CN104151535B - A kind of polyester block copolymer and preparation method thereof - Google Patents
A kind of polyester block copolymer and preparation method thereof Download PDFInfo
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- CN104151535B CN104151535B CN201410389543.7A CN201410389543A CN104151535B CN 104151535 B CN104151535 B CN 104151535B CN 201410389543 A CN201410389543 A CN 201410389543A CN 104151535 B CN104151535 B CN 104151535B
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Abstract
The present invention is a kind of polyester block copolymer and preparation method thereof, and the structural formula of described multipolymer is such as formula shown in (I).The present invention directly adopts organic catalyst, and this step in polymer purification process is easy, and can not remain the heavy metal ion in traditional method in polymkeric substance.The present invention the esterification of optionally catalysis acid anhydrides and epoxy compounds can obtain the polyester copolymer with rotamerism segment, by product nmr analysis find can not catalysis epoxide group open loop self-polymeric reaction and generate by product.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to meso-anhydride and epoxy compounds occur under organic catalysis stereoselectivity open loop to generate and remove symmetry, Stereoselective (trans-, cis-) enantiomorph product, takes the method for sequential feeds to prepare the polyester copolymer with rotamerism segment.
Background technology
Aliphatic polyester is biodegradable because of it, extremely the favor of people.But adopt ordinary method be difficult to obtain high-molecular aliphatic polyester, and its thermostability and mechanical property poor, limit the application of aliphatic polyester.Therefore, in order to expand the range of application of aliphatic polyester, the molecular weight of aliphatic polyester need be improved, and modification is carried out to aliphatic polyester.
The common method improving polyester property carries out copolymerization with other monomers or polymkeric substance.Adopt polybutylene terephthalate, butyleneglycol, caprolactone etc. through transesterification reaction as US Patent No. 2006/0252864A1 discloses, then polycondensation is being carried out, finally obtain the multipolymer of PBT-PCL, but in reaction process, polybutylene terephthalate inevitably participates in transesterification reaction, cause wherein soft section be a kind of structure of random distribution with hard section.
For random copolymers, segmented copolymer can make its crystal property by Quality Initiative segment structure, and fusing point and mechanical property are all better.The synthetic method of olefin based block copolymer is many comparatively ripe again, but polyester type block copolymer and preparation method thereof then and imperfection, the method that bibliographical information is maximum is ester-interchange method (Chinese patent 200810118233.6, Chinese patent 201110416884.5), namely adopt the polyester of two kinds of high molecular, under catalyzer and high temperature, transesterification reaction occurs, a kind of biodegradable aliphatic polyester/aromatic polyester multi-block copolymer and preparation method thereof and application disclosed in Chinese patent 200910092100.0, it is synthetic fat race polyester prepolyer A first, resynthesis aliphatics or aromatic polyester B, segmented copolymer is synthesized under the effect of chainextender, its advantage with crystallinity aliphatic polyester in introduce rigidity non-crystalline polyester segment, good mechanical property can be obtained, but its weak point is that chain extension efficiency is poor, the molecular weight of polyesters of preparation is lower.
The microtexture of polymer segment determines the key of polymer performance especially, and tacticity often has a significant impact polymer crystallization performance, thermostability, tough performance.Therefore in the polymerization, the stereochemistry of polymkeric substance is regulated and controled, exploitation have special property novel material to theoretical investigation or industry be produce all valuable.If Guang-PengWu and Xiao-BingLu is at J.Am.Chem.Soc.2012,134, the degree of isotacticity that 5682 – 5688 and Chinese patent CN102229745A report is the poly-cyclohexene carbonate (PCHC) of 98%, and fusing point (Tm) is up to 216 DEG C.Crystal habit research simultaneously shows, the spherocrystal of single optical purity (R)-PCHC grows in a clockwise direction with the spherocrystal counterclockwise growing (S)-PCHC.Two kinds of spherocrystal balanced mix obtain the crystalline morphology of lath-shaped, and show stronger heat resistanceheat resistant deformability (fusing point is up to 230 DEG C).And for example Jian-ZhaoLiu and Ben-ZhongTang is at Chem.Rev.2009, 109, the polyacetylene (PA) reported in 5799 – 5867 structurally carbon atom is that the form replaced with single double bond is connected with each other, its configuration has trans, cis-trans and anti-cis three kinds of isomer, find that sulfuration all has considerable influence for the relative stability of polyacetylene cis-trans-isomer and facing conductive performance etc. by sulfuration research, the most stable and conductivity best on the transconfiguration energy of PA, after sulfuration, cis-structure facing conductive performance will obviously strengthen, instead, cis conductive capability reaches unanimity, but trans Polyacetylene sulfide structure is more stable on energy.
Not only valuable to polymer architecture fundamental research to the accurate control of polymer stereochemistry, and once work out there is high molecular, high tacticity multipolymer, be just expected to develop the high performance polymer material with special property.
Summary of the invention
The object of the present invention is to provide a kind of polyester block copolymer and novel preparation method thereof, obtain a kind of polyester block copolymer of novel texture by controlling charging process, the ratio particularly exactly by controlling to add acid anhydrides and epoxy can obtain the polyester copolymer with (trans-or cis-) structure.Inner mold-the norbornene dicarboxylic anhydride selecting us to select of material and external form-norbornene dicarboxylic anhydride, the polymkeric substance obtained is the new texture with rotamerism segment.In preparation method, the selection of acid anhydrides and epoxy is most important, and the polymkeric substance that the acid anhydrides of such as inner mold and epoxide polymerization obtain is trans-configuration, and the acid anhydrides of external form and epoxide polymerization obtain polymkeric substance then can keep cis-configuration.Meanwhile, adopt quaternary ammonium salt organic catalyst, can efficiently catalysis acid anhydrides and epoxy compounds esterification fast, and by the regulation and control of charging process, obtain a kind of new polyester segmented copolymer.
Technical scheme of the present invention is:
A kind of polyester block copolymer, the structural formula of described multipolymer is such as formula shown in (I):
Wherein-R
1,-R
3independently be selected from-H,
-R
2,-R
4independently be selected from-CH
2cl,
m＝1～2500，n＝1～500。
The preparation method of described polyester block copolymer, comprises the following steps:
A), under argon shield, quaternary ammonium compound, the first epoxy compounds and the first acid anhydrides are joined after anhydrous solvent dissolves, carry out the first polyreaction, temperature of reaction is 60 ~ 110 DEG C, and the reaction times is 1h ~ 50h, obtains polyester;
Wherein, material proportion is mol ratio quaternary ammonium compound: the first epoxy compounds: the first acid anhydrides=1:1 ~ 2500:1 ~ 2500;
B) the second epoxy compounds and the second anhydrides compound are dissolved in after dissolving in anhydrous solvent, be added in the first polymerization reactor and carry out the second polyreaction, temperature of reaction 60 ~ 110 DEG C, the reaction times is 4h ~ 50h, obtains polyester block copolymer;
Wherein, material proportion is mol ratio the second epoxy compounds: the second anhydrides compound: first ring oxygen compound=1:1:1 ~ 2500;
Described quaternary ammonium compound is two-(dihalotriphenylphosphoranes base) ammonium chloride.
The first described anhydrides compound is succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-ring [2.2.2] octyl group-5-alkene-2, 3-dicarboxylic anhydride, methyl-5-norbornylene-2, 3-dicarboxylic anhydride, dimethyl maleic anhydride, 3, 4, 5, 6-Tetra Hydro Phthalic Anhydride, six hydrogen-4-methyl nadic anhydrides, allyl succinic anhydride, trimellitic acid 1,2-anhydride, 1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, 4-chloro-phthalic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, phenylsuccinic acid acid anhydride, cyclohexyl dicarboxylic acid's acid anhydride, 2, 3-diphenyl maleic anhydride or cis-3-carboxyl glutaconic anhydride,
The first described epoxy compounds is specially epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min., 3,4-epoxy-1-tetrahydrobenzene, methyl isophthalic acid, 2-cyclopentenes epoxy material, (2,3-epoxypropyl) benzene, (1S, 2S)-1-phenylpropylene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second epoxy compounds is specially epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min., 3,4-epoxy-1-tetrahydrobenzene, methyl isophthalic acid, 2-cyclopentenes epoxy material, (2,3-epoxypropyl) benzene, (1S, 2S)-1-phenylpropylene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second anhydrides compound is selected from succinyl oxide respectively, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-ring [2.2.2] octyl group-5-alkene-2, 3-dicarboxylic anhydride, methyl-5-norbornylene-2, 3-dicarboxylic anhydride, dimethyl maleic anhydride, 3, 4, 5, 6-Tetra Hydro Phthalic Anhydride, six hydrogen-4-methyl nadic anhydrides, allyl succinic anhydride, trimellitic acid 1,2-anhydride, 1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, 4-chloro-phthalic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, phenylsuccinic acid acid anhydride, cyclohexyl dicarboxylic acid's acid anhydride, 2, 3-diphenyl maleic anhydride or cis-3-carboxyl glutaconic anhydride,
Described step a) middle mol ratio is preferably the first anhydrides compound: the first epoxy compounds: quaternary ammonium compound=100:100:1, or the first anhydrides compound: the first epoxy compounds: quaternary ammonium compound=50:50:1.
Preferably, the first epoxy compounds described is selected from epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min. respectively.
Preferably, the first described anhydrides compound is selected from succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2 respectively, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1,2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride.
Described step b) in the mol ratio of first ring oxygen compound and the second epoxy compounds and the second anhydrides compound be 1:1:1.
Described step a) and step b) described anhydrous solvent is preferably toluene.
Beneficial effect
The invention provides a kind of method that epoxy compounds and anhydride copolymers prepare segmented copolymer, the method adopts PPNCl (two-(dihalotriphenylphosphoranes base) ammonium chloride) as catalyzer, catalysis acid anhydrides and open loop of epoxy compound polyreaction at temperature of reaction 60 ~ 110 DEG C, by controlling the structure of order of addition(of ingredients) regulation and control multipolymer, the polyester copolymer with rotamerism segment can be obtained.With the ring-opening polymerization of bibliographical information associated catalytic anhydride epoxy, we do not adopt the method adding metal catalyst, but directly adopting organic catalyst, this step in polymer purification process is easy, and can not remain the heavy metal ion in traditional method in polymkeric substance.The method can the esterification of optionally catalysis acid anhydrides and epoxy compounds, by product nmr analysis find can not catalysis epoxide group open loop self-polymeric reaction and generate by product.
Accompanying drawing explanation
Fig. 1 is gained first polymerisate and block polymerization product nuclear-magnetism stacking diagram in embodiment 1.
Embodiment:
Embodiment 1
The withstand voltage reaction tubes of 25ml heavy wall of dried and clean is got under ar gas environment, add 5mmol exo norbornene dicarboxylic anhydride, 0.1mmol pair-(dihalotriphenylphosphoranes base) ammonium chloride, 5mmol epoxy cyclohexane, 1ml toluene dissolves (quantity of solvent can make quaternary ammonium compound, epoxy compounds, acid anhydrides etc. dissolve), reacts 1h at 110 DEG C; The mixing solutions (toluene amount can make quaternary ammonium compound, epoxy compounds, acid anhydrides etc. dissolve) of 5mmol inner mold norbornene dicarboxylic anhydride, 5mmol epoxy cyclohexane and 1ml toluene is added again under argon shield; after reacting 4h at 110 DEG C; reaction system being poured into volume is sedimentation in the methyl alcohol of solvent 50ml; filter; washing; by the product that obtains at 45 DEG C of vacuum-drying 24h, obtain R
1, R
3for the norbornylene that prosposition replaces; R
2, R
4it is the polyester block copolymer of 1,2 substituted cyclohexanes.
Wherein, m value is 15, (molecular-weight average measured by GPC can prove that m value is at 1-2500 to n value for 16, n value is within the scope of 1-500, because the molecular weight of each segment can calculate according to molecular formula, the molecular weight of polymkeric substance is exactly number and m, n value that the molecular weight of each segment is multiplied by segment), yield 86%, it is 8200 that GPC records molecular-weight average, molecular weight distribution 1.4.
Figure above in Fig. 1 is when reaction is polymerized with epoxy cyclohexane the product obtained by exo norbornene dicarboxylic anhydride, in nuclear-magnetism figure only there is the unimodal of hydrogen atom in cis structure double bond in 6.17ppm place, illustrate that polymkeric substance keeps cis configuration, the characteristic peak of exo norbornene ring and cyclohexyl can be seen, figure is when adding inner mold norbornylene acid anhydrides and epoxy cyclohexane prepares segmented copolymer after external form acid anhydrides and epoxide polymerization below, will 6.25 on nuclear-magnetism figure, 6.02 have more that trans structure double bond hydrogen splits point bimodal, compare in Tu Bentu the characteristic peak adding inner mold norbornylene ring, the block polyester copolymer obtaining one section of cis configuration, one section of trans configuration is described, and do not find in the drawings to occur epoxy cyclohexane autohemagglutination product peak at 3.8ppm place.
Embodiment 2
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 7050, m value be 13, n value is 18 that yield 84%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 3
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 5775, m value be 11, n value is 14 that yield 85%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 4
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol Tetra hydro Phthalic anhydride, epoxy compounds is 10mmol epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 phenyl ring replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 15120, m value be 29, n value is 30 that yield 73%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 5
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 7850, m value be 15, n value is 16 that yield 86%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 6
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) in acid anhydrides be 5mmol succinyl oxide, epoxy compounds is the mixture of 5mmol epoxy cyclohexane and 1ml toluene.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 6799, m value be 13, n value is 17 that yield 81%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 7
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 10mmol epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 12590, m value be 24, n value is 30 that yield 73%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 8
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 phenyl ring replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 7601, m value be 14, n value is 15 that yield 82%, GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 9
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the hexanaphthene that 1,2 replace.It is 7579, m value be 15, n value is 16 that yield 82%, GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 10
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1, R
3for the norbornylene that prosposition replaces; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 8310, m value be 16, n value is 17 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 11
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol epoxy chloropropane; Step b) middle acid anhydrides is 10mmol succinyl oxide, epoxy compounds is 10mmol epoxy chloropropane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 13080, m value be 25, n value is 39 that yield 80%, GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 12
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 7365, m value be 15, n value is 18 that yield 87%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 13
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 phenyl ring replaced; R
2, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 7964, m value be 15, n value is 17 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 14
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 7685, m value be 14, n value is 17 that yield 86%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 15
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol epoxy chloropropane; Step b) middle acid anhydrides is 10mmol succinyl oxide, epoxy compounds is 10mmol epoxy chloropropane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 9973, m value be 19, n value is 26 that yield 61%, GPC records molecular-weight average, molecular weight distribution 1.9.
Embodiment 16
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 6211, m value be 12, n value is 15 that yield 74%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 17
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 phenyl ring replaced; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 6600, m value be 13, n value is 14 that yield 72%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 18
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the chloropropane that 1,2 replace.It is 6500, m value be 12, n value is 14 that yield 73%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 19
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1, R
3for the norbornylene that prosposition replaces; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.It is 17620, m value be 34, n value is 31 that yield 85%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 20
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 8502, m value be 16, n value is 19 that yield 91%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 21
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 9800, m value be 21, n value is 20 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 22
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 benzene replaced; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 9094, m value be 18, n value is 16 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 23
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 20200, m value be 34, n value is 38 that yield 83%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 24
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 6913, m value be 13, n value is 15 that yield 74%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 25
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 7362, m value be 14, n value is 16 that yield 77%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 26
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 benzene replaced; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 7766, m value be 15, n value is 14 that yield 76%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 27
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane.Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane that 1,2 replace.It is 15076, m value be 30, n value is 28 that yield 78%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 28
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..R
1, R
3for the norbornylene that prosposition replaces; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.It is 10040, m value be 19, n value is 17 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 29
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the exo norbornene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.It is 8277, m value be 16, n value is 19 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 30
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 8286, m value be 16, n value is 18 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 31
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 10mmol Tetra hydro Phthalic anhydride, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 benzene replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 16520, m value be 32, n value is 31 that yield 82%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 32
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the exo norbornene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 8835, m value be 17, n value is 17 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 33
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 6805, m value be 13, n value is 15 that yield 74%, GPC records molecular-weight average, molecular weight distribution 1.5
Embodiment 34
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 cyclopropane replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 7250, m value be 14, n value is 16 that yield 77%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 35
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 10mmol Tetra hydro Phthalic anhydride, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 benzene replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 15310, m value be 29, n value is 28 that yield 76%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 36
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the inner mold norbornylene that prosposition replaces, R
3be 1,2 pentamethylene replaced; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 7743, m value be 15, n value is 15 that yield 78%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 37
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..R
1for the exo norbornene that prosposition replaces, R
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 8734, m value be 17, n value is 15 that yield 85%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 38
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol succinyl oxide, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 6710, m value be 13, n value is 15 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 39
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 cyclopropane replaced, R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 17920, m value be 35, n value is 39 that yield 87%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 40
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9132, m value be 17, n value is 17 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 41
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9013, m value be 15, n value is 17 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 42
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1for the exo norbornene R that prosposition replaces
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 11200, m value be 19, n value is 20 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 43
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol succinyl oxide, epoxy compounds is 10mmol epoxy chloropropane; Step b) middle acid anhydrides is 10mmol succinyl oxide, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 18931, m value be 41, n value is 43 that yield 83%, GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 44
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 cyclopropane replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9160, m value be 20, n value is 19 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 45
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9534, m value be 17, n value is 18 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 46
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9331, m value be 18, n value is 18 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 47
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1for the exo norbornene that prosposition replaces, R
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 25330, m value be 43, n value is 45 that yield 81%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 48
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol succinyl oxide, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 8990, m value be 20, n value is 21 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 49
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 cyclopropane replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9340, m value be 20, n value is 20 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 50
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 9940, m value be 18, n value is 19 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 51
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 10mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the benzene of 1 replacement.It is 18820, m value be 36, n value is 37 that yield 90%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 52
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 10021, m value be 20, n value is 19 that yield 91%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 53
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol succinyl oxide, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1, R
3for hydrogen; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 8130, m value be 21, n value is 21 that yield 92%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 54
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1, R
3be 1,2 cyclopropane replaced; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 8744, m value be 22, n value is 21 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 55
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol Tetra hydro Phthalic anhydride, epoxy compounds is 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol Tetra hydro Phthalic anhydride, epoxy compounds is 10mmol epoxy chloropropane.Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 19133, m value be 38, n value is 40 that yield 84%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 56
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy chloropropane.Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 hexanaphthenes replaced, R
4it is the block polyester copolymer of the chloropropane that 1,2 replace.It is 9022, m value be 20, n value is 19 that yield 86%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 57
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 10400, m value be 18, n value is 18 that yield 87%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 58
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol succinyl oxide, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol succinyl oxide, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3for hydrogen; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 8703, m value be 20, n value is 19 that yield 91%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 59
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 10mmol epoxy chloropropane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3be 1,2 cyclopropane replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 15650, m value be 30, n value is 33 that yield 89%, GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 60
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 9243, m value be 17, n value is 17 that yield 88%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 61
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 chloropropanes replaced, R
4it is the block polyester copolymer of the vinyl cyclohexane that 1,2 replace.It is 9130, m value be 17, n value is 18 that yield 87%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 62
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol exo norbornene dicarboxylic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol inner mold norbornene dicarboxylic anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1for the exo norbornene that prosposition replaces, R
3for the inner mold norbornylene that prosposition replaces; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the hexanaphthene that 1,2 replace.It is 11230, m value be 22, n value is 21 that yield 91%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 63
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 10mmol succinyl oxide, epoxy compounds is 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol succinyl oxide, epoxy compounds is 10mmol epoxy cyclohexane.Obtain R
1, R
3for hydrogen; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the hexanaphthene that 1,2 replace.It is 17340, m value be 33, n value is 44 that yield 85%, GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 64
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1, R
3be 1,2 cyclopropane replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the hexanaphthene that 1,2 replace.It is 9134, m value be 22, n value is 21 that yield 86%, GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 65
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol Tetra hydro Phthalic anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1, R
3be 1,2 benzene replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the hexanaphthene that 1,2 replace.It is 9587, m value be 20, n value is 20 that yield 87%, GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 66
All the other operations with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds is 5mmol epoxy cyclohexane.Obtain R
1, R
3be 1,2 pentamethylene replaced; R
2be 1,2 vinyl cyclohexane replaced, R
4it is the block polyester copolymer of the hexanaphthene that 1,2 replace.It is 9350, m value be 20, n value is 19 that yield 86%, GPC records molecular-weight average, molecular weight distribution 1.6.
Table 1: proton magnetic spectrum data (300MHz, the CDCl of polyester block copolymer
3, ppm)
Claims (6)
1. a polyester block copolymer, is characterized by the structural formula of described multipolymer such as formula shown in (I):
Wherein-R
1,-R
3independently be selected from-H,
-R
2,-R
4independently be selected from-CH
2cl,
m＝1～2500，n＝1～500；
Described polyester block copolymer is prepared from by following methods, it is characterized by and comprises the following steps:
A), under argon shield, quaternary ammonium compound, the first epoxy compounds and the first acid anhydrides are joined after anhydrous solvent dissolves, carry out the first polyreaction, temperature of reaction is 60 ~ 110 DEG C, and the reaction times is 1h ~ 50h, obtains polyester;
Wherein, material proportion is mol ratio quaternary ammonium compound: the first epoxy compounds: the first acid anhydrides=1:1 ~ 2500:1 ~ 2500;
B) the second epoxy compounds and the second anhydrides compound are dissolved in after dissolving in anhydrous solvent, be added in the first polymerization reactor and carry out the second polyreaction, temperature of reaction 60 ~ 110 DEG C, the reaction times is 4h ~ 50h, obtains polyester block copolymer;
Wherein, material proportion is mol ratio the second epoxy compounds: the second anhydrides compound: first ring oxygen compound=1:1:1 ~ 2500;
Described quaternary ammonium compound is two-(dihalotriphenylphosphoranes base) ammonium chloride;
The first described anhydrides compound is succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-ring [2.2.2] octyl group-5-alkene-2, 3-dicarboxylic anhydride, methyl-5-norbornylene-2, 3-dicarboxylic anhydride, dimethyl maleic anhydride, 3, 4, 5, 6-Tetra Hydro Phthalic Anhydride, six hydrogen-4-methyl nadic anhydrides, allyl succinic anhydride, trimellitic acid 1,2-anhydride, 1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, 4-chloro-phthalic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, phenylsuccinic acid acid anhydride, cyclohexyl dicarboxylic acid's acid anhydride, 2, 3-diphenyl maleic anhydride or cis-3-carboxyl glutaconic anhydride,
The first described epoxy compounds is specially epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min., 3,4-epoxy-1-tetrahydrobenzene, methyl isophthalic acid, 2-cyclopentenes epoxy material, (2,3-epoxypropyl) benzene, (1S, 2S)-1-phenylpropylene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second epoxy compounds is specially epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min., 3,4-epoxy-1-tetrahydrobenzene, methyl isophthalic acid, 2-cyclopentenes epoxy material, (2,3-epoxypropyl) benzene, (1S, 2S)-1-phenylpropylene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second anhydrides compound is selected from succinyl oxide respectively, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-ring [2.2.2] octyl group-5-alkene-2, 3-dicarboxylic anhydride, methyl-5-norbornylene-2, 3-dicarboxylic anhydride, dimethyl maleic anhydride, 3, 4, 5, 6-Tetra Hydro Phthalic Anhydride, six hydrogen-4-methyl nadic anhydrides, allyl succinic anhydride, trimellitic acid 1,2-anhydride, 1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, 4-chloro-phthalic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, phenylsuccinic acid acid anhydride, cyclohexyl dicarboxylic acid's acid anhydride, 2, 3-diphenyl maleic anhydride or cis-3-carboxyl glutaconic anhydride.
2. polyester block copolymer as claimed in claim 1, it is characterized by described preparation method, described step a) middle mol ratio is the first anhydrides compound: the first epoxy compounds: quaternary ammonium compound=100:100:1, or the first anhydrides compound: the first epoxy compounds: quaternary ammonium compound=50:50:1.
3. polyester block copolymer as claimed in claim 1, it is characterized by described preparation method, the first epoxy compounds described is epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane or Styrene oxide 98min..
4. polyester block copolymer as claimed in claim 1, it is characterized by described preparation method, the first described anhydrides compound is selected from succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2 respectively, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1,2-dicarboxylic acid anhydride, inner mold norbornene dicarboxylic anhydride, exo norbornene dicarboxylic anhydride.
5. polyester block copolymer as claimed in claim 1, is characterized by described preparation method, described step b) in the mol ratio of first ring oxygen compound and the second epoxy compounds and the second anhydrides compound be 1:1:1.
6. polyester block copolymer as claimed in claim 1, is characterized by described preparation method, described step a) and step b) described anhydrous solvent is toluene.
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| CN105199091B (en) * | 2015-08-12 | 2017-01-04 | 东华大学 | It is applicable to poly ion liquid type acid-base indicator and the preparation thereof of non-polar solven |
| CN107337785B (en) * | 2017-08-07 | 2019-04-16 | 南方医科大学 | A kind of water solubility antibacterial unsaturated aliphatic polyester and its preparation method and application |
| CN109679077B (en) * | 2018-12-09 | 2021-03-16 | 中山大学 | Method for preparing polyester by (thio) urea/organic base catalytic ring-opening copolymerization of epoxide and cyclic anhydride |
| CN109575261B (en) * | 2018-12-20 | 2024-02-06 | 浙江工业大学 | Isotactic chiral polyester compound and preparation method thereof |
| CN109914110A (en) * | 2019-02-20 | 2019-06-21 | 常州海瑞纺织品有限公司 | A kind of low temperature spinning sizing agent and preparation method thereof |
| CN110218303B (en) * | 2019-06-26 | 2021-02-12 | 西北师范大学 | Method for synthesizing aliphatic polyester by copolymerization of epoxide and cyclic anhydride under catalysis of metal-free catalyst |
| CN111944134B (en) * | 2020-08-24 | 2021-08-03 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN118359803A (en) * | 2024-06-20 | 2024-07-19 | 淄博云川化工有限公司 | Preparation method of low-foam block modified fatty alcohol polyether |
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