CN103642017B - A kind of blowing polyester elastomer and preparation method thereof - Google Patents
A kind of blowing polyester elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of blowing polyester elastomer and preparation method thereof, percentage, comprising: thermoplastic polyester elastomer 88.0 ~ 96.9%; Thermotropic liquid crystalline polyester macromolecular compound 3.0 ~ 10.0%; Isocyanurate compound 0.1 ~ 2.0%.Its preparation method first obtains thermoplastic polyester elastomer by esterification or transesterification reaction, polycondensation, then adds thermotropic liquid crystalline polyester macromolecular compound and isocyanurate compound reacts, and to obtain final product.The present invention by adding thermotropic liquid crystalline polyester macromolecular compound and isocyanurate compound in thermoplastic polyester elastomer, the melting index of the blowing polyester elastomer obtained is between 0.5-1.5, there is higher melt strength, product appearance better quality, and the course of processing is also than being easier to, possesses excellent mechanical property.
Description
Technical field
The present invention relates to polyester elastomer field, be specifically related to a kind of blowing polyester elastomer and preparation method thereof.
Background technology
Polyester thermoplastic elastomer has the characteristic of rubber and thermoplastic engineering plastic concurrently, at room temperature presents rubber property, and at high temperature presents the characteristic of thermoplastics, can plasticizing forming, easy to process.Its molecular structure is made up of hard section and soft section of two portions, and hard section is aromatic polyester (PET or PBT), and the polyethers lower using second-order transition temperature or polyester block are as soft section.The high-temperature behavior that the rigidity of its hard segment, polarity and crystallinity make it have and oil resistant, good solubility-resistence, the low Tg of soft chain segment polyethers and saturability make it have excellent low-temperature performance and resistance to deterioration.Its range of application, from the highly elastic fiber of initial stage textile industry, expands to the fields such as automobile, high polymer alloy, bio-medical material, electronic apparatus, film, becomes a kind of indispensable type material.
The processing characteristics of fluid property to polymkeric substance of polymkeric substance has very important significance.Because usually need polymkeric substance to have lower shear viscosity, such polymer processing is just than being easier to.Meanwhile, polymer melt also must have enough intensity and dimensional stability, once after melt forming, can keep dimensional stability in melt cools.Under normal circumstances, the melt strength of polymkeric substance can be improved by the molecular weight improving polymkeric substance.But after the molecular weight raising of polymkeric substance, its shear viscosity must improve, the pressure that when must cause forming polymer, needs are larger, the energy consumption of such equipment is just higher, sometimes also needs the equipment bought costly, even causes working (machining) efficiency lower.In addition, molecular weight improves, and processing temperature needs to improve, and causes polymkeric substance easily to be degraded.
Therefore, the melt strength improving polymkeric substance by introducing long-chain branch in polyester elastomer is a kind of very effective approach.As CN96109103 polyester elastomer and multifunction group epoxy modified polymer blend comprise PET resin, polyester elastomer, polyfunctional epoxy resin, nucleator and glass fibre.It is 220 ~ 270 DEG C that the preparation method of said composition has processing temperature, and fluidity of molten is good, and can obtain moulded work surface-brightening, shock strength is high, is easy to industrialized polyester product.The hard section that CN200680048076.5 provides a kind of polyester be made up of aromatic dicarboxylic acid and aliphatics or alicyclic diol to be formed and primarily of the soft section of thermoplastic polyester elastomer be combined into that aliphatic polycarbonate is formed, has outstanding thermotolerance, heat-resistant aging, water tolerance, photostabilization and cold property concurrently.CN02132277.5 has prepared polyester elastomer by melt phase polycondensation, add 1 in the elastomer) polyisocyanates of 0.3-5 part, 2) epoxy resin of 0.3-5 part, by twin screw reactive extrursion, can obtain smooth surface, melt strength exponential sum melting index is all less than the blowing level polyester elastomer of 3.0.CN200910247644.X discloses a kind of polyester elastomer foam materials with high fondant-strength and preparation method thereof, primarily of aromatic series dicarboxylic acid dimethyl ester (or aromatic series dioctyl phthalate), α, ω-aliphatic diol, polyether glycol and inorganic precursor composition, inorganic part in matrix material is by inorganic precursor in-situ preparation, the hydroxide groups of mineral surfaces and the hydroxyl at polyester elastomer two ends react, thus make some polyesters elastomer molecules chain be grafted to mineral surfaces, this matrix material has higher melt strength than pure polyester elastomer, foam elastomer can be obtained after adding whipping agent, the use temperature of this porous plastics is higher than general porous plastics 80 ~ 100 degree, and there is the feature of high strength.
But the actual effect of aforesaid method is limited, sometimes polymkeric substance rheological property do not improve as expected, be mainly manifested in melting index enough not low, add man-hour melt in blowing stable not.Although polymkeric substance has good rheological property sometimes, its crystal property is good not again, cause the performance of product even not, and the course of processing is very difficult to control, and repeatable poor, industrialization is difficult to realize.
Summary of the invention
The object of the invention is to overcome the shortcoming of the not good or processing difficulties of rheological that prior art exists, provide one to have higher melt intensity, crystal property is good, product appearance better quality, the blowing polyester elastomer of resistance toheat and good mechanical performance.
Another object of the present invention is the preparation method providing above-mentioned blowing polyester elastomer.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of blowing polyester elastomer, percentage, comprises following component:
Thermoplastic polyester elastomer 88.0 ~ 96.9%
Thermotropic liquid crystalline polyester macromolecular compound 3.0 ~ 10.0%
Isocyanurate compound 0.1 ~ 2.0%;
Described thermoplastic polyester elastomer comprises the hard section of polyester of 40-80wt% and soft section of the polyether ester composition of 20-60wt%; The limiting viscosity of described thermoplastic polyester elastomer is 1.3-2.1dl/g;
The hard section of described polyester is made up of aromatic acid or its esterified derivative and aliphatic dihydroxy alcohol;
Soft section of described polyether ester is made up of copolyether and aromatic acid or its esterified derivative;
Described aromatic acid is one or more the mixture in terephthalic acid, m-phthalic acid, naphthalic acid; Described aliphatic dihydroxy alcohol is one or more the mixture in 1,3-PD, 1,2-butyleneglycol, BDO, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol or Isosorbide.
Described copolyether is made up of polyoxyethylene glycol, polytetrahydrofuran and the polyether Glycols containing aromatic nucleus; The number-average molecular weight scope of described polyoxyethylene glycol and polytetrahydrofuran is 800 ~ 2000;
The described polyether Glycols containing aromatic nucleus has the molecular structure shown in formula II:
（Ⅱ）
Wherein, R
1for-H ,-CH
3or-C
2h
5; R
2-H ,-CH
3or-C
2h
5, a, b are numeral, are selected from the positive count meeting a+b=2 ~ 30 condition;
The weight of the described polyether Glycols containing aromatic nucleus accounts for the 3-15% of copolyether weight fraction.
Described thermotropic liquid crystalline polyester macromolecular compound has the structural formula of following formula I:
（Ⅰ）。
The melting range of described thermotropic liquid crystalline polyester macromolecular compound is 23-250 DEG C, and range of viscosities is 0.6 ~ 0.8dl/g.
Described isocyanurate compound comprises: B1:80% ~ 98wt%; B2:2% ~ 20wt%;
Described B1 is dimer or the tripolymer of the vulcabond of Carbodiimide-Modified, masked isocyanate or vulcabond; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, m-xylylene diisocyanate, isoflurane chalcone diisocyanate, hexamethylene-diisocyanate, 2,6-vulcabond methyl caproate, methylcyclohexane diisocyanate, 2,2,4-trimethylhexane diisocyanate, isopropylidene two (cyclohexyl diisocyanate-4), organosilicon vulcabond or containing any one in the diphenylmethanediisocyanate of carbodiimide or two or more mixtures.
Described B2 is isocyanuric acid ester cyclopolyol or isocyanurate ring polyether glycol, has the molecular structure as shown in formula III:
（Ⅲ）
Wherein, R
10, R
11, R
12identical or different, be-H ,-CH
3or-CH
2cH
3; M, n, k are numeral, are selected from the positive count meeting m+n+k=3 ~ 30 condition.
The preparation method of blowing polyester elastomer of the present invention, comprise the steps: first by aromatic acid or its esterified derivative, aliphatic dihydroxy alcohol, copolyether successively by esterification or transesterification reaction and polycondensation synthetic thermoplastic polyester elastomer; Then add thermotropic liquid crystalline polyester macromolecular compound, isocyanurate compound reaction, obtain blowing polyester elastomer.
Described thermotropic liquid crystalline polyester macromolecular compound, isocyanurate compound are different can carry out with the reaction of polyester elastomer in reactor, forcing machine or kneader.
In prior art, thermoplastic polyester is the polymkeric substance obtained by polycondensation by dibasic alcohol and diprotic acid.Via different types of diprotic acid and dibasic alcohol, the multiple polyester with different characteristics can be synthesized.Commercial principal item mainly contains: polybutylene terephthalate, polyethylene terephthalate, poly terephthalic acid-Isosorbide-5-Nitrae-cyclohexane dicarboxylates, PBN and thermotropic liquid crystalline polyester series of polymers, polyarylester, polyester elastomer etc.Along with the difference of polyester kind and manufacturer, also there is difference in its synthesis and preparation process and synthetic method.Usually, production of polyester has batch production process and continous way production process two kinds.Basic, the chemical process of polyester synthesis is substantially via esterification stage, transesterification reaction stage, polycondensation stage, and according to polyester kind and the difference of synthesizing control method, the Equipments Setting in each stage and processing requirement exist again respective feature.
Thermoplastic polyester elastomer of the present invention, its preparation method includes esterification stage, transesterification reaction stage and polycondensation stage, the processing condition of preparation method of the present invention can with reference to prior art, esterification in preparation method of the present invention or transesterification reaction phase temperature scope are 150 ~ 240 DEG C, preferably 170 ~ 220 DEG C, can carry out at ambient pressure, the polycondensation stage can carry out within the scope of reduced pressure and 160 ~ 250 DEG C, preferably 230 ~ 250 DEG C.
Catalyzed reaction can be carried out by adding appropriate catalyzer in reaction process when preparing polyester elastomer by polycondensation, this kind of catalyzer comprises the mixture based on element ti, Ge, La, Ce, Zn, Fe, Mn, Co, V, Zr, Li, Ca, especially the organo-metallic mixture of these elements, as the organic acid salt of these elements, alkoxyl group salt and acetylacetonate.
In polycondensation process, in order to prevent unnecessary degraded and/or crosslinking reaction, can add appropriate stablizer in this reaction process, this kind of stablizer comprises: trialkyl phosphite, trialkylphosphate, phosphoric acid, phosphorous acid, hindered phenolic antioxidant, amine antioxidants etc.
The content of the catalyzer added in polyester elastomer involved in the present invention is at 0.01 ‰ weight part to 3 ‰ weight parts, and preferably 0.5 ‰ weight parts are to 2 ‰ weight parts.For efficient Titanium series catalyst, its addition can control within the scope of the order of magnitude of 1,000,000/weight part.When reaction proceeds to remove unnecessary dibasic alcohol, or after formation oligopolymer, add catalyzer.Catalyzer can be made into certain density solution and add, and also can carry out catalyst based for different element certain compatibility and adds in reactant.
Compared with prior art, the present invention has following beneficial effect:
1) blowing polyester elastomer of the present invention is in thermoplastic polyester elastomer, introduce a small amount of thermotropic liquid crystalline polyester macromolecular material, the introducing of thermotropic liquid crystalline polyester macromolecular material can improve the crystal property of thermoplastic polyester, its crystallization velocity is increased, improve the mechanical property of material, reduce shaping cycle.Meanwhile, thermotropic liquid crystalline polyester macromolecular material add also can change thermoplastic polyester material soft or hard degree, improve Drawing abillity and mechanical property;
2) the present invention also by introducing isocyanurate compound in thermoplastic polyester elastomer, isocyanurate compound add the consistency that can improve thermoplastic polyester elastomer and thermotropic liquid crystalline polyester macromolecular material, make the terminal hydroxy group of isocyanate compound and polyester elastomer or end carboxyl react simultaneously, improve the melt strength of polyester elastomer; The multicomponent isocyanate added can make the molecule of polyester elastomer have branched structure, and then the melt strength of polyester elastomer is improved, and is conducive to the processing stability improving blow molded product;
3) introduce the polyether Glycols containing aromatic nucleus in the polyester soft segment of thermoplastic polyester elastomer of the present invention, the resistance toheat of polyester can be made to improve;
4) blowing polyester elastomer of the present invention can be used for blow molding, the melting index of the goods obtained between 0.5-1.5,
There is higher melt strength, product appearance better quality, and the course of processing is also than being easier to, possesses excellent mechanical property.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
In embodiment, the testing method of index of correlation is as follows:
1, characteristic viscosity determining method: 25 DEG C of mensuration, using phenol-orthodichlorobenzene mixed solution (mass ratio 3:2) as solvent, adopt the limiting viscosity of determination of ubbelohde viscometer sample, sample concentration is 0.005g/mL;
2, melting index test condition: 230 DEG C, 2.16kg;
,liquid crystal high molecular compound, self-control, with reference to prior art, with in the reactor of agitator, add a certain amount of refining PHB, diacetyl oxide and acetic acid, under the katalysis of sulfuric acid, then add polyethylene terephthalate (PET) and appropriate borontrifluoride two antimony, use nitrogen replacement air, under certain vacuum tightness, by heating material, then inflated with nitrogen, heat up and continue reaction, obtain the opaque PET/PHB copolyesters of khaki color.
embodiment 1
30gDMT is added in flask, 25gBDO and 25gPTMEG (Mn=1000), 0.25g is containing polyether Glycols (the wherein R1=R2=H of aromatic nucleus, a=b=1), add 20mg tetrabutyl titanate and 10mg antioxidant 1010, the normal pressure at 170 ~ 180 DEG C that heats up carries out transesterification reaction simultaneously, remove by-product carbinol, generate terephthalic acid and mix diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (100-200Pa) stage carries out copolycondensation, and temperature rises to 230 ~ 250 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.2dL/g, the 50g polyester elastomer obtained, 2g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor 109810mg joins in flask, 230 DEG C of meltings, then add 0.5g diphenylmethanediisocyanate, 0.02gB2(R10, R11, R12 are-H, m=n=k=1), the viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 30min, take out polymkeric substance, melting index is 0.6g/10min.
embodiment 2
Add 50gDMT at flask, 40gBDO and 56gPTMEG (Mn=1000), 2.5g are containing polyether Glycols (wherein R1=H, the R2=CH of aromatic nucleus
3, a=b=1) and add 50mg tetrabutyl titanate and 40mg antioxidant 1010 simultaneously, the normal pressure at 160 ~ 180 DEG C that heats up carries out transesterification reaction, remove by-product carbinol, generate terephthalic acid and mix diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (100-200Pa) stage carries out copolycondensation, and temperature rises to 230 ~ 250 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 0.82dL/g, the 50g polyester elastomer obtained, 5g thermotropic liquid crystalline polyester macromolecular compound, joins in flask, 240 DEG C of meltings, then 0.5g hexamethylene diisocyanate is added, 0.02gB2(R10, R11, R12 are-H, m=n=k=1) viscosity of polymkeric substance rises, fast at 240 DEG C of reaction 30min, take out polymkeric substance, melting index is 1.0g/10min.
embodiment 3
In flask, add 35gDMT, 20gBDO and 48gPTMEG (Mn=2000), 3g are containing polyether Glycols (wherein R1=H, the R2=CH of aromatic nucleus
3, a=b=1), add 50mg tetrabutyl titanate and 15mg antioxidant 1010 simultaneously, the normal pressure at 170 ~ 180 DEG C that heats up carries out transesterification reaction, removes by-product carbinol, generates terephthalic acid and mixes diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 230 ~ 250 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.5dL/g, the 50g polyester elastomer obtained, 4g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor TLTDP10mg is added in flask, 230 DEG C of meltings, then 0.5g hexamethylene diisocyanate is added, 0.03gB2(R10, R11, R12 are-H, m=n=k=2) viscosity of polymkeric substance rises, fast at 230 DEG C of reaction 7min, take out polymkeric substance, melting means is 0.7g/10min.
embodiment 4
In 20L reactor, add 4.5kgDMT, 3kgBDO and 4.2kgPTMEG (Mn=1500), 20g are containing polyether Glycols (wherein R1=H, the R2=CH of aromatic nucleus
3, a=b=2), add 1g tetrabutyl titanate and 0.5g antioxidant 1010 simultaneously, the normal pressure at 160 ~ 180 DEG C that heats up carries out transesterification reaction, removes by-product carbinol, generates terephthalic acid and mixes diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260 ~ 270 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; The molecular weight of gained polymers is 1.0dl/g, polyester elastomer 60g, 4g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor 44510mg joins 230 DEG C of melting 2min in Haake kneader, then 0.3g hexamethylene diisocyanate trimer is added, 0.01gB2(R10, R11, R12 are-H, m=1, n=k=2) moment of torsion rises fast, show that the viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 10min, take out polymkeric substance, melting index is 1.2g/10min.
embodiment 5
In flask, add 35gDMT, 54gBDO and 37gPTMEG (Mn=2000), 2.5g are containing polyether Glycols (wherein R1=H, the R2=CH of aromatic nucleus
3, a=b=2) and add 20mg tetrabutyl titanate and 15 antioxidant 1010s simultaneously, the normal pressure at 160 ~ 180 DEG C that heats up carries out transesterification reaction, remove by-product carbinol, generate terephthalic acid and mix diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260 ~ 270 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; The molecular weight of gained polymers is 1.0dl/g, polyester elastomer 60g, 3g thermotropic liquid crystalline polyester macromolecular compound, 10mg antioxidant 330 joins 230 DEG C of melting 2min in static mixer, then adds 0.3g hexamethylene diisocyanate trimer, 0.01gB2(R10, R11, R12 are-CH3, m=n=k=2) moment of torsion rises fast, shows that the viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 15min, take out polymkeric substance, melting index is 1.0g/10min.
embodiment 6
In flask, add 50gDMT, 54gBDO and 60gPTMEG (Mn=1000), 4g are containing polyether Glycols (wherein R1=-H, the R2=-CH of aromatic nucleus
3, a=b=2) and add 50mg tetrabutyl titanate and 20mg antioxidant 1010 simultaneously, the normal pressure at 160 ~ 180 DEG C that heats up carries out transesterification reaction, remove by-product carbinol, generate terephthalic acid and mix diol ester and its oligopolymer, when the methyl alcohol amount of reserving is 95% of theoretical amount, terminate transesterification reaction; After transesterification reaction after product pressure, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260 ~ 270 DEG C, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, disappear vacuum, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.7dL/g, the 50g polyester elastomer obtained, 3g thermotropic liquid crystalline polyester macromolecular compound, 20mg irgasfos 168, join in flask, 230 DEG C of meltings, then add 0.5g hexamethylene diisocyanate trimer, 0.01gB2(R10, R11, R12 are-CH3, m=n=k=2) viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 30min, take out polymkeric substance, melting index is 1.1g/10min.
embodiment 7
Polyester elastomer 60g is obtained by embodiment 6,3g thermotropic liquid crystalline polyester macromolecular compound, join 230 DEG C of melting 2min in Haake kneader, then add 0.3g hexamethylene diisocyanate trimer, 0.01gB2(R10, R11, R12 are-CH3, m=n=k=2) moment of torsion rises fast, show that the viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 15min, take out polymkeric substance, melting index is 0.8g/10min.
comparative example 1
Polyester elastomer 50g is obtained by embodiment 1, oxidation inhibitor 109810mg joins in flask, at 230 DEG C of melting 2min, then 0.5g diphenylmethanediisocyanate is added, moment of torsion rises fast, shows that the viscosity of polymkeric substance rises fast, at 230 DEG C of reaction 15min, take out polymkeric substance, melting index is 0.8g/10min.
comparative example 2
Obtain polyester elastomer 50g by embodiment 2 and join 240 DEG C of melting 2min in flask, then add 5g thermotropic liquid crystalline polyester macromolecular compound, at 230 DEG C of reaction 15min, take out polymkeric substance, melting index is 15g/10min.
comparative example 3
By the 50g polyester elastomer that embodiment 3 is obtained, 4g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor TLTDP10mg is added in flask, 230 DEG C of meltings, then add 0.5g hexamethylene diisocyanate, at 230 DEG C of reaction 15min, take out polymkeric substance, melting index is 3.0g/10min.
The performance test results of embodiment 1 ~ 7 and the blowing polyester elastomer obtained by comparative example 1 ~ 3 is as shown in table 1, and the hard segment content of product is confirmed by nuclear-magnetism, and the total content of soft or hard section is 100%.
Table 1
T1/2 is that elongation at break is down to the half of the raw material time used.
As can be seen from the above results, the present invention by adding thermotropic liquid crystalline polyester macromolecular compound and isocyanurate compound in thermoplastic polyester elastomer, the goods obtained melting index between 0.6-1.2, there is higher melt strength, the smooth in appearance of product, and possess excellent mechanical property.
Claims (8)
1. a blowing polyester elastomer, is characterized in that, percentage, comprises following component:
Thermoplastic polyester elastomer 88.0 ~ 96.9%
Thermotropic liquid crystalline polyester macromolecular compound 3.0 ~ 10.0%
Isocyanurate compound 0.1 ~ 2.0%
Described isocyanurate compound comprises:
B1：80%~98wt%；
B2：2%~20wt%；
Described B1 is dimer or the tripolymer of the vulcabond of Carbodiimide-Modified, masked isocyanate or vulcabond;
Described B2 is isocyanuric acid ester cyclopolyol or isocyanurate ring polyether glycol, has the molecular structure as shown in formula II:
（Ⅱ）
Wherein, R
10, R
11, R
12identical or different, be-H ,-CH
3or-CH
2cH
3; M, n, k are numeral, are selected from the positive count meeting m+n+k=3 ~ 30 condition.
2. blowing polyester elastomer according to claim 1, is characterized in that, the melting range of described thermotropic liquid crystalline polyester macromolecular compound is 23-250 DEG C, and range of viscosities is 0.6 ~ 0.8dl/g, has the structural formula of following formula I:
（Ⅰ）。
3. a blowing polyester elastomer according to claim 1, it is characterized in that, described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, m-xylylene diisocyanate, isoflurane chalcone diisocyanate, hexamethylene-diisocyanate, 2, 6-vulcabond methyl caproate, methylcyclohexane diisocyanate, 2, 2, 4-trimethylhexane diisocyanate, isopropylidene two (cyclohexyl diisocyanate-4), organosilicon vulcabond or containing any one or the two or more mixtures in the diphenylmethanediisocyanate of carbodiimide.
4. blowing polyester elastomer according to claim 1, is characterized in that, described thermoplastic polyester elastomer comprises the hard section of polyester of 40-80wt% and soft section of the polyether ester composition of 20-60wt%; The limiting viscosity of described thermoplastic polyester elastomer is 1.3-2.1dl/g;
The hard section of described polyester is made up of aromatic acid or its esterified derivative and aliphatic dihydroxy alcohol;
Soft section of described polyether ester is made up of copolyether and aromatic acid or its esterified derivative.
5. blowing polyester elastomer according to claim 4, is characterized in that, described aromatic acid is one or more the mixture in terephthalic acid, m-phthalic acid, naphthalic acid; Described aliphatic dihydroxy alcohol is one or more the mixture in 1,3-PD, 1,2-butyleneglycol, BDO, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol or Isosorbide.
6. blowing polyester elastomer according to claim 4, is characterized in that, described copolyether is made up of polyoxyethylene glycol, polytetrahydrofuran and the polyether Glycols containing aromatic nucleus; The number-average molecular weight scope of described polyoxyethylene glycol and polytetrahydrofuran is 800 ~ 2000;
The described polyether Glycols containing aromatic nucleus has the molecular structure shown in formula III:
（Ⅲ）
Wherein, R
1for-H ,-CH
3or-C
2h
5; R
2-H ,-CH
3or-C
2h
5, a, b are numeral, are selected from the positive count meeting a+b=2 ~ 30 condition;
The weight of the described polyether Glycols containing aromatic nucleus accounts for the 3-15% of copolyether weight fraction.
7. the preparation method of blowing polyester elastomer described in any one of claim 1 ~ 6, it is characterized in that, comprise the steps: first to obtain thermoplastic polyester elastomer by esterification or transesterification reaction, polycondensation, then add thermotropic liquid crystalline polyester macromolecular compound and isocyanurate compound reacts, obtain blowing polyester elastomer.
8. the preparation method of blowing polyester elastomer according to claim 7, it is characterized in that, described esterification or transesterification reaction are carried out at normal pressure 170 ~ 220 DEG C; Described polycondensation, at decompression 100 ~ 200Pa, is carried out at 230 ~ 250 DEG C.
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| KR20180067396A (en) * | 2016-12-09 | 2018-06-20 | 주식회사 삼양사 | Thermoplastic polyether ester elastomer comprising anhydrosugar alcohol derivative and method for preparing the same |
| KR101797579B1 (en) | 2017-08-14 | 2017-11-15 | 정우화인 주식회사 | Method of producing Polyurethane Foam Board and Polyurethane Foam Pannel with Isocyanuric Polyol and Polyester Polyol |
| KR102139366B1 (en) * | 2017-12-29 | 2020-07-29 | 주식회사 삼양사 | Thermoplastic elastomer resin composition |
| CN109535408B (en) * | 2018-11-21 | 2021-07-09 | 广东中瀚新材料有限公司 | Fluorine-silicon-containing thermoplastic polyester elastomer material and preparation method and application thereof |
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| US6120895A (en) * | 1996-09-20 | 2000-09-19 | Basf Aktiengesellschaft | Biodegradable polyesters |
| US6284333B1 (en) * | 1997-09-10 | 2001-09-04 | Scimed Life Systems, Inc. | Medical devices made from polymer blends containing low melting temperature liquid crystal polymers |
| CN1480478A (en) * | 2002-09-04 | 2004-03-10 | 中纺投资发展股份有限公司 | Method for preparing polyether ester elastomer in blow molding grade |
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