CN104151535A - Segmented polyester copolymer and preparation method thereof - Google Patents
Segmented polyester copolymer and preparation method thereof Download PDFInfo
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- CN104151535A CN104151535A CN201410389543.7A CN201410389543A CN104151535A CN 104151535 A CN104151535 A CN 104151535A CN 201410389543 A CN201410389543 A CN 201410389543A CN 104151535 A CN104151535 A CN 104151535A
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Abstract
The invention discloses a segmented polyester copolymer and a preparation method thereof. A structural formula of the copolymer is shown as a formula (I). An organic catalyst is directly adopted, so that the steps are simple and convenient in a polymer purification process, and heavy metal ions in a conventional method cannot be remained in a polymer. The esterification reaction of acid anhydride and an epoxy compound can be selectively catalyzed to obtain the polyester copolymer with geometrical isomerism chain segments, and generation of byproducts caused by catalysis of the open-loop auto-polymerization reaction of an epoxy group is avoided by the nuclear magnetic analysis of products.
Description
Technical field
The present invention relates to technical field of polymer, relating in particular to stereoselectivity open loop that under organic catalysis, meso-anhydride and epoxy compounds occur generates and removes symmetry, Stereoselective (trans-, cis-) enantiomorph product, takes the reinforced method of order to prepare the polyester copolymer with rotamerism segment.
Background technology
Aliphatic polyester is biodegradable because of it, extremely people's favor.But adopt ordinary method be difficult to obtain high-molecular aliphatic polyester, and its thermostability and mechanical property poor, limited the application of aliphatic polyester.Therefore,, in order to expand the range of application of aliphatic polyester, need to improve the molecular weight of aliphatic polyester, and aliphatic polyester is carried out to modification.
The common method of improving polyester property is to carry out copolymerization with other monomers or polymkeric substance.As US Patent No. 2006/0252864A1 discloses employing polybutylene terephthalate, butyleneglycol, caprolactone etc. through transesterification reaction, then carrying out polycondensation, finally obtain the multipolymer of PBT-PCL, but in reaction process, polybutylene terephthalate inevitably participates in transesterification reaction, causes wherein soft section to 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 olefines segmented copolymer is often comparatively ripe again, but polyester type block copolymer and preparation method thereof and imperfection, the method that bibliographical information is maximum is ester-interchange method (Chinese patent 200810118233.6, Chinese patent 201110416884.5), adopt the polyester of two kinds of high molecular, under catalyzer and high temperature, transesterification reaction occurs, as Chinese patent 200910092100.0 disclosed a kind of biodegradable aliphatic polyester/aromatic polyester multi-block copolymers and preparation method thereof and application, it is the polyester prepolyer A of synthetic fat family first, resynthesis aliphatics or aromatic polyester B, synthetic segmented copolymer under the effect of chainextender, its advantage with crystallinity aliphatic polyester in introduced rigidity non-crystalline polyester segment, can obtain good mechanical property, 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 polyreaction, 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-Peng Wu and Xiao-Bi ng Lu are at J.Am.Chem.Soc.2012,134, the poly-cyclohexene carbonate (PCHC) that the degree of isotacticity of 5682 – 5688 and Chinese patent CN102229745 A report is 98%, fusing point (Tm) is up to 216 DEG C.Crystal habit research shows simultaneously, and the spherocrystal of single optical purity (R)-PCHC is grown in a clockwise direction with the spherocrystal of (the S)-PCHC that counterclockwise grows.Two kinds of spherocrystal balanced mix obtain the crystalline morphology of lath-shaped, and have shown stronger heat resistanceheat resistant deformability (fusing point is up to 230 DEG C).And for example Jian-Zhao Liu and Ben-Zhong Tang are at Chem.Rev.2009, 109, in 5799 – 5867 polyacetylene (PA) of report structurally carbon atom be that the form that replaces with Dan Shuanjian is connected with each other, its configuration has trans, three kinds of isomer of cis-trans and anti-cis, study and find that sulfuration all has considerable influence for the relative stability of polyacetylene cis-trans-isomer with relative conductivity etc. by sulfuration, the most stable and conductivity is best on the transconfiguration energy of PA, after sulfuration, the relative conductivity of cis-structure 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, once and 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, the polyester block copolymer that obtains a kind of novel texture by controlling charging process, adds the ratio of acid anhydrides and epoxy can obtain the polyester copolymer with (trans-or cis-) structure by control particularly exactly.Interior type-norbornene dicarboxylic anhydride and the external form-norbornene dicarboxylic anhydride of selecting us to select of material, the polymkeric substance obtaining is the new texture with rotamerism segment.In preparation method, the selection of acid anhydrides and epoxy is most important, and for example the acid anhydrides of interior type and the polymkeric substance that epoxide polymerization obtains are trans-configurations, and the acid anhydrides of external form and epoxide polymerization obtain polymkeric substance can keep cis-configuration.Meanwhile, adopt quaternary ammonium salt organic catalyst, efficiently catalysis acid anhydrides and epoxy compounds esterification fast, and by the regulation and control of charging process, make 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 suc 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 dissolving, 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) after the second epoxy compounds and the second anhydrides compound be dissolved in dissolve in anhydrous solvent, be added to and in the first polymerization reactor, carry out the second polyreaction, 60～110 DEG C of temperature of reaction, 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-(triphenyl phosphoranyl) ammonium chloride.
Described the first anhydrides compound is succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-encircles [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 anhydride, allyl group succinyl oxide, 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 the first 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-phenyl propylidene 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-phenyl propylidene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second anhydrides compound is selected from respectively succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-encircles [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 anhydride, allyl group succinyl oxide, 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, described the first epoxy compounds is selected from respectively epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane, Styrene oxide 98min..
Preferably, described the first anhydrides compound is selected from respectively succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2,4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1,2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form 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 be preferably toluene.
Beneficial effect
The invention provides a kind of epoxy compounds and acid anhydrides copolymerization and prepare the method for segmented copolymer, the method adopts PPNCl (two-(triphenyl phosphoranyl) ammonium chloride) as catalyzer, catalysis acid anhydrides and open loop of epoxy compound polyreaction at 60～110 DEG C of temperature of reaction, can, by controlling the structure of order of addition(of ingredients) regulation and control multipolymer, obtain the polyester copolymer with rotamerism segment.Catalysis anhydride epoxy relevant to bibliographical information ring-opening polymerization, we do not adopt the method that adds metal catalyst, but directly adopting organic catalyst, this step in polymer purification process is easy, and heavy metal ion in can residual traditional method in polymkeric substance.The method is the esterification of catalysis acid anhydrides and epoxy compounds optionally, by product nmr analysis find not can catalysis epoxide group open loop self-polymeric reaction generate by product.
Brief description of the drawings
Fig. 1 is gained the first polymerisate and block polymerization product nuclear-magnetism stacking diagram in embodiment 1.
Embodiment:
Embodiment 1
Under ar gas environment, get the withstand voltage reaction tubes of 25ml heavy wall of dried and clean, add 5mmol external form norbornene dicarboxylic anhydride, 0.1mmol pair-(triphenyl phosphoranyl) 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; Under argon shield, add again the mixing solutions (toluene amount can make quaternary ammonium compound, epoxy compounds, acid anhydrides etc. dissolve) of type norbornene dicarboxylic anhydride in 5mmol, 5mmol epoxy cyclohexane and 1ml toluene; at 110 DEG C, react after 4h; pour reaction system in the methyl alcohol that volume is solvent 50ml sedimentation; filter; washing; the product obtaining, at 45 DEG C of vacuum-drying 24h, is obtained to R
1, R
3for the norbornylene of prosposition replacement; R
2, R
4it is the polyester block copolymer of 1,2 substituted cyclohexane.
Wherein, m value is 15, n value is that 16 (the measured molecular-weight average of GPC can prove that m value is at 1-2500, 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 be exactly the molecular weight of the each segment number that is multiplied by segment be m, n value), yield 86%, it is 8200 that GPC records molecular-weight average, molecular weight distribution 1.4.
Figure above in Fig. 1 is in the time of the product that reaction obtains by external form norbornene dicarboxylic anhydride and epoxy cyclohexane polymerization, in nuclear-magnetism figure only there is the unimodal of hydrogen atom on the two keys of cis structure in 6.17ppm place, illustrate that polymkeric substance keeps cis configuration, can see the characteristic peak of external form norbornylene ring and cyclohexyl, figure is in the time adding interior type norbornylene acid anhydrides and epoxy cyclohexane prepare segmented copolymer after external form acid anhydrides and epoxide polymerization below, will be 6.25 on nuclear-magnetism figure, 6.02 have more bimodal that the two key hydrogen of trans structure splits point, compare the characteristic peak that has increased interior type norbornylene ring in Tu Bentu, the block polyester copolymer that has obtained one section of trans configuration of one section of cis configuration is described, and do not find in the drawings to occur at 3.8ppm place epoxy cyclohexane autohemagglutination product peak.
Embodiment 2
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 84%, it is that 7050, m value is that 13, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 3
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol 3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 85%, it is that 5775, m value is that 11, n value is 14 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 4
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 10mmol Tetra hydro Phthalic anhydride, epoxy compounds are 10mmol epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the phenyl ring of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 73%, it is that 15120, m value is that 29, n value is 30 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 5
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 86%, it is that 7850, m value is that 15, n value is 16 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 6
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are the mixture of 5mmol epoxy cyclohexane and 1ml toluene.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 81%, it is that 6799, m value is that 13, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 7
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 10mmol epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 73%, it is that 12590, m value is that 24, n value is 30 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 8
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the phenyl ring of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 82%, it is that 7601, m value is that 14, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 9
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the hexanaphthene of 1,2 replacement.Yield 82%, it is that 7579, m value is that 15, n value is 16 that GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 10
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1, R
3for the norbornylene of prosposition replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 89%, it is that 8310, m value is that 16, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 11
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol epoxy chloropropane; Step b) middle acid anhydrides is that 10mmol succinyl oxide, epoxy compounds are 10mmol epoxy chloropropane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 80%, it is that 13080, m value is that 25, n value is 39 that GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 12
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 87%, it is that 7365, m value is that 15, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 13
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the phenyl ring of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 88%, it is that 7964, m value is that 15, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 14
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 86%, it is that 7685, m value is that 14, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 15
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol epoxy chloropropane; Step b) middle acid anhydrides is that 10mmol succinyl oxide, epoxy compounds are 10mmol epoxy chloropropane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 61%, it is that 9973, m value is that 19, n value is 26 that GPC records molecular-weight average, molecular weight distribution 1.9.
Embodiment 16
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 74%, it is that 6211, m value is that 12, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 17
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the phenyl ring of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 72%, it is that 6600, m value is that 13, n value is 14 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 18
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the chloropropane of 1,2 replacement.Yield 73%, it is that 6500, m value is that 12, n value is 14 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 19
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1, R
3for the norbornylene of prosposition replacement; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.Yield 85%, it is that 17620, m value is that 34, n value is 31 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 20
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 91%, it is that 8502, m value is that 16, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 21
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol 3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 88%, it is that 9800, m value is that 21, n value is 20 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 22
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3be the benzene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 89%, it is that 9094, m value is that 18, n value is 16 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 23
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 83%, it is that 20200, m value is that 34, n value is 38 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 24
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 74%, it is that 6913, m value is that 13, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 25
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 77%, it is that 7362, m value is that 14, n value is 16 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 26
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3be the benzene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 76%, it is that 7766, m value is that 15, n value is 14 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 27
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol 4 vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane.Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the polyester block copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 78%, it is that 15076, m value is that 30, n value is 28 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 28
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min..R
1, R
3for the norbornylene of prosposition replacement; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.Yield 90%, it is that 10040, m value is that 19, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 29
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the polyester block copolymer of the benzene of 1 replacement.Yield 90%, it is that 8277, m value is that 16, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 30
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 88%, it is that 8286, m value is that 16, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 31
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that 10mmol Tetra hydro Phthalic anhydride, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene that prosposition replaces, R
3be the benzene of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 82%, it is that 16520, m value is that 32, n value is 31 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 32
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene that prosposition replaces, R
3it is the pentamethylene of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 89%, it is that 8835, m value is that 17, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 33
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the interior type norbornylene that prosposition replaces, R
3for hydrogen; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 74%, it is that 6805, m value is that 13, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.5
Embodiment 34
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the interior type norbornylene that prosposition replaces, R
3it is the cyclopropane of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 77%, it is that 7250, m value is that 14, n value is 16 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 35
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol Styrene oxide 98min.; Step b) middle acid anhydrides is that 10mmol Tetra hydro Phthalic anhydride, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1for the interior type norbornylene that prosposition replaces, R
3be the benzene of 1,2 replacement; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 76%, it is that 15310, m value is that 29, n value is 28 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 36
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min.; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the interior type norbornylene that prosposition replaces, R
3be 1,, the pentamethylene of 2 replacements; R
2, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 78%, it is that 7743, m value is that 15, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 37
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min..R
1for the external form norbornylene that prosposition replaces, R
3for the interior type norbornylene of prosposition replacement; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 85%, it is that 8734, m value is that 17, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 38
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol succinyl oxide, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 88%, it is that 6710, m value is that 13, n value is 15 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 39
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 cyclopropane replacing, R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 87%, it is that 17920, m value is that 35, n value is 39 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 40
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3be 1,2 benzene replacing; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 89%, it is that 9132, m value is that 17, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 41
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3it is 1,2 pentamethylene replacing; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 88%, it is that 9013, m value is that 15, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 42
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene R of prosposition replacement
3for the interior type norbornylene of prosposition replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 90%, it is that 11200, m value is that 19, n value is 20 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 43
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol succinyl oxide, epoxy compounds are 10mmol epoxy chloropropane; Step b) middle acid anhydrides is that 10mmol succinyl oxide, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 83%, it is that 18931, m value is that 41, n value is 43 that GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 44
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3it is the cyclopropane of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 88%, it is that 9160, m value is that 20, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 45
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3be the benzene of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 89%, it is that 9534, m value is that 17, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 46
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3it is the pentamethylene of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 88%, it is that 9331, m value is that 18, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 47
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 10mmol, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1for the external form norbornylene that prosposition replaces, R
3for the interior type norbornylene of prosposition replacement; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 81%, it is that 25330, m value is that 43, n value is 45 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 48
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol succinyl oxide, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3for hydrogen; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 90%, it is that 8990, m value is that 20, n value is 21 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 49
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3it is the cyclopropane of 1,2 replacement; R
2be 1,2 vinyl cyclohexane replacing, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 89%, it is that 9340, m value is that 20, n value is 20 that GPC records molecular-weight average, molecular weight distribution 1.7.
Embodiment 50
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol Styrene oxide 98min..Obtain R
1, R
3be the benzene of 1,2 replacement; R
2be 1,2 vinyl cyclohexane replacing, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 90%, it is that 9940, m value is that 18, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 51
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 10mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 10mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 10mmol Styrene oxide 98min..Obtain R
1, R
3it is the pentamethylene of 1,2 replacement; R
2be 1,2 vinyl cyclohexane replacing, R
4it is the block polyester copolymer of the benzene of 1 replacement.Yield 90%, it is that 18820, m value is that 36, n value is 37 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 52
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for the interior type norbornylene of prosposition replacement; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 91%, it is that 10021, m value is that 20, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 53
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol succinyl oxide, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1, R
3for hydrogen; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 92%, it is that 8130, m value is that 21, n value is 21 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 54
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1, R
3it is the cyclopropane of 1,2 replacement; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 89%, it is that 8744, m value is that 22, n value is 21 that GPC records molecular-weight average, molecular weight distribution 1.5.
Embodiment 55
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol Tetra hydro Phthalic anhydride, epoxy compounds are 10mmol epoxy cyclohexane; Step b) middle acid anhydrides is that 10mmol Tetra hydro Phthalic anhydride, epoxy compounds are 10mmol epoxy chloropropane.Obtain R
1, R
3be the benzene of 1,2 replacement; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 84%, it is that 19133, m value is that 38, n value is 40 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 56
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy chloropropane.Obtain R
1, R
3it is the pentamethylene of 1,2 replacement; R
2be the hexanaphthene of 1,2 replacement, R
4it is the block polyester copolymer of the chloropropane of 1,2 replacement.Yield 86%, it is that 9022, m value is that 20, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 57
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for the interior type norbornylene of prosposition replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 87%, it is that 10400, m value is that 18, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 58
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol succinyl oxide, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that 5mmol succinyl oxide, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3for hydrogen; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 91%, it is that 8703, m value is that 20, n value is 19 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 59
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 10mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 10mmol epoxy chloropropane; Step b) middle acid anhydrides is 10mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3it is the cyclopropane of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 89%, it is that 15650, m value is that 30, n value is 33 that GPC records molecular-weight average, molecular weight distribution 1.8.
Embodiment 60
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3be the benzene of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 88%, it is that 9243, m value is that 17, n value is 17 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 61
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy chloropropane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane.Obtain R
1, R
3it is the pentamethylene of 1,2 replacement; R
2be the chloropropane of 1,2 replacement, R
4it is the block polyester copolymer of the vinyl cyclohexane of 1,2 replacement.Yield 87%, it is that 9130, m value is that 17, n value is 18 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 62
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol external form norbornene dicarboxylic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that type norbornene dicarboxylic anhydride in 5mmol, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1for the external form norbornylene that prosposition replaces, R
3for the interior type norbornylene of prosposition replacement; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the hexanaphthene of 1,2 replacement.Yield 91%, it is that 11230, m value is that 22, n value is 21 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 63
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 10mmol succinyl oxide, epoxy compounds are 10mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 10mmol succinyl oxide, epoxy compounds are 10mmol epoxy cyclohexane.Obtain R
1, R
3for hydrogen; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the hexanaphthene of 1,2 replacement.Yield 85%, it is that 17340, m value is that 33, n value is 44 that GPC records molecular-weight average, molecular weight distribution 1.6.
Embodiment 64
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol3-oxabicyclo [3.1.0] hexane-2,4-diketone, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol3-oxabicyclo [3.1.0] hexane-2, and 4-diketone, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1, R
3it is the cyclopropane of 1,2 replacement; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the hexanaphthene of 1,2 replacement.Yield 86%, it is that 9134, m value is that 22, n value is 21 that GPC records molecular-weight average, molecular weight distribution 1.3.
Embodiment 65
All the other operate with embodiment 1, difference be step a) in acid anhydrides be that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is that 5mmol Tetra hydro Phthalic anhydride, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1, R
3be the benzene of 1,2 replacement; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the hexanaphthene of 1,2 replacement.Yield 87%, it is that 9587, m value is that 20, n value is 20 that GPC records molecular-weight average, molecular weight distribution 1.4.
Embodiment 66
All the other operate with embodiment 1, difference be step a) in acid anhydrides be 5mmol pentamethylene-1,2-dicarboxylic acid anhydride, epoxy compounds are 5mmol4-vinyl epoxy cyclohexane; Step b) middle acid anhydrides is 5mmol pentamethylene-1, and 2-dicarboxylic acid anhydride, epoxy compounds are 5mmol epoxy cyclohexane.Obtain R
1, R
3it is the pentamethylene of 1,2 replacement; R
2be the vinyl cyclohexane of 1,2 replacement, R
4it is the block polyester copolymer of the hexanaphthene of 1,2 replacement.Yield 86%, it is that 9350, m value is that 20, n value is 19 that 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 (7)
1. a polyester block copolymer, is characterized by the structural formula of described multipolymer suc 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。
2. the preparation method of polyester block copolymer as claimed in claim 1, is characterized by and comprise the following steps:
A) under argon shield, quaternary ammonium compound, the first epoxy compounds and the first acid anhydrides are joined after anhydrous solvent dissolving, 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) after the second epoxy compounds and the second anhydrides compound be dissolved in dissolve in anhydrous solvent, be added to and in the first polymerization reactor, carry out the second polyreaction, 60～110 DEG C of temperature of reaction, 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-(triphenyl phosphoranyl) ammonium chloride;
Described the first anhydrides compound is succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-encircles [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 anhydride, allyl group succinyl oxide, 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 the first 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-phenyl propylidene 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-phenyl propylidene epoxy, cyclopentane epoxide, benzyloxymethyl oxyethane, epoxypropyl phenyl ether or epoxypropyl-2-methyl phenyl ether;
Described the second anhydrides compound is selected from respectively succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2, 4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1, 2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form norbornene dicarboxylic anhydride, outward-3, 6-epoxy-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, endo-bis-encircles [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 anhydride, allyl group succinyl oxide, 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.
3. the preparation method of polyester block copolymer as claimed in claim 2, step described in it is characterized by 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.
4. the preparation method of polyester block copolymer as claimed in claim 2, is characterized by described the first epoxy compounds and is preferably epoxy chloropropane, epoxy cyclohexane, 4 vinyl epoxy cyclohexane or Styrene oxide 98min..
5. the preparation method of polyester block copolymer as claimed in claim 2, it is characterized by preferred, described the first anhydrides compound is selected from respectively succinyl oxide, 3-oxabicyclo [3.1.0] hexane-2,4-diketone, Tetra hydro Phthalic anhydride, pentamethylene-1,2-dicarboxylic acid anhydride, interior type norbornene dicarboxylic anhydride, external form norbornene dicarboxylic anhydride.
6. the preparation method of polyester block copolymer as claimed in claim 2, it is characterized by 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.
7. the preparation method of polyester block copolymer as claimed in claim 2, it is characterized by described step a) and step b) described anhydrous solvent be preferably toluene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1497370A2 (en) * | 2002-04-22 | 2005-01-19 | NOVAMONT S.p.A. | Biodegradable polyesters obtained by reactive extrusion |
| CN102020772A (en) * | 2009-09-15 | 2011-04-20 | 中国科学院化学研究所 | Biodegradable aliphatic polyester / aromatic polyester multi-block copolymer and preparation method and application thereof |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| CN103772677A (en) * | 2013-12-23 | 2014-05-07 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and preparation method thereof |
-
2014
- 2014-08-09 CN CN201410389543.7A patent/CN104151535B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1497370A2 (en) * | 2002-04-22 | 2005-01-19 | NOVAMONT S.p.A. | Biodegradable polyesters obtained by reactive extrusion |
| CN102020772A (en) * | 2009-09-15 | 2011-04-20 | 中国科学院化学研究所 | Biodegradable aliphatic polyester / aromatic polyester multi-block copolymer and preparation method and application thereof |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| CN103772677A (en) * | 2013-12-23 | 2014-05-07 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and preparation method thereof |
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