CN104356372A - Cladodified fat-aromatic copolyester and synthesis method thereof - Google Patents
Cladodified fat-aromatic copolyester and synthesis method thereof Download PDFInfo
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- CN104356372A CN104356372A CN201410585146.7A CN201410585146A CN104356372A CN 104356372 A CN104356372 A CN 104356372A CN 201410585146 A CN201410585146 A CN 201410585146A CN 104356372 A CN104356372 A CN 104356372A
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Abstract
The invention belongs to the technical field of cladodified fat-aromatic copolyester material preparation, and in particular relates to a cladodified fat-aromatic copolyester and a synthesis method thereof. The cladodified fat-aromatic copolyester is prepared by: carrying out polymerization reaction on glycidyl ether or unimolecular substitution ethylene oxide cladodified monomer, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and aliphatic diol with a commonly used esterification and ester exchange catalyst under the classic polyester preparation process conditions by using an esterification and vacuum polycondensation two-stage method. The prepared polyester has higher molecular weight and low terminal carboxyl content, the intrinsic viscosity of the prepared polyester is within 1.2-1.7 dl/g, and the terminal carboxyl content can be lower than 10 mol/t. The prepared copolyester has excellent mechanical property and hydrolysis resistance stability.
Description
Technical field
The invention belongs to cladodification aliphatic-aromatic copolyester technical field of material, be specifically related to a kind of cladodification aliphatic-aromatic copolyester and synthetic method thereof.
Background technology
Plastics due to its intensity, performance and function and easy to use etc. in advantage, more and more extensive in the use of packaging, agricultural, building, machinery and social all respects.Nondegradable plastics can remain in soil when being landfilled process, and some plastics also can produce obnoxious flavour when burning disposal, easily causes landscape damage time discarded.Along with environmental problem becomes increasingly conspicuous, the application of biodegradable polyesters attracts attention.Aliphatic-aromatic copolyester material, on the one hand there is aromatic polyester production cost low, the advantages such as mechanical property, thermal characteristics and processing use properties are good, also have the good biodegradability of aliphatic polyester on the other hand, have wide industrial applications prospect.
Kingdom's profit waits people in patent CN102344556A, disclose a kind of biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer and preparation method thereof, have employed three kinds of methods and prepared branched aromatic polyester-aliphatic polyester segmented copolymer, have that melt viscosity is high, melt strength is high and the advantage such as excellent in stability.Metabolix Inc. discloses a kind of aliphatic-aromatic polyester blend and synthetic method thereof of branching in patent CN102482482A, under a kind of suitable superoxide exists as branching agent, carry out reactive blending, obtaining rheology, thermostability, processing and characteristic aspect has synergistic material.
In cladodification aliphatic-aromatic copolyester, on main chain, the introducing of phenyl ring improves the thermostability of polymer materials, improves the mechanical property of polymkeric substance, but steric effect simultaneously due to phenyl ring is large, and biological degradability is deteriorated.In aliphatic-aromatic copolyester, introduce side chain, melt strength and the melt viscosity of polymer materials can be improved, improve the tear strength of materials application when film article.Therefore, cladodification aliphatic-aromatic copolyester is a kind of material with excellent biological degradability, thermostability and mechanical property.
In recent years due to the development of biotechnology, biological process succinic acid and being had made great progress by work such as the further hydrogenation synthesis Isosorbide-5-Nitrae-glycol of biological process succinic acid.Therefore, the polymkeric substance research of development bio-based source also receives increasing concern, and this is just being applicable to the aliphatic character in the present invention.Monomer selected by the present invention is easy to get and cheap, can be suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, and a kind of cladodification aliphatic-aromatic copolyester and synthetic method thereof are provided.
A synthetic method for cladodification aliphatic-aromatic copolyester, comprises the steps:
(1) esterification: by aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic diol and the mixing of cladodification monomer add in reactor, protection of inert gas, under 1kPa to condition of normal pressure, adds appropriate catalyzer, mechanical stirring is installed, and connects a point moisture distillation unit; Be warming up to 100 DEG C ~ 140 DEG C, be uniformly mixed.Then be warming up to 220 DEG C ~ 280 DEG C, until absence of liquid distillates, and in reaction system, mixed solution becomes clarification; Wherein the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid and the ratio of aliphatic diol and cladodification monomer molar number sum are 1:1.02 to 1:2.0; Wherein the mole number of aliphatic dicarboxylic acid is 0.3:0.7 to 0.95:0.05 with the ratio of the mole number of aromatic dicarboxylic acid; Wherein the mole number of cladodification monomer is 0.01:0.99 to 0.3:0.7 with the ratio of the mole number of aliphatic diol; Wherein the add-on of catalyzer is aliphatic dicarboxylic acid, aromatic dicarboxylic acid, 0.0005% ~ 5% of aliphatic diol and cladodification monomer mass summation;
(2) vacuum polycondensation: after esterification terminates, adds stablizer and adds proper catalyst, and being evacuated to absolute pressure is below 100Pa, maintain the temperature at 220 DEG C ~ 280 DEG C, keep violent stirring state, isothermal reaction 2h ~ 5h, obtain cladodification aliphatic-aromatic copolyester; Wherein the add-on of catalyzer is aliphatic dicarboxylic acid, aromatic dicarboxylic acid, 0.001% ~ 10% of aliphatic diol and cladodification monomer mass summation; The add-on of stablizer is 0.001% ~ 1% of aliphatic dicarboxylic acid and aromatic dicarboxylic acid quality summation.
Cladodification monomer described in step (1) is one or more in monoglycidyl ether, monosubstituted oxyethane, and the structural formula of described monosubstituted oxyethane is formula (I),
Wherein, the one in the cycloalkyl that the alkyl that the cycloalkyl that the aryl that the alkyl that the alkyl of the aryl that R is alkyl, aryl, cycloalkyl, alkyl replace, the cycloalkyl of alkyl replacement, halogen substiuted, the aryl of halogen substiuted, the cycloalkyl of halogen substiuted, alkoxyl group replace, alkoxyl group replace, alkoxyl group replace, aryl replace, the aryl of aryl replacement, aryl replace.
Preferably, described in step (1), cladodification monomer is propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, 1,2-epoxypentane, 1,2-oxepane, 1,2-oxepane, 1,2-octylene oxide, 1,2-decamethylene, 2-phenyl-oxirane, sec.-propyl oxyethane, methyl glycidyl ether, n-butyl glycidyl ether, tertiary butyl glycidyl ether, isopropyl glycidyl ether, octyl glycidyl ether, C
8-10-alkyl glycidyl ether, C
12-14-alkyl glycidyl ether, C
10-16-alkyl glycidyl ether, proyl glycidyl ether, glycidyl allyl ether, furans glycidyl ether, furfuryl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trityl-(S/R)-glycidyl ether, 2-toluene glycidyl ether, 4-nonyl phenyl glycidyl glyceryl ether, 4-tert-butyl-phenyl glycidyl ether, O-SEC-butylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, guaiacol glycidyl ether, adjacent phenyl glycidyl ether, dibromomethylbenzene base glycidyl ethers, naphthalene glycidyl ether, γ-glycidyl ether oxygen propyl trimethoxy silicane [(4-fluorophenoxy) methyl] oxyethane, 3-(2, 3-epoxy third oxygen) propyl trimethoxy silicane, one or more in glycidyl ether ten hexafluoro nonyl ethers,
Described in step (1), aliphatic dicarboxylic acid is C
3~ C
8one or more in chain docosandioic acid, it is for chemosynthesis or derive from biomass resource;
Described in step (1), aromatic dicarboxylic acid is terephthalic acid, m-phthalic acid, phthalic acid, one or more in naphthalic acid, biphenyl-4,4 '-dioctyl phthalate, biphenyl-3,4 '-dioctyl phthalate;
Described in step (1), aliphatic diol is C
2~ C
10one or more in alkanediol, it is for chemosynthesis or derive from biomass resource.
Preferably, the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid described in step (1) and the ratio of aliphatic diol and cladodification monomer molar number sum are 1:1.05 to 1:1.6.
Preferably, the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid described in step (1) and the ratio of aliphatic diol and cladodification monomer molar number sum are 1:1.2 to 1:1.6.
Preferably, the mole number of aliphatic dicarboxylic acid described in step (1) is 0.45:0.55 to 0.7:0.3 with the ratio of the mole number of aromatic dicarboxylic acid.
Preferably, the mole number of aliphatic dicarboxylic acid described in step (1) is 0.45:0.55 to 0.55:0.45 with the ratio of the mole number of aromatic dicarboxylic acid.
Preferably, cladodification monomer described in step (1) is 0.1:0.9 to 0.25:0.75 with the ratio of the mole number of aliphatic diol.
Catalyzer described in step (1) and (2) is one or more in tetrabutyl titanate, tetraethoxy, titanium tetraisopropylate acid esters, ethylene glycol tin, antimonous oxide, antimony acetate, cobaltous acetate, silicon-dioxide, germanium dioxide, methyl ethyl diketone hafnium, Samarium trioxide, cerium oxide, lanthanum trioxide, yttrium oxide.
Described in step (2), stablizer is phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, organophosphate, organophosphite, phenol stabilizer, thioesters class stablizer, trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, four [3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyl benzyl) benzene, octadecyl 3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester, the two dodecane ester of thio-2 acid, one or more in the two octadecyl of thio-2 acid.
The cladodification aliphatic-aromatic copolyester prepared by above-mentioned synthetic method.
Beneficial effect of the present invention is: the method that the present invention adopts is that esterification-vacuum polycondensation two-step approach is prepared, the cladodification aliphatic-aromatic copolyester of final preparation has higher molecular weight and low terminal carboxy content, its limiting viscosity is 1.2 ~ 1.7dl/g, and the most low energy of content of carboxyl end group reaches 10mol/t.
Embodiment
The invention provides a kind of cladodification aliphatic-aromatic copolyester and synthetic method thereof, be specially: by glycidyl ether or monosubstituted oxyethane cladodification monomer, be polymerized by esterification, vacuum polycondensation two-step approach with aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic diol and synthesize cladodification aliphatic-aromatic copolyester.Enumerate embodiment to be below explained the present invention further, but do not limit the present invention in any way.
The thermal property of cladodification aliphatic-aromatic copolyester provided by the invention is detected by differential scanning calorimeter; Degree of crystallinity calculates gained by X-ray diffractometer at room temperature sweep test; Limiting viscosity, with phenol tetrachloroethane (chemical pure) mixed solution, utilizes Ubbelohde viscometer to detect at 25 DEG C; The structure of polyester and composition take deuterochloroform as solvent, and the result of testing with JOEL JNM-ECA300 nuclear magnetic resonance spectrometer characterizes; Molecular weight is solvent by chloroform, and polystyrene is standard specimen, adopts the GPC of Viscotek TDA 302 model to measure.
Embodiment 1
By succinic acid 0.18mol; terephthalic acid 0.22mol; 1; 4-butyleneglycol 0.4356mol, n-butyl glycidyl ether 0.0044mol, mixing adds in there-necked flask reactor; add the catalyzer tetrabutyl titanate of 0.05%; wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 100 DEG C, be uniformly mixed.Then gradient increased temperature to 240 DEG C, reaction 2h, until mixed solution becomes clarification in reaction system, namely esterification terminates.Add the catalyzer tetrabutyl titanate of 1% and the stablizer trimethyl phosphite 99 of 0.001%, being evacuated to absolute pressure is 20Pa, and is rapidly heated to 240 DEG C of isothermal reaction 4h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, and can obtain cladodification aliphatic-aromatic copolyester, takes out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, the mol ratio that can calculate succinic acid and terephthalic acid is 46.8:53.2,1, the mol ratio of 4-butyleneglycol and n-butyl glycidyl ether is 99.04:0.96, fusing point measured by differential scanning calorimeter is 134.6 DEG C, and XRD measurement degree of crystallinity is 53.6%, weight-average molecular weight Mw is 187689, limiting viscosity is 1.2104dl/g, content of carboxyl end group 20mol/t.
Embodiment 2
By hexanodioic acid 0.22mol; terephthalic acid 0.18mol, BDO 0.432mol; 1; 2-oxepane 0.048mol, mixing adds in there-necked flask reactor, adds the catalyzer silicon-dioxide of 5%; wherein pass into enough nitrogen protections flatly; connect mechanical stirrer flatly, another mouth connects water trap and prolong, and system is evacuated to 1kPa.Be warming up to 140 DEG C, be uniformly mixed.Then gradient increased temperature to 280 DEG C, reaction 3h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyzer silicon-dioxide of 10% and the stablizer triphenyl phosphite of 0.05%, being evacuated to absolute pressure is below 100Pa, and is rapidly heated to 280 DEG C of isothermal reaction 3h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, and can obtain cladodification aliphatic-aromatic copolyester, takes out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, the mol ratio calculating hexanodioic acid and terephthalic acid is 55.7:44.3,1,4-butyleneglycol: the mol ratio of 1,2-oxepane is 90.2:9.8, fusing point measured by differential scanning calorimeter is 116.3 DEG C, it is 29.64% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 168793, and limiting viscosity is 1.1987dl/g, content of carboxyl end group 18mol/t.
Embodiment 3
By hexanodioic acid 0.12mol, terephthalic acid 0.252mol, m-phthalic acid 0.028mol; 1; 4-butyleneglycol 0.72mol, 1,2-oxepane 0.08mol; mixing adds in there-necked flask reactor; add the catalyzer tetrabutyl titanate of 0.001%, wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly; another mouth connects water trap and prolong, and system is evacuated to 10kPa.Be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 220 DEG C, reaction 3h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add 0.001% catalyzer tetrabutyl titanate and tetraethoxy (mass ratio is 10:1) and 1% 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyl benzyl) benzene and triphenyl phosphite are as stablizer, and being evacuated to absolute pressure is below 60Pa, and is rapidly heated to 220 DEG C of isothermal reaction 2h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, and can obtain cladodification aliphatic-aromatic copolyester, takes out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein hexanodioic acid: terephthalic acid: the mol ratio of m-phthalic acid is 28.38:64.74:6.88,1, the mol ratio of 4-butyleneglycol and 1,2-oxepane is 76.2:23.8, and fusing point measured by differential scanning calorimeter is 154.5 DEG C, it is 30.58% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 168793, and limiting viscosity is 1.1879dl/g, content of carboxyl end group 21mol/t.
Embodiment 4
By hexanodioic acid 0.28mol; terephthalic acid 0.12mol, BDO 0.4032mol; 1; 6-hexylene glycol 0.0448mol, phenyl glycidyl ether 0.192mol, mixing adds in there-necked flask reactor; add the catalyst oxidation samarium of 0.0005%; wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 260 DEG C, reaction 2h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyst oxidation samarium of 0.1% and the two dodecane ester of stablizer thio-2 acid of 0.1%, being evacuated to absolute pressure is 80Pa, and be rapidly heated to 260 DEG C of isothermal reaction 5h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the mol ratio of hexanodioic acid and terephthalic acid is 68.9:31.1,1, the mol ratio of 4-butyleneglycol, 1,6-hexylene glycol and phenyl glycidyl ether is 64.9:8.6:26.5, and fusing point measured by differential scanning calorimeter is 67.4 DEG C, it is 37.52% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 156987, and limiting viscosity is 1.1939dl/g, content of carboxyl end group 17mol/t.
Embodiment 5
By hexanodioic acid 0.24mol; terephthalic acid 0.16mol; 1,6-hexylene glycol 0.54mol, n-butyl glycidyl ether 0.054mol; phenyl glycidyl ether 0.006mol mixing adds in there-necked flask reactor; add the catalyzer titanium tetraisopropylate acid esters of 1%, wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly; another mouth connects water trap and prolong, and system is evacuated to 100kPa.Be warming up to 100 DEG C, be uniformly mixed.Then gradient increased temperature to 250 DEG C, reaction 2.5h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the titanium tetraisopropylate acid esters catalyzer of 0.3% and the stablizer triphenyl phosphite of 0.1%, being evacuated to absolute pressure is below 30Pa, and be rapidly heated to 250 DEG C of isothermal reaction 4h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, the mol ratio calculating hexanodioic acid and terephthalic acid is 59.2:40.8,1,4-butyleneglycol, hexylene glycol: n-butyl glycidyl ether: the mol ratio of phenyl glycidyl ether is 90.2:38.73:1.04, fusing point measured by differential scanning calorimeter is 91.2 DEG C, it is 30.61% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 167890, and limiting viscosity is 1.1968dl/g, content of carboxyl end group 16mol/t.
Embodiment 6
By succinic acid 0.016mol; hexanodioic acid 0.144mol; terephthalic acid 0.24mol, BDO 0.448mol; phenyl glycidyl ether 0.112mol; mixing adds in there-necked flask reactor, adds the catalyst acetyl acetone hafnium of 0.005%, wherein passes into enough nitrogen protections flatly; connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 140 DEG C, be uniformly mixed.Then gradient increased temperature to 260 DEG C, reaction 2h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyst acetyl acetone hafnium of 0.01% and the stablizer dimethyl phosphate of 0.08%, being evacuated to absolute pressure is below 50Pa, and be rapidly heated to 260 DEG C of isothermal reaction 4h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, the mol ratio wherein calculating succinic acid, hexanodioic acid and terephthalic acid is 4.12:35.9:59.98,1, the mol ratio of 4-butyleneglycol and phenyl glycidyl ether is 80.3:19.7, fusing point measured by differential scanning calorimeter is 132.1 DEG C, and XRD measurement degree of crystallinity is 26.79%, weight-average molecular weight Mw is 168971, limiting viscosity is 1.1967dl/g, content of carboxyl end group 15mol/t.
Embodiment 7
By succinic acid 0.162mol, hexanodioic acid 0.018mol, terephthalic acid 0.22mol; 1; 4-butyleneglycol 0.284mol, 1,6-hexylene glycol 0.031mol; benzyl glycidyl ether 0.105mol; mixing adds in there-necked flask reactor, adds the catalyzer tetrabutyl titanate of 0.005%, wherein passes into enough nitrogen protections flatly; connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 260 DEG C, reaction 3h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyzer tetrabutyl titanate of 5% and the stablizer dimethyl phosphate of 0.08%, being evacuated to absolute pressure is below 50Pa, and is rapidly heated to 260 DEG C of isothermal reaction 4h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, and can obtain cladodification aliphatic-aromatic copolyester, takes out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the mol ratio of succinic acid, hexanodioic acid and terephthalic acid is 39.62:4.41:55.97,1,4-butyleneglycol: 1,6-hexylene glycol: the mol ratio of benzyl glycidyl ether is 67.95:7.32:24.73, fusing point measured by differential scanning calorimeter is 127.3 DEG C, it is 29.71% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 154986, and limiting viscosity is 1.1926dl/g, content of carboxyl end group 18mol/t.
Embodiment 8
By hexanodioic acid 0.22mol; terephthalic acid 0.18mol, BDO 0.54mol; n-butyl glycidyl ether 0.122mol; 1,2-oxepane 0.018mol, mixing adds in there-necked flask reactor; add the catalyst oxidation samarium of 0.5%; wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 240 DEG C, reaction 3h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyst oxidation samarium of 0.5% and the stablizer trimethyl phosphite 99 of 0.08%, being evacuated to absolute pressure is below 50Pa, and is rapidly heated to 240 DEG C of isothermal reaction 3.5h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, and can obtain cladodification aliphatic-aromatic copolyester, takes out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the mol ratio of hexanodioic acid and terephthalic acid is 53.6:46.4,1,4-butyleneglycol: n-butyl glycidyl ether: the mol ratio of 1,2-oxepane is 81.05:16.8:2.15, fusing point measured by differential scanning calorimeter is 105.3 DEG C, it is 31.23% that XRD measures degree of crystallinity, weight-average molecular weight Mw is 149796, and limiting viscosity is 1.1910dl/g, content of carboxyl end group 10mol/t.
Embodiment 9
By hexanodioic acid 0.22mol, terephthalic acid 0.18mol, 1; 6-hexylene glycol 0.576mol, 1,2-oxepane 0.1296mol; 1; 2-oxepane 0.0144mol, mixing adds in there-necked flask reactor, adds the catalyzer tetrabutyl titanate of 0.5%; wherein pass into enough nitrogen protections flatly; connect mechanical stirrer flatly, another mouth connects water trap and prolong, and system is evacuated to 10kPa.Under normal pressure, be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 240 DEG C, reaction 3.5h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyzer tetrabutyl titanate of 0.01% and the stablizer trimethyl phosphite 99 of 0.05%, being evacuated to absolute pressure is below 60Pa, and be rapidly heated to 240 DEG C of isothermal reaction 3.5h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the ratio of hexanodioic acid and terephthalic acid is 53.3:46.7,1,6-hexylene glycol: 1,2-oxepane: 1, the mol ratio of 2-oxepane is 80.5:17.6:1.9, fusing point measured by differential scanning calorimeter is 107.6 DEG C, and XRD measurement degree of crystallinity is 29.14%, weight-average molecular weight Mw is 188760, limiting viscosity is 1.2209dl/g, content of carboxyl end group 19mol/t.
Embodiment 10
By succinic acid 0.38mol; terephthalic acid 0.02mol; 1; 6-hexylene glycol 0.3672mol, 4-tert-butyl-phenyl glycidyl ether 0.0408mol, mixing adds in there-necked flask reactor; add the catalyst Ti isopropyl propionate of 0.5%; wherein pass into enough nitrogen protections flatly, connect mechanical stirrer flatly, another mouth connects water trap and prolong.Under normal pressure, be warming up to 120 DEG C, be uniformly mixed.Then gradient increased temperature to 240 DEG C, reaction 3.5h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and namely esterification terminates.Add the catalyst Ti isopropyl propionate of 0.01% and the stablizer triphenylphosphate of 0.05%, being evacuated to absolute pressure is below 60Pa, and be rapidly heated to 240 DEG C of isothermal reaction 3.5h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the ratio of succinic acid and terephthalic acid is 95.4:4.6,1,6-hexylene glycol: the mol ratio of 4-tert-butyl-phenyl glycidyl ether is 91.5:8.5, fusing point measured by differential scanning calorimeter is 110.1 DEG C, and XRD measurement degree of crystallinity is 38.92%, weight-average molecular weight Mw is 176708, limiting viscosity is 1.2437dl/g, content of carboxyl end group 17mol/t.
Embodiment 11
By the succinic acid 0.18mol (purity 99% of Biological preparation; purified by crystallisation), terephthalic acid 0.22mol, 1; 4-butyleneglycol 0.684mol; n-butyl glycidyl ether 0.076mol, mixing adds in there-necked flask reactor, adds the catalyzer tetrabutyl titanate of 1%; wherein pass into enough nitrogen protections flatly; connect mechanical stirrer flatly, another mouth connects water trap and prolong, and system is evacuated to 10kPa.Be warming up to 100 DEG C, be uniformly mixed.Then gradient increased temperature to 240 DEG C, reaction 3h, rear increase division box, point water is until no longer include liquid and distillate, and in reaction system, mixed solution becomes clarification, and the prepolymer obtained in the reactor violent stirring no longer splashes, and namely esterification terminates.Add the catalyzer tetrabutyl titanate of 0.01% and the stablizer trimethyl phosphite 99 of 0.05%, being evacuated to absolute pressure is below 30Pa, and be rapidly heated to 240 DEG C of isothermal reaction 5h, rod climbing phenomenon is obvious, namely vacuum polycondensation terminates, cladodification aliphatic-aromatic copolyester can be obtained, take out this copolyesters.
Chloroform dissolves cladodification aliphatic-aromatic copolyester, makes cladodification aliphatic-aromatic copolyester solution, by methanol wash 3 times, obtains pure cladodification aliphatic-aromatic copolyester.Cladodification aliphatic-aromatic copolyester carries out nucleus magnetic hydrogen spectrum sign and calculating, wherein the mol ratio of succinic acid and terephthalic acid is 43.9:56.1,1, the mol ratio of 4-butyleneglycol and n-butyl glycidyl ether is 99.06:0.94, fusing point measured by differential scanning calorimeter is 127.9 DEG C, and XRD measurement degree of crystallinity is 28.19%, weight-average molecular weight Mw is 173291, limiting viscosity is 1.2019dl/g, content of carboxyl end group 22mol/t.
Claims (14)
1. a synthetic method for cladodification aliphatic-aromatic copolyester, is characterized in that, comprises the steps:
(1) esterification: by aliphatic dicarboxylic acid, aromatic dicarboxylic acid, aliphatic diol and the mixing of cladodification monomer add in reactor, protection of inert gas, under 1kPa to condition of normal pressure, adds appropriate catalyzer, mechanical stirring is installed, and connects a point moisture distillation unit; Be warming up to 100 DEG C ~ 140 DEG C, be uniformly mixed; Then be warming up to 220 DEG C ~ 280 DEG C, until absence of liquid distillates, and in reaction system, mixed solution becomes clarification; Wherein the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid and the ratio of aliphatic diol and cladodification monomer molar number sum are 1:1.02 to 1:2.0; Wherein the mole number of aliphatic dicarboxylic acid is 0.3:0.7 to 0.95:0.05 with the ratio of the mole number of aromatic dicarboxylic acid; Wherein the mole number of cladodification monomer is 0.01:0.99 to 0.3:0.7 with the ratio of the mole number of aliphatic diol; Wherein the add-on of catalyzer is aliphatic dicarboxylic acid, aromatic dicarboxylic acid, 0.0005% ~ 5% of aliphatic diol and cladodification monomer mass summation;
(2) vacuum polycondensation: after esterification terminates, adds stablizer and adds proper catalyst, and being evacuated to absolute pressure is below 100Pa, maintains the temperature at 220 DEG C ~ 280 DEG C, keeps whipped state, isothermal reaction 2h ~ 5h, obtains cladodification aliphatic-aromatic copolyester; Wherein the add-on of catalyzer is aliphatic dicarboxylic acid, aromatic dicarboxylic acid, 0.001% ~ 10% of aliphatic diol and cladodification monomer mass summation; The add-on of stablizer is 0.001% ~ 1% of aliphatic dicarboxylic acid and aromatic dicarboxylic acid quality summation.
2. synthetic method according to claim 1, it is characterized in that, cladodification monomer described in step (1) is one or more in monoglycidyl ether, monosubstituted oxyethane, and described monosubstituted ethylene oxide structure formula is formula (I)
Wherein, the one in the cycloalkyl that the alkyl that the cycloalkyl that the aryl that the alkyl that the alkyl of the aryl that R is alkyl, aryl, cycloalkyl, alkyl replace, the cycloalkyl of alkyl replacement, halogen substiuted, the aryl of halogen substiuted, the cycloalkyl of halogen substiuted, alkoxyl group replace, alkoxyl group replace, alkoxyl group replace, aryl replace, the aryl of aryl replacement, aryl replace.
3. synthetic method according to claim 1, is characterized in that, described in step (1), cladodification monomer is propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, 1,2-epoxypentane, 1,2-oxepane, 1,2-oxepane, 1,2-octylene oxide, 1,2-decamethylene, 2-phenyl-oxirane, sec.-propyl oxyethane, methyl glycidyl ether, n-butyl glycidyl ether, tertiary butyl glycidyl ether, isopropyl glycidyl ether, octyl glycidyl ether, C
8-10-alkyl glycidyl ether, C
12-14alkyl glycidyl ether, C
10-16-alkyl glycidyl ether, proyl glycidyl ether, glycidyl allyl ether, furans glycidyl ether, furfuryl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trityl-(S/R)-glycidyl ether, 2-toluene glycidyl ether, 4-nonyl phenyl glycidyl glyceryl ether, 4-tert-butyl-phenyl glycidyl ether, O-SEC-butylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, guaiacol glycidyl ether, adjacent phenyl glycidyl ether, dibromomethylbenzene base glycidyl ethers, naphthalene glycidyl ether, γ-glycidyl ether oxygen propyl trimethoxy silicane [(4-fluorophenoxy) methyl] oxyethane, 3-(2, 3-epoxy third oxygen) propyl trimethoxy silicane, one or more in glycidyl ether ten hexafluoro nonyl ethers.
4. synthetic method according to claim 1, is characterized in that, described in step (1), aliphatic dicarboxylic acid is C
3~ C
8one or more in chain docosandioic acid.
5. synthetic method according to claim 1, it is characterized in that, described in step (1), aromatic dicarboxylic acid is terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, biphenyl-4, one or more in 4 '-dioctyl phthalate, biphenyl-3,4 '-dioctyl phthalate.
6. synthetic method according to claim 1, is characterized in that, described in step (1), aliphatic diol is C
2~ C
10one or more in alkanediol.
7. synthetic method according to claim 1, is characterized in that, the ratio of the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid described in step (1) and aliphatic diol and cladodification monomer molar number sum is 1:1.05 to 1:1.6.
8. synthetic method according to claim 7, is characterized in that, the ratio of the mole number sum of aliphatic dicarboxylic acid and aromatic dicarboxylic acid described in step (1) and aliphatic diol and cladodification monomer molar number sum is 1:1.2 to 1:1.6.
9. synthetic method according to claim 1, is characterized in that, described in step (1), the mole number of aliphatic dicarboxylic acid is 0.45:0.55 to 0.7:0.3 with the ratio of the mole number of aromatic dicarboxylic acid.
10. synthetic method according to claim 9, is characterized in that, described in step (1), the mole number of aliphatic dicarboxylic acid is 0.45:0.55 to 0.55:0.45 with the ratio of the mole number of aromatic dicarboxylic acid.
11. synthetic methods according to claim 1, is characterized in that, described in step (1), cladodification monomer is 0.1:0.9 to 0.25:0.75 with the ratio of the mole number of aliphatic diol.
12. synthetic methods according to claim 1, it is characterized in that, described catalyzer is one or more in tetrabutyl titanate, tetraethoxy, titanium tetraisopropylate acid esters, ethylene glycol tin, antimonous oxide, antimony acetate, cobaltous acetate, silicon-dioxide, germanium dioxide, methyl ethyl diketone hafnium, Samarium trioxide, cerium oxide, lanthanum trioxide, yttrium oxide.
13. synthetic methods according to claim 1, it is characterized in that, stablizer described in step (2) is phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, organophosphate, organophosphite, phenol stabilizer, thioesters class stablizer, trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, four [3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyl benzyl) benzene, octadecyl 3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester, the two dodecane ester of thio-2 acid, one or more in the two octadecyl of thio-2 acid.
The cladodification aliphatic-aromatic copolyester that described in 14. claim 1-13 any one claims prepared by synthetic method.
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| CN106032403A (en) * | 2015-03-12 | 2016-10-19 | 中国石油化工股份有限公司 | Long-chain branched aliphatic-aromatic copolyester and preparing method thereof |
| CN112934150A (en) * | 2020-12-29 | 2021-06-11 | 中国纺织科学研究院有限公司 | Biodegradable copolyester production system, preparation method and copolyester |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN102295779A (en) * | 2011-05-17 | 2011-12-28 | 浙江大学 | Long-chain branched polyester and preparation method thereof |
| US20120116020A1 (en) * | 2010-11-04 | 2012-05-10 | Far Eastern New Century Corporation | Copolyester composition and method for producing copolyester polymer |
| CN102869723A (en) * | 2010-03-24 | 2013-01-09 | 巴斯夫欧洲公司 | Process for producing cling films |
| CN103113563A (en) * | 2013-01-18 | 2013-05-22 | 清华大学 | Branched aliphatic polyester and synthetic method thereof |
-
2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN102869723A (en) * | 2010-03-24 | 2013-01-09 | 巴斯夫欧洲公司 | Process for producing cling films |
| US20120116020A1 (en) * | 2010-11-04 | 2012-05-10 | Far Eastern New Century Corporation | Copolyester composition and method for producing copolyester polymer |
| CN102295779A (en) * | 2011-05-17 | 2011-12-28 | 浙江大学 | Long-chain branched polyester and preparation method thereof |
| CN103113563A (en) * | 2013-01-18 | 2013-05-22 | 清华大学 | Branched aliphatic polyester and synthetic method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106032403A (en) * | 2015-03-12 | 2016-10-19 | 中国石油化工股份有限公司 | Long-chain branched aliphatic-aromatic copolyester and preparing method thereof |
| CN106032403B (en) * | 2015-03-12 | 2018-05-29 | 中国石油化工股份有限公司 | A kind of long chain branching aliphatic-aromatic copolyester and preparation method thereof |
| CN112934150A (en) * | 2020-12-29 | 2021-06-11 | 中国纺织科学研究院有限公司 | Biodegradable copolyester production system, preparation method and copolyester |
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