CN103254412B - Preparation method of polyether ester block polymer - Google Patents
Preparation method of polyether ester block polymer Download PDFInfo
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- CN103254412B CN103254412B CN201210424457.6A CN201210424457A CN103254412B CN 103254412 B CN103254412 B CN 103254412B CN 201210424457 A CN201210424457 A CN 201210424457A CN 103254412 B CN103254412 B CN 103254412B
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- block polymer
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- polyether
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 32
- 229920000570 polyether Polymers 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002148 esters Chemical class 0.000 title claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 5
- 229920001400 block copolymer Polymers 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- -1 polyethylene terephthalate Polymers 0.000 claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 19
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 150000002009 diols Chemical class 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of polyether ester block polymer, which is characterized in that flexible polyether diol with a terminal group as a hydroxyl group is subjected to ring-opening polymerization to obtain polyester cyclic monomers, and various polyether ester block copolymers of different types are prepared by a ring-opening polymerization method. The product prepared by the method has the advantages of clear structure, lower reaction temperature, safer reaction, energy conservation, high efficiency and simple steps.
Description
Technical field
The present invention relates to a kind of field of material preparation, that be specifically related to is a kind of preparation method of polyether ester block polymer.
Background technology
Using dystectic crystalline polyester segment as the hard section of block polymer, the mechanical property of material, upper limit use temperature and good solubility-resistence etc. can be improved.When the mid-block adopted is for having comparatively lower glass transition temperatures (T
g) polymkeric substance time, what obtain is thermoplastic elastomer.But the controlledly synthesis of three blocks or multi-block polyester with clear and definite structure has larger difficulty.
In prior art, usual melt-polycondensation in autoclave with dimethyl terephthalate (DMT) (DMT), 1,4-butyleneglycol (BDO), polyoxyethylene glycol (PEG) are Material synthesis polyoxyethylene glycol polybutylene terephthalate block polymer, and it be unclear that the level of application of other polyester.There is the loaded down with trivial details shortcoming of preparation process in this method, the polymkeric substance obtained is random copolymers, and structure is indefinite.
Summary of the invention
The object of the invention is to the above problem overcoming prior art existence, a kind of preparation method of polyether ester block polymer is provided, easy, efficient, environmental protection ground synthetic polymer.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A kind of preparation method of polyether ester block polymer, take end group as the flexible polyether glycol ring-opening polymerization polyester cyclic monomer of hydroxyl, prepare various dissimilar polyetherester block copolymer by polymerization process, wherein, the chemical structural formula of described polyester cyclic monomer is
, in formula, the value of n is the value of 2 ~ 4, m is 2 ~ 6, and described polyether glycol, chemical structural formula is
, n is wherein 1 ~ 4, R is H or methyl, and molecular weight ranges is 2000 to 10000 g/mol.
Further, described polymerization process comprises solution polymerization process and melt polymerization process,
The reaction equation of described polymerization process is as follows:
。
Further, described solution polymerization process comprises the following steps:
Step 1) is being equipped with magnetic agitation, reflux exchanger, water-and-oil separator and N
2in two mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing monomer, polyether glycol, tetrachloroethane, be heated to certain temperature, first steam part tetrachloroethane, then cool to temperature of reaction, add isopropyl titanate as catalyzer, at logical N
2stirring reaction certain hour is continued in situation;
Step 2) after reaction terminates, poured into by reactant in bulk petroleum ether, sedimentation and filtration, is placed in vacuum drying oven by product, dry within 24 hours, obtains final product.
Further, described melt polymerization process comprises the following steps:
Step 1) is being equipped with mechanical stirring, N
2in three mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing, polyether glycol, logical nitrogen is heated to 120 degree, constant temperature 10 minutes;
Step 2) add catalyzer, be heated to temperature of reaction, at logical N
2continue in situation to stir certain hour, obtain final product.
Further, described cyclic oligomeric thing is the one in polyethylene terephthalate cyclic oligomeric thing, Poly(Trimethylene Terephthalate) cyclic oligomeric thing or polybutylene terephthalate cyclic oligomeric thing; The polymkeric substance of described polyether glycol to be end group be glycol; Described catalyzer is the one in the titanic acid ester such as isopropyl titanate, tetrabutyl titanate.
The invention has the beneficial effects as follows:
Product structure prepared by the present invention is clear and definite, and temperature of reaction is lower, and react safer and energy-conservation, efficiency is very high, and step is easy.
Accompanying drawing explanation
Fig. 1 is osmogels chromatogram (GPC) figure of block polymer a, b, c;
Fig. 2 is differential scanning calorimetric analysis (DSC) the intensification melting figure of block polymer a, b, c;
Fig. 3 is osmogels chromatogram (GPC) figure of block polymer d, e, f;
Fig. 4 be block polymer e nuclear magnetic spectrum (
1h NMR).
Embodiment
Below in conjunction with embodiment, describe the present invention in detail.
A kind of preparation method of polyether ester block polymer, take end group as the flexible polyether glycol ring-opening polymerization polyester cyclic monomer of hydroxyl, prepare various dissimilar polyetherester block copolymer by polymerization process, wherein, the chemical structural formula of described polyester cyclic monomer is
, in formula, the value of n is the value of 2 ~ 4, m is 2 ~ 6, and described polyether glycol, chemical structural formula is
, n is wherein 1 ~ 4, R is H or methyl, and molecular weight ranges is 2000 to 10000 g/mol.
Further, described polymerization process comprises solution polymerization process and melt polymerization process,
The reaction equation of described polymerization process is as follows:
。
Further, described solution polymerization process comprises the following steps:
Step 1) is being equipped with magnetic agitation, reflux exchanger, water-and-oil separator and N
2in two mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing, polyether glycol, tetrachloroethane, be heated to certain temperature, first steam part tetrachloroethane, then cool to temperature of reaction, add isopropyl titanate as catalyzer, at logical N
2stirring reaction certain hour is continued in situation;
Step 2) after reaction terminates, poured into by reactant in bulk petroleum ether, sedimentation and filtration, is placed in vacuum drying oven by product, dry within 24 hours, obtains final product.
Further, described melt polymerization process comprises the following steps:
Step 1) is being equipped with mechanical stirring, N
2in three mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing, polyether glycol, logical nitrogen is heated to 120 degree, constant temperature 10 minutes;
Step 2) add catalyzer, be heated to temperature of reaction, at logical N
2continue in situation to stir certain hour, obtain final product.
Further, described cyclic oligomeric thing is the one in polyethylene terephthalate cyclic oligomeric thing, Poly(Trimethylene Terephthalate) cyclic oligomeric thing or polybutylene terephthalate cyclic oligomeric thing; The polymkeric substance of described polyether glycol to be end group be glycol; Described catalyzer is the one in isopropyl titanate or tetrabutyl titanate
Embodiment 1
The preparation of polyoxyethylene glycol polybutylene terephthalate block polymer
In 250 mL bis-neck flasks, add mutual-phenenyl two acid bromide two alcohol ester's cyclic oligomeric thing (7.5 g), molecular weight be 10,000 polyoxyethylene glycol (7.5 g), adds solvent tetrachloroethane (100 mL) subsequently, logical N
2165 ~ 175 are warming up to while stirring in situation
o, separate about 20 mL tetrachloroethane with water-and-oil separator, cool to 165
o, then add catalyst Ti isopropyl propionate, continue reaction 4 hours, reaction solution is slowly joined in 300 ~ 400 mL sherwood oils of vigorous stirring, obtain white or light yellow solid.Finally product is placed in vacuum drying oven, drying obtains final product in 24 hours.
The block polymer (table 1) of different molecular weight has been synthesized by controlling different feed ratio.From GPC scheme (Fig. 1), the polymkeric substance obtained is monodispersed, illustrates obtain be block polymer.Further, along with the increase of mutual-phenenyl two acid bromide two alcohol ester's cyclic oligomeric thing charging capacity, block polymer molecules amount also increases thereupon, further illustrates and obtains block polymer.
Table 1
| Feed ratio # | M n HNMR * | M n GPC * | M w GPC * | PDI | |
| Polymkeric substance a | 2:1 | 17.3 | 3.60 | 7.00 | 1.94 |
| Polymkeric substance b | 1:1 | 24.2 | 4.10 | 8.70 | 2.12 |
| Polymkeric substance c | 1:2 | 33.7 | 5.20 | 11.0 | 2.12 |
#: the ratio of polyether glycol and polyester cyclic oligomeric thing; *: kg/mol.
Secondly, DSC detection has been carried out to block polymer, under the speed of 5 DEG C/min, has investigated the melting heating curve (Fig. 2) of block polymer.Can see that polymkeric substance has 2 crystalline melting peak, belong to the peak crystallization of polybutylene terephthalate and polyoxyethylene glycol respectively.And along with the increase of polybutylene terephthalate content, move after polybutylene terephthalate Tc, peak crystallization area also increases thereupon.
Embodiment 2
The preparation of polytetrahydrofuran Poly(Trimethylene Terephthalate) block polymer
In 150ml tri-mouthfuls of round-bottomed bottles that mechanical stirring, N2 conduit are housed, add Poly(Trimethylene Terephthalate) cyclic oligomeric thing 15g, molecular weight is the polytetrahydrofuran 15g of 2900, logical nitrogen is heated to 120 degree, constant temperature 10 minutes, then add tetrabutyl titanate as catalyzer, be heated to 230 degree, at logical N
2continuing stirring in situation 1 hour, obtain final product, is white solid.
By controlling the block polymer (table 2) having synthesized different molecular weight of feed ratio.Scheme (Fig. 3) from GPC, the polymkeric substance obtained is monodispersed.Further, along with the increase of propylene glycol ester terephthalate's cyclic oligomeric thing charging capacity, block polymer molecules amount also increases thereupon, illustrate obtain for block polymer.
Table 2
| Feed ratio # | M n HNMR * | M n GPC * | M w GPC * | PDI | |
| Polymkeric substance d | 3:1 | 4.32 | 2.19 | 3.84 | 1.75 |
| Polymkeric substance e | 2:1 | 4.78 | 3.31 | 6.44 | 1.95 |
| Polymkeric substance f | 1:1 | 5.58 | 4.87 | 8.34 | 1.71 |
#: the ratio of polyether glycol and polyester cyclic oligomeric thing; *: kg/mol.
Embodiment 3
The preparation of polytetrahydrofuran polyethylene terephthalate block polymer
In 150ml tri-mouthfuls of round-bottomed bottles that mechanical stirring, N2 conduit are housed, add polyethylene terephthalate cyclic oligomeric thing 15g, molecular weight is the polytetrahydrofuran 15g of 2900, logical nitrogen is heated to 120 degree, constant temperature 10 minutes, then add tetrabutyl titanate as catalyzer, be heated to 260 degree, at logical N
2continuing stirring in situation 1 hour, obtain final product, is white solid.
Claims (4)
1.
a kind of preparation method of polyether ester block polymer, it is characterized in that: the flexible polyether glycol ring-opening polymerization polyester cyclic monomer taking end group as hydroxyl, prepare various dissimilar polyetherester block copolymer by polymerization process, wherein, the chemical structural formula of described polyester cyclic monomer is , in formula, the value of a is the value of 2-4, m is 2-6, and described polyether glycol, chemical structural formula is , R structure is wherein , n is the polymerization degree of polyether glycol, and molecular weight ranges is 2000 to 10000 g/mol.
2. the preparation method of polyether ester block polymer according to claim 1, is characterized in that: described polymerization process comprises solution polymerization process and melt polymerization process,
The reaction equation of described polymerization process is as follows:
。
3. the preparation method of polyether ester block polymer according to claim 2, is characterized in that, described solution polymerization process comprises the following steps:
Step 1) is being equipped with magnetic agitation, reflux exchanger, water-and-oil separator and N
2in two mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing, polyether glycol, tetrachloroethane, be heated to certain temperature, first steam part tetrachloroethane, then cool to temperature of reaction, add isopropyl titanate as catalyzer, at logical N
2stirring reaction certain hour is continued in situation;
Step 2) after reaction terminates, poured into by reactant in bulk petroleum ether, sedimentation and filtration, is placed in vacuum drying oven by product, dry within 24 hours, obtains final product.
4. the preparation method of polyether ester block polymer according to claim 2, is characterized in that, described melt polymerization process comprises the following steps:
Step 1) is being equipped with mechanical stirring, N
2in three mouthfuls of reaction flasks of conduit, add cyclic oligomeric thing, polyether glycol, logical nitrogen is heated to 120 degree, constant temperature 10 minutes;
Step 2) add catalyzer, be heated to temperature of reaction, at logical N
2continue in situation to stir certain hour, obtain final product.
5. the preparation method of the polyether ester block polymer according to claim 3 or 4, is characterized in that: described cyclic oligomeric thing is the one in polyethylene terephthalate cyclic oligomeric thing, Poly(Trimethylene Terephthalate) cyclic oligomeric thing or polybutylene terephthalate cyclic oligomeric thing; The polymkeric substance of described polyether glycol to be end group be glycol; Described catalyzer is the titanate ester catalyzer of isopropyl titanate, tetrabutyl titanate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424457.6A CN103254412B (en) | 2012-10-31 | 2012-10-31 | Preparation method of polyether ester block polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210424457.6A CN103254412B (en) | 2012-10-31 | 2012-10-31 | Preparation method of polyether ester block polymer |
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| CN103254412B true CN103254412B (en) | 2015-08-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104693447A (en) * | 2015-03-10 | 2015-06-10 | 苏州大学 | Preparation method of polyether ester multi-block alternating copolymer |
| CN106008945B (en) * | 2016-06-07 | 2018-07-03 | 苏州大学 | Preparation method of polyester |
| CN111393617B (en) * | 2019-11-29 | 2023-01-24 | 开滦（集团）有限责任公司 | Performance-adjustable thermoplastic polyester elastomer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918209A (en) * | 2004-02-05 | 2007-02-21 | 帝斯曼知识产权资产管理有限公司 | Block copolyetherester elastomer and preparation thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918209A (en) * | 2004-02-05 | 2007-02-21 | 帝斯曼知识产权资产管理有限公司 | Block copolyetherester elastomer and preparation thereof |
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