CN106008945B - Preparation method of polyester - Google Patents
Preparation method of polyester Download PDFInfo
- Publication number
- CN106008945B CN106008945B CN201610396857.9A CN201610396857A CN106008945B CN 106008945 B CN106008945 B CN 106008945B CN 201610396857 A CN201610396857 A CN 201610396857A CN 106008945 B CN106008945 B CN 106008945B
- Authority
- CN
- China
- Prior art keywords
- preparation
- polyester
- reaction
- monomer
- glycol adipate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000728 polyester Polymers 0.000 title abstract description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- -1 glycol ester Chemical class 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229920000562 Poly(ethylene adipate) Polymers 0.000 claims description 6
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- KKSAZXGYGLKVSV-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO KKSAZXGYGLKVSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical class OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- 239000001361 adipic acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 11
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002601 oligoester Polymers 0.000 abstract 3
- 239000012895 dilution Substances 0.000 abstract 2
- 238000010790 dilution Methods 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- CKWZJJMOVHRFJN-UHFFFAOYSA-N 2-methylpropane-1,3-diol;terephthalic acid Chemical class OCC(C)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 CKWZJJMOVHRFJN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 210000003739 neck Anatomy 0.000 description 4
- 150000003384 small molecules Chemical group 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical class OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- CXPHSWDCSMIRFM-UHFFFAOYSA-N C(COCCOCCO)O.C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC Chemical compound C(COCCOCCO)O.C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC CXPHSWDCSMIRFM-UHFFFAOYSA-N 0.000 description 1
- 101000771022 Trichoderma longibrachiatum Chlorophenol O-methyltransferase Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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
The invention provides a preparation method of polyester, which comprises the following steps: under the condition of 'pseudo high dilution', diol and diacid chloride with equal molar weight are dripped into dichloromethane or chloroform solution containing catalyst and triethylamine to synthesize cyclic oligomeric ester monomer; under the conditions of temperature of 200-250 ℃ and vacuumizing or nitrogen gas introduction, the ring-opening polymerization of the cyclic oligoester monomer is carried out under the catalyst, and the product polyester is obtained after the reaction is carried out for 30-90 minutes. The invention synthesizes a series of cyclic oligoester monomers under the condition of pseudo high dilution, and utilizes the obtained cyclic oligoester monomers to carry out ring-opening polymerization to successfully prepare linear polyester with higher molecular weight, thereby effectively solving the problem that the traditional condensation polymerization is difficult to synthesize the linear polyester and having important application value.
Description
Technical field
The technical field more particularly to a kind of preparation method of polyester prepared the invention belongs to polymer.
Background technology
By traditional condensation polymerization method, i.e. bifunctional monomer's gradually condensation method, synthesizing linear polyester polymers are early in upper
The forties in century has just been studied.Linear polyester polymers are divided into linear aliphatic adoption ester and linear aromatic polyester two is big
Class, common linear aliphatic adoption ester have polyglycolide (PGA), polylactide (PLA), glycolide-lactide copolymer (Poly
(GA-co- LA)), polycaprolactone (PCL) etc., synthon be usually existing hydroxyl have again carboxyl bifunctional monomer or
Corresponding lactone compound is mainly used in biodegradable medical macromolecular materials, such as operation suture thread, bone renovating material
Deng.And common linear aromatic polyester has polyethylene terephthalate (PET), polypropylene terephthalate
(PTT) and polybutylene terephthalate (PBT) (PBT) etc., synthon is usually corresponding terephthalic acid (TPA) and glycol list
Body is mainly used in engineering plastics and fiber.Although these polymer are all easy to get by traditional condensation polymerization method to poly-
The later stage is closed since viscosity increases, obtained polymer molecular weight is not high, the methods of needing to pass through solid stated to its molecular weight into
Row further increases.
The main reason for linear polyester molecular weight prepared by traditional polycondensation polymerization is not high:On the one hand, traditional polycondensation polymerize
There is small molecule by-product generation in method reaction process, reaction need to be carried out under high temperature high vacuum to discharge small molecule, however anti-
Should the later stage due in polymerization system polymer viscosity increase, the discharge of small molecule by-product is more difficult, it is difficult to obtain macromolecule
The linear polyester of amount;On the other hand, side reaction occurs at high temperature for the glycol of reaction or diacid monomer, leads to the equivalent of acid and alcohol
No longer it is proper equivalent reaction, it is difficult to obtain the polymer of such high molecular weight than changing.And open loop gathers
It closes reaction to generate without small molecule by-product, reaction temperature is relatively low, and the reaction time is shorter, so ring-opening polymerization can be
It is carried out under normal pressure, without the harsh conditions of high temperature high vacuum, the linear polyester with high molecular weight can be obtained.
Compared with traditional polycondensation polymerization, it is not high that ring-opening polymerisation method efficiently solves traditional polycondensation polymerization middle-molecular-weihydroxyethyl
The problem of, and without the condition of high temperature high vacuum.In addition, ring-opening polymerisation method is also simple with reaction step(Normal pressure, a step are thrown
Material, one pot reaction), the advantages that polymerization speed is fast.
Invention content
The technical issues of solution:The shortcomings of molecular weight is not high existing for polyester, this hair are prepared for traditional polycondensation polymerization
It is bright that a kind of preparation method of polyester is provided.
Technical solution:A kind of the step of preparation method of polyester, this method, is as follows:
(1)The preparation of cyclic oligomeric ester monomer:
Under the conditions of " false high dilute ", the glycol of equimolar amounts and diacid chloride are added dropwise to two containing catalyst and triethylamine
In chloromethanes or chloroformic solution, synthesis of cyclic oligomerization ester monomer;
(2)The preparation of polyester:
Under conditions of temperature is 200-250 DEG C, vacuumizes or lead to nitrogen, cyclic oligomeric ester monomer occurs under catalyst
Ring-opening polymerisation, up to product polyester after reacting 30-90 minutes.
Step described above(1)In glycol for aliphatic diol or condensed ethandiol, diacid chloride is aliphatic diacid chloride
Or aromatic diacid chlorides.
Aliphatic diol described above is ethylene glycol, propylene glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3-
Propylene glycol, 2- methyl-2-propyl -1,3- propylene glycol, butanediol, condensed ethandiol for diglycol, triethylene-glycol or
Tetraethylene-glycol.
Step described above(1)In catalyst be pyridine or triethylene diamine.
Step described above(2)In catalyst be butyl titanate.
Advantageous effect:A kind of preparation method of polyester provided by the invention, has the advantages that:
1. the present invention synthesizes a series of cyclic oligomeric ester monomers in " false high dilute " condition, reaction yield for 29.2%-
49.3%, provide possibility for its large-scale production;
2. the present invention carries out ring-opening polymerisation using the cyclic oligomeric ester monomer of gained, successfully it has been made with higher molecular
The linear polyester of amount efficiently solve the problems, such ass that traditional polycondensation polymerization is difficult to synthesize such linear polyester, has important answer
With value.
Description of the drawings
Fig. 1 is the reaction equation of the preparation process of the polyethylene glycol adipate in embodiment 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the cyclic oligomeric ethylene glycol adipate monomer in embodiment 1.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the polyethylene glycol adipate in embodiment 1.
Fig. 4 is the gel permeation chromatography figure (mobile phase THF) of the polyethylene glycol adipate in embodiment 1.
Fig. 5 is the reaction equation of the preparation process of the poly terephthalic acid diglycol ester in embodiment 2.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the cyclic oligomeric terephthalic acid (TPA) diglycol ester monomer in embodiment 2.
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the poly terephthalic acid diglycol ester in embodiment 2.
Fig. 8 is that (mobile phase is for the gel permeation chromatography figure of the poly terephthalic acid diglycol ester in embodiment 2
THF)。
Fig. 9 is the reactional equation of the preparation process of the poly terephthalic acid -2- methyl-1,3-propanediol esters in embodiment 3
Formula.
Figure 10 is the nuclear magnetic resonance of the cyclic oligomeric terephthalic acid (TPA) -2- methyl-1,3-propanediol ester monomers in embodiment 3
Hydrogen spectrogram.
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of the poly terephthalic acid -2- methyl-1,3-propanediol esters in embodiment 3.
Figure 12 is the gel permeation chromatography figure (stream of the poly terephthalic acid -2- methyl-1,3-propanediol esters in embodiment 3
Dynamic is mutually THF).
Figure 13 is the poly terephthalic acid -2- methyl-1,3-propanediols that the molecular weight in embodiment 3 is 20.6 kg/mol
The stress-strain curve of ester.
Figure 14 is the poly terephthalic acid -2- methyl-1,3-propanediols that the molecular weight in embodiment 3 is 45.2 kg/mol
The stress-strain curve of ester.
Specific embodiment
Embodiment 1
Polyethylene glycol adipate(PEA)Preparation method, preparation process is as follows:
(1)Cyclic oligomeric ethylene glycol adipate monomer(COEAs)Preparation:
10.1 g triethylamines, 0.40 g pyridines and the anhydrous dichloromethanes of 500 mL are added in 500 mL three neck round bottom
Alkane opens mechanical agitation.Be packed into 250 mL constant pressure funnels preformulation by 3.10 g ethylene glycol, 9.15 g fourths two
The solution of acyl chlorides and 120 mL dichloromethane composition.It flows back at 40 DEG C, it under nitrogen protection will be molten in constant pressure funnel
Drop enters in three-neck flask, and mechanical agitation is reacted, and rate of addition is, per dripping within 1-2 seconds, continues to stir after completion of dropwise addition
30 minutes, then adding in 5-10 mL ammonium hydroxide, reaction was completed.It filters, filters off insoluble linear polymer and ammonium salt, filter cake is used
50 mL chloroforms wash, and obtained filtrate is washed with dilute hydrochloric acid, then is washed with deionized to neutrality, and anhydrous magnesium sulfate is done
It is filtered after dry.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographs post separation, and leacheate is that volume ratio is 1:The third of 25
Ketone/dichloromethane solution.Revolving removes solvent, is dried in vacuo to get cyclic oligomeric ethylene glycol adipate monomer, weighs
3.03 g, yield are 35.2 %.
The nucleus magnetic hydrogen spectrum figure of cyclic oligomeric ethylene glycol adipate monomer is shown in Fig. 1, it was demonstrated that it is successfully synthesized.
(2)The preparation of polyethylene glycol adipate:
34.8mg 1,10- decanediols initiators and 6.0g cyclic oligomeric adipic acids second two are added in 50mL three-neck flasks
Under nitrogen atmosphere, three-neck flask is placed in 200 DEG C of salt baths for ester monomer, after solid in three-necked bottle completely melting, is added in
30 μL a concentration of 0.5wtThe positive four butanol titanium catalyst of %, mechanic whirl-nett reaction 30 minutes, reaction was completed, takes out in bottle and produces
Object is to get polyethylene glycol adipate.
The nucleus magnetic hydrogen spectrum figure of polyethylene glycol adipate is shown in Fig. 2, it was demonstrated that the successful synthesis of polyethylene glycol adipate, by
Nuclear-magnetism can be calculated polyethylene glycol adipate molecular weight as 7.6 kg/mol.The gel permeation chromatography of polyethylene glycol adipate
See Fig. 3, number-average molecular weight is 11 kg/mol, PDI 1.45.
Embodiment 2
Poly terephthalic acid diglycol ester(PDEGT)Preparation method, preparation process is as follows:
(1)The preparation of cyclic oligomeric terephthalic acid (TPA) diglycol ester monomer (CODEGTs):
It is anhydrous that 10.1 g triethylamines, 0.56 g triethylene diamines and 500 mL are added in 500 mL three neck round bottom
Dichloromethane opens mechanical agitation.Be packed into 250 mL constant pressure funnels preformulation by 5.30 g, mono- contracting diethyls two
The solution of alcohol, 10.2 g paraphthaloyl chlorides and 120 mL tetrahydrofurans composition.Under ice-water bath and nitrogen protection, by constant pressure
Solution in dropping funel is instilled in three-neck flask, and mechanical agitation is reacted, and control rate of addition drips for 1-2 seconds to be every,
Continue stirring 30 minutes after completion of dropwise addition, then adding in 5-10 mL ammonium hydroxide, reaction was completed.It filters, filters off insoluble linear polymerization
Object and some ammonium salts, filter cake are washed with 50 mL chloroforms, and obtained filtrate is washed with dilute hydrochloric acid, then with a large amount of deionizations
Water washing is filtered to neutrality after anhydrous magnesium sulfate drying.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographs post separation,
Leacheate is that volume ratio is 1:10 acetone/dichloromethane solution.Revolving removes solvent, up to cyclic annular few after solid vacuum drying
Poly terephthalic acid diglycol ester weighs to obtain 5.84 g, about 49.3 % of yield.
Cyclic oligomeric terephthalic acid (TPA) diglycol ester nucleus magnetic hydrogen spectrum figure is shown in Fig. 4, it was demonstrated that it is successfully synthesized.
(2)Poly terephthalic acid diglycol ester(PDEGT)Preparation:
0.2 mmol 1,10- decanediols initiators and 10.0 g cyclic oligomerics are added in the three-neck flask of 50 mL to benzene
Under nitrogen atmosphere, three-neck flask is placed in 220 DEG C of salt baths for dioctyl phthalate diglycol ester monomer, is treated solid in three-necked bottle
After body melting completely, 20 are added inμL a concentration of 0.2wtThe positive four butanol titanium catalyst of %, mechanic whirl-nett reaction 30 minutes.It carries
Go out three-neck flask, a certain amount of chloroform dissolving is added in, and instill to stand in a large amount of ethyl acetate dropwise and sink after being cooled to room temperature
Drop filters, 2 times repeatedly, up to poly terephthalic acid diglycol ester after filter cake vacuum drying.
The nucleus magnetic hydrogen spectrum figure of poly terephthalic acid diglycol ester is shown in Fig. 5, it was demonstrated that the contracting of poly terephthalic acid one two
The successful synthesis of glycol ester can be calculated poly terephthalic acid diglycol ester molecule amount as 50.6 kg/ by nuclear-magnetism
mol.Poly terephthalic acid diglycol gels permeation chromatography is shown in Fig. 6, and number-average molecular weight is 18 kg/mol, and PDI is
1.32。
Embodiment 3
Poly terephthalic acid -2- methyl-1,3-propanediol esters(PMPT)Preparation method, preparation process is as follows:
(1)Cyclic oligomeric terephthalic acid (TPA) -2- methyl-1,3-propanediol ester monomers(COMPTs)Preparation:
It is anhydrous that 10.1 g triethylamines, 0.56 g triethylene diamines and 500 mL are added in 500 mL three neck round bottom
Dichloromethane opens mechanical agitation.Be packed into 250 mL constant pressure funnels preformulation by 4.50 g 2- methyl-1s,
The solution of 3-propanediol, 10.2 g paraphthaloyl chlorides and 120 mL tetrahydrofurans composition.It, will under ice-water bath, nitrogen protection
Solution in constant pressure funnel is instilled in three-neck flask, and mechanical agitation is reacted, and control rate of addition is drop one per 1-2 seconds
Drop continues stirring 30 minutes after completion of dropwise addition, then adding in 5-10 mL ammonium hydroxide, reaction was completed.It filters, filters off insoluble linear
Polymer and some ammonium salts, filter cake are washed with 50 mL chloroforms, and obtained filtrate is washed with dilute hydrochloric acid, then with largely going
Ion water washing is filtered to neutrality after anhydrous magnesium sulfate drying.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographic column point
From leacheate is that volume ratio is 1:10 acetone/dichloromethane solution.Revolving removes solvent, up to right after solid vacuum drying
Phthalic acid -2- methyl-1s, 3-propanediol ester monomer weigh to obtain 5.14 g, yield about 46.5%.
Cyclic oligomeric terephthalic acid (TPA) -2- methyl-1s, 3-propanediol ester monomer nucleus magnetic hydrogen spectrum figure be shown in Fig. 7, it was demonstrated that benzene
The successful synthesis of dioctyl phthalate -2- methyl-1,3-propanediol ester monomers.
(2)The preparation of poly terephthalic acid -2- methyl-1,3-propanediol esters:
0.2 mmol 1,10- decanediols initiators and 10.0 g cyclic oligomerics are added in the three-neck flask of 50 mL to benzene
Dioctyl phthalate -2- methyl-1s, 3-propanediol ester monomer under nitrogen atmosphere, three-neck flask are placed in 240 DEG C of salt baths, treats three necks
In bottle after solid melting completely, 20 are added inμA concentration of the 0.2 of LwtThe positive four butanol titanium catalyst of %, mechanic whirl-nett reaction 30
Minute, find basic monomer-free residual, reaction was completed, and product is to get poly terephthalic acid -2- methyl-1s, 3- third in taking-up bottle
Diol ester.
Poly terephthalic acid -2- methyl-1s, the nucleus magnetic hydrogen spectrum figure of 3-propanediol ester be shown in Fig. 8, it was demonstrated that poly terephthalic acid -
2- methyl-1s, the successful synthesis of 3-propanediol ester can be calculated poly terephthalic acid -2- methyl-1s, 3-propanediol ester by nuclear-magnetism
Molecular weight be about 41 kg/mol.Gel permeation chromatography is shown in Fig. 9, measures two poly terephthalic acid -2- methyl-1s, 3- the third two
The molecular weight of alcohol ester is respectively that 20.6 kg/mol, 45.2 kg/mol, PDI are followed successively by 1.64,1.69.To poly terephthalic acid-
2- methyl-1s, the hot pressing of 3-propanediol ester polymer have carried out extension test after forming a film, and load-deformation curve is shown in Figure 10 and Figure 11.
The polymer of Figure 10, molecular weight be 20.6 kg/mol, elongation at break (<10%) it is 45.2 well below Figure 11 middle-molecular-weihydroxyethyls
The sample of kg/mol (460%), and its fracture strength illustrates the raising of molecular weight to polyester also not as good as the sample of high molecular weight
The promotion of material property has extremely important influence.
In addition, being prepared with ring-opening polymerisation method, the polyester process is similar to the above, and polyester is specific as follows:Polyadipate second two
Alcohol ester, polypropylene glycol adipate, polyethylene glycol succinate, poly adipate succinic acid ester;One contracting diethyl two of polyphenyl dioctyl phthalate
Alcohol ester, polyphenyl dioctyl phthalate Triethylene Glycol, polyphenyl dioctyl phthalate tetraethylene-glycol ester gather(Phthalic acid -2- methyl-1s,
3-propanediol ester), it is poly-(Phthalic acid -2,2-dimethyl-1,3-propanediol ester), it is poly-(Phthalic acid -2- methyl-2-propyl -1,
3-propanediol ester), wherein phthalic acid can be terephthalic acid (TPA) or M-phthalic acid.
The foregoing is merely the preferred embodiments of invention, are not intended to restrict the invention, for the technology of this field
For personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (1)
1. polyethylene glycol adipate(PEA)Preparation method, which is characterized in that the step of this method, is as follows:
(1)Cyclic oligomeric ethylene glycol adipate monomer(COEAs)Preparation:
10 .1 g triethylamines, 0 .40 g pyridines and the anhydrous dichloromethanes of 500 mL are added in 500 mL three neck round bottom
Alkane opens mechanical agitation;Be packed into 250 mL constant pressure funnels preformulation by 3 .10 g ethylene glycol, 9 .15 g fourths
The solution of diacid chloride and 120 mL dichloromethane composition;It flows back at 40 DEG C, it under nitrogen protection will be in constant pressure funnel
Solution is instilled in three-neck flask, and mechanical agitation is reacted, and rate of addition is, per dripping within 1-2 seconds, continues to stir after completion of dropwise addition
It mixes 30 minutes, then adding in 5-10 mL ammonium hydroxide, reaction was completed;It filters, filters off insoluble linear polymer and ammonium salt, filter cake
It is washed with 50mL chloroforms, obtained filtrate is washed with dilute hydrochloric acid, then is washed with deionized to neutrality, and anhydrous magnesium sulfate is done
It is filtered after dry;Filtrate obtains crude product after being spin-dried for;Crude on silica gel chromatographs post separation, and leacheate is that volume ratio is 1:The third of 25
Ketone/dichloromethane solution;Revolving removes solvent, is dried in vacuo to get cyclic oligomeric ethylene glycol adipate monomer;
(2)The preparation of polyethylene glycol adipate:
34 .8 mg 1,10- decanediols initiator and 6 .0 g cyclic oligomeric adipic acid second are added in 50 mL three-neck flasks
Under nitrogen atmosphere, three-neck flask is placed in 200 DEG C of salt baths for glycol ester monomer, after solid in three-necked bottle completely melting, is added
Enter the positive four butanol titanium catalyst of a concentration of 0.5 wt % of 30 μ L, mechanic whirl-nett reaction 30 minutes, reaction was completed, takes out in bottle and produces
Object is to get polyethylene glycol adipate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610396857.9A CN106008945B (en) | 2016-06-07 | 2016-06-07 | Preparation method of polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610396857.9A CN106008945B (en) | 2016-06-07 | 2016-06-07 | Preparation method of polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106008945A CN106008945A (en) | 2016-10-12 |
CN106008945B true CN106008945B (en) | 2018-07-03 |
Family
ID=57089828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610396857.9A Active CN106008945B (en) | 2016-06-07 | 2016-06-07 | Preparation method of polyester |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106008945B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108395527B (en) * | 2018-04-04 | 2020-08-04 | 苏州大学 | Azobenzene polyether ester multi-block copolymer elastomer with photoinduced deformation performance and preparation method thereof |
CN109134836B (en) * | 2018-08-26 | 2020-09-08 | 苏州大学 | Polyether ester elastomer capable of being coordinated and crosslinked with metal ions, and preparation method and application thereof |
CN115260460B (en) * | 2022-09-26 | 2023-02-10 | 苏州大学 | Copolyester and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254412B (en) * | 2012-10-31 | 2015-08-05 | 苏州大学 | Preparation method of polyether ester block polymer |
CN104693447A (en) * | 2015-03-10 | 2015-06-10 | 苏州大学 | Preparation method of polyether ester multi-block alternating copolymer |
-
2016
- 2016-06-07 CN CN201610396857.9A patent/CN106008945B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN106008945A (en) | 2016-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Morales-Huerta et al. | Poly (alkylene 2, 5-furandicarboxylate) s (PEF and PBF) by ring opening polymerization | |
CN106008945B (en) | Preparation method of polyester | |
CN105358604B (en) | The technique that makrolon is prepared by the polymerization of five-membered ring cyclic carbonate | |
CN104797627B (en) | Aliphatic Polycarbonate Copolymers with HMW and preparation method thereof | |
CN109400574B (en) | Purification method and application of crude lactide | |
CN106750334B (en) | Amphiphilic tadpole-shaped block copolymer and preparation method thereof | |
JP5385108B2 (en) | Polymer obtained from betulin and process for producing the same | |
CN110563941B (en) | Preparation method of medical biodegradable high polymer material polycaprolactone | |
ES2524988T3 (en) | Improved procedure for the preparation of L-lactide of high chemical performance and optical purity | |
JP5460840B2 (en) | Polymer obtained from betulin and process for producing the same | |
JP2016505531A (en) | Method for producing liquid tin (II) alkoxide | |
CN101565498A (en) | Polyaspartic diol ester containing amino side chain, synthesis method and application thereof | |
CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
CN113735817B (en) | Preparation method of aliphatic cyclic oligoester | |
CN103739834B (en) | The production method of solid phase titanium polyester | |
Sajjad et al. | Ring opening polymerization of β-acetoxy-δ-methylvalerolactone, a triacetic acid lactone derivative | |
CN110396180B (en) | Method for precisely preparing aliphatic polyester by utilizing betaine | |
KR101144730B1 (en) | Fabracating method of thermoplastic cellulose polyester | |
CN108350153A (en) | Block copolymer of cyclic ester and preparation method thereof | |
Xiao et al. | Ethylene glycol aluminum as a novel catalyst for the synthesis of poly (ethylene terephthalate) | |
CN109503817B (en) | Biodegradable poly (ethylene succinate-co-ethylene oxalate) ester and preparation method thereof | |
CN102786673B (en) | Cyclic aliphatic polyester preparation method | |
CN111690126B (en) | Method for preparing polyester by ring-opening polymerization | |
CN108239262B (en) | Production process of oligomeric L-lactic acid | |
CN107759778B (en) | Preparation and application of polymalic acid and high-crystallinity poly (benzyl malate) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |