Patent Application
20250136751
The present invention relates to the technical field of biodegradable polyesters, specifically relates to a polyester, a preparation method therefor and use thereof, and in particular to a polyester with a specific content of dimer(1,4-butanediol), a preparation method therefor and use thereof.
Currently, thermoplastic aromatic polyesters widely used in industry and daily life have good thermal stability and mechanical properties, and are easy to process and low in price. For example, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have been extensively applied in the manufacture of fibers, films, and containers. However, these aromatic polyesters are hardly degraded after being discarded. Up to now, no microorganism has yet been observed to directly and obviously degrade aromatic polyesters such as, PET and PBT.
In this context, aliphatic polyesters, as eco-friendly plastics, have been concerned. Aliphatic polyesters can be obtained by the esterification reaction and melt polycondensation between aliphatic dicarboxylic acids and aliphatic diols. The raw material aliphatic dicarboxylic acids (e.g., succinic acid and adipic acid) can be produced by glucose derived from plants via fermentation; aliphatic diols (e.g., ethylene glycol, propylene glycol, and butylene glycol) also can be produced via raw materials derived from plants, which thus can strive for saving fossil fuel resources. Meanwhile, plant can absorb carbon dioxide in the air during its growth process and thus, can make great contributions to the reduction of carbon dioxide emission. Furthermore, aliphatic polyesters are further known to show excellent biodegradability; so to speak, they are triple-eco-friendly plastics.
However, due to the problems such as more side reactions during polymerization and prone thermal degradation, the color of the polymerisates of aliphatic polyesters is not good, which becomes a great challenge to the production of aliphatic polyesters.
For the improvement of the polyester color, it is generally controlled by adding a stabilizer during the polycondensation in the industry, which has become a conventional technology to aromatic polyesters such as PET and PBT. For example, it is indicated in the (Rieckmann, T.; Volker, S., 2. Poly(ethylene terephthalate) Polymerization—Mechanism, Catalysis, Kinetics, Mass Transfer and Reactor Design. In Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters, Scheirs, J.; Long, T. E., Eds. John Wiley & Sons, Ltd.: Chichester, 2003; p 63.) that compounds of phosphoric acid (e.g., triphenyl phosphate and triphenyl phosphite) are added during the polymerization of PET as a stabilizer to greatly reduce the yellowing degree of PET. It is also indicated in W02018/219708A1 that the addition of 0.03% to 0.04% by weight of a phosphorus compound during the condensation of the aliphatic-aromatic polyester causes it to have a whiteness index of at least 25 according to ASTM E313-73.
CN212560068U discloses a production system for a biodegradable polyester. The esterification reactor of the production system is connected to a process column; water and tetrahydrofuran produced in the process of esterification together with the excessive 1,4-butanediol, etc. enter the process column for rectification; the bottom of the process column is heated via a liquid heating medium; the recovered 1,4-butanediol discharged from the bottom of the tower was sent back to the reflux inlet of the esterification kettle. In this way, the recovered 1,4-butanediol enters into the reaction system via the reflux inlet and participates in the esterification reaction again. However, such a simple rectification via the process column only distills off low-boiling point water, tetrahydrofuran, etc. from the top of the process column; the remaining substances are totally refluxed to the esterification kettle from the bottom of the process column; these remaining substances contain a large number of 1,4-butanediol polymers and other by-products. These by-products will take part in the polymerization reaction after entering the esterification kettle, leading to the performance deterioration of the subsequent aliphatic-aromatic polyester.
In conclusion, those skilled in the art have not yet recognized that by-product impurities will affect the performance, particularly color of polyesters at present.
The object of the present invention is to overcome the shortcomings of the prior art and to provide a polyester with a specific content of dimer(1,4-butanediol), a preparation method therefor, and use thereof.
The aforesaid object of the present invention is achieved by the following technical solution.
In one aspect, provided is a polyester, including repeating units derived from the following components:
It is found in the present invention that based on the total molar weight of the first component A, the molar content of the repeating unit —CH2CH2CH2CH2—O— in the third component C is controlled to 0.05-3.0 mol %, so that the resin color of the polyester can be effectively improved, and the performance of the obtained polyester will be kept. The first component A is preferably totally succinic acid or an ester derivative thereof or an anhydride derivative thereof.
As a detailed embodiment, the component a2) is selected from one or more of oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, methylsuccinic acid, glutaric acid, dimethyl glutarate, bis(2-hydroxyethyl) glutarate, bis(3-hydroxypropyl)glutarate, bis(4-hydroxybutyl) glutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, bis(2-hydroxyethyl) adipate, bis(3-hydroxypropyl) adipate, bis(4-hydroxybutyl) adipate, 3-methyladipic acid, 2,2,5,5-tetramethyladipic acid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, decanedioic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, undecandioic acid, 1,12-dodecanedicarboxylic acid, hexadecanedioic acid, eicosandioic acid, tetracosandioic acid, dimer acid, terephthalic acid, dimethyl terephthalate, bis(2-hydroxyethyl) terephthalate, bis(3-hydroxypropyl) terephthalate, bis(4-hydroxybutyl) terephthalate, isophthalic acid, dimethyl isophthalate, bis(2-hydroxyethyl) isophthalate, bis(3-hydroxypropyl) isophthalate, bis(4-hydroxybutyl) isophthalate, 2,6-naphthalenedicarboxylic acid, dimethyl 2,6-benzenedicarboxylate, 2,7-naphthalenedicarboxylic acid, dimethyl 2,7-benzenedicarboxylate, 3,4′-diphenylether dicarboxylic acid, dimethyl 3,4′-diphenylether dicarboxylate, 4,4′-diphenylether dicarboxylic acid, dimethyl 4,4′-diphenylether dicarboxylate, 3,4′-phenylthioether dicarboxylic acid, dimethyl 3,4′-phenylthioether dicarboxylate, 4,4′-phenylthioether dicarboxylic acid, dimethyl 4,4′-phenylthioether dicarboxylate, 3,4′-diphenylsulfone dicarboxylic acid, dimethyl 3,4′-diphenylsulfone dicarboxylate, 4,4′-diphenylsulfone dicarboxylic acid, dimethyl 4,4′-diphenylsulfone dicarboxylate, 3,4′-benzophenone dicarboxylic acid, dimethyl 3,4′-benzophenone dicarboxylate, 4,4′-benzophenone dicarboxylic acid, dimethyl 4,4′-benzophenone dicarboxylate, 1,4-naphthalenedicarboxylic acid, dimethyl 1,4-naphthalene dicarboxylate, 4,4′-methylenebis(benzoic acid), 4,4′-methylenebis(dimethyl benzoate), and an ester derivative thereof and an anhydride derivative thereof; preferably, selected from one or more of adipic acid, decanedioic acid, 1,12-dodecanedicarboxylic acid, terephthalic acid, and an ester derivative thereof and an anhydride derivative thereof; more preferably, selected from one or two of adipic acid, decanedioic acid, terephthalic acid, and an ester derivative thereof and an anhydride derivative thereof; and most preferably, being adipic acid, terephthalic acid, or an ester derivative thereof or an anhydride derivative thereof.
In the present invention, the polyester further includes a fourth component D if necessary; the fourth component D is a compound containing at least three functional groups, preferably, a compound containing three to six functional groups, more preferably, selected from one or more of tartaric acid, citric acid, malic acid, fumaric acid, maleic acid, trimethylolpropane, trimethylolethane, pentaerythritol, polyether triol, glycerol, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic acid, and pyromellitic dianhydride; and preferably, selected from one or more of malic acid, citric acid, fumaric acid, maleic acid, and glycerol;
The polyester may further include a fifth component E as a chain extender.
The chain extender is one or a mixture of more of an isocyanate, an isocyanurate, a peroxide, an epoxide, oxazoline, oxazine, lactam, carbodiimide and polycarbodiimide that contain two or more functional groups.
The isocyanate containing two or more functional groups may be an aromatic isocyanate or an aliphatic isocyanate, preferably, aromatic diisocyanate or aliphatic diisocyanate. Preferably, the aromatic diisocyanate is preferably toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 2,2′-diisocyanate, diphenylmethane 2,4′-diisocyanate, diphenylmethane 4,4′-diisocyanate, naphthalene 1,5-diisocyanate, or xylene diisocyanate. More preferably, the aromatic diisocyanate is diphenylmethane 2,2′-diisocyanate, diphenylmethane 2,4′-diisocyanate, or diphenylmethane 4,4′-diisocyanate.
Preferably, the aliphatic diisocyanate is preferably any linear or branched alkylene diisocyanate or cycloalkylene diisocyanate containing 2-20 carbon atoms. More preferably, the aliphatic diisocyanate is any linear or branched alkylene diisocyanate or cycloalkylene diisocyanate containing 3-12 carbon atoms. The aliphatic diisocyanate may be hexamethylene 1,6-diisocyanate, isophorone diisocyanate, or methylenebis(4-isocyanatocyclohexane). Most preferably, the aliphatic diisocyanate is hexamethylene 1,6-diisocyanate, and isophorone diisocyanate.
The isocyanate containing two or more functional groups may be further tri-(4-isocyanatophenyl) methane with three rings.
Preferably, the isocyanurate containing two or more functional groups may be an aliphatic isocyanurate derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2-20 carbon atoms, preferably, 3-12 carbon atoms, e.g., isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane). The alkylene diisocyanates may be linear or branched compounds, particularly, preferably cyclic tripolymer, pentamer, or higher oligomer isocyanurates based on n-hexamethylene diisocyanates, e.g., hexamethylene 1,6-diisocyanate.
Preferably, the peroxide containing two or more functional groups is preferably benzoyl peroxide, 1,1-di(tert-butylperoxo)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxo)methylcyclododecane, 4,4-di(butylperoxo) n-butyl valerate, dicumyl peroxide, tert-butyl peroxybenzoate, dibutyl peroxide, α,α-di(tert-butylperoxo)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxo)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxo)hexyl-3-yne, and tert-butylcumyl peroxide.
Preferably, the epoxide containing two or more functional groups is preferably hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl diglycidyl phthalate, phenylene diglycidyl ether, ethylidene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene diglycidyl ether, sorbitol diglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethanediol diglycidyl ether, diglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutylene glycol diglycidyl ether.
The epoxide containing two or more functional groups is preferably a copolymer based on styrene, acrylate, and/or methacrylate and containing an epoxy group; the epoxy group is preferably glycidyl methacrylate (GMA). It has been proved that the beneficial compound is a copolymer having a GMA ratio of higher than 20 wt %, preferably higher than 30 wt %, and more preferably higher than 50 wt %. The epoxide equivalent weight in these copolymers is preferably 150-3000 g/equivalent, and more preferably 200-500 g/equivalent. The weight-average molecular weight (Mw) of the copolymers is preferably 2,000-25,000, and more preferably 3,000-8,000. The number-average molecular weight (Mn) of the copolymers is preferably 400-6,000, and more preferably 1,000-4,000. Polydispersity index (Q=Mw/Mn) is preferably 1.5-5.
The oxazoline/oxazine containing two or more functional groups is preferably dioxazoline or dioxazine, its bridging portion is a single bond, (CH2)z-alkylene, where z 2, 3 or 4, e.g., methylene, ethyl-1,2-diyl, propyl-1,3-diyl, or phenylene. Specifically, the dioxazoline is 2,2′-di(2-oxazoline), di(2-oxazolinyl)methane, 1,2-di(2-oxazolinyl)ethane, 1,3-di(2-oxazolinyl)propane, 1,4-di(2-oxazolinyl)butane, 2,2′-di(2-oxazoline), 2,2′-di(4-methyl-2-oxazoline), 2,2′-di(4,4′-dimethyl-2-oxazoline), 2,2′-di(4-ethyl-2-oxazoline), 2,2′-di(4,4′-diethyl-2-oxazoline), 2,2′-di(4-propyl-2-oxazoline), 2,2′-di(4-butyl-2-oxazoline), 2,2′-di(4-hexyl-2-oxazoline), 2,2′-di(4-phenyl-2-oxazoline), 2,2′-di(4-cyclohexyl-2-oxazoline), 2,2′-di(4-phenylmethyl-2-oxazoline), 2,2′-p-phenylenedi(4-methyl-2-oxazoline), 2,2′-p-phenylenedi(4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenedi(4-methyl-2-oxazoline), 2,2′-m-phenylenedi(4,4′-dimethyl-2-oxazoline), 2,2′-hexamethylenedi(2-oxazoline), 2,2′-octamethylenedi(2-oxazoline), 2,2′-decamethylenedi(2-oxazoline), 2,2′-ethylidenedi(4-methyl-2-oxazoline), 2,2′-tetramethylenedi(4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethanedi(2-oxazoline), 2,2′-cyclohexylenedi(2-oxazoline), or 2,2′-diphenylene(2-oxazoline).
Specifically, dioxazine is 2,2′-di(2-dioxazine), di(2-dioxazinyl)methane, 1,2-di(2-dioxazinyl)ethane, 1,3-di(2-dioxazinyl)propane, 1,4-di(2-dioxazinyl)butane, 1,4-di(2-dioxazinyl)benzene, 1,2-di(2-dioxazinyl)benzene, or 1,3-di(2-dioxazinyl)benzene.
The carbodiimide or polycarbodiimide containing two or more functional groups is preferably N,N′-di-2,6-diisopropylphenyl carbodiimide, N,N′-di-o-tolyl carbodiimide, N,N′-diphenyl carbodiimide, N,N′-dioctyldecyl carbodiimide, N,N′-di-2,6-dimethylphenyl carbodiimide, N-tolyl-N′-cyclohexyl carbodiimide, N,N′-di-2,6-di-tert-butylphenyl carbodiimide, N-tolyl-N′-phenyl carbodiimide, N,N′-di-p-nitrophenyl carbodiimide, N,N′-di-p-aminophenyl carbodiimide, N,N′-di-p-hydroxyphenyl carbodiimide, N,N′-dicyclohexyl carbodiimide, N,N′-di-p-tolyl carbodiimide, p-phenylenebis-di-o-tolyl carbodiimide, p-phenylenebis-dicyclohexyl carbodiimide, hexamethylenebis-dicyclohexyl carbodiimide, 4,4′-dicyclohexylmethane carbodiimide, ethylidenebisdiphenyl carbodiimide, N,N′-phenylmethyl-carbodiimide, N-octadecyl-N′-phenyl carbodiimide, N-benzyl-N′-phenyl carbodiimide, N-octadecyl-N″-tolyl carbodiimide, N-cyclohexyl-N′-tolyl carbodiimide, N-phenyl-N′-tolyl carbodiimide, N-benzyl-N′-tolyl carbodiimide, N,N′-di-o-ethylphenyl carbodiimide, N,N′-di-p-ethylphenyl carbodiimide, N,N′-di-o-isopropylphenyl carbodiimide, N,N′-di-p-isopropylphenyl carbodiimide, N,N′-di-o-isobutylphenyl carbodiimide, N,N′-di-p-isobutylphenyl carbodiimide, N,N′-di-2,6-diethylphenyl carbodiimide, N,N′-di-2-ethyl-6-isopropylphenyl carbodiimide, N,N′-di-2-isobutyl-6-isopropylphenyl carbodiimide, N,N′-di-2,4,6-trimethylphenyl carbodiimide, N,N′-di-2,4,6-triisopropylphenyl carbodiimide, N,N′-di-2,4,6-triisobutylphenyl carbodiimide, diisopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, tert-butylisopropyl carbodiimide, di-β-naphthyl carbodiimide, or di-tert-butyl carbodiimide.
Preferably, the fifth component E is added in an amount of 0.01-5 mol % of a total molar weight of the first component A.
Preferably, the polyester has a viscosity number of 100-350 ml/g as determined in a phenol/o-dichlorobenzene solution having a weight ratio of 1:1 in a 25±0.05° C. thermostatic water bath in accordance with the provision of GB/T 17931-1999.
Preferably, the polyester has a carboxyl group content of 10-70 mmol/kg, and further preferably, 20-60 mmol/kg.
On the other hand, the present invention further provides a method for preparing the above polyester, including the following steps:
Preferably, in the step S1, the purification device connected to the esterification reactor is a combination of a process column and a short-path distiller.
Molecular distillation is a distilling method operated in high vacuum; at this time, the mean free path of steam molecules is greater than the distance between the evaporation surface and condensation surface such that liquid mixture is separated by means of the difference in the evaporation rate of each component in the feed liquid.
Short-path distiller is designed according to the principle of molecular distillation, and is a model to simulate molecular distillation. Due to the distance between its heating surface and the cooling surface is very small, and resistance is very small, it is thus called a short-path distiller. A built-in condenser can function in liquifying vaporized vapor phases instantaneously to shrink volume and thus, can maintain the high vacuum in the equipment. The operating vacuum of the short-path distiller may be up to 0.1 Pa (absolute pressure), which is unreachable to other evaporation/distillation equipment. Therefore, the short-path distiller is especially suitable for the materials that possess a high boiling point at normal pressure and can be hardly isolated by a common separation method. As a novel liquid-liquid separation equipment, the short-path distiller has been successfully applied in many industries.
The short-path distiller may be an SPD short-path distiller from Wuxi Hengyi Chemical Machinery Co., Ltd. (http://www.wxhengyi.com/index.asp).
The process column is mainly to separate substances with a low-boiling point, e.g., tetrahydrofuran, water and other by-products. These substances with a low-boiling point flow out of the tower top and then flow into a tetrahydrofuran purification apparatus; substances with a high-boiling point, 1,4-butanediol and other by-products flow out of the tower bottom, and flow into a SPD short-path distiller, and recovered into the esterification reactor after being purified by the short-path distiller.
In the step S2, the remaining catalyst may be added if necessary. In the step S2, the reaction temperature is more preferably 210-230° C. In the step S2, the pressure is generally set as 0.1-0.5 bar, and preferably, 0.2-0.4 bar at the beginning; and the pressure is generally set as 5-200 mbar, and more preferably, 10-100 mbar at the end of the S2.
In the step S3, a passivator may be mixed with a prepolyester if necessary. The available passivator is usually a phosphorus compound including phosphoric acid, phosphorous acid, and esters thereof. A passivator is usually added to the step S3 when a high-active titanium catalyst is used in the system.
In the step S3, the reaction temperature of the continuous polycondensation is preferably 230-260° C. In the step S3, the pressure is usually controlled within 0.2-5 mbar, and more preferably, 0.5-3 mbar at the beginning the reaction. The reaction time of the continuous polycondensation is preferably 2-7 h, and more preferably 3-6 h. The carboxyl group content in the polyester after the reaction in the S3 is preferably 20-60 mmol/kg.
At the end of the step S3, a step S4 is performed as follows if necessary: adding the polyester obtained in the step S3 to a twin-screw extruder together with a fifth component E as a chain extender in an amount of 0.01-5.0 mol % (based on the total molar weight of the first component A) for retention for 0.5-15 min at a reaction temperature of 200-270° C. to obtain a polyester; the polyester has a viscosity number of 150-350 ml/g as determined in a phenol/o-dichlorobenzene solution having a weight ratio of 1:1 in a 25±0.05° C. thermostatic water bath in accordance with the provision of GB/T 17931-1999.
In a further aspect, the present invention further provides a polyester molding composition, including the following components in weight percentage:
As a detailed embodiment, the additive and/or other polymers may be, at least one or more components selected from aliphatic polyesters, polycaprolactones, starch, cellulose, polyhydroxyalkanoates, and polylactic acids.
In a still further aspect, the present invention further provides use of the above polyester in preparing a compost-degradable product; the compost-degradable product is a fiber, a film, or a container, etc.
The present invention further provides use of the above polyester in preparing a straw. Polyester may be blended with polylactic acid (PLA), etc. and modified, and then used as a raw material of a straw. The straw is required to have certain hydrolysis resistance as it contacts liquid. Moreover, considering the degradable requirement, the hydrolysis resistance should be not too strong, or otherwise the degradation cycle is too long. Based on the practical use, the degradation property is evaluated by testing the 30-day weight retention rate. The 30-day weight retention rate should be within a range of 50-60% better, and the higher the retention rate is, the better the degradation property is within such a range. When the 30-day weight retention rate is greater than 65%, the degradation property is too poor, when it is lower than 45%, degradation is too fast.
Compared with the prior art, the present invention has the following beneficial effects:
The present invention provides a polyester and a preparation method therefor. Based on the total molar weight of the diacid, the molar content of the repeating unit —CH2CH2CH2CH2—O— in dimer(1,4-butanediol) is controlled to 0.05-3.0 mol %, and thus, the resin color of the polyester can be effectively improved, and the performance of the polyester will be also kept.
Raw materials, reagents and solvents used in the present invention, are commercially available without any treatment, unless otherwise specified. The present invention will be further described specifically in combination with examples; however, the embodiments of the present invention are not limited to the following examples. Moreover, any other changes, modifications, replacements, combinations and simplifications without departing from the spirit and principle of the present invention shall be equivalent replacements and thus, shall fall within the scope of protection of the present invention. In addition, “part(s)” and “%” in the description, unless otherwise specified, denote “part(s) by mass” and “mass %”, respectively.
Method for testing the purity of fresh 1,4-butanediol, recovered coarse 1,4-butanediol, recovered high-purity 1,4-butanediol is as follows.
The purity of 1,4-butanediol is tested by reference to the national standard GB/T 24768-2009 1,4-Butanediol for industrial use.
The fresh 1,4-butanediol in all the examples and comparative examples has the same purity of not less than 99.7%, and purchased from MarkorChem. Raw materials such as terephthalic acid, succinic acid, adipic acid, glycerol, tetrabutyl orthotitanate, and phosphorous acid are commercially available.
Method for testing the content of the third component C in the polyester (PBS obtained by the reaction between succinic acid and 1,4-butanediol in Example 1 of the present invention is set as an example):
As can be seen from the reference: Park, Y. H.; Cho, C. G., Synthesis and characterization of poly[(butylene succinate)-co-(butylene terephthalate)]-b-poly(tetramethylene glycol) segmented block copolymer. J. Appl. Polym. Sci. 2001, 79(11): 2067-2075., the 4 hydrogen atoms in the succinic acid repeating units appeared nearby 2.6 ppm; the 4 hydrogen atoms of the two CH2 units, in the succinic acid repeating units of PBS, adjacent to the ester group appeared nearby 4.1 ppm; and the 4 hydrogen atoms of the central two CH2 units, in the butanediol repeating units of PBS appeared nearby 1.69 ppm. The results are shown in
Furthermore, as can be seen from the reference: Miles, W. H; Ruddy, D. A.; Tinorgah, S.; Geisler, R. L., Acylative Dimerization of Tetrahydrofuran Catalyzed by Rare-Earth Triflates. Synth. Commun. 2004, 34(10): 1871-1880, the 1H NMR chemical shift (labeled on the corresponding carbon atoms of the structural formula, unit: ppm) of the product obtained from dimer(1,4-butanediol) and acetic acid is shown in the following figure:
The above two references validate the following conclusion together: peaks of the 4 hydrogen atoms in the two CH2 units linked to the ether bond in PBS of dimer(1,4-butanediol) should appear nearby 3.4 ppm, and are triple peaks, as shown in
It can be thus calculated by the following formula: based on the total molar weight of the first component A, the molar content of the repeating unit —CH2CH2CH2CH2—O— in the third component C dimer(1,4-butanediol) is as follows:
The viscosity number was determined in a phenol/o-dichlorobenzene solution having a weight ratio of 1:1 in a 25±0.05° C. thermostatic water bath in accordance with the provision of GB/T 17931-1999; the sample has a concentration of 5 mg/ml.
Color of the polyester: the pelletized and dried sample was taken and tested in accordance with the provision of GB/T 14190-2017 5.5.2 Method B (Dry method). Hunter Lab, L, a, and b values were obtained via the test and Hunter whiteness was defined as follows:
The greater the WH is, the better the sample color is.
The biodegradation experiment of the polyester is performed by reference to the test of GB/T 19277-2003. The polyester test sample was first pressed to a film having a thickness of 0.10 mm, and then cut into a 1.2 cm×2.0 cm sample sheet; the sample weight was denoted as a0 at this time. The sample sheet was then embedded into composting soil and put to an incubator; the composting soil was the city compost after being aerated for 56-70 d and sieved; the experimental temperature was kept at (58±2°) C, 30 d later, the composted sample sheet was taken out, washed, dried and weighed; the sample weight was denoted as a1 at this time. The 30-day weight retention rate=a1/a0×100%. The higher the 30-day weight retention rate is, the more difficult the material degradation is; and the lower the 30-day weight retention rate is, the faster the material degradation rate is. Based on the practical use, the 30-day weight retention rate is within a range of 50-60% better, and the higher the retention rate is, the better the degradation property is within such a range. When the 30-day weight retention rate is greater than 65%, the degradation property is too poor, when it is lower than 45%, degradation is too fast.
From Examples 1 to 6, based on the total molar weight of the first component A, the repeating unit —CH2CH2CH2CH2—O— in the third component C has a molar content of 0.05-3.0 mol %, leading to a higher whiteness and a better 30-day weight retention rate. In Example 7, due to the structure rigidity of the benzene ring in terephthalic acid, the 30-day weight retention rate also increases, but color is not very good. In Example 8, the viscosity number and 30-day weight retention rate decrease to a certain extent due to the absence of glycerol. In Example 9, the 30-day weight retention rate decreases slightly, but is still within the commercially acceptable range due to the presence of adipic acid.
In Comparative Example 1, the molar content of the repeating unit —CH2CH2CH2CH2—O— exceeds the range, leading to poor color of the resin. Similarly, in the resin obtained in Comparative Example 2, the molar content of the repeating unit —CH2CH2CH2CH2—O— in the third component C is too low; the resin has a fine color, but has a too high 30-day weight retention rate; moreover, the excessive butanediol may not be recovered; the running cost of the production line is expensive, and there is thus no commercial value. In Comparative Example 3, the content of terephthalic acid is too high, and the degradation property of the resin is poor (too high 30-day weight retention rate).
Because the recovered 1,4-butanediol may contain multiple products obtained after the polymerization of 1,4-butanediol, e.g., (1,4-butanediol) and poly(1,4-butanediol), to further verify the correlation between the resin color and each of these products, the correlations among different types of dimer(1,4-butanediol) as well as poly(1,4-butanediol) and the resin color were studied. The raw materials 1,4-butanediol used in this example were all fresh 1,4-butanediol having a purity of not less than 99.7%.
As can be seen the reference (Alexander, K; Schniepp, L. E., 4,4′-Dichlorodibutyl Ether and its Derivatives from Tetrahydrofuran. J. Am. Chem. Soc. 1948, 70(5): 1839-1842.), dimer(1,4-butanediol) was synthesized; poly(1,4-butanediol) having the Mn of 1000 and 650 were purchased from Sigma-Aldrich.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 20 g of dimer(1,4-butanediol), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 10 g of dimer(1,4-butanediol), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 5 g of dimer(1,4-butanediol), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 2.5 g of dimer(1,4-butanediol), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 2.26 g of poly(1,4-butanediol) (Sigma-Aldrich, Mn: about 1000), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
Under the protection of high-purity nitrogen, 2.36 kg of succinic acid, 3.02 kg of 1,4-butanediol, 2.28 g of poly(1,4-butanediol) (Sigma-Aldrich, Mn ˜650), 2.75 g of glycerol, and 2.02 g of titanium tetrabutoxide were put into a reaction kettle, heated up to 220-240° C. and kept for 120 min. 0.52 g of phosphorous acid were then put into the reaction kettle. The pressure in the reaction kettle was reduced to 50 Pa below within 30-60 min, and then the above materials were subjected to reaction for 60-120 min at 220-260° C. High-purity nitrogen was introduced into the reaction kettle after stopping stirring, and the resin was squeezed out of the reaction kettle, and water-granulated to obtain the polyester product. The performance results are shown in Table 2.
As can be seen from the Examples 10.5-10.1 of Table 2, the resin color gets worse obviously with the increase of the dimer(1,4-butanediol) added. Meanwhile, the resin color is not obviously affected when other types of poly(1,4-butanediol) having a higher molecular weight (Examples 10.6 and 10.7) are added to the polymerization system. The data of Example 10 further indicates that the resin color is affected by dimer(1,4-butanediol), and the higher the content of the dimer(1,4-butanediol), the worse the resin color is.
Finally, it should be indicated that the above examples are merely used to specify the technical solutions of the present invention, but are not construed as limiting the protection scope of the present invention. Even though the present invention is described specifically with reference to the preferred embodiments, it is understood that those skilled in the art can still amend the technical solutions of the present invention, or make equivalent substitutions on a portion of the technical solutions of the present invention in the premise of not departing from the spirit and scope of the technical solutions in the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111075507.X | Sep 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/118113 | 9/9/2022 | WO |
