CN106008945A - Preparation method for polyester - Google Patents
Preparation method for polyester Download PDFInfo
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- CN106008945A CN106008945A CN201610396857.9A CN201610396857A CN106008945A CN 106008945 A CN106008945 A CN 106008945A CN 201610396857 A CN201610396857 A CN 201610396857A CN 106008945 A CN106008945 A CN 106008945A
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- polyester
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- 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
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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
- 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
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- 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 for polyester. The method comprises the following steps: adding diol and diacyl chloride of equal mol weight into a dichloromethane or chloroform solution containing a catalyst and triethylamine drop by drop under pseudo-high dilution conditions to synthesize cyclic oligoester monomer; and subjecting the cyclic oligoester monomer to ring-opening polymerization for 30 to 90 min under the conditions of a temperature of 200 to 250 DEG C and vacuum-pumping or nitrogen introduction so as to obtain the product polyester. According to the invention, a series of cyclic oligoester monomers are synthesized under pseudo-high dilution conditions, and the obtained cyclic oligoester monomers are subjected to ring-opening polymerization, so the linear polyester with high molecular weight is successively prepared; thus, the method provided by the invention effectively overcomes the problem that the linear polyester is difficult to synthesize through traditional condensation and polymerization and has important application value.
Description
Technical field
The invention belongs to technical field prepared by polymer, particularly relate to the preparation method of a kind of polyester.
Background technology
By traditional condensation polymerization method, i.e. bifunctional monomer's progressively condensation method, synthesizing linear polyester polymers is as far back as upper
The forties in century is the most studied.Linear polyester polymers is divided into linear aliphatic adoption ester and linear aromatic polyester two big
Class, common linear aliphatic adoption ester has PGA (PGA), polylactide (PLA), glycolide-lactide copolymer (Poly
(GA-co-LA)), polycaprolactone (PCL) etc., its 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), PTT
(PTT) and polybutylene terephthalate (PBT) (PBT) etc., its synthon is usually corresponding p-phthalic acid and glycol list
Body, is mainly used in engineering plastics and fiber.Although these polymer are all easy to get to by traditional condensation polymerization method, but poly-
The conjunction later stage increases due to viscosity, and the polymer molecular weight obtained is the highest, needs to be entered its molecular weight by methods such as solid stated
Row increases further.
The main cause that linear polyester molecular weight prepared by traditional polycondensation polymerization is the highest: on the one hand, traditional polycondensation is polymerized
Having small molecule by-product to produce in method course of reaction, reaction need to carry out discharging little molecule under high temperature fine vacuum, but instead
Answering the later stage due to polymer viscosity increase in polymerization system, the discharge of small molecule by-product is the most difficult, it is difficult to obtain macromolecule
The linear polyester of amount；On the other hand, at high temperature there is side reaction in the glycol of reaction or diacid monomer, causes the equivalent of acid and alcohol
Ratio changes, and is no longer the reaction of proper equivalent, it is difficult to obtain the polymer of this type of high molecular.And open loop gathers
Closing reaction without small molecule by-product generation, reaction temperature is relatively low, and the response time is shorter, so ring-opening polymerization can be
Carry out under normal pressure, it is not necessary to the harsh conditions of high temperature fine vacuum, the linear polyester with high molecular can be obtained.
Compared with traditional polycondensation polymerization, it is the highest that ring-opening polymerisation method efficiently solves traditional polycondensation polymerization middle-molecular-weihydroxyethyl
Problem, and without the condition of high temperature fine vacuum.Additionally, ring-opening polymerisation method also has reactions steps simple (normal pressure, a step throwing
Material, one pot reaction), the advantage such as polymerization speed is fast.
Summary of the invention
Solve the technical problem that: prepare, for traditional polycondensation polymerization, the shortcomings such as molecular weight is the highest that polyester exists, this
The preparation method of a kind of polyester of bright offer.
Technical scheme: the preparation method of a kind of polyester, the step of the method is as follows:
(1) preparation of cyclic oligomeric ester monomer:
Under the conditions of " false high dilute ", glycol and the diacid chloride of equimolar amounts are added dropwise to the dichloromethane containing catalyst and triethylamine
In alkane or chloroformic solution, synthesis of cyclic widow's polyester monocase；
(2) preparation of polyester:
Under conditions of temperature is 200-250 DEG C, evacuation or logical nitrogen, there is open loop in cyclic oligomeric ester monomer under catalyst
Polymerization, i.e. obtains product polyester after reacting 30-90 minute.
Glycol in step (1) described above is aliphatic diol or condensed ethandiol, and diacid chloride is aliphatic diacid chloride
Or aromatic diacid chlorides.
Aliphatic diol described above is ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-
Propylene glycol, 2-methyl-2-propyl-1,3-propylene glycol, butanediol, condensed ethandiol be diglycol, triethylene-glycol or
Tetraethylene-glycol.
Catalyst in step (1) described above is pyridine or triethylene diamine.
Catalyst in step (2) described above is butyl titanate.
Beneficial effect: the preparation method of a kind of polyester that the present invention provides, has the advantages that
1. the present invention synthesizes a series of cyclic oligomeric ester monomers in " false high dilute " condition, and reaction yield is 29.2%-49.3%, for
Its large-scale production provides probability；
2. the present invention utilizes the cyclic oligomeric ester monomer of gained to carry out ring-opening polymerisation, has successfully prepared and has had higher molecular weight
Linear polyester, efficiently solves traditional polycondensation polymerization and is difficult to synthesize the problem of such linear polyester, have important application valency
Value.
Accompanying drawing explanation
Fig. 1 is the reaction equation of the preparation process of the 10PE27 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 10PE27 in embodiment 1.
Fig. 4 is the gel permeation chromatography figure (flowing is mutually for THF) of the 10PE27 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 p-phthalic acid 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 the gel permeation chromatography figure of the poly terephthalic acid diglycol ester in embodiment 2 (flows and is mutually
THF)。
Fig. 9 is the reactional equation of the preparation process of the poly terephthalic acid-2-methyl-1,3-propanediol ester in embodiment 3
Formula.
Figure 10 is the nuclear magnetic resonance, NMR of the cyclic oligomeric p-phthalic acid-2-methyl-1,3-propanediol ester monomer in embodiment 3
Hydrogen spectrogram.
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of the poly terephthalic acid-2-methyl-1,3-propanediol ester in embodiment 3.
Figure 12 is the gel permeation chromatography figure (stream of the poly terephthalic acid-2-methyl-1,3-propanediol ester in embodiment 3
Dynamic is THF mutually).
Figure 13 be the molecular weight in embodiment 3 be the poly terephthalic acid-2-methyl-1,3-propanediol of 20.6 kg/mol
The stress-strain curve of ester.
Figure 14 be the molecular weight in embodiment 3 be the poly terephthalic acid-2-methyl-1,3-propanediol of 45.2 kg/mol
The stress-strain curve of ester.
Detailed description of the invention
Embodiment 1
The preparation method of 10PE27 (PEA), its preparation process is as follows:
(1) preparation of cyclic oligomeric ethylene glycol adipate monomer (COEAs):
10.1 g triethylamines, 0.40 g pyridine and 500 mL anhydrous methylene chlorides are added in 500 mL three neck round bottoms,
Open mechanical agitation.250 mL constant pressure funnels load preformulation by 3.10 g ethylene glycol, 9.15 g succinyl
Chlorine and the solution of 120 mL dichloromethane composition.Reflux at 40 DEG C, under nitrogen protection by the solution in constant pressure funnel
In instillation three-neck flask, mechanical agitation is reacted, and rate of addition is to drip every 1-2 second, continues stirring 30 after completion of dropwise addition
Minute, it is subsequently adding 5-10 mL ammonia and terminates reaction.Sucking filtration, filters off insoluble linear polymer and ammonium salt, and filter cake is with 50
ML chloroform washs, and the filtrate obtained is washed with dilute hydrochloric acid, then is washed with deionized to neutrality, and anhydrous magnesium sulfate is dried
Rear sucking filtration.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographic column separate, leacheate be volume ratio be 1:25 acetone/
Dichloromethane solution.Rotation solvent is evaporated off, vacuum drying, obtain cyclic oligomeric ethylene glycol adipate monomer, weigh 3.03
G, productivity is 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 successfully synthesizes.
(2) preparation of 10PE27:
34.8 mg 1,10-decanediol initiators and 6.0 g cyclic oligomeric adipate glycols are added in 50 mL three-neck flasks
Ester monomer, under nitrogen atmosphere, is placed in three-neck flask in 200 DEG C of salt baths, after solid in three-necked bottle is completely melted, adds 30μL concentration is 0.5wtThe positive erythrol titanium catalyst of %, mechanic whirl-nett reaction 30 minutes, terminates reaction, produces in taking out bottle
Thing, obtains 10PE27.
The nucleus magnetic hydrogen spectrum figure of 10PE27 is shown in Fig. 2, it was demonstrated that the successful synthesis of 10PE27, by
It is 7.6 kg/mol that nuclear-magnetism can be calculated 10PE27 molecular weight.The gel permeation chromatography of 10PE27
Seeing Fig. 3, number-average molecular weight is 11 kg/mol, and PDI is 1.45.
Embodiment 2
The preparation method of poly terephthalic acid diglycol ester (PDEGT), its preparation process is as follows:
(1) preparation of cyclic oligomeric p-phthalic acid diglycol ester monomer (CODEGTs):
10.1 g triethylamines, 0.56 g triethylene diamine and the anhydrous dichloro of 500 mL is added in 500 mL three neck round bottoms
Methane, opens mechanical agitation.250 mL constant pressure funnels load preformulation by 5.30 g diglycols,
10.2 g paraphthaloyl chlorides and the solution of 120 mL oxolanes composition.Under ice-water bath and nitrogen are protected, by constant pressure addition
Solution in funnel instills in three-neck flask, and mechanical agitation is reacted, and controlling rate of addition is to drip every 1-2 second, dropping
Continue stirring 30 minutes after end, be subsequently adding 5-10 mL ammonia and terminate reaction.Sucking filtration, filter off insoluble linear polymer with
And some ammonium salts, filter cake washs with 50 mL chloroform, and the filtrate obtained is washed with dilute hydrochloric acid, then washes with a large amount of deionizations
Wash to neutrality, the dried sucking filtration of anhydrous magnesium sulfate.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographic column separates, drip washing
Liquid be volume ratio be the acetone/dichloromethane solution of 1:10.Rotation is evaporated off solvent, i.e. obtains cyclic oligomeric pair after solid vacuum drying
Phthalic acid diglycol ester, weighs to obtain 5.84 g, productivity about 49.3 %.
Cyclic oligomeric p-phthalic acid diglycol ester nucleus magnetic hydrogen spectrum figure is shown in Fig. 4, it was demonstrated that it successfully synthesizes.
(2) preparation of poly terephthalic acid diglycol ester (PDEGT):
0.2 mmol 1,10-decanediol initiator and 10.0 g cyclic oligomeric terephthaldehydes are added in the three-neck flask of 50 mL
Acid diglycol ester monomer, under nitrogen atmosphere, is placed in three-neck flask in 220 DEG C of salt baths, and in treating three-necked bottle, solid is complete
After full-fusing, add 20μL concentration is 0.2wtThe positive erythrol titanium catalyst of %, mechanic whirl-nett reaction 30 minutes.Propose three
Neck flask, adds a certain amount of chloroform and dissolves, and dropwise instill standing sedimentation in a large amount of ethyl acetate, take out after being cooled to room temperature
Filter, 2 times repeatedly, i.e. obtains 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 poly terephthalic acid one contracts two
The successful synthesis of glycol ester, nuclear-magnetism can be calculated poly terephthalic acid diglycol ester molecule amount is 50.6 kg/
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 isophthalic acid, the preparation method of ammediol ester (PMPT), its preparation process is as follows:
(1) preparation of cyclic oligomeric p-phthalic acid-2-methyl-1,3-propanediol ester monomer (COMPTs):
10.1 g triethylamines, 0.56 g triethylene diamine and the anhydrous dichloro of 500 mL is added in 500 mL three neck round bottoms
Methane, opens mechanical agitation.250 mL constant pressure funnels load preformulation by 4.50 g 2-methyl isophthalic acids, 3-third
Glycol, 10.2 g paraphthaloyl chlorides and the solution of 120 mL oxolanes composition.Under ice-water bath, nitrogen protection, by constant voltage
Solution in Dropping funnel instills in three-neck flask, and mechanical agitation is reacted, and controlling rate of addition is to drip every 1-2 second,
Continue stirring 30 minutes after completion of dropwise addition, be subsequently adding 5-10 mL ammonia and terminate reaction.Sucking filtration, filters off insoluble linear polymerization
Thing and some ammonium salts, filter cake washs with 50 mL chloroform, and the filtrate obtained is washed with dilute hydrochloric acid, then uses a large amount of deionization
Water washing is to neutrality, the dried sucking filtration of anhydrous magnesium sulfate.Filtrate obtains crude product after being spin-dried for.Crude on silica gel chromatographic column separates,
Leacheate be volume ratio be the acetone/dichloromethane solution of 1:10.Rotation is evaporated off solvent, i.e. obtains benzene two after solid vacuum drying
Formic acid-2-methyl isophthalic acid, ammediol ester monomer, weigh to obtain 5.14 g, productivity about 46.5%.
Cyclic oligomeric p-phthalic acid-2-methyl isophthalic acid, ammediol ester monomer nucleus magnetic hydrogen spectrum figure is shown in Fig. 7, it was demonstrated that to benzene
The successful synthesis of dioctyl phthalate-2-methyl-1,3-propanediol ester monomer.
(2) preparation of poly terephthalic acid-2-methyl-1,3-propanediol ester:
0.2 mmol 1,10-decanediol initiator and 10.0 g cyclic oligomeric terephthaldehydes are added in the three-neck flask of 50 mL
Acid-2-methyl isophthalic acid, ammediol ester monomer, under nitrogen atmosphere, three-neck flask is placed in 240 DEG C of salt baths, in treating three-necked bottle
After solid is completely melted, add 20μThe concentration of L is 0.2wtThe positive erythrol titanium catalyst of %, mechanic whirl-nett reaction 30 points
Clock, finds that basic monomer-free remains, and terminates reaction, takes out product in bottle, obtains poly terephthalic acid-2-methyl isophthalic acid, 3-the third two
Alcohol ester.
Poly terephthalic acid-2-methyl isophthalic acid, the nucleus magnetic hydrogen spectrum figure of ammediol ester is shown in Fig. 8, it was demonstrated that poly terephthalic acid-
2-methyl isophthalic acid, the successful synthesis of ammediol ester, nuclear-magnetism can be calculated poly terephthalic acid-2-methyl isophthalic acid, ammediol ester
Molecular weight be about 41 kg/mol.Gel permeation chromatography is shown in Fig. 9, records two poly terephthalic acid-2-methyl isophthalic acids, 3-the third two
The molecular weight of alcohol ester is respectively 20.6 kg/mol, 45.2 kg/mol, and PDI is followed successively by 1.64,1.69.To poly terephthalic acid-
2-methyl isophthalic acid, ammediol ester polymer hot pressing film forming laggard row extension test, load-deformation curve is shown in Figure 10 and Figure 11.
The polymer of Figure 10, molecular weight is 20.6 kg/mol, and its elongation at break (< 10%) is 45.2 well below Figure 11 middle-molecular-weihydroxyethyl
The sample of kg/mol (460%), and its fracture strength is also not as good as the sample of high molecular, illustrates that the raising of molecular weight is to polyester
The lifting of material property has extremely important impact.
It addition, it is similar to the above to prepare described polyester process with ring-opening polymerisation method, polyester is specific as follows: polyadipate second two
Alcohol ester, polypropylene glycol adipate, polyethylene glycol succinate, poly adipate succinic acid ester；Polyphenyl dioctyl phthalate one contracting diethyl two
Alcohol ester, polyphenyl dioctyl phthalate Triethylene Glycol, polyphenyl dioctyl phthalate tetraethylene-glycol ester, poly-(phthalic acid-2-methyl isophthalic acid,
Ammediol ester), poly-(phthalic acid-2，2-dimethyl-1，3-propanediol ester), poly-(phthalic acid-2-methyl-2-propyl-1,
Ammediol ester), wherein phthalic acid can be p-phthalic acid or M-phthalic acid.
The foregoing is only the preferred embodiment of invention, be not limited to the present invention, for the technology of this area
For personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (5)
1. the preparation method of a polyester, it is characterised in that the step of the method is as follows:
(1) preparation of cyclic oligomeric ester monomer:
Under the conditions of " false high dilute ", glycol and the diacid chloride of equimolar amounts are added dropwise to the dichloromethane containing catalyst and triethylamine
In alkane or chloroformic solution, synthesis of cyclic widow's polyester monocase；
(2) preparation of polyester:
Under conditions of temperature is 200-250 DEG C, evacuation or logical nitrogen, there is open loop in cyclic oligomeric ester monomer under catalyst
Polymerization, i.e. obtains product polyester after reacting 30-90 minute.
The preparation method of a kind of polyester the most according to claim 1, it is characterised in that: the glycol in described step (1) is
Aliphatic diol or condensed ethandiol, diacid chloride is aliphatic diacid chloride or aromatic diacid chlorides.
The preparation method of a kind of polyester the most according to claim 2, it is characterised in that: described aliphatic diol is second two
Alcohol, propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propylene glycol, 2-methyl-2-propyl-1,3-propylene glycol, fourth
Glycol, condensed ethandiol are diglycol, triethylene-glycol or tetraethylene-glycol.
The preparation method of a kind of polyester the most according to claim 1, it is characterised in that: the catalyst in described step (1)
For pyridine or triethylene diamine.
The preparation method of a kind of polyester the most according to claim 1, it is characterised in that: the catalyst in described step (2)
For butyl titanate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395527A (en) * | 2018-04-04 | 2018-08-14 | 苏州大学 | A kind of azobenzene polyether ester segmented copolymer elastomer and preparation method thereof with photo-deformable performance |
| CN109134836A (en) * | 2018-08-26 | 2019-01-04 | 苏州大学 | A kind of polyester elastomer and the preparation method and application thereof that can be crosslinked with metallic ion coordination |
| WO2024066194A1 (en) * | 2022-09-26 | 2024-04-04 | 苏州大学 | Copolyester and preparation method therefor |
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| CN103254412A (en) * | 2012-10-31 | 2013-08-21 | 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 |
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| CN103254412A (en) * | 2012-10-31 | 2013-08-21 | 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395527A (en) * | 2018-04-04 | 2018-08-14 | 苏州大学 | A kind of azobenzene polyether ester segmented copolymer elastomer and preparation method thereof with photo-deformable performance |
| CN109134836A (en) * | 2018-08-26 | 2019-01-04 | 苏州大学 | A kind of polyester elastomer and the preparation method and application thereof that can be crosslinked with metallic ion coordination |
| 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 |
| WO2024066194A1 (en) * | 2022-09-26 | 2024-04-04 | 苏州大学 | Copolyester and preparation method therefor |
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