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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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 27
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 31
- 150000002148 esters Chemical class 0.000 claims description 22
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical group C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000994 depressogenic effect Effects 0.000 claims 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 150000002009 diols Chemical class 0.000 abstract description 3
- 125000004036 acetal group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 125000003003 spiro group Chemical group 0.000 abstract 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 26
- 238000006068 polycondensation reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000009477 glass transition Effects 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 230000032050 esterification Effects 0.000 description 14
- 238000005886 esterification reaction Methods 0.000 description 14
- -1 poly-ester carbonate Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000005809 transesterification reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 229960002479 isosorbide Drugs 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- HKEUSHDVFNSFLJ-UHFFFAOYSA-N C(C=1C(C(=O)OC2=CC=CC=C2)=CC=CC1)(=O)OC1=CC=CC=C1.[C] Chemical compound C(C=1C(C(=O)OC2=CC=CC=C2)=CC=CC1)(=O)OC1=CC=CC=C1.[C] HKEUSHDVFNSFLJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CEZUZYHRQJWRAF-UHFFFAOYSA-N butane-1,4-diol;carbonic acid Chemical compound OC(O)=O.OCCCCO CEZUZYHRQJWRAF-UHFFFAOYSA-N 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了一种脂肪族聚碳酸酯共聚物，所述共聚物包含式(Ⅰ)重复单元，其中，R1为C3‑C8的亚烷基，R2为双五元环基团或具有缩醛官能团的脂肪族螺环基团，R3为双五元环基团或具有缩醛官能团的脂肪族螺环基团。制备方法为：(a)将二元酯单体、二元醇单体和催化剂混合均匀，加热熔融后，升温至150‑220℃，反应2‑4小时，得到低聚物；(b)将上述步骤(a)制得的低聚物加热，减压蒸馏除去副产物，升温至180‑250℃，再降压至200Pa以下，反应1‑4小时，制得脂肪族聚碳酸酯共聚物。本发明的脂肪族聚碳酸酯共聚物的分子中，含有链状重复单元和刚性环状重复单元，共聚物不仅具有较高的分子量，并且共聚物具有优异的热学性能。The invention discloses an aliphatic polycarbonate copolymer, which comprises repeating units of formula (I), Wherein, R 1 is a C3-C8 alkylene group, R 2 is a double five-membered ring group or an aliphatic spiro group with an acetal functional group, R 3 is a double five-membered ring group or an acetal functional group Aliphatic spiro group. The preparation method is as follows: (a) uniformly mix the dibasic ester monomer, the diol monomer and the catalyst, heat and melt, then raise the temperature to 150-220°C, and react for 2-4 hours to obtain an oligomer; (b) mix The oligomer prepared in the above step (a) is heated, the by-products are removed by distillation under reduced pressure, the temperature is raised to 180-250° C., and the pressure is lowered to below 200 Pa, and the reaction is carried out for 1-4 hours to obtain an aliphatic polycarbonate copolymer. The molecules of the aliphatic polycarbonate copolymer of the present invention contain chain repeating units and rigid cyclic repeating units, and the copolymer not only has relatively high molecular weight, but also has excellent thermal properties.
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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