CN109096478A - A kind of Aliphatic Polycarbonate Copolymers and preparation method thereof - Google Patents
A kind of Aliphatic Polycarbonate Copolymers and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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Abstract
The invention discloses a kind of Aliphatic Polycarbonate Copolymers, the copolymer includes formula (I) repetitive unit,Wherein, R1For the alkylidene of C3-C8, R2For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality, R3For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality.The preparation method comprises the following steps: binary ester monomer, glycol monomer and catalyst are uniformly mixed by (a), after heating melting, it is warming up to 150-220 DEG C, reacts 2-4 hours, obtains oligomer；(b) oligomer made from above-mentioned steps (a) is heated, vacuum distillation removes by-product, is warming up to 180-250 DEG C, then be depressurized to 200Pa hereinafter, reacting 1-4 hours, Aliphatic Polycarbonate Copolymers are made.In the molecule of Aliphatic Polycarbonate Copolymers of the invention, containing chain repetitive unit and rigid annular repetitive unit, copolymer not only molecular weight with higher, and copolymer has excellent thermal property.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of Aliphatic Polycarbonate Copolymers and its preparation
Method.
Background technique
Fatty poly-ester carbonate is a kind of degradable macromolecule material with excellent degradability, biocompatibility and hypotoxicity
Material, the especially fatty poly-ester carbonate of high molecular weight have high tensile and elongation at break, are expected to as degradable material
Material solves white pollution problems to substitute conventional plastic.The melting temperature and glass transition temperature phase of fatty poly-ester carbonate
It is to hinder its widely applied main bottleneck to lower.Polytetramethylene carbonate diol (PBC) has excellent performance, although it is molten
Melt the height of all more similar fatty poly-ester carbonate of temperature, glass transition temperature, tensile strength and elongation at break, but it is difficult
To be widely applied, therefore by being modified to it, and then improving its thermal property is the emphasis studied at present.
Random copolymerization is to adjust and improve the simple and effective important means of one kind of polymer material performance.In recent years
Come, lot of documents, which reports, much to work about fatty poly-ester carbonate study on the modification, in general, dimethyl carbonate (DMC) or carbon
Diphenyl phthalate (DPC), it is anti-that 1.4- butanediol (BD) and dihydric alcohol or binary ester monomer carry out transesterification under the effect of the catalyst
It answers, polycondensation is carried out under the conditions of high-temperature low-pressure and obtains high molecular weight copolymer.Such as use 1,6-HD and DMC, BD copolymerization
Obtain a series of random copolymer PBHC, Tg < -38 DEG C, Tm < 60 DEG C, but its thermal stability is with the increase of HC unit content
And increase.A series of poly- (butylene-are prepared for by melt polycondensation using trans- 1,4-CHDM (CHDM) and DPC, BD
Co- cyclohexanedimethyleterephthalate carbonic ester) Copolycarbonate (PBCC), when CHDM content is 50%, Tg is 8.2 DEG C.Using 1,
10- decanediol and DMC, BD copolymerization poly- (butylene -co- decamethylene carbonic ester) (PBDC), Tg < -32 DEG C, Tm < 60 DEG C,
But introduce decamethylene carbonic ester (DC) unit significantly improve PBC crystallization rate (RSC Adv., 2015,5,2213-
2222).It is shown using terephthalate (DMT) and DMC, BD copolymerization high molecular weight PBCT copolymer, copolymer
High melting temperature and glass transition temperature.Using 2,5- furandicarboxylic acid dimethyl ester (DMFD) and DMC, BD copolymerization
Poly- (carbonic ester -co- polyester) (PBCF), wherein the Tg of PBCF50 is 4.9 DEG C, only when 80% or more PBF content, is just showed
Higher glass transition temperature and melting temperature out, and molecular weight is lower leads to mechanical degradation.These research explanations
Rigid structure unit is introduced to main polymer chain using random copolymerization mode, the calorifics of fatty poly-ester carbonate can be improved
Energy.
Although the thermodynamic property of polymer, copolymerization can be improved by introducing rigid structure unit in the polymer backbone
The melting temperature and glass transition temperature of object there is no the raising of conspicuousness, unless in the case that modified monomer dosage is big
Higher Thermal Parameter can be obtained, but its molecular weight and other performances can be influenced.
Summary of the invention
It is an object of the invention to: above-mentioned deficiency in the prior art is solved, it is total to provide a kind fatty poly-ester carbonate
Polymers and preparation method thereof improves melting temperature, the glass of polymer by introducing annular rigid structural unit to main polymer chain
Glass transition temperature, while molecular weight also with higher.In particular, making polymer under the premise of modified monomer dosage is few
Hot property be significantly improved.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of Aliphatic Polycarbonate Copolymers, it is described
Copolymer includes formula (I) repetitive unit,
Wherein, R1For the alkylidene of C3-C8,
R2For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality,
R3For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality.
Further, the R2 isOne of, the R3 isOne of.
The method for preparing the Aliphatic Polycarbonate Copolymers, includes the following steps,
(a) binary ester monomer, glycol monomer and catalyst by proportion are uniformly mixed, after heating melting, are warming up to
It 150-220 DEG C, reacts 2-4 hours, obtains oligomer；
(b) oligomer made from above-mentioned steps (a) to be heated, vacuum distillation removes by-product, it is warming up to 180-250 DEG C,
200Pa is depressurized to again hereinafter, reacting 1-4 hours, and Aliphatic Polycarbonate Copolymers are made；
Wherein, the glycol monomer includes monomer A and monomer B, the monomer A are the monomer containing R1 group, described
Monomer B is the monomer containing R2 and/or R3 group.
Further, in the step (a), the monomer of the group containing R1 is the glycol of C3-C8, such as Isosorbide-5-Nitrae butanediol,
1,5-PD, neopentyl glycol, 1,6- hexylene glycol, 1,3- hexylene glycol, pentaerythrite, dipentaerythritol, tripentaerythritol etc..
Further, the monomer of the group containing R2 is double five-membered ring dihydric alcohols, is specifically One of.
Further, the monomer of the group containing R3 is the aliphatic the spiroglycol containing spiral shell acetal units, is specificallyOne kind.
Further, the binary ester monomer is diphenyl carbonate, dimethyl carbonate, dimethyl succinate, glutaric acid two
One of methyl esters.
Further, the binary ester monomer and the molar ratio of the glycol monomer are binary ester monomer: dihydric alcohol list
Body=1:1-1.3.
Further, the dosage of the catalyst is the total amount of binary ester monomer or glycol monomer with molar fraction
0.1%-1mol%.
Further, the catalyst is one of inorganic metal salt, organic base or oxide type solid base.Inorganic gold
Belonging to salt is based on Zn, Cu, Mg, the Acetates compound of Mn, Ca；Organic base is CH3ONa, CH3CH2ONa, 4- dimethylamino
Pyridine (DMAP)；Oxide type solid base is Ca, the oxide and Ca of Mg, Mg composite oxides
By adopting the above-described technical solution, the beneficial effects of the present invention are:
In the molecule of Aliphatic Polycarbonate Copolymers of the invention, repeated containing chain repetitive unit and rigid annular single
Member, copolymer not only molecular weight with higher, and copolymer has excellent thermal property.The preparation of present copolymer
Method: it using dibasic ester and dihydric alcohol as monomer, under the effect of the catalyst, carries out that transesterification and polycondensation reaction, dibasic ester occurs
And the ratio of dihydric alcohol controls between 1:1-1.3, can get high molecular weight and the good polymer of thermal property, with the prior art
It compares, preparation method of the invention greatly reduces the dosage of modified monomer, reduces production cost.
Specific embodiment
Illustrate embodiments of the present invention according to specific embodiment, and corresponding survey is done to the result of each embodiment
Examination, using the number-average molecular weight of gel permeation chromatograph (GPC) measurement polymer, weight average molecular weight and polydispersity, mobile phase
Respectively tetrahydrofuran or chloroform, polystyrene are reference standard.And DSC is used, TGA is steady to the hot property and heat of copolymer
It is qualitative to be characterized.
Embodiment 1
[1] diphenyl carbonate, 1,4- butanediol and tetramethyl spiral shell glycol (molar ratio 1:0.9:0.1) are placed in reactor
In, using magnesia (molal quantity as diphenyl carbonate or the molal quantity of glycol monomer total amount 0.1%) as transesterification and contracting
Poly- catalyst, and nitrogen is passed through into reactor, heating melting reactant, and be sufficiently stirred.Reactant is heated to 200 DEG C
Esterification occurs, reacts 3 hours.
[2] after the esterification products for obtaining [1] are cooling, 120 DEG C are heated to, and the pressure of reaction system is slowly dropped to
1.3KPa, under this condition react 1 hour removing by-product, until fraction no longer flows out, then by pressure be down to 200Pa with
Under, and 210 DEG C are warming up to, it reacts 2 hours, obtains polycarbonate (butanediol carbonic ester-co- spiral shell glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 123470gmol-1, Mn 62537gmol-1, PDI
It is 1.97.Dsc analysis, product TmIt is 54.06 DEG C, Δ HmFor 6.012J/g (heat up for the first time), glass transition temperature is-
5.05 DEG C (second of heating).TG analysis, 5% thermal decomposition temperature T of the productD, 5%For 283.04 DEG C, decomposition mechanism temperature
Td,max.1For 318.42 DEG C and Td,max.2It is 409.97 DEG C.
Embodiment 2
[1] diphenyl carbonate, 1,4- butanediol and tetramethyl spiral shell glycol (molar ratio 1:0.7:0.3) are placed in reaction flask
In, magnesia (molal quantity be the molal quantity of diphenyl carbonate or glycol monomer total amount 0.1%) is used as transesterification and polycondensation
Catalyst, be passed through nitrogen, heating melting is simultaneously sufficiently stirred.Then reactant is heated to 200 DEG C of progress esterifications, maintained
3 hours.
[2] after the esterification products for obtaining [1] are cooling, 130 DEG C is heated to, the pressure of reaction system is slowly dropped to
1.1KPa is reacted 1 hour, until fraction no longer flows out with removing by-product.System is down to 200Pa or less again, and is risen
Temperature maintains 2 hours to 210 DEG C of progress polycondensation reactions, obtains polycarbonate (butanediol carbonic ester-co- spiral shell glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 134156gmol-1, Mn 64278gmol-1,
PDI is 2.09.Dsc analysis, product Tm are 150.91 DEG C, Δ HmIt (heats up for the first time) for 4.10J/g, glass transition temperature
For 33.70 DEG C (second of heating).TG analysis, 5% thermal decomposition temperature T of the productD, 5%For 301.76 DEG C, decomposition mechanism temperature
Spend Td,max.1For 323.21 DEG C and Td,max.2It is 427.11 DEG C.
Embodiment 3
[1] diphenyl carbonate, 1,4- butanediol and tetramethyl spiral shell glycol (molar ratio 1:0.5:0.5) are placed in reaction flask
In, calcium oxide (molal quantity be the molal quantity of diphenyl carbonate or glycol monomer total amount 0.1%) is used as transesterification and polycondensation
Catalyst, be passed through nitrogen, heating melting is simultaneously sufficiently stirred.Then reactant is heated to 200 DEG C of progress esterifications, reacted
3 hours.
[2] after the esterification products for obtaining [1] are cooling, 130 DEG C is heated to, the pressure of reaction system is slowly dropped to
1.3KPa is reacted 1 hour, until fraction no longer flows out with removing by-product.System is down to 200Pa again hereinafter, and rising
Temperature maintains 3 hours to 210 DEG C of progress polycondensation reactions, obtains carbonic ester (butanediol carbonic ester-co- spiral shell glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 70010gmol-1, Mn 29662gmol-1, PDI is
2.36.Dsc analysis, product Tm.1It is 179.02 DEG C, Δ Hm.1It (heats up for the first time) for 8.27J/g, glass transition temperature is
55.11 DEG C, Tm.2It is 179.58 DEG C, Δ Hm.2For 6.56J/g (second of heating).TG analysis, 5% thermal decomposition temperature of product
TD, 5%For 290.38 DEG C, decomposition mechanism temperature Td,max.1For 320.82 DEG C and Td,max.2It is 413.54 DEG C.
Embodiment 4
[1] under nitrogen protection, diphenyl carbonate, 1,4-butanediol and spiral shell glycol (molar ratio 1:0.5:0.5) are placed in instead
It answers in bottle, (MgO:CaO molar ratio is 1:1 to calcium and magnesium composite oxides, and catalyst amount is that diphenyl carbonate or glycol monomer are total
The 0.1% of the molal quantity of amount) catalyst as transesterification and polycondensation reaction, heating melting is simultaneously sufficiently stirred, then heats to
200 DEG C of progress ester exchange reactions maintain 4 hours.
[2] after the esterification products for obtaining [1] are cooling, 140 DEG C are heated to, system pressure is slowly dropped to 1.5KPa, to remove
By-product is removed, is reacted 0.5 hour, until fraction no longer flows out.Pressure is down to 200Pa again, and is warming up to 210 DEG C, into
Row polycondensation reaction maintains 2 hours, obtains polycarbonate (1.4- butanediol carbonic ester-co- spiral shell glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 63137gmol-1, number-average molecular weight Mn is 26
307g·mol-1, PDI 2.40.
Embodiment 5
[1] under nitrogen protection, by diphenyl carbonate, 1,4-butanediol, isobide and tetramethyl spiral shell glycol (molar ratio 1:
It 0.5:0.1:0.4) is placed in a reaction flask, (molal quantity is the molal quantity of diphenyl carbonate or glycol monomer total amount to magnesia
0.1%) catalyst as transesterification and polycondensation reaction, heating melting are simultaneously sufficiently stirred, and then heat to 200 DEG C of progress ester friendships
Reaction is changed, is maintained 3 hours.
[2] after the esterification products for obtaining [1] are cooling, 150 DEG C are heated to, system pressure is slowly dropped to 1.3KPa, reaction 1
Hour to remove by-product, until fraction no longer flows out.Pressure is down within 200Pa again and is warming up to 250 DEG C, progress
Polycondensation reaction maintains 3 hours, obtains carbonate polymer (1.4- butanediol carbonic ester-co- isosorbide carbonate-co-
Spiral shell glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 104317gmol-1, number-average molecular weight MnFor
42024g·mol-1, PDI 2.47.DSC test, product TmIt is 173.73 DEG C, Δ HmIt (heats up for the first time) for 9.636J/g,
Glass transition temperature is 72.46 DEG C (second of heating).
Embodiment 6
[1] under nitrogen protection, by diphenyl carbonate, 1,4-butanediol, isobide and tetramethyl spiral shell glycol (molar ratio 1:
It 0.5:0.2:0.3) is placed in a reaction flask, (molal quantity is the molal quantity of diphenyl carbonate or glycol monomer total amount to magnesia
0.1%) catalyst as transesterification and polycondensation reaction, heating melting are simultaneously sufficiently stirred, and then heat to 200 DEG C of progress ester friendships
Reaction is changed, is maintained 2.5 hours.
[2] after the esterification products for obtaining [1] are cooling, 150 DEG C are heated to, system pressure is slowly dropped to 1.5KPa, reaction
0.8 hour, until fraction no longer flows out, to remove by-product.Pressure is down within 200Pa and is warming up to again, 240 DEG C
Polycondensation reaction is carried out, maintains 3 hours, obtains polycarbonate (1.4- butanediol carbonic ester-co- isosorbide carbonate-co- spiral shell
Glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 95882gmol-1, number-average molecular weight MnFor 39221g
mol-1, PDI 2.44.DSC test, product TmIt is 132.81 DEG C, Δ HmIt (heats up for the first time) for 4.438J/g, vitrifying turns
Temperature is 57.96 DEG C (second of heating).
Embodiment 7
[1] under nitrogen protection, by diphenyl carbonate, 1,4-butanediol, isobide and tetramethyl spiral shell glycol (molar ratio 1:
It 0.5:0.3:0.2) is placed in a reaction flask, (molal quantity is the molal quantity of diphenyl carbonate or glycol monomer total amount to calcium oxide
0.1%) catalyst as transesterification and polycondensation reaction, heating melting are simultaneously sufficiently stirred, and then heat to 210 DEG C of progress ester friendships
Reaction is changed, is maintained 2 hours.
[2] after the esterification products for obtaining [1] are cooling, 160 DEG C are heated to, system pressure is slowly dropped to 1.0KPa, reaction 1
Hour, until fraction no longer flows out, to remove by-product.Pressure is down within 200Pa again and is warming up to 250 DEG C of progress
Polycondensation reaction maintains 3 hours, obtains polycarbonate (1.4- butanediol carbonic ester-co- isosorbide carbonate-co- spiral shell glycol
Carbonic ester).
GPC test shows copolymer weight average molecular weight MWFor 65414gmol-1, number-average molecular weight Mn is 28398g
mol-1, PDI 2.30.DSC test, the product glass transition temperature are 63.53 DEG C (second of heating).
Embodiment 8
[1] under nitrogen protection, by diphenyl carbonate, 1,4-butanediol, isobide and tetramethyl spiral shell glycol (molar ratio 1:
It 0.5:0.4:0.1) is placed in a reaction flask, (molal quantity is the molal quantity of diphenyl carbonate or glycol monomer total amount to magnesia
0.1%) catalyst as transesterification and polycondensation reaction, heating melting are simultaneously sufficiently stirred, and then heat to 200 DEG C of progress ester friendships
Reaction is changed, is reacted 3 hours.
[2] after the esterification products for obtaining [1] are cooling, 170 DEG C are heated to, system pressure is slowly dropped to 1.4KPa, reaction
0.7 hour, to remove by-product until fraction no longer flows out.Pressure is down within 200Pa again, and is warming up to 210-
250 DEG C of progress polycondensation reactions maintain 1-3 hours, obtain poly- (1.4- butanediol carbonic ester-co- isosorbide carbonate-co- spiral shell
Glycol carbonate).
GPC test shows copolymer weight average molecular weight MWFor 61 115gmol-1, number-average molecular weight MnIt is 27
219g·mol-1, PDI 2.25.DSC test, the product glass transition temperature are 70.32 DEG C (second of heating).
Embodiment 9:[1] under nitrogen protection, by diphenyl carbonate, 1,4-butanediol, isobide and spiral shell glycol (molar ratio
It 1:0.5:0.3:0.2) is placed in a reaction flask, (MgO:CaO molar ratio is 1:1 to calcium and magnesium composite oxides, and catalyst amount is carbonic acid
The 0.1% of diphenyl ester or the molal quantity of glycol monomer total amount) catalyst as transesterification and polycondensation reaction, heating melting is simultaneously
It is sufficiently stirred, then heats to 200 DEG C of progress ester exchange reactions, react 2-3 hours.
[2] after the esterification products for obtaining [1] are cooling, it is heated to 120-180 DEG C, system pressure is slowly dropped to 1.5KPa,
Reaction, 1 hour, to remove by-product until fraction no longer flows out.Pressure is down within 200Pa again, and is warming up to 240
DEG C carry out polycondensation reaction, maintain 2 hours, obtain poly- (1.4- butanediol carbonic ester-co- isosorbide carbonate-co- spiral shell glycol
Carbonic ester).
GPC test shows copolymer weight average molecular weight MWFor 57 544gmol-1, number-average molecular weight MnFor
25349g·mol-1, PDI 2.27.
Comparative experimental example: diphenyl carbonate and 1.4- butanediol (molar ratio 1.0:1.0) are placed in a reaction flask by [1], oxygen
Change catalyst of the magnesium (molal quantity is the 0.1% of diphenyl carbonate molal quantity) as transesterification and polycondensation, is passed through nitrogen, heating is molten
Melt and is sufficiently stirred.Then reactant is heated to 200 DEG C of progress esterifications, maintained 3 hours.
[2] after the esterification products for obtaining [1] are cooling, it is heated to 90-130 DEG C, the pressure of reaction system is slowly dropped to
To remove by-product within the scope of 1.5KPa, react 1 hour, until fraction no longer flows out.System is down to 200Pa or less again
And 250 DEG C of progress polycondensation reactions are warming up to, it maintains 2 hours, obtains polytetramethylene carbonate diol.
GPC test shows copolymer weight average molecular weight MWFor 158 206gmol-1, Mn 95555gmol-1, PDI
It is 1.66.Dsc analysis, product TmIt is 65.65 DEG C, Δ HmFor 37.66J/g (heat up for the first time), glass transition temperature is-
31.15 DEG C (second of heating).TG analysis, poly- 5% thermal decomposition temperature T of carbonic acid 1,4-butanediol esterD, 5%For 284.14 DEG C, maximum
Decomposition rate temperature Td,maxIt is 320.02 DEG C.
Compared to the Thermal Parameter (T for the polytetramethylene carbonate diol that comparative experimental example 1 obtainsmIt is 65 DEG C, TgIt is -32 DEG C),
The copolymer glass transition temperature with higher obtained using the embodiment of the present invention 1-9, melting temperature and thermal stability.
The especially copolymer not only molecular weight height (M that obtains of example 2 and 3W> 70 000g/mol), and Tm(> 150 DEG C) and Tg(>30
DEG C) relatively also very high.Ternary polymerization carbonic ester (embodiment 5-9) all has high glass transition temperature (> 60 DEG C), the copolymerization
Object has very extensive potentiality application prospect in the fields such as packaging and thin-film material.
By above-mentioned analysis, the Aliphatic Polycarbonate Copolymers of preparation of the invention melting temperature with higher and glass
Glass transition temperature, and thermal stability is good, and the molecular weight of polymer is high, and the dosage of the modified monomer in preparation process
It is few.
More specific and detailed description is made that the present invention above, the case study on implementation only describes the portion of the application
Divide embodiment, but it is not intended to limit the scope of the present invention.It should be pointed out that for the technology for being engaged in the field
Personnel, similar modification or variation made by all methods according to the technique and scheme of the present invention etc., are covered by protection of the invention
In range.
Claims (10)
1. a kind of Aliphatic Polycarbonate Copolymers, it is characterised in that: the copolymer includes formula (I) repetitive unit,
Wherein, R1For the alkylidene of C3-C8,
R2For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality,
R3For double five-membered ring groups or the aliphatic spiro-cyclic groups with acetal functionality.
2. Aliphatic Polycarbonate Copolymers according to claim 1, it is characterised in that: the R2 isOne of, the R3 is One of.
3. preparation is as according to claim 1 or the method for Aliphatic Polycarbonate Copolymers described in 2, it is characterised in that: wrap
Include following steps,
(a) binary ester monomer, glycol monomer and catalyst by proportion are uniformly mixed, after heating melting, are warming up to 150-220
DEG C, it reacts 2-4 hours, obtains oligomer；
(b) oligomer made from above-mentioned steps (a) is heated, vacuum distillation removes by-product, is warming up to 180-250 DEG C, then drop
200Pa is depressed into hereinafter, reacting 1-4 hours, Aliphatic Polycarbonate Copolymers are made；
Wherein, the glycol monomer includes monomer A and monomer B, the monomer A are the monomer containing R1 group, the monomer B
For the monomer containing R2 and/or R3 group.
4. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: in the step
(a) in, the monomer of the group containing R1 is the glycol of C3-C8.
5. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the base containing R2
Group monomer beOne of.
6. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the base containing R3
Group monomer beOne kind.
7. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the dibasic ester
Monomer is diphenyl carbonate, dimethyl carbonate, dimethyl succinate, one of dimethyl glutarate.
8. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the dibasic ester
The molar ratio of monomer and the glycol monomer is binary ester monomer: glycol monomer=1:1-1.3.
9. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the catalyst
Dosage with molar fraction, be the 0.1%-1mol% of binary ester monomer or glycol monomer total amount.
10. the preparation method of Aliphatic Polycarbonate Copolymers according to claim 3, it is characterised in that: the catalysis
Agent is one of inorganic metal salt, organic base or oxide type solid base.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115784877A (en) * | 2022-12-06 | 2023-03-14 | 大连理工大学 | Method for recovering dimethyl terephthalate from waste poly (terephthalic acid) -butylene carbonate and repolymerization method |
| CN116023640A (en) * | 2022-11-30 | 2023-04-28 | 北京服装学院 | Method for preparing biodegradable polybutylene terephthalate-co-butylene carbonate from waste polyester textiles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116023640A (en) * | 2022-11-30 | 2023-04-28 | 北京服装学院 | Method for preparing biodegradable polybutylene terephthalate-co-butylene carbonate from waste polyester textiles |
| CN116023640B (en) * | 2022-11-30 | 2023-09-26 | 北京服装学院 | Method for preparing biodegradable polybutylene terephthalate-co-butylene carbonate from waste polyester textiles |
| CN115784877A (en) * | 2022-12-06 | 2023-03-14 | 大连理工大学 | Method for recovering dimethyl terephthalate from waste poly (terephthalic acid) -butylene carbonate and repolymerization method |
| CN115784877B (en) * | 2022-12-06 | 2024-05-31 | 大连理工大学 | Method for recycling dimethyl terephthalate from waste poly (terephthalic acid) -carbonic acid-butanediol ester and repolymerization method |
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Application publication date: 20181228 |