | 2022-10-20 | 2023-01-06 | 浙江大学 | High-heat-resistance and high-transparency copolyester resin and preparation method thereof |
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| CN116330790A (en) * | 2023-05-31 | 2023-06-27 | 合肥长阳新材料科技有限公司 | Furanyl high-barrier transparent heat-resistant polyester film and preparation method thereof |
| CN116330790B (en) * | 2023-05-31 | 2023-08-29 | 合肥长阳新材料科技有限公司 | Furanyl high-barrier transparent heat-resistant polyester film and preparation method thereof |
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