CN103159907B - A kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof - Google Patents
A kind of high molecular weight polyesters plastics based on 2,3-butanediol and preparation method thereof Download PDFInfo
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- CN103159907B CN103159907B CN201110407049.5A CN201110407049A CN103159907B CN 103159907 B CN103159907 B CN 103159907B CN 201110407049 A CN201110407049 A CN 201110407049A CN 103159907 B CN103159907 B CN 103159907B
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- 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
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- 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 kind of based on 2, the high molecular weight polyesters plastics of 3 butanediols, this polyester plastics has a following constitutional repeating unit:Wherein, R1It is selected from P=0 11；R2It is selected from R3It is selected from
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of high molecular weight polyesters based on 2,3-butanediol
Plastics and preparation method thereof.
Background technology
Oil is as most important industrial chemicals, recently as gradually exploitation and the increase day by day of consumption, the ground of the mankind
The amount stored on ball and be available for exploiting is fewer and feweri.And these heavy chemicals create during using and be discarded
Substantial amounts of CO2, result in a series of serious environmental problems such as global warming, directly threaten the existence of the mankind.How to reduce
Or the use of these non-renewable resources of petroleum replacing, just becomes one of problem of whole world mankind's facing.
2,3-butanediol will not be exhausted as Renewable resource, and will not cause the environmental problems such as greenhouse effect, permissible
Glucose, sucrose, molasses, glycerol, starch even straw is utilized to be produced by antibacterial-klebsiella or fermentation of bacillus.
Patent CN200910012175.3 discloses a kind of method producing 2,3-butanediol for raw material bacterial fermentation with wheat stalk；Specially
Profit CN200910015400.9 discloses a kind of method producing 2,3-butanediol for raw material fermentable with starch；Patent
CN200810057041.9 discloses a kind of by preparing ethanol from wood fiber raw material with the method for 2,3-butanediol.
The a lot of science of recent decades and research worker have carried out comprehensive and systematic research to the performance of 2,3-butanediol.2,
3-butanediol is the liquid chemicals of colorless and odorless, has three kinds of configurations, has the highest boiling point and relatively low freezing point, by extensively
Be used as prepare butadiene and antifreezing agent.Additionally, the thermal capacitance of 2,3-butanediol is 27200J/g, with ethanol (29100J/g), first
Alcohol (22100J/g) is suitable, thus can serve as liquid fuel and fuel additive.2,3-butanediol dehydration obtains industrial solvent
Butanone, butanone can be as solvent for production of resins and painting industry.Butanone is dehydrated generation 1,3-butadiene further
(elastomeric initiation material is also the important monomer of polymer industry).Butanone hydrogenation obtains high-octane high-quality
Flight fuel, the diacetate that catalytic dehydrogenation esterification obtains is the food additive of a kind of high price.Additionally, 2,3-butanediol is at oil
There is potential using value in the fields such as ink, cosmetics, fragrance fumette, softening agent, plasticizer, explosive and pharmaceutical carrier.
But when 2,3-butanediol is used as polymerization monomer, although as its isomers BDO, tool
Having two hydroxyls, but the two hydroxyl is secondary hydroxyl, reactivity is the lowest, in polycondensation process, is difficult to and binary acid
Reaction obtains higher molecular weight, has the esterification products of practical value.U.S.Pat.No.4600768 points out for dicarboxylic acids
The product prepared with 2,3-butanediol is it is not yet reported that mistake, mainly due to lacking a kind of suitably preparation method.
U.S.Pat.No.2502686 utilizes phthalic acid and 2,3-butanediol to be prepared for the poly-of a kind of low-molecular-weight (1000-3000)
Ester, this low-molecular-weight makes them can not be used to prepare profiled part, such as thin film and thin slice.
U.S.Pat.No.3714126 using 2,3-butanediol as the modifying agent of PET, but be at most applied only to 8%.
Summary of the invention
The present invention is aiming at the defect of above-mentioned prior art existence and provides a kind of macromolecule based on 2,3-butanediol
Weight polyester plastics, this polyester plastics has higher molecular weight, higher transparency and the mechanical property etc. of excellence.
It is a further object of the present invention to provide the preparation method of above-mentioned high molecular weight polyesters plastics based on 2,3-butanediol,
The method uses highly active monomer to react with the polyester diol of low-molecular-weight, efficiently solves 2,3-butanediol steric hindrance big,
It is difficult to obtain the problem of heavy polymer.
The 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 repetitive structure list
Unit:
Wherein, R1It is selected from P=0-11；
R2It is selected from
R3It is selected from
R1、R2And R3Can be the most identical, it is also possible to different, or arbitrarily both are identical；
N=1-1000, m=1-1000.
The preparation method of a kind of high molecular weight polyesters plastics based on 2,3-butanediol, comprises the following steps:
(1) by monomer a, monomer b, 2,3-butanediol, monomer c and the first catalyst, join in reactor, evacuation,
Inflated with nitrogen removes the oxygen in reaction unit, it is ensured that ester exchange and/or esterification are carried out under a nitrogen atmosphere, are added by mixture
Heat is to 170-230 DEG C, after forming homogeneous system, controls reaction temperature and is 170-230 DEG C, carries out anti-under stirring, condensing condition
Answer 1.5-8h, until the by-product of ester exchange and esterification reaches more than the 92% of theoretical amount, the wherein reason of by-product
Opinion amount of calculation is monomer a and 2 times of monomer b mole sum；
(2) add the second catalyst and heat stabilizer, be evacuated to, less than 500Pa, stir 0.5-at 240-280 DEG C
6h, stopped reaction, obtain low molecular weight polyester P, Mw is 500-5000, standby；
(3) the low molecular weight polyester P that weight/mass percentage composition is 80-99.9% drying processed and weight/mass percentage composition
Isocyanates for 20-0.1% puts into high-speed mixer mixing 5-30min, then inputs double screw extruder, squeezes at twin screw
Go out reactive extrursion in machine and obtain the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 30-150 DEG C；
Two-stage nitration: 60-220 DEG C；Three sections: 70-220 DEG C；Four sections: 70-220 DEG C；Five sections: 70-220 DEG C；Head: 70-220 DEG C.
Wherein, in step (1), the by-product of ester exchange and esterification specifically includes that water, methanol, ethanol, normal propyl alcohol, different
Butanol, n-amyl alcohol, neopentyl alcohol or hexanol etc..
In step (2), low molecular weight polyester P evacuation reaction at 240-280 DEG C obtains, unnecessary in order to prevent
Degraded and/or side reaction, before vacuum extraction, add heat stabilizer further.
Preferably, the relationship between quality of described monomer a and monomer b is: the mass fraction of monomer a is 0-100%, monomer b's
Mass fraction is 0-100%, and monomer a does not limits with the ratio of monomer b；2,3-butanediol with the relationship between quality of monomer c is: 2,3-fourths
The mass fraction of glycol is 20-100%, and surplus is monomer c；The gross mass of monomer a and monomer b and 2,3-butanediol and monomer c
The mass ratio of gross mass be 1: 1-1: 4；
Described first catalyst, the second catalyst account for monomer a, monomer b, 2,3-butanediol and the weight of monomer c total amount respectively
Amount mark is 0.001-0.5%；The addition of described first catalyst and the second catalyst is identical or different；
It is 0.001-2% that the addition of described heat stabilizer accounts for the weight fraction of all reactive components, described is responded
Component includes monomer a, monomer b, 2,3-butanediol, monomer c, the first catalyst, the second catalyst and heat stabilizer.
Preferably, described first catalyst, that the second catalyst accounts for monomer a, monomer b, 2,3-butanediol and monomer c respectively is total
The weight fraction of amount is preferably 0.005-0.3%；The weight fraction that the addition of described heat stabilizer accounts for all reactive components is excellent
Elect 0.002-1% as.
Preferably, described monomer a one in aromatic acid, aromatic dicarboxylic ester, aromatic dicarboxylic anhydride
Or it is several；One or more in aliphatic dibasic acid, binary aliphatic ester, binary aliphatic anhydride of described monomer b；Institute
State one or more in aliphatic dihydroxy alcohol or cycloaliphatic diols of monomer c；Described 2,3-butanediol is by glucose, sugarcane
One or more in sugar, molasses, glycerol, starch or straw are produced by antibacterial-klebsiella or fermentation of bacillus
Obtain；
Described first catalyst, the second catalyst be respectively selected from Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir,
One or more in the metallic compound of La, Ce, Li or Ga；Described first catalyst and the second catalyst can be identical, also
Can be different；
Described heat stabilizer is selected from triphenyl phosphite, NSC 6513, NSC 5284, trimethyl phosphate, phosphorus
One or more in triphenyl phosphate ester, triethyl phosphate；
Described isocyanates is two (or many) isocyanates, selected from 2,4 toluene diisocyanate, 2,6-toluene diisocyanate
Acid esters, PPDI, m-benzene diisocyanate, 4,4-methyl diphenylene diisocyanate, hexamethylene diisocyanate, 1,5-
Naphthalene diisocyanate, 3,3-dimethoxy-4 ', 4-biphenyl diisocyanate, m-xylylene diisocyanate, 2,6-bis-is different
One or more in cyanic acid base methyl caproate.
Preferably, described aromatic acid is selected from p-phthalic acid, M-phthalic acid, phthalic acid or 2,6-naphthalene two
One or more in formic acid；
Described aromatic dicarboxylic ester selected from dimethyl terephthalate (DMT), p-phthalic acid diethyl ester, p-phthalic acid-
Diη-propyl ester, p-phthalic acid diisobutyl ester, p-phthalic acid-two n-pentyl ester, p-phthalic acid di neo-pentyl ester, right
Phthalic acid-di-n-hexyl ester, dimethyl isophthalate, 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, isophthalic diformazan
Acid-di-n-hexyl ester, dimethyl phthalate, diethyl phthalate, phthalic acid-diη-propyl ester, adjacent benzene
Dioctyl phthalate diisobutyl ester, phthalic acid two n-pentyl ester, phthalic acid di neo-pentyl ester, phthalic acid di-n-hexyl
Ester, NDA dimethyl ester, NDA diethyl ester, NDA diη-propyl ester, 2,6-naphthalene diformazan
Acid diisobutyl ester, NDA two n-pentyl ester, NDA di neo-pentyl ester or NDA two are just
One or more in hexyl ester；
Described aromatic dicarboxylic anhydride one in terephthalic anhydride, phthalic anhydride or isophthalic anhydride
Or it is several.
Preferably, the preferred p-phthalic acid of described aromatic acid；The described preferred p-phthalic acid of aromatic dicarboxylic ester
Dimethyl ester；The preferred terephthalic anhydride of described aromatic dicarboxylic anhydride.
Preferably, described aliphatic dibasic acid is selected from straight-chain aliphatic binary acid or the ring-type alicyclic ring of C5-C10 of C2-C15
One or more in race's binary acid；
Described binary aliphatic ester is the C of above-mentioned aliphatic dibasic acid1-C6Arrcostab；
One or more in ethanedioic acid acid anhydride, succinic anhydride or adipic anhydride of described binary aliphatic anhydride.
Preferably, described aliphatic dibasic acid selected from ethanedioic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid.,
Suberic acid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, 1,2-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-
One or more in cyclohexane cyclohexanedimethanodibasic；
Described binary aliphatic ester one in dimethyl adipate, dimethyl sebacate or dimethyl succinate or
Several；
The described preferred succinic anhydride of binary aliphatic anhydride.
Preferably, one or more in the preferred adipic acid of described aliphatic dibasic acid, decanedioic acid or succinic acid.
Preferably, one or more in the alkanediol of C2-C13 of described aliphatic dihydroxy alcohol；Described alicyclic
Dihydroxylic alcohols is selected from C5-C10Cycloalkanes glycol in one or more.
Preferably, described aliphatic dihydroxy alcohol selected from ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,
5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,
11-undecane, 1,12-dodecanediol, 1,13-tridecane diols or 2-methyl isophthalic acid, the one or several in ammediol
Kind；
Described cycloaliphatic diols is selected from 1,3-ring pentanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-cyclohexanediol, 1,2-hexamethylene
One or more in dimethanol or 1,4-CHDM.
Preferably, one or both in the preferred BDO of described aliphatic dihydroxy alcohol or ethylene glycol.
Preferably, one or more in the described first preferred titanium compound of catalyst or acetate；Described second catalysis
One or more in the preferred titanium compound of agent, tin compound or antimonial.
Preferably, described titanium compound is different selected from tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyl, metatitanic acid four
One or more in propyl ester or the different monooctyl ester of metatitanic acid four；Described acetate one in zinc acetate, magnesium acetate or manganese acetate
Or it is several；Described tin compound is selected from dibutyltin oxide, stannous octoate, dibutyl tin dilaurate or stannous chloride
Plant or several；Described antimonial is selected from one or both in antimony acetate or antimony oxide.
Preferably, one or both in the preferred 2,4 toluene diisocyanate of described isocyanates, hexamethylene diisocyanate.
Compared with prior art, the method have the advantages that
1, the 2,3-butanediol that the present invention produces by utilizing biofermentation prepares polyester plastics for raw material, decreases stone
The dependency of the non-renewable resources such as change, is conducive to the sustainable development of this type of polymeric material.
2, the present invention utilizes the high activity of isocyanate-monomer, the low molecular weight polyester two produced with 2,3-butanediol polycondensation
Unit's alcohol (Mw is 500-5000) reaction, overcomes the problem that 2,3-butanediol secondary hydroxyl reactivity is the highest, obtains having higher
Molecular weight, excellent mechanical performance and the polyester plastics of serviceability.
3, the present invention obtains low molecular weight polyester dihydroxylic alcohols, then by 2,3-butanediol and binary acid, diol reaction
Adding isocyanates chain extension, obtain the polyester plastics of high molecular, this polyester plastics is deposited due to 2,3-butanediol pendant methyl
, destroy the regularity of polyester molecule chain, for transparent polyester plastics, excellent in mechanical performance, at Injection moulded part, optics device
The aspects such as part, thin film, laminated material are all with a wide range of applications.
4, the present invention obtains low molecular weight polyester dihydroxylic alcohols, then by 2,3-butanediol and binary acid, diol reaction
Add isocyanates chain extension, obtain the polyester plastics of high molecular.By aromatic unit, aliphatic unit in regulation binary acid
Ratio, the ratio of 2,3-butanediol and dihydroxylic alcohols, the ratio of isocyanate-monomer and polyester diol, can be in certain limit
The interior thermodynamic property to gained copolyesters is finely adjusted, and meets the different field diversity requirements to material.
5, the present invention obtains low molecular weight polyester two by 2,3-butanediol and binary acid, diol reaction
Unit's alcohol, is subsequently adding isocyanates chain extension, obtains the polyester plastics of high molecular.This polyester plastics can be with other
Plastics such as polyethylene terephthalate, PA 66 etc., and various filler such as Pulvis Talci, calcium carbonate etc., be blended
Improve its thermodynamic property, obtain the engineering plastics with particular requirement, further expand its range of application.
Detailed description of the invention
The present invention is described in detail below in conjunction with each embodiment.
In examples provided below, use following detection method:
Use differential scanning calorimetry (DSC) Per kin Elmer DSC7, under following mode of heating, measure glass transition temperature
Degree Tg:
Scanning, with 50 DEG C/min, is warmed up to 270 DEG C from-100 DEG C for the first time；
Second time scanning, with 10 DEG C/min, cools to-100 DEG C from 270 DEG C；
Third time scanning, with 20 DEG C/min, is warmed up to 270 DEG C from-100 DEG C.
Weight average molecular weight Mw measures on Waters 600E series GPC system, and wherein chloroform is as eluent and polyphenyl second
Alkene standard sample is used for calibration curve.
Embodiment 1
73g adipic acid, 83g p-phthalic acid, the 2,3-butanediol of 230g, 0.15g zinc acetate are joined equipped with machinery
In the 500mL there-necked flask of agitating device.After all of material adds, assemble a set of condensing unit, evacuation, inflated with nitrogen three to flask
Secondary, remove the oxygen in reaction vessel to ensure that esterification is carried out under a nitrogen atmosphere.It is heated to 225 DEG C, question response thing shape
Becoming after homogeneous system, controlling reaction temperature is 225 DEG C, carries out esterification 3h under stirring, condensing condition, in the process,
Water is distilled out of from reactant mixture as side-product, until the amount of fraction liquid reaches the 92% of theoretical amount.(water theory meter
Calculation amount is adipic acid and the twice of p-phthalic acid mole sum).
(i.e. second urges respectively as the catalyst of polycondensation reaction for 0.10g tetra-n-butyl titanate, 0.12g triphenyl phosphite
Agent), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 260 DEG C, evacuation stirring 2h, stops
Only reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product polyadipate-co-p-phthalic acid (50%
Mol) 2,3-butanediol low molecular weight polyester, Mw is 3100.
By polyadipate-co-p-phthalic acid (50%mol) 2,3-butanediol low molecular weight polyester dried for 95g, 5g
2,4 toluene diisocyanate put into high-speed mixer mixing 10min, then input double screw extruder, at twin-screw extrusion
In machine, reactive extrursion obtains the polyester plastics granule of high molecular, and each section of temperature of double screw extruder is followed successively by: one section: 80 DEG C；
Two-stage nitration: 130 DEG C；Three sections: 140 DEG C；Four sections: 140 DEG C；Five sections: 145 DEG C；Head: 145 DEG C.
Gained polyester plastics granule carries out the test of DSC, mechanical property, and test result is shown in Table 1.
Embodiment 2
37g adipic acid, 125g p-phthalic acid, the 2,3-butanediol of 210g, 0.10g tetra-n-butyl titanate are joined dress
Have in the 500mL there-necked flask of mechanical stirring device.After all of material adds, assemble a set of condensing unit to flask, evacuation, fill
Nitrogen three times, removes the oxygen in reaction vessel to ensure that esterification is carried out under a nitrogen atmosphere.It is heated to 215 DEG C, treats anti-
After answering thing to form homogeneous system, controlling reaction temperature is 215 DEG C, carries out esterification 4h, in this mistake under stirring, condensing condition
Cheng Zhong, water is distilled out of from reactant mixture as side-product, until the amount of fraction liquid reaches the 92% of theoretical amount.(water
Theoretical amount is adipic acid and the twice of p-phthalic acid mole sum).
0.15g antimony oxide, 0.10g trimethyl phosphate are respectively as catalyst (i.e. second catalysis of polycondensation reaction
Agent), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 255 DEG C, is evacuated to less than 500Pa,
Stirring 3h, stopped reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product polyadipate-co-p-phthalic acid (75%
Mol) 2,3-butanediol low molecular weight polyester, Mw is 2600.
By polyadipate-co-p-phthalic acid (75%mol) 2,3-butanediol low molecular weight polyester dried for 94g, 6g
2,4 toluene diisocyanate put into high-speed mixer mixing 12min, then input double screw extruder, at twin-screw extrusion
In machine, reactive extrursion obtains the polyester plastics granule of high molecular, and each section of temperature of double screw extruder is followed successively by: one section: 90 DEG C；
Two-stage nitration: 150 DEG C；Three sections: 160 DEG C；Four sections: 165 DEG C；Five sections: 165 DEG C；Head: 170 DEG C.
Gained polyester plastics granule carries out the test of DSC, mechanical property, and test result is shown in Table 1.
Embodiment 3
By 131g dimethyl adipate, 49g dimethyl terephthalate (DMT), the 2,3-butanediol of 70g, the Isosorbide-5-Nitrae-fourth two of 140g
Alcohol, 0.10g magnesium acetate, the different monooctyl ester of 0.05g metatitanic acid four join equipped with in the 500mL there-necked flask of mechanical stirring device.All of
After material adds, assemble a set of condensing unit, evacuation, inflated with nitrogen three times to flask, remove the oxygen in reaction vessel to ensure
Ester exchange reaction is carried out under a nitrogen atmosphere.It is heated to 230 DEG C, after question response thing forms homogeneous system, controls reaction temperature and exist
230 DEG C, in stirring, carry out ester exchange reaction 2h under condensing condition, in the process, methanol as side-product from reactant mixture
In be distilled out of, until the amount of fraction liquid reaches the 92% of theoretical amount.(methanol theoretical amount is dimethyl adipate and right
The twice of dimethyl phthalate mole sum).
0.13g dibutyltin oxide, 0.12g triphenyl phosphate are respectively as catalyst (i.e. second catalysis of polycondensation reaction
Agent), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 250 DEG C, evacuation stirring 4h, stops
Reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product polyadipate-co-p-phthalic acid (25%
Mol) 2,3-butanediol-co-1,4-butanediol (67%mol) low molecular weight polyester, Mw is 1000.
By polyadipate-co-p-phthalic acid (25%mol) 2,3-butanediol-co-1 dried for 90g, 4-butanediol
(67%mol) low molecular weight polyester, the 2,4 toluene diisocyanate of 10g put into high-speed mixer mixing 20min, then input
Double screw extruder, in double screw extruder, reactive extrursion obtains the polyester plastics granule of high molecular, double screw extruder
Each section of temperature is followed successively by: one section: 40 DEG C；Two-stage nitration: 60 DEG C；Three sections: 75 DEG C；Four sections: 75 DEG C；Five sections: 75 DEG C；Head: 80 DEG C.
Gained polyester plastics granule carries out the test of DSC, mechanical property, and test result is shown in Table 1.
Embodiment 4
By 30g succinic acid, 44g dimethyl adipate, 42g p-phthalic acid, 49g dimethyl terephthalate (DMT), 330g
2,3-butanediol, 1.23g manganese acetate join equipped with in the 500mL there-necked flask of mechanical stirring device.After all of material adds, give
Flask assembles a set of condensing unit, evacuation, inflated with nitrogen three times, removes the oxygen in reaction vessel to ensure ester exchange and esterification
Reaction is carried out under a nitrogen atmosphere.Being heated to 200 DEG C, question response thing is formed after homogeneous system, controls reaction temperature at 200 DEG C,
In stirring, carry out being esterified and ester exchange reaction 5.5h under condensing condition, in the process, first alcohol and water as side-product from reaction
Mixture is distilled out of, until the amount of fraction liquid reaches the 92% of theoretical amount.(methanol theoretical amount is adipic acid diformazan
Ester and the twice of dimethyl terephthalate (DMT) mole sum, water theory amount of calculation be succinic acid and p-phthalic acid mole it
The twice of sum).
1.23g stannous octoate, 5.02g NSC 6513 are respectively as catalyst (i.e. second catalysis of polycondensation reaction
Agent), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 265 DEG C, evacuation stirring 1h, stops
Reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product poly-succinic-co-adipic acid (25%
Mol)-co-p-phthalic acid (25%mol) 2,3-butanediol low molecular weight polyester, Mw is 4200.
By poly-succinic-co-adipic acid (25%mol)-co-p-phthalic acid (25%mol) 2 dried for 97g, 3-fourth
Glycol low molecular weight polyester, the hexamethylene diisocyanate of 3g put into high-speed mixer mixing 15min, then input twin-screw extrusion
Machine, in double screw extruder, reactive extrursion obtains the polyester plastics granule of high molecular, and each section of temperature of double screw extruder depends on
Secondary it is: one section: 80 DEG C；Two-stage nitration: 130 DEG C；Three sections: 140 DEG C；Four sections: 140 DEG C；Five sections: 145 DEG C；Head: 145 DEG C.
Gained polyester plastics granule carries out the test of DSC, mechanical property, and test result is shown in Table 1.
Embodiment 5
166g p-phthalic acid, the 2,3-butanediol of 166g, 0.0034g zinc acetate are joined equipped with mechanical stirring device
500mL there-necked flask in.After all of material adds, assemble a set of condensing unit, evacuation, inflated with nitrogen three times to flask, remove
Oxygen in reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere.Being heated to 230 DEG C, question response thing forms homogeneous body
After system, control reaction temperature, at 230 DEG C, carries out esterification 1.5h, in the process, water conduct under stirring, condensing condition
Side-product is distilled out of from reactant mixture, until the amount of fraction liquid reaches the 92% of theoretical amount.(water theory amount of calculation is
The twice of p-phthalic acid mole).
0.0034g tetra-n-butyl titanate, 0.0034g triphenyl phosphite are respectively as the catalyst (i.e. of polycondensation reaction
Two catalyst), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 240 DEG C, and evacuation stirs
6h, stopped reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain low point of product poly terephthalic acid 2,3-butanediol
Sub-weight polyester, Mw is 5000.
By poly terephthalic acid 2,3-butanediol low molecular weight polyester dried for 99.9g, the 2 of 0.1g, 4-toluene two is different
Cyanate puts into high-speed mixer mixing 30min, then inputs double screw extruder, and in double screw extruder, reactive extrursion obtains
To the polyester plastics granule of high molecular, each section of temperature of double screw extruder is followed successively by: one section: 150 DEG C；Two-stage nitration: 220 DEG C；Three
Section: 220 DEG C；Four sections: 220 DEG C；Five sections: 220 DEG C；Head: 220 DEG C.
Embodiment 6
147g adipic acid, the 2,3-butanediol of 117g, the ethylene glycol of 468g, 3.66g zinc acetate are joined equipped with machinery
In the 1000mL there-necked flask of agitating device.After all of material adds, assemble a set of condensing unit, evacuation, inflated with nitrogen to flask
Three times, remove the oxygen in reaction vessel to ensure that esterification is carried out under a nitrogen atmosphere.It is heated to 170 DEG C, question response thing
After forming homogeneous system, control reaction temperature, at 170 DEG C, carries out esterification 8h, in this process under stirring, condensing condition
In, water is distilled out of from reactant mixture as side-product, until the amount of fraction liquid reaches the 92% of theoretical amount.(water is managed
Opinion amount of calculation is the twice of adipic acid mole).
3.66g tetra-n-butyl titanate, 15g triethyl phosphate are respectively as catalyst (i.e. second catalysis of polycondensation reaction
Agent), heat stabilizer joins in reactant mixture.Polyreaction is carried out at a temperature of 280 DEG C, evacuation stirring 0.5h, stops
Only reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product polyadipate 2,3-butanediol-co-second two
Alcohol (80%mol) low molecular weight polyester, Mw is 500.
By dried for 80g polyadipate 2,3-butanediol-co-ethylene glycol (80%mol) low molecular weight polyester, 20g
Hexamethylene diisocyanate puts into high-speed mixer mixing 5min, then inputs double screw extruder, reacts in double screw extruder
Extrusion obtains the polyester plastics granule of high molecular, and each section of temperature of double screw extruder is followed successively by: one section: 30 DEG C；Two-stage nitration: 60
℃；Three sections: 70 DEG C；Four sections: 70 DEG C；Five sections: 70 DEG C；Head: 70 DEG C.
Comparative example
73g adipic acid, 83g p-phthalic acid, the 2,3-butanediol of 230g, 0.1g zinc acetate are joined and stir equipped with machinery
Mix in the 500mL there-necked flask of device.After all of material adds, assemble a set of condensing unit, evacuation, inflated with nitrogen three to flask
Secondary, remove the oxygen in reaction vessel to ensure that esterification is carried out under a nitrogen atmosphere.It is heated to 210 DEG C, question response thing shape
Become after homogeneous system, control reaction temperature at 210 DEG C, under stirring, condensing condition, carry out esterification 4h, in the process,
Water is distilled out of from reactant mixture as side-product, until the amount of fraction liquid reaches the 92% of theoretical amount.(water theory meter
Calculation amount is adipic acid and the twice of p-phthalic acid mole sum).
0.15g tetra-n-butyl titanate, 0.13g triphenyl phosphite are respectively as the catalyst of polycondensation reaction, heat stabilizer
Join in reactant mixture.Polyreaction is carried out at a temperature of 260 DEG C, evacuation stirring 2.5h, stopped reaction.
Reactant mixture is taken out from bottle, cools down in water, obtain product polyadipate-co-p-phthalic acid (50%
Mol) 2,3-butanediol copolyesters.It is carried out the test of DSC, mechanical property, and test result is shown in Table 1.
Table 1
By performance test and the implementation process of each embodiment of table 1, it is known that by the invention by 2,3-butanediol and two
Unit's acid, diol reaction obtain low molecular weight polyester dihydroxylic alcohols, are subsequently adding isocyanates chain extension, obtain the polyester of high molecular
Plastics.Overcome the problem that 2,3-butanediol secondary hydroxyl reactivity is the highest, obtain that there is higher molecular weight, excellent mechanical performance
With the polyester plastics of serviceability, have a wide range of applications field and application prospect.Decrease non-renewable to petrochemical industry etc. simultaneously
The dependency of resource, is conducive to the sustainable development of this type of polymeric material.
Embodiment 7
(1) by monomer a terephthalic anhydride, monomer b ethanedioic acid acid anhydride, 2,3-butanediol, monomer c 1,2-PD and
One catalyst tetraethyl titanate, joins in reactor, and evacuation, inflated with nitrogen remove the oxygen in reaction unit, it is ensured that ester is handed over
Change and/or esterification is carried out under a nitrogen atmosphere, heat the mixture to 180 DEG C, after forming homogeneous system, control reaction temperature
Degree is 180 DEG C, carries out reacting 2h under stirring, condensing condition, until the by-product of ester exchange and esterification reaches theoretical meter
More than the 92% of calculation amount, wherein the theoretical amount of by-product is monomer a and 2 times of monomer b mole sum；
The relationship between quality of monomer a and monomer b is: the mass fraction of monomer a is 99%, and the mass fraction of monomer b is 1%；
2,3-butanediol with the relationship between quality of monomer c is: the mass fraction of 2,3-butanediol is 91%, and the mass fraction of monomer c is
9%；The gross mass of monomer a and monomer b is 1: 1 with the mass ratio of 2,3-butanediol and the gross mass of monomer c；First catalyst accounts for
The weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.001%.
(2) add the second catalyst tetraethyl titanate and heat stabilizer NSC 5284, be evacuated to little at 246 DEG C
In 500Pa, stirring 2.5h, stopped reaction, obtain low molecular weight polyester P, Mw is 600, standby；
It is 0.005% that second catalyst accounts for the weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount；Heat is steady
Determine the addition of agent accounting for the weight fraction of all reactive components is 0.001%.These all reactive components include monomer a, monomer b,
2,3-butanediol, monomer c, the first catalyst, the second catalyst and heat stabilizer.
(3) the low molecular weight polyester P that weight/mass percentage composition is 82% and weight/mass percentage composition drying processed is
The 2 of 18%, 6-toluene di-isocyanate(TDI) puts into high-speed mixer mixing 18min, then inputs double screw extruder, at double spiral shells
In bar extruder, reactive extrursion obtains the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 100 DEG C；
Two-stage nitration: 150 DEG C；Three sections: 160 DEG C；Four sections: 160 DEG C；Five sections: 180 DEG C；Head: 200 DEG C.
Embodiment 8
(1) monomer a M-phthalic acid, monomer b decanedioic acid, 2,3-butanediol, monomer c 1,3-PD and first are urged
Agent magnesium acetate, joins in reactor, and evacuation, inflated with nitrogen remove the oxygen in reaction unit, it is ensured that ester exchange and/or ester
Changing reaction to carry out under a nitrogen atmosphere, heat the mixture to 185 DEG C, after forming homogeneous system, controlling reaction temperature is 185
DEG C, carry out reacting 5.5h, until the by-product of ester exchange and esterification reaches theoretical amount under stirring, condensing condition
More than 92%, wherein the theoretical amount of by-product is monomer a and 2 times of monomer b mole sum；
The relationship between quality of monomer a and monomer b is: the mass fraction of monomer a is 66%, and the mass fraction of monomer b is 34%；
2,3-butanediol with the relationship between quality of monomer c is: the mass fraction of 2,3-butanediol is 30%, and the mass fraction of monomer c is
70%；The gross mass of monomer a and monomer b is 1: 4 with the mass ratio of 2,3-butanediol and the gross mass of monomer c；First catalyst
The weight fraction accounting for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.5%.
(2) add the second catalyst metatitanic acid four n-propyl and heat stabilizer triphenyl phosphite, be evacuated at 270 DEG C
Less than 500Pa, stirring 4.5h, stopped reaction, obtain low molecular weight polyester P, Mw is 2500, standby；
It is 0.5% that second catalyst accounts for the weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount；Thermally-stabilised
It is 0.002% that the addition of agent accounts for the weight fraction of all reactive components.
(3) the low molecular weight polyester P that weight/mass percentage composition is 99% and weight/mass percentage composition drying processed is 1%
M-benzene diisocyanate put into high-speed mixer mixing 22min, then input double screw extruder, in double screw extruder
Reactive extrursion obtains the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 120 DEG C；Two-stage nitration: 180
℃；Three sections: 200 DEG C；Four sections: 200 DEG C；Five sections: 200 DEG C；Head: 220 DEG C.
Embodiment 9
(1) by monomer a p-phthalic acid diisobutyl ester, monomer b dimethyl sebacate, 2,3-butanediol, monomer c 1,
3-ring pentanediol and the first catalyst acetic acid manganese, join in reactor, and evacuation, inflated with nitrogen remove the oxygen in reaction unit
Gas, it is ensured that ester exchange and/or esterification are carried out under a nitrogen atmosphere, heats the mixture to 215 DEG C, forms homogeneous system
After, controlling reaction temperature is 215 DEG C, carries out reacting 7h under stirring, condensing condition, until ester exchange and the pair of esterification
Product reaches more than the 92% of theoretical amount, and wherein the theoretical amount of by-product is monomer a and monomer b mole sum
2 times；
The relationship between quality of monomer a and monomer b is: the mass fraction of monomer a is 5%, and the mass fraction of monomer b is 95%；
2,3-butanediol with the relationship between quality of monomer c is: the mass fraction of 2,3-butanediol is 52%, and the mass fraction of monomer c is
48%；The gross mass of monomer a and monomer b is 1: 2 with the mass ratio of 2,3-butanediol and the gross mass of monomer c；First catalyst
The weight fraction accounting for monomer a, monomer b, 2,3-butanediol and monomer c total amount is 0.005%.
(2) add the second catalyst dibutyl tin dilaurate and heat stabilizer NSC 6513, take out true at 250 DEG C
Sky, to less than 500Pa, stirs 1.5h, stopped reaction, obtains low molecular weight polyester P, and Mw is 3500, standby；
It is 0.001% that second catalyst accounts for the weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount；Heat is steady
Determine the addition of agent accounting for the weight fraction of all reactive components is 1%.
(3) the low molecular weight polyester P that weight/mass percentage composition is 86% and weight/mass percentage composition drying processed is
The 1 of 14%, 5-naphthalene diisocyanate puts into high-speed mixer mixing 12min, then inputs double screw extruder, squeezes at twin screw
Go out reactive extrursion in machine and obtain the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 100 DEG C；Two
Section: 120 DEG C；Three sections: 150 DEG C；Four sections: 150 DEG C；Five sections: 160 DEG C；Head: 180 DEG C.
Embodiment 10
(1) by monomer a p-phthalic acid diethyl ester, monomer b succinic anhydride, 2,3-butanediol, monomer c Isosorbide-5-Nitrae-hexamethylene
Glycol and the first catalyst tetraisopropyl titanate, join in reactor, and evacuation, inflated with nitrogen remove the oxygen in reaction unit
Gas, it is ensured that ester exchange and/or esterification are carried out under a nitrogen atmosphere, heats the mixture to 205 DEG C, forms homogeneous system
After, controlling reaction temperature is 205 DEG C, carries out reacting 7.5h under stirring, condensing condition, until ester exchange and the pair of esterification
Product reaches more than the 92% of theoretical amount, and wherein the theoretical amount of by-product is monomer a and monomer b mole sum
2 times；
The relationship between quality of monomer a and monomer b is: the mass fraction of monomer a is 50%, and the mass fraction of monomer b is 50%；
2,3-butanediol with the relationship between quality of monomer c is: the mass fraction of 2,3-butanediol is 60%, and the mass fraction of monomer c is
40%；The gross mass of monomer a and monomer b is 1: 1.5 with the mass ratio of 2,3-butanediol and the gross mass of monomer c；First catalysis
It is 0.3% that agent accounts for the weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount.
(2) add the second catalyst acetic acid antimony and heat stabilizer trimethyl phosphate, be evacuated to be less than at 270 DEG C
500Pa, stirs 3.5h, stopped reaction, obtains low molecular weight polyester P, and Mw is 4800, standby；
It is 0.3% that second catalyst accounts for the weight fraction of monomer a, monomer b, 2,3-butanediol and monomer c total amount；Thermally-stabilised
It is 2% that the addition of agent accounts for the weight fraction of all reactive components.
(3) the low molecular weight polyester P that weight/mass percentage composition is 94.9% and weight/mass percentage composition drying processed is
The PPDI of 5.1% puts into high-speed mixer mixing 28min, then inputs double screw extruder, squeezes at twin screw
Go out reactive extrursion in machine and obtain the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 60 DEG C；Two-stage nitration:
90℃；Three sections: 100 DEG C；Four sections: 100 DEG C；Five sections: 120 DEG C；Head: 150 DEG C.
The several specific embodiments being only the application disclosed above, but the application is not limited to this, any this area
Technical staff can think change, all should fall in the protection domain of the application.
Claims (16)
1. high molecular weight polyesters plastics based on 2,3-butanediol, it is characterised in that this polyester plastics has following weight
Complex structure unit:
Wherein, R1 is selected from P=0-11；
R2 is selected from Q=2-13；
R3 is selected from
N=1-1000, m=1-1000；
The preparation method of described a kind of based on 2,3-butanediol high molecular weight polyesters plastics, comprises the following steps:
(1) by monomer a, monomer b, 2,3-butanediol, monomer c and the first catalyst, join in reactor, evacuation, nitrogen charging
Gas removes the oxygen in reaction unit, it is ensured that ester exchange and/or esterification are carried out under a nitrogen atmosphere, heat the mixture to
170-230 DEG C, after forming homogeneous system, control reaction temperature and be 170-230 DEG C, react under stirring, condensing condition
1.5-8h, until the by-product of ester exchange and esterification reaches more than the 92% of theoretical amount, the wherein theory of by-product
Amount of calculation is monomer a and 2 times of monomer b mole sum；
(2) add the second catalyst and heat stabilizer, be evacuated to, less than 500Pa, stir 0.5-6h, stop at 240-280 DEG C
Only reaction, obtains low molecular weight polyester P, and Mw is 500-5000, standby；
(3) the low molecular weight polyester P that weight/mass percentage composition is 80-99.9% and weight/mass percentage composition drying processed is
The isocyanates of 20-0.1% puts into high-speed mixer mixing 5-30min, then inputs double screw extruder, at twin-screw extrusion
In machine, reactive extrursion obtains the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 30-150 DEG C；Two
Section: 60-220 DEG C；Three sections: 70-220 DEG C；Four sections: 70-220 DEG C；Five sections: 70-220 DEG C；Head: 70-220 DEG C；
One or more in aromatic acid, aromatic dicarboxylic ester, aromatic dicarboxylic anhydride of described monomer a；Described
One or more in aliphatic dibasic acid, binary aliphatic ester, binary aliphatic anhydride of monomer b；Described monomer c is selected from
One or more in aliphatic dihydroxy alcohol or cycloaliphatic diols.
2. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol, it is characterised in that comprise the following steps:
(1) by monomer a, monomer b, 2,3-butanediol, monomer c and the first catalyst, join in reactor, evacuation, nitrogen charging
Gas removes the oxygen in reaction unit, it is ensured that ester exchange and/or esterification are carried out under a nitrogen atmosphere, heat the mixture to
170-230 DEG C, after forming homogeneous system, control reaction temperature and be 170-230 DEG C, react under stirring, condensing condition
1.5-8h, until the by-product of ester exchange and esterification reaches more than the 92% of theoretical amount, the wherein theory of by-product
Amount of calculation is monomer a and 2 times of monomer b mole sum；
(2) add the second catalyst and heat stabilizer, be evacuated to, less than 500Pa, stir 0.5-6h, stop at 240-280 DEG C
Only reaction, obtains low molecular weight polyester P, and Mw is 500-5000, standby；
(3) the low molecular weight polyester P that weight/mass percentage composition is 80-99.9% and weight/mass percentage composition drying processed is
The isocyanates of 20-0.1% puts into high-speed mixer mixing 5-30min, then inputs double screw extruder, at twin-screw extrusion
In machine, reactive extrursion obtains the polyester plastics granule of high molecular；Each section of temperature of extruder is followed successively by: one section: 30-150 DEG C；Two
Section: 60-220 DEG C；Three sections: 70-220 DEG C；Four sections: 70-220 DEG C；Five sections: 70-220 DEG C；Head: 70-220 DEG C；
One or more in aromatic acid, aromatic dicarboxylic ester, aromatic dicarboxylic anhydride of described monomer a；Described
One or more in aliphatic dibasic acid, binary aliphatic ester, binary aliphatic anhydride of monomer b；Described monomer c is selected from
One or more in aliphatic dihydroxy alcohol or cycloaliphatic diols.
3. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 2, it is characterised in that
The relationship between quality of described monomer a and monomer b is: the mass fraction of monomer a is 0-100%, and the mass fraction of monomer b is 0-
100%, monomer a does not limits with the ratio of monomer b；2,3-butanediol with the relationship between quality of monomer c is: the quality of 2,3-butanediol is divided
Number is 20-100%, and surplus is monomer c；The gross mass of monomer a and monomer b and 2,3-butanediol and the matter of the gross mass of monomer c
Amount ratio is 1:1-1:4；
Described first catalyst, the second catalyst account for the weight of monomer a, monomer b, 2,3-butanediol and monomer c total amount respectively and divide
Number is 0.001-0.5%；The addition of described first catalyst and the second catalyst is identical or different；
It is 0.001-2% that the addition of described heat stabilizer accounts for the weight fraction of all reactive components, described all reactive components
Including monomer a, monomer b, 2,3-butanediol, monomer c, the first catalyst, the second catalyst and heat stabilizer.
4. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 3, it is characterised in that
The weight fraction that described first catalyst, the second catalyst account for monomer a, monomer b, 2,3-butanediol and monomer c total amount respectively is excellent
Elect 0.005-0.3% as；The addition of described heat stabilizer accounts for the weight fraction of all reactive components and is preferably 0.002-1%.
5. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 2, it is characterised in that
Described 2,3-butanediol is passed through antibacterial-Cray by one or more in glucose, sucrose, molasses, glycerol, starch or straw
Primary Salmonella or fermentation of bacillus produce and obtain；
Described first catalyst, the second catalyst be respectively selected from Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La,
One or more in the metallic compound of Ce, Li or Ga；Described first catalyst and the second catalyst can be identical, it is also possible to
Different；
Described heat stabilizer is selected from triphenyl phosphite, NSC 6513, NSC 5284, trimethyl phosphate, tricresyl phosphate
One or more in phenyl ester, triethyl phosphate；
Described isocyanates is diisocyanate, selected from 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), to benzene two
Isocyanates, m-benzene diisocyanate, 4,4-methyl diphenylene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene two Carbimide.
Ester, 3,3-dimethoxy-4 ', 4-biphenyl diisocyanate, m-xylylene diisocyanate, 2,6-bis-isocyanate group caproic acid
One or more in methyl ester.
6. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, it is characterised in that
Described aromatic acid one in p-phthalic acid, M-phthalic acid, phthalic acid or 2,6-naphthalenedicarboxylic acid or
Several；
Described aromatic dicarboxylic ester is selected from dimethyl terephthalate (DMT), p-phthalic acid diethyl ester, p-phthalic acid two positive third
Base ester, p-phthalic acid diisobutyl ester, p-phthalic acid two n-pentyl ester, p-phthalic acid di neo-pentyl ester, terephthaldehyde
Acid di-n-hexyl ester, dimethyl isophthalate, M-phthalic acid diethyl ester, M-phthalic acid diη-propyl ester, isophthalic two
Formic 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, diethyl phthalate, phthalic acid diη-propyl ester, phthalic acid two isobutyl
Base ester, phthalic acid two n-pentyl ester, phthalic acid di neo-pentyl ester, phthalic acid di-n-hexyl ester, 2,6-naphthalene two
Formic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid diethyl ester, 2,6-naphthalenedicarboxylic acid diη-propyl ester, 2,6-naphthalenedicarboxylic acid diisobutyl
In ester, 2,6-naphthalenedicarboxylic acid two n-pentyl ester, 2,6-naphthalenedicarboxylic acid di neo-pentyl ester or 2,6-naphthalenedicarboxylic acid di-n-hexyl ester
One or more；
Described aromatic dicarboxylic anhydride one or several in terephthalic anhydride, phthalic anhydride or isophthalic anhydride
Kind.
7. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 6, it is characterised in that
The preferred p-phthalic acid of described aromatic acid；The described preferred dimethyl terephthalate (DMT) of aromatic dicarboxylic ester；Described fragrance
The preferred terephthalic anhydride of race's dibasic acid anhydride.
8. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, it is characterised in that
Described aliphatic dibasic acid is selected from the straight-chain aliphatic binary acid of C2-C15 or the ring-type cycloaliphatic diacid of C5-C10
Plant or several；
Described binary aliphatic ester is the C1-C6 Arrcostab of above-mentioned aliphatic dibasic acid；
One or more in ethanedioic acid acid anhydride, succinic anhydride or adipic anhydride of described binary aliphatic anhydride.
9. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 8, it is characterised in that
Described aliphatic dibasic acid selected from ethanedioic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid,
In decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, 1,2-cyclohexane cyclohexanedimethanodibasic or 1,4 cyclohexanedicarboxylic acid
One or more；
Described binary aliphatic ester one or several in dimethyl adipate, dimethyl sebacate or dimethyl succinate
Kind；
The described preferred succinic anhydride of binary aliphatic anhydride.
10. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 9, its feature exists
In, one or more in the preferred adipic acid of described aliphatic dibasic acid, decanedioic acid or succinic acid.
The preparation method of 11. high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, its feature exists
In, one or more in the alkanediol of C2-C13 of described aliphatic dihydroxy alcohol；Described cycloaliphatic diols is selected from C5-
One or more in the cycloalkanes glycol of C10.
12. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 11, its feature exists
In, described aliphatic dihydroxy alcohol selected from ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,5-PD, new
Pentanediol, 1,6-HD, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-hendecane two
One or more in alcohol, 1,12-dodecanediol, 1,13-tridecane diols or 2-methyl-1,3-propanediol；
Described cycloaliphatic diols is selected from 1,3-ring pentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,2-hexamethylene diformazan
One or more in alcohol or 1,4 cyclohexane dimethanol.
The preparation method of 13. high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 12, its feature exists
In, one or both in the preferred BDO of described aliphatic dihydroxy alcohol or ethylene glycol.
The preparation method of 14. high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, its feature exists
In, one or more in the described first preferred titanium compound of catalyst or acetate；The described second preferred titanizing of catalyst is closed
One or more in thing, tin compound or antimonial.
The preparation method of 15. high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 14, its feature exists
In, described titanium compound is selected from tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyl, tetraisopropyl titanate or metatitanic acid four
One or more in different monooctyl ester；One or more in zinc acetate, magnesium acetate or manganese acetate of described acetate；Described stannum
One or more in dibutyltin oxide, stannous octoate, dibutyl tin dilaurate or stannous chloride of compound；Described
Antimonial is selected from one or both in antimony acetate or antimony oxide.
16. the preparation method of high molecular weight polyesters plastics based on 2,3-butanediol as claimed in claim 5, its feature exists
In, one or both in the preferred 2,4 toluene diisocyanate of described isocyanates, hexamethylene diisocyanate.
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| 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 |
| 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 |
| CN109369893B (en) * | 2018-10-23 | 2020-04-17 | 东华大学 | Polyester with low oligomer content and preparation method thereof |
| KR102478598B1 (en) * | 2019-08-30 | 2022-12-15 | 코오롱인더스트리 주식회사 | Polymer comprising cyclic monomer from biomass and method for preparing comprising the same |
| CN112745491B (en) * | 2019-10-29 | 2022-11-18 | 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 |
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| 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 |
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| 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 |
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