CN103159907A - High-molecular-weight polyester plastic based on 2,3-butanediol and preparation method for same - Google Patents
High-molecular-weight polyester plastic based on 2,3-butanediol and preparation method for same Download PDFInfo
- Publication number
- CN103159907A CN103159907A CN2011104070495A CN201110407049A CN103159907A CN 103159907 A CN103159907 A CN 103159907A CN 2011104070495 A CN2011104070495 A CN 2011104070495A CN 201110407049 A CN201110407049 A CN 201110407049A CN 103159907 A CN103159907 A CN 103159907A
- Authority
- CN
- China
- Prior art keywords
- acid
- monomer
- ester
- butanediol
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- AFZZYIJIWUTJFO-UHFFFAOYSA-N CCc1cccc(CC)c1 Chemical compound CCc1cccc(CC)c1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 1
- HHJWGAHWTIBBCH-UHFFFAOYSA-N Cc(c(OC)c1)ccc1-c1cc(OC)c(C)cc1 Chemical compound Cc(c(OC)c1)ccc1-c1cc(OC)c(C)cc1 HHJWGAHWTIBBCH-UHFFFAOYSA-N 0.000 description 1
- HZAWPPRBCALFRN-UHFFFAOYSA-N Cc1ccc(Cc2ccc(C)cc2)cc1 Chemical compound Cc1ccc(Cc2ccc(C)cc2)cc1 HZAWPPRBCALFRN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention discloses a high-molecular-weight polyester plastic based on 2,3-butanediol. The polyester plastic has a repetition structure unit shown in the formula, wherein R1 is defined in the specification, p is 0-11, R2 is defined in the specification, R3 is defined in the specification, n is 1-1000, and m is 1-1000. The invention further discloses a preparation method for the high-molecular-weight polyester plastic based on 2,3-butanediol. The polyester plastic is a transparent polyester plastic due to the existence of the side-chain methyl of 2,3-butanediol, as well as is high in molecular weight, excellent in mechanical property, and wide in application prospect in the aspects of injection-moulded parts, optical devices, thin films, laminated materials and the like.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof.
Background technology
Oil is as most important industrial chemicals, and in recent years along with the mankind's exploitation gradually and the increase day by day of consumption, on the earth, storage is fewer and feweri with the amount that can supply to exploit.And these heavy chemicals have produced a large amount of CO in the process of using and finally discarding
2, caused a series of serious environmental problems such as Global warming, directly threaten the mankind's existence.How to reduce or the use of these Nonrenewable resources of petroleum replacing, with regard to one of problem of becoming whole world mankind's facing.
2,3-butanediol can be exhausted as renewable resources, and can not cause the environmental problem such as Greenhouse effect, can utilize glucose, sucrose, molasses, glycerine, starch even stalk by bacterium-klebsiella or fermentation of bacillus production.Patent CN200910012175.3 discloses a kind of method of producing 2,3-butanediol take wheat stalk as the raw material fermentation using bacteria; Patent CN200910015400.9 discloses a kind of method of producing 2,3-butanediol take starch as the raw material microbial fermentation; Patent CN200810057041.9 discloses a kind of method by preparing ethanol from wood fiber raw material and 2,3-butanediol.
Nearly decades, a lot of science and research worker carried out comprehensive and systematic research to the performance of 2,3-butanediol.2,3-butanediol is the liquid chemical of colorless and odorless, and three kinds of configurations are arranged, and has very high boiling point and lower zero pour, is used as widely preparation divinyl and frostproofer.In addition, the thermal capacitance of 2,3-butanediol is 27200J/g, and is suitable with ethanol (29100J/g), methyl alcohol (22100J/g), thereby can be used as liquid fuel and fuel dope.The 2,3-butanediol dehydration obtains the industrial solvent methylethylketone, and methylethylketone can be used as solvent and is used for production of resins and system paint industry.Methylethylketone further dewaters and generates 1,3-butadiene (elastomeric starting raw material is also the important monomer of polymer industry).The methylethylketone hydrogenation obtains high-octane high quality flight fuel, and the diacetate that the catalytic dehydrogenation esterification obtains is a kind of foodstuff additive of high price.In addition, 2,3-butanediol has potential using value in fields such as printing ink, makeup, fragrance fumette, tenderizer, softening agent, explosive and pharmaceutical carriers.
But when 2, when the 3-butyleneglycol is used as polymerization single polymerization monomer, although with its isomers 1, the 4-butyleneglycol is the same, have two hydroxyls, but these two hydroxyls are secondary hydroxyl, reactive behavior is very low, in polycondensation process, be difficult to the esterified prod that obtains higher molecular weight, has practical value with the diprotic acid reaction.Pointing out in U.S.Pat.No.4600768 also not report for the product of dicarboxylic acid and 2,3-butanediol preparation, is mainly owing to lacking a kind of suitable preparation method.U.S.Pat.No.2502686 utilizes phthalic acid and 2,3-butanediol to prepare the polyester of a kind of lower molecular weight (1000-3000), and this lower molecular weight makes them can not be used to prepare profiled part, for example film and thin slice.U.S.Pat.No.3714126 still at most only has been added to 8% with the properties-correcting agent of 2,3-butanediol as PET.
Summary of the invention
The present invention is exactly the defective that exists for above-mentioned prior art and a kind of high molecular weight polyesters plastics based on 2,3-butanediol are provided, and this polyester plastics has higher molecular weight, higher transparency and excellent mechanical property etc.
Another object of the present invention is to provide above-mentioned based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol, the method adopt highly active monomer and the reaction of low-molecular-weight polyester diol, efficiently solve 2,3-butyleneglycol steric hindrance is large, is difficult to obtain the problem of high-molecular weight polymer.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high molecular weight polyesters plastics based on 2,3-butanediol, this polyester plastics has following repeated structural unit:
Wherein, R
1Be selected from
P=0-11;
R
2Be selected from
R
3Be selected from
R
1, R
2And R
3Can be all identical, also can be different, perhaps both are identical arbitrarily;
n＝1-1000，m＝1-1000。
A kind of preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol comprises the following steps:
(1) with monomer a, monomer b, 2, the 3-butyleneglycol, monomer c and the first catalyzer, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 170-230 ℃, after forming homogeneous system, controlling temperature of reaction is 170-230 ℃, stirring, react 1.5-8h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
(2) add the second catalyzer and thermo-stabilizer, be evacuated to less than 500Pa under 240-280 ℃, stir 0.5-6h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 500-5000, and is standby;
(3) the quality percentage composition of drying being processed is that the low-molecular-weight polyester P of 80-99.9% and isocyanic ester that the quality percentage composition is 20-0.1% drop into high-speed mixer mixing 5-30min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 30-150 ℃; Two sections: 60-220 ℃; Three sections: 70-220 ℃; Four sections: 70-220 ℃; Five sections: 70-220 ℃; Head: 70-220 ℃.
Wherein, in step (1), the by product of transesterify and esterification mainly comprises: water, methyl alcohol, ethanol, n-propyl alcohol, isopropylcarbinol, Pentyl alcohol, neopentyl alcohol or n-hexyl alcohol etc.
In step (2), low-molecular-weight polyester P vacuumizes to react under 240-280 ℃ and obtains, and in order to prevent unnecessary degraded and/or side reaction, before vacuumizing, further adds thermo-stabilizer.
Preferably, the relationship between quality of described monomer a and monomer b is: the massfraction of monomer a is 0-100%, and the massfraction of monomer b is 0-100%, and the ratio of monomer a and monomer b is not limit; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 20-100%, and surplus is monomer c; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 1-1: 4;
The weight fraction that described the first catalyzer, the second catalyzer account for respectively monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.001-0.5%; The add-on of described the first catalyzer and the second catalyzer is identical or different;
The weight fraction that the add-on of described thermo-stabilizer accounts for all reactive components is 0.001-2%, and described all reactive components comprise monomer a, monomer b, 2,3-butanediol, monomer c, the first catalyzer, the second catalyzer and thermo-stabilizer.
Preferably, described the first catalyzer, the second catalyzer weight fraction that accounts for respectively monomer a, monomer b, 2,3-butanediol and monomer c total amount is preferably 0.005-0.3%; The weight fraction that the add-on of described thermo-stabilizer accounts for all reactive components is preferably 0.002-1%.
Preferably, described monomer a is selected from one or more in aromatic acid, aromatic dicarboxylic ester, aromatic dicarboxylic anhydride; Described monomer b is selected from one or more in aliphatic dibasic acid, binary aliphatic ester, binary aliphatic acid anhydrides; Described monomer c is selected from one or more in aliphatic dihydroxy alcohol or alicyclic dibasic alcohol; Described 2,3-butanediol is obtained by bacterium-klebsiella or fermentation of bacillus production by one or more in glucose, sucrose, molasses, glycerine, starch or stalk;
Described the first catalyzer, the second catalyzer are selected from respectively one or more in the metallic compound of Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li or Ga; Described the first catalyzer and the second catalyzer can be identical, also can be different;
Described thermo-stabilizer is selected from one or more in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate;
Described isocyanic ester is two (or many) isocyanic ester, be selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, PPDI, m-benzene diisocyanate, 4,4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethoxy-4 ', 4-biphenyl diisocyanate, mphenylenedimethylim-vulcabond, 2, one or more in 6-two isocyanato methyl caproates.
Preferably, described aromatic acid is selected from one or more in terephthalic acid, m-phthalic acid, phthalic acid or NDA;
described aromatic dicarboxylic ester is selected from dimethyl terephthalate (DMT), the terephthalic acid diethyl ester, terephthalic acid-diη-propyl ester, terephthalic acid diisobutyl ester, terephthalic acid-two n-pentyl ester, terephthalic acid di neo-pentyl ester, terephthalic acid-di-n-hexyl ester, dimethyl isophthalate, the m-phthalic acid diethyl ester, m-phthalic acid-diη-propyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid-two n-pentyl ester, m-phthalic acid di neo-pentyl ester, m-phthalic acid-di-n-hexyl ester, dimethyl phthalate, the phthalic acid diethyl ester, phthalic acid-diη-propyl ester, o-benzene butyl phthalate ester, phthalic acid two n-pentyl esters, phthalic acid di neo-pentyl ester, phthalic acid di-n-hexyl ester, the NDA dimethyl ester, the NDA diethyl ester, NDA diη-propyl ester, NDA diisobutyl ester, NDA two n-pentyl esters, one or more in NDA di neo-pentyl ester or NDA di-n-hexyl ester,
Described aromatic dicarboxylic anhydride is selected from one or more in terephthalic anhydride, Tetra hydro Phthalic anhydride or isophthalic anhydride.
Preferably, the preferred terephthalic acid of described aromatic acid; The preferred dimethyl terephthalate (DMT) of described aromatic dicarboxylic ester; The preferred terephthalic anhydride of described aromatic dicarboxylic anhydride.
Preferably, described aliphatic dibasic acid is selected from one or more in the alicyclic diprotic acid of ring-type of the straight chain aliphatic dibasic acid of C2-C15 or C5-C10;
Described binary aliphatic ester is the C of above-mentioned aliphatic dibasic acid
1-C
6Alkyl ester;
Described binary aliphatic acid anhydrides is selected from one or more in oxalic acid acid anhydride, Succinic anhydried or adipic anhydride.
Preferably, described aliphatic dibasic acid is selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1, one or more in 2-cyclohexane cyclohexanedimethanodibasic or 1,4 cyclohexanedicarboxylic acid;
Described binary aliphatic ester is selected from one or more in dimethyl adipate, dimethyl sebacate or dimethyl succinate;
The preferred Succinic anhydried of described binary aliphatic acid anhydrides.
Preferably, one or more in the preferred hexanodioic acid of described aliphatic dibasic acid, sebacic acid or succinic acid.
Preferably, described aliphatic dihydroxy alcohol is selected from one or more in the alkanediol of C2-C13; Described alicyclic dibasic alcohol is selected from C
5-C
10The cycloalkanes glycol in one or more.
Preferably, described aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,2-PD, 1, ammediol, BDO, 1,5-PD, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane glycol, 1,12-dodecanediol, 1,13-tridecane glycol or 2-methyl isophthalic acid, one or more in ammediol;
Described alicyclic dibasic alcohol is selected from 1,3-ring pentanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1, one or more in 2-cyclohexanediol, 1,2-CHDM or 1,4 cyclohexane dimethanol.
Preferably, one or both in the preferred BDO of described aliphatic dihydroxy alcohol or ethylene glycol.
Preferably, one or more in described the first preferred titanium compound of catalyzer or acetate; One or more in described the second preferred titanium compound of catalyzer, tin compound or antimony compounds.
Preferably, described titanium compound is selected from one or more in tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyls, titanium isopropylate or the different monooctyl ester of metatitanic acid four; Described acetate is selected from one or more in zinc acetate, magnesium acetate or manganese acetate; Described tin compound is selected from one or more in dibutyltin oxide, stannous octoate, dibutyl tin dilaurate or tin protochloride; Described antimony compounds is selected from one or both in antimony acetate or antimonous oxide.
Preferably, one or both in the preferred 2,4 toluene diisocyanate of described isocyanic ester, hexamethylene diisocyanate.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention prepares polyester plastics by the 2,3-butanediol that utilizes biological fermentation to produce for raw material, has reduced the dependency to Nonrenewable resources such as petrochemical industry, is conducive to the sustainable development of this type of polymer materials.
2, the present invention utilizes the high reactivity of isocyanate-monomer, with 2, low-molecular-weight polyester dibasic alcohol (Mw the is 500-5000) reaction that the polycondensation of 3-butyleneglycol produces, overcome 2, the not high problem of 3-butyleneglycol secondary hydroxyl reactive behavior obtains having higher molecular weight, the polyester plastics of excellent mechanical property and use properties.
3, the present invention is by 2,3-butyleneglycol and diprotic acid, diol reaction obtain the low-molecular-weight polyester dibasic alcohol, then add the isocyanic ester chain extension, obtain the polyester plastics of high molecular, this polyester plastics is due to the existence of 2,3-butanediol pendant methyl, destroyed the regularity of polyester molecule chain, be transparent polyester plastics, mechanical property is excellent, all is with a wide range of applications at aspects such as Injection moulded part, optics, film, laminating materials.
4, the present invention obtains the low-molecular-weight polyester dibasic alcohol by 2,3-butanediol and diprotic acid, diol reaction, then adds the isocyanic ester chain extension, obtains the polyester plastics of high molecular.By regulating the ratio of aromatic series unit in diprotic acid, aliphatics unit, 2, the ratio of 3-butyleneglycol and dibasic alcohol, the ratio of isocyanate-monomer and polyester diol, can finely tune the thermomechanical property of gained copolyesters within the specific limits, satisfy different field to the diversity requirement of material.
5, the present invention obtains low-molecular-weight polyester two by 2,3-butanediol and diprotic acid, diol reaction
Then unit's alcohol add the isocyanic ester chain extension, obtains the polyester plastics of high molecular.This polyester plastics can with other plastics such as polyethylene terephthalate, PA 66 etc., and various fillers such as talcum powder, calcium carbonate etc., blend improves its thermomechanical property, obtains having the engineering plastics of particular requirement, further expands its range of application.
Embodiment
Describe the present invention in detail below in conjunction with each embodiment.
In the following embodiment that provides, detection method below adopting:
Adopt differential scanning calorimeter Per kin Elmer DSC7, measure second-order transition temperature T under following type of heating
g:
Scanning, with 50 ℃/min, be warmed up to 270 ℃ from-100 ℃ for the first time;
Scanning, with 10 ℃/min, cool to-100 ℃ from 270 ℃ for the second time;
Scanning, with 20 ℃/min, be warmed up to 270 ℃ from-100 ℃ for the third time.
Weight-average molecular weight Mw measures in Waters 600E series GPC system, and wherein chloroform is used for working curve as elutriant and polystyrene standard sample.
Embodiment 1
2,3-butanediol, the 0.15g zinc acetate of 73g hexanodioic acid, 83g terephthalic acid, 230g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Be heated to 225 ℃, after the question response thing formed homogeneous system, controlling temperature of reaction was 225 ℃, carry out esterification 3h under stirring, condensing condition, in this process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(the water theory calculated amount is the twice of hexanodioic acid and terephthalic acid molar weight sum).
0.10g tetra-n-butyl titanate, 0.12g triphenyl phosphite join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 260 ℃, vacuumizes to stir 2h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get the poly-hexanodioic acid of product-co-terephthalic acid (50%mol) 2,3-butanediol low-molecular-weight polyester, Mw is 3100.
With the dry poly-hexanodioic acid of crossing of 95g-co-terephthalic acid (50%mol) 2,2 of 3-butyleneglycol low-molecular-weight polyester, 5g, the 4-tolylene diisocyanate drops into high-speed mixer mixing 10min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 80 ℃; Two sections: 130 ℃; Three sections: 140 ℃; Four sections: 140 ℃; Five sections: 145 ℃; Head: 145 ℃.
Gained polyester plastics particle carries out the test of DSC, mechanical property, and test result sees Table 1.
Embodiment 2
2,3-butanediol, the 0.10g tetra-n-butyl titanate of 37g hexanodioic acid, 125g terephthalic acid, 210g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Be heated to 215 ℃, after the question response thing formed homogeneous system, controlling temperature of reaction was 215 ℃, carry out esterification 4h under stirring, condensing condition, in this process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(the water theory calculated amount is the twice of hexanodioic acid and terephthalic acid molar weight sum).
0.15g antimonous oxide, 0.10g trimethyl phosphite 99 join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 255 ℃, is evacuated to less than 500Pa, stirs 3h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get the poly-hexanodioic acid of product-co-terephthalic acid (75%mol) 2,3-butanediol low-molecular-weight polyester, Mw is 2600.
With the dry poly-hexanodioic acid of crossing of 94g-co-terephthalic acid (75%mol) 2,2 of 3-butyleneglycol low-molecular-weight polyester, 6g, the 4-tolylene diisocyanate drops into high-speed mixer mixing 12min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 90 ℃; Two sections: 150 ℃; Three sections: 160 ℃; Four sections: 165 ℃; Five sections: 165 ℃; Head: 170 ℃.
Gained polyester plastics particle carries out the test of DSC, mechanical property, and test result sees Table 1.
Embodiment 3
2,3-butanediol, the BDO of 140g, 0.10g magnesium acetate, the different monooctyl ester of 0.05g metatitanic acid four of 131g dimethyl adipate, 49g dimethyl terephthalate (DMT), 70g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee transesterification reaction.Be heated to 230 ℃, after the question response thing forms homogeneous system, control temperature of reaction at 230 ℃, carry out transesterification reaction 2h under stirring, condensing condition, in this process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(methyl alcohol Theoretical Calculation amount is the twice of dimethyl adipate and dimethyl terephthalate (DMT) molar weight sum).
0.13g dibutyltin oxide, 0.12g triphenylphosphate join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 250 ℃, vacuumizes to stir 4h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get the poly-hexanodioic acid of product-co-terephthalic acid (25%mol) 2,3-butanediol-co-1,4-butyleneglycol (67%mol) low-molecular-weight polyester, Mw is 1000.
With the dry poly-hexanodioic acid of crossing of 90g-co-terephthalic acid (25%mol) 2,3-butyleneglycol-co-1,2 of 4-butyleneglycol (67%mol) low-molecular-weight polyester, 10g, the 4-tolylene diisocyanate drops into high-speed mixer mixing 20min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 40 ℃; Two sections: 60 ℃; Three sections: 75 ℃; Four sections: 75 ℃; Five sections: 75 ℃; Head: 80 ℃.
Gained polyester plastics particle carries out the test of DSC, mechanical property, and test result sees Table 1.
Embodiment 4
2,3-butanediol, the 1.23g manganese acetate of 30g succinic acid, 44g dimethyl adipate, 42g terephthalic acid, 49g dimethyl terephthalate (DMT), 330g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee transesterify and esterification.Be heated to 200 ℃, after the question response thing forms homogeneous system, control temperature of reaction at 200 ℃, carry out esterification and transesterification reaction 5.5h under stirring, condensing condition, in this process, the first alcohol and water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(methyl alcohol Theoretical Calculation amount is the twice of dimethyl adipate and dimethyl terephthalate (DMT) molar weight sum, and the water theory calculated amount is the twice of succinic acid and terephthalic acid molar weight sum).
1.23g stannous octoate, 5.02g trimethyl phosphite join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 265 ℃, vacuumizes to stir 1h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get product poly-succinic-co-hexanodioic acid (25%mol)-co-terephthalic acid (25%mol) 2,3-butanediol low-molecular-weight polyester, Mw is 4200.
With the dry poly-succinic of crossing of 97g-co-hexanodioic acid (25%mol)-co-terephthalic acid (25%mol) 2, the hexamethylene diisocyanate of 3-butyleneglycol low-molecular-weight polyester, 3g drops into high-speed mixer mixing 15min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 80 ℃; Two sections: 130 ℃; Three sections: 140 ℃; Four sections: 140 ℃; Five sections: 145 ℃; Head: 145 ℃.
Gained polyester plastics particle carries out the test of DSC, mechanical property, and test result sees Table 1.
Embodiment 5
2,3-butanediol, the 0.0034g zinc acetate of 166g terephthalic acid, 166g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Be heated to 230 ℃, after the question response thing forms homogeneous system, control temperature of reaction at 230 ℃, carry out esterification 1.5h under stirring, condensing condition, in this process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(the water theory calculated amount is the twice of terephthalic acid molar weight).
0.0034g tetra-n-butyl titanate, 0.0034g triphenyl phosphite join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 240 ℃, vacuumizes to stir 6h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get product poly terephthalic acid 2,3-butanediol low-molecular-weight polyester, Mw is 5000.
With the dry poly terephthalic acid 2 of crossing of 99.9g, 2 of 3-butyleneglycol low-molecular-weight polyester, 0.1g, the 4-tolylene diisocyanate drops into high-speed mixer mixing 30min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 150 ℃; Two sections: 220 ℃; Three sections: 220 ℃; Four sections: 220 ℃; Five sections: 220 ℃; Head: 220 ℃.
Embodiment 6
2,3-butanediol, the ethylene glycol of 468g, the 3.66g zinc acetate of 147g hexanodioic acid, 117g are joined in the 1000mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Be heated to 170 ℃, after the question response thing forms homogeneous system, control temperature of reaction at 170 ℃, carry out esterification 8h under stirring, condensing condition, in this process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(the water theory calculated amount is the twice of hexanodioic acid molar weight).
3.66g tetra-n-butyl titanate, 15g triethyl phosphate join in reaction mixture as catalyzer (i.e. the second catalyzer), the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 280 ℃, vacuumizes to stir 0.5h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get the poly-hexanodioic acid 2,3-butanediol of product-co-ethylene glycol (80%mol) low-molecular-weight polyester, Mw is 500.
With the dry poly-hexanodioic acid 2 of crossing of 80g, the hexamethylene diisocyanate of 3-butyleneglycol-co-ethylene glycol (80%mol) low-molecular-weight polyester, 20g drops into high-speed mixer mixing 5min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder, and each section of twin screw extruder temperature is followed successively by: one section: 30 ℃; Two sections: 60 ℃; Three sections: 70 ℃; Four sections: 70 ℃; Five sections: 70 ℃; Head: 70 ℃.
Comparative Examples
2,3-butanediol, the 0.1g zinc acetate of 73g hexanodioic acid, 83g terephthalic acid, 230g are joined in the 500mL there-necked flask that mechanical stirring device is housed.After all material add, to flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Be heated to 210 ℃, after the question response thing forms homogeneous system, control temperature of reaction at 210 ℃, carry out esterification 4h under stirring, condensing condition, in this process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of Theoretical Calculation amount.(the water theory calculated amount is the twice of hexanodioic acid and terephthalic acid molar weight sum).
0.15g tetra-n-butyl titanate, 0.13g triphenyl phosphite join in reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction is carried out at the temperature of 260 ℃, vacuumizes to stir 2.5h, stopped reaction.
Reaction mixture is taken out from bottle, cooling in water, namely get the poly-hexanodioic acid of product-co-terephthalic acid (50%mol) 2,3-butanediol copolyesters.To its test of carrying out DSC, mechanical property, test result sees Table 1.
Table 1
By the performance test of table 1 and the implementation process of each embodiment, obtain the low-molecular-weight polyester dibasic alcohol by the present invention by 2,3-butanediol and diprotic acid, diol reaction as can be known, then add the isocyanic ester chain extension, obtain the polyester plastics of high molecular.Overcome the not high problem of 2,3-butanediol secondary hydroxyl reactive behavior, obtained having higher molecular weight, the polyester plastics of excellent mechanical property and use properties, had wide application field and application prospect.Reduce simultaneously the dependency to Nonrenewable resources such as petrochemical industry, be conducive to the sustainable development of this type of polymer materials.
Embodiment 7
(1) with monomer a terephthalic anhydride, monomer b oxalic acid acid anhydride, 2, the 3-butyleneglycol, monomer c 1, 2-propylene glycol and the first catalyzer metatitanic acid tetra-ethyl ester, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 180 ℃, after forming homogeneous system, controlling temperature of reaction is 180 ℃, stirring, react 2h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
The relationship between quality of monomer a and monomer b is: the massfraction of monomer a is 99%, and the massfraction of monomer b is 1%; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 91%, and the massfraction of monomer c is 9%; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 1; The weight fraction that the first catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.001%.
(2) add the second catalyzer metatitanic acid tetra-ethyl ester and thermo-stabilizer triethyl-phosphite, be evacuated to less than 500Pa under 246 ℃, stir 2.5h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 600, and is standby;
The weight fraction that the second catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.005%; The weight fraction that the add-on of thermo-stabilizer accounts for all reactive components is 0.001%.These all reactive components comprise monomer a, monomer b, 2,3-butanediol, monomer c, the first catalyzer, the second catalyzer and thermo-stabilizer.
(3) the quality percentage composition of drying being processed be 82% low-molecular-weight polyester P and quality percentage composition be 18% 2, the 6-tolylene diisocyanate drops into high-speed mixer mixing 18min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 100 ℃; Two sections: 150 ℃; Three sections: 160 ℃; Four sections: 160 ℃; Five sections: 180 ℃; Head: 200 ℃.
Embodiment 8
(1) with monomer a m-phthalic acid, monomer b sebacic acid, 2, the 3-butyleneglycol, monomer c 1, ammediol and the first catalyst acetic acid magnesium, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 185 ℃, after forming homogeneous system, controlling temperature of reaction is 185 ℃, stirring, react 5.5h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
The relationship between quality of monomer a and monomer b is: the massfraction of monomer a is 66%, and the massfraction of monomer b is 34%; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 30%, and the massfraction of monomer c is 70%; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 4; The weight fraction that the first catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.5%.
(2) add the second catalyzer metatitanic acid four n-propyls and thermo-stabilizer triphenyl phosphite, be evacuated to less than 500Pa under 270 ℃, stir 4.5h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 2500, and is standby;
The weight fraction that the second catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.5%; The weight fraction that the add-on of thermo-stabilizer accounts for all reactive components is 0.002%.
(3) the quality percentage composition of drying being processed is that 99% low-molecular-weight polyester P and quality percentage composition are that 1% m-benzene diisocyanate drops into high-speed mixer mixing 22min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 120 ℃; Two sections: 180 ℃; Three sections: 200 ℃; Four sections: 200 ℃; Five sections: 200 ℃; Head: 220 ℃.
Embodiment 9
(1) with monomer a terephthalic acid diisobutyl ester, monomer b dimethyl sebacate, 2, the 3-butyleneglycol, monomer c 1, 3-ring pentanediol and the first catalyst acetic acid manganese, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 215 ℃, after forming homogeneous system, controlling temperature of reaction is 215 ℃, stirring, react 7h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
The relationship between quality of monomer a and monomer b is: the massfraction of monomer a is 5%, and the massfraction of monomer b is 95%; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 52%, and the massfraction of monomer c is 48%; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 2; The weight fraction that the first catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.005%.
(2) add the second catalyzer dibutyl tin dilaurate and thermo-stabilizer trimethyl phosphite, be evacuated to less than 500Pa under 250 ℃, stir 1.5h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 3500, and is standby;
The weight fraction that the second catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.001%; The weight fraction that the add-on of thermo-stabilizer accounts for all reactive components is 1%.
(3) the quality percentage composition of drying being processed be 86% low-molecular-weight polyester P and quality percentage composition be 14% 1, the 5-naphthalene diisocyanate drops into high-speed mixer mixing 12min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 100 ℃; Two sections: 120 ℃; Three sections: 150 ℃; Four sections: 150 ℃; Five sections: 160 ℃; Head: 180 ℃.
Embodiment 10
(1) with monomer a terephthalic acid diethyl ester, monomer b Succinic anhydried, 2, the 3-butyleneglycol, monomer c 1, 4-cyclohexanediol and the first catalyzer metatitanic acid four isopropyl esters, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 205 ℃, after forming homogeneous system, controlling temperature of reaction is 205 ℃, stirring, react 7.5h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
The relationship between quality of monomer a and monomer b is: the massfraction of monomer a is 50%, and the massfraction of monomer b is 50%; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 60%, and the massfraction of monomer c is 40%; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 1.5; The weight fraction that the first catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.3%.
(2) add the second catalyst acetic acid antimony and thermo-stabilizer trimethyl phosphite 99, be evacuated to less than 500Pa under 270 ℃, stir 3.5h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 4800, and is standby;
The weight fraction that the second catalyzer accounts for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.3%; The weight fraction that the add-on of thermo-stabilizer accounts for all reactive components is 2%.
(3) the quality percentage composition of drying being processed is that 94.9% low-molecular-weight polyester P and quality percentage composition are that 5.1% PPDI drops into high-speed mixer mixing 28min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 60 ℃; Two sections: 90 ℃; Three sections: 100 ℃; Four sections: 100 ℃; Five sections: 120 ℃; Head: 150 ℃.
Above disclosed be only several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of all should drop in the application's protection domain.
Claims (16)
1. the high molecular weight polyesters plastics based on 2,3-butanediol, is characterized in that, this polyester plastics has following repeated structural unit:
Wherein, R
1Be selected from
P=0-11;
R
2Be selected from
Q=2-13;
R
3Be selected from
n＝1-1000，m＝1-1000。
2. the preparation method based on the high molecular weight polyesters plastics of 2,3-butanediol, is characterized in that, comprises the following steps:
(1) with monomer a, monomer b, 2, the 3-butyleneglycol, monomer c and the first catalyzer, join in reactor, vacuumize, inflated with nitrogen is removed the oxygen in reaction unit, assurance transesterify and/or esterification are carried out under condition of nitrogen gas, with mixture heating up to 170-230 ℃, after forming homogeneous system, controlling temperature of reaction is 170-230 ℃, stirring, react 1.5-8h under condensing condition, until the by product of transesterify and esterification reaches more than 92% of Theoretical Calculation amount, wherein the Theoretical Calculation amount of by product is monomer a and monomer b molar weight sum 2 times,
(2) add the second catalyzer and thermo-stabilizer, be evacuated to less than 500Pa under 240-280 ℃, stir 0.5-6h, stopped reaction obtains low-molecular-weight polyester P, and Mw is 500-5000, and is standby;
(3) the quality percentage composition of drying being processed is that the low-molecular-weight polyester P of 80-99.9% and isocyanic ester that the quality percentage composition is 20-0.1% drop into high-speed mixer mixing 5-30min, then input twin screw extruder, the polyester plastics particle that obtains high molecular is extruded in reaction in twin screw extruder; Each section of forcing machine temperature is followed successively by: one section: 30-150 ℃; Two sections: 60-220 ℃; Three sections: 70-220 ℃; Four sections: 70-220 ℃; Five sections: 70-220 ℃; Head: 70-220 ℃.
3. as claimed in claim 2 based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol is characterized in that, the relationship between quality of described monomer a and monomer b is: the massfraction of monomer a is 0-100%, the massfraction of monomer b is 0-100%, and the ratio of monomer a and monomer b is not limit; The relationship between quality of 2,3-butanediol and monomer c is: the massfraction of 2,3-butanediol is 20-100%, and surplus is monomer c; The mass ratio of the total mass of the total mass of monomer a and monomer b and 2,3-butanediol and monomer c is 1: 1-1: 4;
The weight fraction that described the first catalyzer, the second catalyzer account for respectively monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.001-0.5%; The add-on of described the first catalyzer and the second catalyzer is identical or different;
The weight fraction that the add-on of described thermo-stabilizer accounts for all reactive components is 0.001-2%, and described all reactive components comprise monomer a, monomer b, 2,3-butanediol, monomer c, the first catalyzer, the second catalyzer and thermo-stabilizer.
4. as claimed in claim 3 based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol, it is characterized in that, the weight fraction that described the first catalyzer, the second catalyzer account for respectively monomer a, monomer b, 2,3-butanediol and monomer c total amount is preferably 0.005-0.3%; The weight fraction that the add-on of described thermo-stabilizer accounts for all reactive components is preferably 0.002-1%.
5. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 2, is characterized in that, described monomer a is selected from one or more in aromatic acid, aromatic dicarboxylic ester, aromatic dicarboxylic anhydride; Described monomer b is selected from one or more in aliphatic dibasic acid, binary aliphatic ester, binary aliphatic acid anhydrides; Described monomer c is selected from one or more in aliphatic dihydroxy alcohol or alicyclic dibasic alcohol; Described 2,3-butanediol is obtained by bacterium-klebsiella or fermentation of bacillus production by one or more in glucose, sucrose, molasses, glycerine, starch or stalk;
Described the first catalyzer, the second catalyzer are selected from respectively one or more in the metallic compound of Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li or Ga; Described the first catalyzer and the second catalyzer can be identical, also can be different;
Described thermo-stabilizer is selected from one or more in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate;
Described isocyanic ester is two (or many) isocyanic ester, be selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, PPDI, m-benzene diisocyanate, 4,4-diphenylmethanediisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethoxy-4 ', 4-biphenyl diisocyanate, mphenylenedimethylim-vulcabond, 2, one or more in 6-two isocyanato methyl caproates.
6. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, is characterized in that, described aromatic acid is selected from one or more in terephthalic acid, m-phthalic acid, phthalic acid or NDA;
described aromatic dicarboxylic ester is selected from dimethyl terephthalate (DMT), the terephthalic acid diethyl ester, terephthalic acid diη-propyl ester, terephthalic acid diisobutyl ester, terephthalic acid two n-pentyl esters, terephthalic acid di neo-pentyl ester, terephthalic acid di-n-hexyl ester, dimethyl isophthalate, the m-phthalic acid diethyl ester, m-phthalic acid diη-propyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid two n-pentyl esters, m-phthalic acid di neo-pentyl ester, m-phthalic acid di-n-hexyl ester, dimethyl phthalate, the phthalic acid diethyl ester, phthalic acid diη-propyl ester, o-benzene butyl phthalate ester, phthalic acid two n-pentyl esters, phthalic acid di neo-pentyl ester, phthalic acid di-n-hexyl ester, the NDA dimethyl ester, the NDA diethyl ester, NDA diη-propyl ester, NDA diisobutyl ester, NDA two n-pentyl esters, one or more in NDA di neo-pentyl ester or NDA di-n-hexyl ester,
Described aromatic dicarboxylic anhydride is selected from one or more in terephthalic anhydride, Tetra hydro Phthalic anhydride or isophthalic anhydride.
7. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 6, is characterized in that the preferred terephthalic acid of described aromatic acid; The preferred dimethyl terephthalate (DMT) of described aromatic dicarboxylic ester; The preferred terephthalic anhydride of described aromatic dicarboxylic anhydride.
8. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, is characterized in that, described aliphatic dibasic acid is selected from one or more in the alicyclic diprotic acid of ring-type of the straight chain aliphatic dibasic acid of C2-C15 or C5-C10;
Described binary aliphatic ester is the C of above-mentioned aliphatic dibasic acid
1-C
6Alkyl ester;
Described binary aliphatic acid anhydrides is selected from one or more in oxalic acid acid anhydride, Succinic anhydried or adipic anhydride.
9. as claimed in claim 8 based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol, it is characterized in that, described aliphatic dibasic acid is selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1, one or more in 2-cyclohexane cyclohexanedimethanodibasic or 1,4 cyclohexanedicarboxylic acid;
Described binary aliphatic ester is selected from one or more in dimethyl adipate, dimethyl sebacate or dimethyl succinate;
The preferred Succinic anhydried of described binary aliphatic acid anhydrides.
10. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 9, is characterized in that one or more in the preferred hexanodioic acid of described aliphatic dibasic acid, sebacic acid or succinic acid.
11. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5 is characterized in that, described aliphatic dihydroxy alcohol is selected from one or more in the alkanediol of C2-C13; Described alicyclic dibasic alcohol is selected from C
5-C
10The cycloalkanes glycol in one or more.
12. as claimed in claim 11 based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol, it is characterized in that, described aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1,3-PD, BDO, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane glycol, 1,12-dodecanediol, 1,13-tridecane glycol or 2-methyl isophthalic acid, one or more in ammediol;
Described alicyclic dibasic alcohol is selected from 1,3-ring pentanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1, one or more in 2-cyclohexanediol, 1,2-CHDM or 1,4 cyclohexane dimethanol.
13. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 12 is characterized in that one or both in the preferred BDO of described aliphatic dihydroxy alcohol or ethylene glycol.
14. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5 is characterized in that one or more in described the first preferred titanium compound of catalyzer or acetate; One or more in described the second preferred titanium compound of catalyzer, tin compound or antimony compounds.
15. as claimed in claim 14 based on 2, the preparation method of the high molecular weight polyesters plastics of 3-butyleneglycol, it is characterized in that, described titanium compound is selected from one or more in tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyls, titanium isopropylate or the different monooctyl ester of metatitanic acid four; Described acetate is selected from one or more in zinc acetate, magnesium acetate or manganese acetate; Described tin compound is selected from one or more in dibutyltin oxide, stannous octoate, dibutyl tin dilaurate or tin protochloride; Described antimony compounds is selected from one or both in antimony acetate or antimonous oxide.
16. the preparation method of the high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5 is characterized in that one or both in the preferred 2,4 toluene diisocyanate of described isocyanic ester, hexamethylene diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110407049.5A CN103159907B (en) | 2011-12-08 | 2011-12-08 | A kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110407049.5A CN103159907B (en) | 2011-12-08 | 2011-12-08 | A kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103159907A true CN103159907A (en) | 2013-06-19 |
| CN103159907B CN103159907B (en) | 2016-09-28 |
Family
ID=48583466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110407049.5A Active CN103159907B (en) | 2011-12-08 | 2011-12-08 | A kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103159907B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| CN106366298A (en) * | 2016-11-02 | 2017-02-01 | 安庆和兴化工有限责任公司 | Preparation method of polybutylene terephthalate succinate |
| CN107698772A (en) * | 2017-10-17 | 2018-02-16 | 成都新柯力化工科技有限公司 | A kind of method of the branched enhancing regenerated plastics in original position |
| CN109369893A (en) * | 2018-10-23 | 2019-02-22 | 东华大学 | A kind of polyester and preparation method thereof that oligomer is low |
| CN112745491A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Polyester and preparation method thereof |
| CN113980217A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of transparent TPU |
| US20220356299A1 (en) * | 2019-08-30 | 2022-11-10 | Kolon Industries, Inc. | Polymer compound comprising biomass-derived cyclic monomer and preparation method therefor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1246448A (en) * | 1967-11-27 | 1971-09-15 | Ici Ltd | Production of aromatic copolyesters |
| US4600768A (en) * | 1985-10-18 | 1986-07-15 | Eastman Kodak Company | Aromatic polyesters derived from 2,3-butanediol |
| CN101293950A (en) * | 2007-04-26 | 2008-10-29 | 德古萨有限责任公司 | Low-temperature-curable polyurethane compositions with uretdione groups, containing polymers based on polyols that carry secondary oh groups |
| CN101535372A (en) * | 2006-09-15 | 2009-09-16 | 斯蒂茨丁荷兰聚合物学会 | Process for the production of a dianhydrohexitol based polyester |
| CN102766326A (en) * | 2011-05-05 | 2012-11-07 | 上海杰事杰新材料(集团)股份有限公司 | Polyurethane foaming plastic and its preparation method |
-
2011
- 2011-12-08 CN CN201110407049.5A patent/CN103159907B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1246448A (en) * | 1967-11-27 | 1971-09-15 | Ici Ltd | Production of aromatic copolyesters |
| US4600768A (en) * | 1985-10-18 | 1986-07-15 | Eastman Kodak Company | Aromatic polyesters derived from 2,3-butanediol |
| CN101535372A (en) * | 2006-09-15 | 2009-09-16 | 斯蒂茨丁荷兰聚合物学会 | Process for the production of a dianhydrohexitol based polyester |
| CN101293950A (en) * | 2007-04-26 | 2008-10-29 | 德古萨有限责任公司 | Low-temperature-curable polyurethane compositions with uretdione groups, containing polymers based on polyols that carry secondary oh groups |
| CN102766326A (en) * | 2011-05-05 | 2012-11-07 | 上海杰事杰新材料(集团)股份有限公司 | Polyurethane foaming plastic and its preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| CN106366298A (en) * | 2016-11-02 | 2017-02-01 | 安庆和兴化工有限责任公司 | Preparation method of polybutylene terephthalate succinate |
| CN107698772A (en) * | 2017-10-17 | 2018-02-16 | 成都新柯力化工科技有限公司 | A kind of method of the branched enhancing regenerated plastics in original position |
| CN107698772B (en) * | 2017-10-17 | 2018-10-09 | 浙江中邦塑胶股份有限公司 | A kind of method of the branched enhancing regenerated plastics in original position |
| CN109369893A (en) * | 2018-10-23 | 2019-02-22 | 东华大学 | A kind of polyester and preparation method thereof that oligomer is low |
| US20220356299A1 (en) * | 2019-08-30 | 2022-11-10 | Kolon Industries, Inc. | Polymer compound comprising biomass-derived cyclic monomer and preparation method therefor |
| CN112745491A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Polyester and preparation method thereof |
| CN113980217A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of transparent TPU |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103159907B (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103159907A (en) | High-molecular-weight polyester plastic based on 2,3-butanediol and preparation method for same | |
| CN102336896B (en) | Preparation method of lightly-crosslinked aliphatic-aromatic copolyester | |
| TWI603994B (en) | Method of continuously preparing biodegradable aliphatic/aromatic polyester copolymer | |
| EP2820063B1 (en) | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof | |
| CN101314637A (en) | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof | |
| KR102162280B1 (en) | Heat shrinkable film composition comprising polyethyleneterephtalate resin and copolymer polyester resin, and heat shrinkable film | |
| CA2947716A1 (en) | Transesterified furan based polyesters and articles made therefrom | |
| CN103570925A (en) | Biodegradable polyester and preparation method thereof | |
| CN102276808A (en) | Preparation method of polyterephthalic acid ethane diacid glycol copolyester | |
| CN104418997A (en) | Synthetic method of polyethylene glycol terephthalate from biomass glycol | |
| JP2018505287A (en) | Bio-based copolyester or copolyethylene terephthalate | |
| CN103087305A (en) | Biodegradable aromatic-aliphatic copolyester and preparation method thereof | |
| CN110903469B (en) | Low-crystallinity biodegradable polyester and preparation method thereof | |
| CN101921386A (en) | High-molecular-weight polyethylene terephthalate-lactic acid copolymer | |
| US11306179B2 (en) | Polyester copolymer | |
| KR101212703B1 (en) | Manufacturing method of biodegradable polyester | |
| WO2024077921A1 (en) | Recycling method for waste pet and biodegradable copolyester prepared by using same | |
| CN114479032A (en) | Polyesters based on 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, methods of making and articles thereof | |
| CN102093543A (en) | Method for preparing 2,3-polybutylece terephthalate and copolyester thereof | |
| CN102093544B (en) | 1, 2-propanediol copolyester polyterephthalate with high 1, 2-propanediol content and preparation method thereof | |
| CN110862524B (en) | Bio-based high-transparency polymer film and preparation method thereof | |
| CN102585180B (en) | Copolyester based on 2, 3-butanediol and preparation method thereof | |
| JP2014133824A (en) | Method for producing aliphatic polyester | |
| CN104684974A (en) | Biaxially stretched polyester film for solar cell back surface protection and method for producing polyester resin | |
| CN103665353A (en) | Novel biodegradable copolyester and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Correlation module identifying method based on 2-type heterogeneous network Effective date of registration: 20191202 Granted publication date: 20160928 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |