CN103642017A - Polyester elastomer for blow molding and preparation method thereof - Google Patents
Polyester elastomer for blow molding and preparation method thereof Download PDFInfo
- Publication number
- CN103642017A CN103642017A CN201310537313.6A CN201310537313A CN103642017A CN 103642017 A CN103642017 A CN 103642017A CN 201310537313 A CN201310537313 A CN 201310537313A CN 103642017 A CN103642017 A CN 103642017A
- Authority
- CN
- China
- Prior art keywords
- polyester elastomer
- polyester
- blowing
- vulcabond
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(N*O)OC Chemical compound CC(N*O)OC 0.000 description 2
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polyester elastomer for blow molding and preparation method thereof, and the polyester elastomer comprises the following components by weight percent: 88.0-96.9% of thermoplastic polyester elastomer, 3.0-10.0% of polyester liquid crystal macromolecular compounds, and 0.1-2.0% of isocyanurate compounds. The preparation method comprises the following steps: obtaining thermoplastic polyester elastomers by esterification reaction or transesterification reaction and condensation polymerization; adding polyester liquid crystal macromolecular compound and isocyanurate compound for reaction; obtaining the product. According to the invention, thermoplastic polyester elastomers are added with polyester liquid crystal macromolecular compounds and isocyanurate compounds, and the melt index of the obtained polyester elastomer for blow molding is between 0.5-1.5, and the product has higher melt-strength with good appearance quality, easier processing process and excellent mechanical properties.
Description
Technical field
The present invention relates to polyester elastomer field, be specifically related to polyester elastomer and preparation method thereof for a kind of blowing.
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, and easy to process.Its molecular structure forms with soft section of two portions by hard section, and hard section is aromatic polyester (PET or PBT), and the polyethers that the second-order transition temperature of usining is lower or polyester block are as soft section.The rigidity of its hard segment, polarity and crystallinity make high-temperature behavior that it has had and anti-oil, good solubility-resistence, and the low Tg of soft chain segment polyethers and saturability make it have good 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 fluid property of polymkeric substance has very important significance to the processing characteristics of polymkeric substance.Because conventionally need polymkeric substance to have lower shear viscosity, polymer processing is just than being easier to like this.Meanwhile, polymer melt also must have enough intensity and dimensional stability, once after melt forming, can keep dimensional stability in melt cools.Generally, can improve by improving the molecular weight of polymkeric substance the melt strength of polymkeric substance.Yet after the molecular weight of polymkeric substance improves, its shear viscosity must improve, the larger pressure of needs when must cause forming polymer, the energy consumption of equipment is just higher like this, sometimes also needs to buy more expensive equipment, 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 that, improves polymkeric substance by introduce long-chain branch in polyester elastomer is a kind of very effective approach.As CN96109103 comprises PET resin with polyester elastomer and multifunction group epoxy modified polymer blend, polyester elastomer, polyfunctional epoxy resin, nucleator and glass fibre.It is 220 ~ 270 ℃ that the preparation method of said composition has processing temperature, and fluidity of molten is good, can obtain moulded work surface-brightening, and shock strength is high, is easy to industrialized polyester product.CN200680048076.5 provides a kind of polyester consisting of aromatic dicarboxylic acid and aliphatics or alicyclic diol formed hard section and the soft section of thermoplastic polyester elastomer being combined into mainly consisting of aliphatic polycarbonate, and has outstanding thermotolerance, heat-resistant aging, water tolerance, photostabilization and cold property concurrently.CN02132277.5 has prepared polyester elastomer by melt phase polycondensation, in elastomerics, add 1) polyisocyanates of 0.3-5 part, 2) epoxy resin of 0.3-5 part, by twin screw, react and extrude, can obtain smooth surface, melt strength exponential sum melting index is all less than 3.0 blowing level polyester elastomer.CN200910247644.X discloses a kind of polyester elastomer foam materials with high fondant-strength and preparation method thereof, mainly by aromatic series dioctyl phthalate dimethyl ester (or aromatic series dioctyl phthalate), α, ω-aliphatic diol, polyether glycol and inorganic precursor form, inorganic part in matrix material is to be generated by inorganic precursor original position, the hydroxide radical group on inorganics surface and the hydroxyl at polyester elastomer two ends react, thereby make part polyester elastomer molecular chain be grafted to inorganics surface, this matrix material has higher melt strength than pure polyester elastomer, after adding whipping agent, can make foam elastomer, the use temperature of this porous plastics is than high 80～100 degree of general porous plastics, and there is high-intensity feature.
Yet the actual effect of aforesaid method is limited, sometimes polymkeric substance rheological property improve as expected, be mainly manifested in melting index enough not low, in blowing, add man-hour melt stable not.Although polymkeric substance has a good rheological property sometimes, its crystal property is good not again, causes 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 shortcoming that the object of the invention is to overcome the not good or processing difficulties of rheological that prior art exists, provides a kind of higher melt intensity that has, and 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 to provide the preparation method of above-mentioned blowing with polyester elastomer.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A blowing polyester elastomer, percentage ratio meter by weight, 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 soft section of composition of polyether ester of the hard section of the polyester of 40-80wt% and 20-60wt%; The limiting viscosity of described thermoplastic polyester elastomer is 1.3-2.1dl/g;
The hard section of described polyester is comprised of aromatic acid or its esterified derivative and aliphatic dihydroxy alcohol;
Soft section of described polyether ester is comprised 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 1,3-PD, 1, the mixture of one or more in 2-butyleneglycol, BDO, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol or Isosorbide.
Described copolyether forms by polyoxyethylene glycol, polytetrahydrofuran with containing the polyether Glycols of 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
2be-H ,-CH
3or-C
2h
5, a, b are numeral, are selected from the positive count that meets 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 ℃, and range of viscosities is 0.6 ~ 0.8dl/g.
Described isocyanurate compound comprises: B1:80% ~ 98 wt %; B2:2% ~ 20 wt %;
Described B1 is dimer or the tripolymer of vulcabond, masked isocyanate or the vulcabond of Carbodiimide-Modified; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, mphenylenedimethylim-vulcabond, isoflurane chalcone diisocyanate, hexamethylene-diisocyanate, 2,6-vulcabond methyl caproate, methylcyclohexane diisocyanate, 2,2,4-trimethyl cyclohexane vulcabond, isopropylidene two (cyclohexyl diisocyanate-4), organosilicon vulcabond or containing any or two or more mixtures in the diphenylmethanediisocyanate of carbodiimide.
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 that meets m+n+k=3 ~ 30 condition.
First the preparation method of polyester elastomer for blowing of the present invention, comprise the steps: 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 is different can in reactor, forcing machine or kneader, carry out with reacting of polyester elastomer.
In prior art, thermoplastic polyester is the polymkeric substance being obtained by polycondensation by dibasic alcohol and diprotic acid.Via different types of diprotic acid and dibasic alcohol, can synthesize the multiple polyester with different characteristics.Commercial principal item mainly contains: polybutylene terephthalate, polyethylene terephthalate, poly terephthalic acid-Isosorbide-5-Nitrae-hexanaphthene dimethyl ester, 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.Conventionally, production of polyester has two kinds of batch production process and continous way production processes.Basic, the synthetic chemical process of polyester is substantially via esterification stage, transesterification reaction stage, polycondensation stage, and according to the difference of polyester kind and synthetic control method, the configuration of the equipment in each stage and processing requirement exist again feature separately.
Thermoplastic polyester elastomer of the present invention, its preparation method includes the esterification stage, transesterification reaction stage and polycondensation stage, preparation method's of the present invention processing condition can be with reference to prior art, esterification in preparation method of the present invention or transesterification reaction phase temperature scope are 150 ~ 240 ℃, preferably 170 ~ 220 ℃, can under normal pressure, carry out, the polycondensation stage can carry out within the scope of reduced pressure and 160 ~ 250 ℃, preferably 230 ~ 250 ℃.
While preparing polyester elastomer by polycondensation, can carry out catalyzed reaction by add appropriate catalyzer in reaction process, this class 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 in this reaction process, add appropriate stablizer, this class stablizer comprises: trialkyl phosphite, trialkylphosphate, phosphoric acid, phosphorous acid, hindered phenolic oxidation inhibitor, amine antioxidants etc.
The content of the catalyzer adding in polyester elastomer involved in the present invention is at 0.01 ‰ weight part to 3 ‰ weight part, preferably 0.5 ‰ weight part to 2 ‰ weight parts.For efficient Titanium series catalyst, its addition can be controlled within the scope of the order of magnitude of 1,000,000/weight part.When reaction proceeds to while removing unnecessary dibasic alcohol, or after forming oligopolymer, add catalyzer.Catalyzer can be made into certain density solution and add, and also can carry out certain compatibility and add in reactant different elements are catalyst based.
Compared with prior art, the present invention has following beneficial effect:
1) blowing polyester elastomer of the present invention is in thermoplastic polyester elastomer, to 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 adds the soft or hard degree that also can change thermoplastic polyester material, improves 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 terminal hydroxy group or the end carboxyl reaction of isocyanate compound and polyester elastomer simultaneously, improve the melt strength of polyester elastomer; The multicomponent isocyanate adding can make the molecule of polyester elastomer have branched structure, and then the melt strength of polyester elastomer is improved, and is conducive to improve the processing stability of blow molded product;
3) in the polyester soft segment of thermoplastic polyester elastomer of the present invention, introduce the polyether Glycols containing aromatic nucleus, can make the elastic resistance toheat of polyester improve;
4) blowing of the present invention can be used for blow molding with polyester elastomer, the melting index of the goods that obtain 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, and possesses excellent mechanical property.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
In embodiment, the testing method of index of correlation is as follows:
1, characteristic viscosity determining method: 25 ℃ 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 0.005 g/mL;
2, melting index test condition: 230 ℃, 2.16kg;
,liquid crystal high molecular compound, self-control, with reference to prior art, in the reactor with 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 three to fluoridize two antimony, use nitrogen replacement air, under certain vacuum tightness, by heating material, inflated with nitrogen then, heat up and continue reaction, obtain the opaque PET/PHB copolyesters of khaki color.
embodiment 1
In flask, add 30g DMT, 25g BDO and 25g PTMEG (Mn=1000), 0.25g is containing the polyether Glycols of aromatic nucleus (R1=R2=H wherein, a=b=1), add 20mg tetrabutyl titanate and 10mg antioxidant 1010, the normal pressure at 170～180 ℃ that heats up carries out transesterification reaction simultaneously, remove by-product carbinol, generating the mixed diol ester of terephthalic acid and its oligopolymer, is theoretical amount until the methyl alcohol amount of reserving 95% time, finishes transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (100-200Pa) stage carries out copolycondensation, and temperature rises to 230～250 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.2 dL/g, the 50g polyester elastomer obtaining, 2g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor 1098 10mg join in flask, 230 ℃ of meltings, then add 0.5g diphenylmethanediisocyanate, 0.02g B2(R10, R11, R12 are-H, m=n=k=1), the viscosity fast rise of polymkeric substance, at 230 ℃ of reaction 30min, take out polymkeric substance, melting index is 0.6g/10min.
embodiment 2
At flask, add 50g DMT, 40g BDO and 56g PTMEG (Mn=1000), 2.5g is containing the polyether Glycols of aromatic nucleus (R1=H wherein, R2=CH
3, a=b=1) adding 50mg tetrabutyl titanate and 40mg antioxidant 1010 simultaneously, the normal pressure at 160～180 ℃ that heats up carries out transesterification reaction, remove by-product carbinol, generating the mixed diol ester of terephthalic acid and its oligopolymer, is theoretical amount until the methyl alcohol amount of reserving 95% time, finishes transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (100-200Pa) stage carries out copolycondensation, and temperature rises to 230～250 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 0.82dL/g, the 50g polyester elastomer obtaining, 5g thermotropic liquid crystalline polyester macromolecular compound, joins in flask, 240 ℃ of meltings, then add 0.5g hexamethylene diisocyanate, 0.02g B2(R10, R11, R12 are-H, m=n=k=1) the viscosity fast rise of polymkeric substance, at 240 ℃ of reaction 30min, take out polymkeric substance, melting index is 1.0g/10min.
embodiment 3
In flask, add 35g DMT, 20g BDO and 48g PTMEG (Mn=2000), 3g is containing the polyether Glycols of aromatic nucleus (R1=H wherein, R2=CH
3, a=b=1), add 50mg tetrabutyl titanate and 15mg antioxidant 1010 simultaneously, intensification normal pressure at 170～180 ℃ carries out transesterification reaction, removes by-product carbinol, generates the mixed diol ester of terephthalic acid and its oligopolymer, until the methyl alcohol amount of reserving, be theoretical amount 95% time, finish transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 230～250 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.5dL/g, the 50g polyester elastomer obtaining, 4g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor TLTDP 10mg is added in flask, 230 ℃ of meltings, then add 0.5g hexamethylene diisocyanate, 0.03g B2(R10, R11, R12 are-H, m=n=k=2) the viscosity fast rise of polymkeric substance, at 230 ℃ of reaction 7min, take out polymkeric substance, molten finger for 0.7g/10min.
embodiment 4
In 20L reactor, add 4.5kg DMT, 3kg BDO and 4.2kg PTMEG (Mn=1500), 20g is containing the polyether Glycols of aromatic nucleus (R1=H wherein, R2=CH
3, a=b=2), add 1g tetrabutyl titanate and 0.5g antioxidant 1010 simultaneously, intensification normal pressure at 160～180 ℃ carries out transesterification reaction, removes by-product carbinol, generates the mixed diol ester of terephthalic acid and its oligopolymer, until the methyl alcohol amount of reserving, be theoretical amount 95% time, finish transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260～270 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, 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 445 10mg join 230 ℃ of melting 2min in Haake kneader, then add 0.3g hexamethylene diisocyanate trimer, be-H of 0.01g B2(R10, R11, R12, m=1, n=k=2) moment of torsion fast rise, the viscosity fast rise that shows polymkeric substance, at 230 ℃ of reaction 10min, take out polymkeric substance, melting index is 1.2g/10min.
embodiment 5
In flask, add 35g DMT, 54g BDO and 37g PTMEG (Mn=2000), 2.5g is containing the polyether Glycols of aromatic nucleus (R1=H wherein, R2=CH
3, a=b=2) adding 20mg tetrabutyl titanate and 15 antioxidant 1010s simultaneously, the normal pressure at 160～180 ℃ that heats up carries out transesterification reaction, remove by-product carbinol, generating the mixed diol ester of terephthalic acid and its oligopolymer, is theoretical amount until the methyl alcohol amount of reserving 95% time, finishes transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260～270 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, 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 ℃ of melting 2min in static mixer, then adds 0.3g hexamethylene diisocyanate trimer, be-CH3 of 0.01g B2(R10, R11, R12, m=n=k=2) moment of torsion fast rise, shows the viscosity fast rise of polymkeric substance, at 230 ℃ of reaction 15min, take out polymkeric substance, melting index is 1.0g/10min.
embodiment 6
In flask, add 50g DMT, 54g BDO and 60g PTMEG (Mn=1000), 4g is containing the polyether Glycols of aromatic nucleus (R1=-H wherein, R2=-CH
3, a=b=2) adding 50mg tetrabutyl titanate and 20mg antioxidant 1010 simultaneously, the normal pressure at 160～180 ℃ that heats up carries out transesterification reaction, remove by-product carbinol, generating the mixed diol ester of terephthalic acid and its oligopolymer, is theoretical amount until the methyl alcohol amount of reserving 95% time, finishes transesterification reaction; After transesterification reaction after product is pressed, proceeding to high vacuum (60Pa) stage carries out copolycondensation, and temperature rises to 260～270 ℃, by power of agitator Numerical Control polycondensation terminal, and inflated with nitrogen, the vacuum that disappears, obtains polyester elastomer; Described polyester elastomer limiting viscosity is 1.7dL/g, the 50g polyester elastomer obtaining, 3g thermotropic liquid crystalline polyester macromolecular compound, 20mg irgasfos 168, join in flask, 230 ℃ of meltings, then add 0.5g hexamethylene diisocyanate trimer, be-CH3 of 0.01g B2(R10, R11, R12, m=n=k=2) the viscosity fast rise of polymkeric substance, at 230 ℃ of reaction 30min, take out polymkeric substance, melting index is 1.1g/10min.
embodiment 7
By embodiment 6, make polyester elastomer 60g, 3g thermotropic liquid crystalline polyester macromolecular compound, join 230 ℃ of melting 2min in Haake kneader, then add 0.3g hexamethylene diisocyanate trimer, 0.01g B2(R10, R11, R12 are-CH3, m=n=k=2) moment of torsion fast rise, the viscosity fast rise that shows polymkeric substance, at 230 ℃ of reaction 15min, take out polymkeric substance, melting index is 0.8g/10min.
comparative example 1
By embodiment 1, make polyester elastomer 50g, oxidation inhibitor 1098 10mg join in flask, at 230 ℃ of melting 2min, then add 0.5g diphenylmethanediisocyanate, moment of torsion fast rise, shows the viscosity fast rise of polymkeric substance, at 230 ℃ of reaction 15min, take out polymkeric substance, melting index is 0.8g/10min.
comparative example 2
By embodiment 2, make polyester elastomer 50g and join 240 ℃ of melting 2min in flask, then add 5g thermotropic liquid crystalline polyester macromolecular compound, at 230 ℃ of reaction 15min, take out polymkeric substance, melting index is 15g/10min.
comparative example 3
The 50g polyester elastomer making by embodiment 3,4g thermotropic liquid crystalline polyester macromolecular compound, oxidation inhibitor TLTDP 10mg is added in flask, 230 ℃ of meltings, then add 0.5g hexamethylene diisocyanate, at 230 ℃ of reaction 15min, take out polymkeric substance, melting index is 3.0g/10min.
The prepared blowing of embodiment 1 ~ 7 and comparative example 1 ~ 3 is as shown in table 1 by the performance test results of polyester elastomer, and the hard segment content of product confirms by nuclear-magnetism, and the total content of soft or hard section is 100%.
Table 1
T1/2 is half time used that elongation at break is down to raw material.
By the above results, can be found out, the present invention by adding thermotropic liquid crystalline polyester macromolecular compound and isocyanurate compound in thermoplastic polyester elastomer, the goods that obtain melting index between 0.6-1.2, there is higher melt strength, the smooth in appearance of product, and possess excellent mechanical property.
Claims (9)
1. a blowing polyester elastomer, is characterized in that, percentage ratio meter by weight 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%.
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 ℃, and range of viscosities is 0.6 ~ 0.8dl/g, has the structural formula of following formula I:
（Ⅰ） 。
3. blowing polyester elastomer according to claim 1, is characterized in that, described isocyanurate compound comprises:
B1：80%~98 wt %；
B2：2%~20 wt %；
Described B1 is dimer or the tripolymer of vulcabond, masked isocyanate or the vulcabond of Carbodiimide-Modified;
Described B2 is isocyanuric acid ester cyclopolyol or isocyanurate ring polyether glycol, has the molecular structure as shown in formula II:
（Ⅱ）
Wherein, R10, R11, R12 are identical or different, be-H ,-CH3 or-CH2CH3; M, n, k are numeral, are selected from the positive count that meets m+n+k=3 ~ 30 condition.
4. a blowing polyester elastomer according to claim 3, it is characterized in that, described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, mphenylenedimethylim-vulcabond, isoflurane chalcone diisocyanate, hexamethylene-diisocyanate, 2, 6-vulcabond methyl caproate, methylcyclohexane diisocyanate, 2, 2, 4-trimethyl cyclohexane vulcabond, isopropylidene two (cyclohexyl diisocyanate-4), organosilicon vulcabond or containing any or two or more mixtures in the diphenylmethanediisocyanate of carbodiimide.
5. blowing polyester elastomer according to claim 1, is characterized in that, described thermoplastic polyester elastomer comprises soft section of composition of polyether ester of the hard section of the polyester of 40-80wt% and 20-60wt%; The limiting viscosity of described thermoplastic polyester elastomer is 1.3-2.1dl/g;
The hard section of described polyester is comprised of aromatic acid or its esterified derivative and aliphatic dihydroxy alcohol;
Soft section of described polyether ester is comprised of copolyether and aromatic acid or its esterified derivative.
6. blowing polyester elastomer according to claim 5, 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 1,3-PD, 1, the mixture of one or more in 2-butyleneglycol, BDO, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol or Isosorbide.
7. blowing polyester elastomer according to claim 5, is characterized in that, described copolyether forms by polyoxyethylene glycol, polytetrahydrofuran with containing the polyether Glycols of 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
2be-H ,-CH
3or-C
2h
5, a, b are numeral, are selected from the positive count that meets a+b=2 ~ 30 condition;
The weight of the described polyether Glycols containing aromatic nucleus accounts for the 3-15% of copolyether weight fraction.
8. the preparation method of polyester elastomer for blowing described in claim 1 ~ 7 any one, 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 to react, obtain blowing polyester elastomer.
9. the preparation method of polyester elastomer for blowing according to claim 8, is characterized in that, described esterification or transesterification reaction are carried out at 170 ~ 220 ℃ of normal pressures; Described polycondensation, at decompression 100 ~ 200Pa, is carried out at 230 ~ 250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310537313.6A CN103642017B (en) | 2013-11-04 | 2013-11-04 | A kind of blowing polyester elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310537313.6A CN103642017B (en) | 2013-11-04 | 2013-11-04 | A kind of blowing polyester elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103642017A true CN103642017A (en) | 2014-03-19 |
| CN103642017B CN103642017B (en) | 2016-03-30 |
Family
ID=50247316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310537313.6A Active CN103642017B (en) | 2013-11-04 | 2013-11-04 | A kind of blowing polyester elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103642017B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503756A (en) * | 2016-01-29 | 2016-04-20 | 西安近代化学研究所 | Pluridentate macromolecular bonding agent and preparation method thereof |
| CN105693642A (en) * | 2016-01-29 | 2016-06-22 | 西安近代化学研究所 | Unsaturated-terminal-group-containing branched-structure polyester ether and preparation method thereof |
| KR101729205B1 (en) | 2015-12-29 | 2017-04-25 | 정우화인 주식회사 | Method of producing Polyester Polyol and Polyurethane Foam Board with 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 |
| US9822306B2 (en) | 2015-06-25 | 2017-11-21 | Industrial Technology Research Institute | Liquid crystal polymer composite film |
| CN109535408A (en) * | 2018-11-21 | 2019-03-29 | 广东中瀚新材料有限公司 | A kind of thermoplastic polyester elastomeric material of fluorine silicon and its preparation method and application |
| CN110050010A (en) * | 2016-12-09 | 2019-07-23 | 株式会社三养社 | Thermoplastic polyether ester elastomer and preparation method thereof comprising anhydrous sugar alcohol derivant |
| US11453775B2 (en) * | 2017-12-29 | 2022-09-27 | Samyang Corporation | Thermoplastic elastomer resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56116749A (en) * | 1980-02-21 | 1981-09-12 | Toyobo Co Ltd | Production of high-viscosity modified polyester elastomer |
| 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 |
-
2013
- 2013-11-04 CN CN201310537313.6A patent/CN103642017B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56116749A (en) * | 1980-02-21 | 1981-09-12 | Toyobo Co Ltd | Production of high-viscosity modified polyester elastomer |
| 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 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9822306B2 (en) | 2015-06-25 | 2017-11-21 | Industrial Technology Research Institute | Liquid crystal polymer composite film |
| KR101729205B1 (en) | 2015-12-29 | 2017-04-25 | 정우화인 주식회사 | Method of producing Polyester Polyol and Polyurethane Foam Board with the Same |
| CN105503756A (en) * | 2016-01-29 | 2016-04-20 | 西安近代化学研究所 | Pluridentate macromolecular bonding agent and preparation method thereof |
| CN105693642A (en) * | 2016-01-29 | 2016-06-22 | 西安近代化学研究所 | Unsaturated-terminal-group-containing branched-structure polyester ether and preparation method thereof |
| CN105503756B (en) * | 2016-01-29 | 2018-07-31 | 西安近代化学研究所 | A kind of multiple tooth shape structural macromolecules bonding agent and preparation method thereof |
| CN105693642B (en) * | 2016-01-29 | 2018-12-11 | 西安近代化学研究所 | A kind of branched structure polyether ester and preparation method thereof containing unsaturated end group |
| CN110050010A (en) * | 2016-12-09 | 2019-07-23 | 株式会社三养社 | Thermoplastic polyether ester elastomer and preparation method thereof comprising anhydrous sugar alcohol derivant |
| CN110050010B (en) * | 2016-12-09 | 2022-07-08 | 株式会社三养社 | Thermoplastic polyetherester elastomer comprising anhydrosugar alcohol derivative and process for producing 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 |
| US11453775B2 (en) * | 2017-12-29 | 2022-09-27 | Samyang Corporation | Thermoplastic elastomer resin composition |
| CN109535408A (en) * | 2018-11-21 | 2019-03-29 | 广东中瀚新材料有限公司 | A kind of thermoplastic polyester elastomeric material of fluorine silicon and its preparation method and application |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103642017B (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103642017B (en) | A kind of blowing polyester elastomer and preparation method thereof | |
| CN102060969B (en) | High melt strength polyster elastomer and preparation method thereof | |
| US4469851A (en) | Molding composition | |
| US9109111B2 (en) | Wholly aromatic liquid crystalline polyester resin compound having improved fluidity | |
| KR20160046615A (en) | Polyurethane elastomer, thermoplastic resin composition comprising polyurethane elastomer, molding made of thermoplastic resin composition and preparation method of polyurethane elastomer | |
| KR20160114073A (en) | Polyester resin composition and molded article using said polyester resin composition | |
| CN113980230B (en) | Moisture-heat resistant thermoplastic polyurethane elastomer material and preparation method thereof | |
| KR20150002624A (en) | Polymers, the process for the synthesis thereof and compositions comprising same | |
| CN103665805B (en) | Glass fibre/lactic acid composite material of a kind of lactic acid oligomer modification of isocyanato end-blocking and preparation method thereof | |
| US5672676A (en) | Polyesteramides with high heat deflection temperatures | |
| CN113121804A (en) | High-performance bio-polyether ester elastomer and preparation method thereof | |
| CN110713700B (en) | Polyester composite material and preparation method and application thereof | |
| KR20040060739A (en) | Thermoplastic elastomer resin | |
| TWI742035B (en) | Flexible polylactic acid resin composition comprising a water scavenger | |
| EP3279178A1 (en) | Compound for preparing copolymerized polyester resin and method for preparing copolymerized polyester resin using same | |
| CN102786676B (en) | Polyester elastomer with branching structure and preparation method thereof | |
| KR101544211B1 (en) | Wholly aromatic liquid crystalline polyester resin with enhanced viscosity stability and method for preparing same and resin compound comprising the resin | |
| CN106478930B (en) | Preparation method of thermoplastic polyester elastomer base material | |
| WO2010038860A1 (en) | Polylactic acid composition and method for producing same | |
| KR20140028493A (en) | Polyetherester elastomer resin and method of preparing the same | |
| JP6189630B2 (en) | Stereocomplex crystalline polylactic acid prepolymer composition | |
| CN111100451A (en) | Modified liquid crystal polyester resin composite material and preparation method thereof | |
| TW201938636A (en) | Production process for polyether ester elastomers | |
| CN111072940A (en) | Copolyester based on spiro ethylene glycol and preparation method and product thereof | |
| JP5050610B2 (en) | Molded product of resin composition with excellent low-temperature characteristics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |