CN101445592B - Biodegradable branched co-polyester and preparation method thereof - Google Patents
Biodegradable branched co-polyester and preparation method thereof Download PDFInfo
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- CN101445592B CN101445592B CN2008102465629A CN200810246562A CN101445592B CN 101445592 B CN101445592 B CN 101445592B CN 2008102465629 A CN2008102465629 A CN 2008102465629A CN 200810246562 A CN200810246562 A CN 200810246562A CN 101445592 B CN101445592 B CN 101445592B
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Abstract
The invention discloses biodegradable branched co-polyester and a preparation method thereof, and belongs to the polymeric chemical field. The preparation of branched co-polyester adopts a mature esterification and fasculation process route, butane diacid and butanediol which are used as main copolymerization units performs a copolymerization action with one or more than one of lateral group-containing aliphatic dibasic acid, C3, C5 to C8 alkane diacid, terephthalic acid or tribasic acid, or performs a copolymerization action with one or more than one of lateral group-containing dibasic alcohol, C2, C3, C5 to C10 alkane diol or aliphatic trivalent alcohol, so as to obtain random branched co-polyester finally. The intrinsic viscosity of prepared co-polyester ranges from 0.6 to 2.2dl/g, the melting point ranges from 70 to 115, the degree of crystallinity ranges from 20 to 70 percent, and the weight average molecular weight ranges from 5 to 300000. The co-polyester preparation method adopts efficient a blended catalyst, so that the polymerization time is reduced greatly, and the molecular weight and the performance of the products are increased. New performances are given to polyester through quoting third components containing lateral groups or multi-functional groups, thereby extending the application range of polyester.
Description
Technical field
The invention belongs to copolyesters product and preparation method thereof technical field, particularly a kind of Biodegradable branched co-polyester and preparation method thereof.
Background technology
In recent years, along with the development of plastics industry and the enhancing of people's environmental consciousness, " white pollution " problem (like the waste plastic film, waste plastic packing bag etc. are to the pollution of environment) by conventional plastic causes just progressively gets more and more people's extensive concerning.How effectively to solve the use of plastic prod and the contradiction between the environmental disruption, what just show is more and more important.Therefore relevant various " environment-friendly materials " the especially research of biological degradation plastics and object of paying close attention to that application has become people.Particularly aliphatic polyester just more and more receives people's favor as a kind of outstanding bio-degradable plastics.
Poly-succinic fourth diester (PBS) has mechanics and biodegradability preferably, therefore from biodegradable aliphatic polyester, shows one's talent, and becomes the research focus of domestic and international researcher.Related prods is commercialization.But the percent crystallinity of PBS is higher, can reach 40%～60%, and is slower at the biodegradation rate of occurring in nature, and the Application Areas of shortcoming further limits PBS such as its molecular weight is low, and melt strength and melt viscosity are low.Compare with aromatic polyester, the aliphatic polyester greatest problem is a poor heat stability, side reactions such as decarboxylation, cyclisation and thermal destruction takes place easily, so be difficult to obtain the high-molecular weight product under comparatively high temps.For this reason, research and the application about polyester chain extender and catalyzer gets more and more people's extensive concerning.People are molecular weight (Zhao J.B, Li K.Y, the Yang W.T that chainextender improves PBS with the two hexanolactams (TBC) of paraphenylene terephthalamide; J Appl Polym Sci, 2007,106; 590), the result shows the molecular weight that improves polyester to a certain extent that is introduced in of chainextender.But there is complex process in this method, to shortcoming such as environment is unfriendly, thereby its application is restricted.In addition, people again with a kind of with TiO
2And SiO
2Copolymerization mixed oxide compound high-activity polyester catalyst be incorporated into (Seidel U, Eckert T, Chem.Fibers Int, 1999,49,27) in the pet reaction.This catalyzer has high reaction activity and high, can reduce the reaction times of polyester, but its existence can make color articles problem such as turn to be yellow mutually, thereby influences the outward appearance of product.Generally speaking, the processing rheological of polymkeric substance is not only relevant with its molecular weight and the size that distributes thereof, but also relevant with the cladodification structure of polymkeric substance.Therefore, the research of relevant branched co-polyester just gets more and more people's extensive concerning.People are that the cladodification agent comes modification PBS with three methanol-based propane, thereby make cladodification PBS (Kim E.K, Bae J.S, J Appl Polym Sci, 2001,80,1388).The result shows that the introducing of cladodification agent can be at the rheological property that has to a certain degree improved PBS.But compare with pure PBS, the molecular weight of cladodification PBS and mechanical property are to a certain degree descending to some extent, thereby influence its range of application.
Summary of the invention
The purpose of this invention is to provide a kind of have an actual application value and competitive relatively Biodegradable branched co-polyester of price, and its preparation method.This copolyesters can overcome the defective on the pure PBS material property, as having higher relatively percent crystallinity and crystallization velocity and lower melt strength and melt viscosity more slowly.
Another object of the present invention is to the defective that improves PBS and molecular weight of copolymer thereof via polycondensation, and a kind of composite catalyst system efficiently is provided.
Biodegradable branched co-polyester provided by the present invention, the component of its repeating unit constitute any a group in following three groups:
A. the acid constituents of (1) repeating unit: Succinic Acid;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%～99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5～C
10In alkanediol or the aliphatic tribasic alcohol one or more;
B. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%～99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5～C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol;
C. the acid constituents of (1) repeating unit: Succinic Acid, the molar content that accounts for total acid is 85%～99%, all the other acid constituentss are aliphatic dibasic acids, the C that contains side group
3, C
5～C
8In chain docosandioic acid, terephthalic acid or the triprotic acid one or more;
(2) alkoxide component of repeating unit: butyleneglycol, the molar content that accounts for total alcohol is 75%～99.5%, all the other alkoxide components are aliphatic diol, the C that contains side group
2, C
3, C
5～C
10In alkanediol or the aliphatic tribasic alcohol one or more;
Wherein, the molar content ratio of alkoxide component and acid constituents is 1.1～1.4 among three groups of A, B and the C;
The intrinsic viscosity of the copolyesters that obtains is 0.6～2.2dl/g; 70～115 ℃ of fusing points; Percent crystallinity 20～70%, weight-average molecular weight are 5～300,000, and tensile strength is 30～60MPa; Elongation at break is 40～500%, and the biodegradability of said copolyesters is according to ASTMD5338 weightlessness 6～17% in a week.
Thermal properties such as the fusing point of Biodegradable branched co-polyester provided by the invention and percent crystallinity are detected by differential scanning calorimeter, and intrinsic viscosity is to be solvent with the trichloromethane, utilize Ubbelohde viscosity number meter to detect down for 25 ℃ in temperature; The composition of branched co-polyester is to be solvent by deuterochloroform, characterizes the structure and the composition of branched co-polyester with result that nuclear magnetic resonance spectrometer is surveyed; Molecular weight is to be solvent by chloroform, and PS is a standard specimen, adopts the GPC method to measure.Tensile strength and elongation at break are tested according to the dumbbell shape sample of ASTM D638 regulation.The biodegradability of material adopts composting process to measure according to ASTM D5338.
Said copolyesters comprises poly-succinic acid-butanediol-common-Succinic Acid 1,2,4-trihydroxybutane ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-pinakon ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1, the 2-pentadiol ester; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2-decanediol ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid pinakon-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic acid-butanediol-altogether-the Succinic Acid pinakon-altogether-Succinic Acid 1,2-pinakon ester; Poly-succinic acid-butanediol-be total to-2,2-dimethyl succinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the pyrovinic acid butanediol ester; Poly-succinic acid-butanediol-altogether-the trimesic acid butanediol ester; Poly-succinic acid-butanediol-altogether-mutual-phenenyl two acid bromide two alcohol ester; Poly-succinic acid-butanediol-altogether-the terephthalic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-the trimesic acid butyleneglycol-altogether-tetramethylene adipate; Poly-succinic acid-butanediol-altogether-Succinic Acid 1,2, the 3-glycerine ester; Poly-succinic, butyleneglycol, hexanodioic acid and 1,2, the copolyesters of 3-USP Kosher or poly-succinic, butyleneglycol, trimesic acid and 1,2, the copolyesters of 3-USP Kosher.
The said aliphatic diol that contains side group is for having the C of alkyl branches (R)
2～C
10Alkanediol, wherein the carbon number of R is 1～12.
The said aliphatic dibasic acids that contains side group is for having the C of alkyl branches (R)
3～C
8The chain docosandioic acid, wherein the carbon number of R is 1～12.
Said aliphatic tribasic alcohol is 1,2,4-trihydroxybutane or 1,2,3-USP Kosher.
Said triprotic acid is trimesic acid or benzene-1.
The preparation method of Biodegradable branched co-polyester provided by the present invention, accomplish according to following operation steps:
(1) prepolymer is synthetic
By acid and pure molar content and component in above-mentioned A, B or the C group; It is joined in the reactor drum with temperature-programmed mode temperature reaction system to 140～250 ℃; Be warmed up to 180～240 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 50～100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 180～220 ℃ of following violent stirring.
(2) polycondensation of multipolymer
Esterification cools to 150～160 ℃ with system after finishing, and connects vacuum system; Be evacuated to below the 0.5mmHg, reaction 5～10min participates in the small molecules of reaction and the water of remnants in the removal system; Stop to vacuumize and feeding nitrogen, add composite catalyst 2 * 10
-4～50 * 10
-4G/g polyester, and stablizer 2 * 10
-4～50 * 10
-4The g/g polyester; Stir 10～30min and guarantee that catalyzer is dispersed in the reaction system; Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 200 ℃～240 ℃ of temperature of reaction; Keep simultaneously stirring fast, isothermal reaction 30～100min promptly obtains product under vacuum state.
Said composite catalyst is one or more in tetrabutyl titanate, isopropyl titanate, titanium oxide and silicon dioxide coprecipitate, Antimony Trioxide: 99.5Min, zinc acetate, Cobaltous diacetate, lanthanum acetate, acetic acid zirconium, acetic acid hafnium, manganese acetate, zinc chloride, Lanthanum trichloride, zirconium chloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone zirconium, methyl ethyl diketone hafnium, inferior tin oxalate or the stannous octoate.Preferred tetrabutyl titanate and the mixture of methyl ethyl diketone lanthanum or the mixture of titanium oxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum, wherein the mol ratio of tetrabutyl titanate or titanium oxide and silicon dioxide coprecipitate and methyl ethyl diketone lanthanum is 1: 1.
Said stablizer is one or more couplings in phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, phosphorous acid diphenyl ester, ammonium phosphite or the primary ammonium phosphate.
The new synthetic method of a kind of Biodegradable branched co-polyester provided by the invention; Compare with the binary polyester; Under the condition of same composition; The preparation technology and the catalystsystem of the present invention's exploitation can shorten the course of processing and time greatly, and the side chain comonomer of introducing simultaneously or the comonomer of trifunctional can be given the new performance of polyester and improve the processing characteristics of polyester, have further expanded the Application Areas of Biodegradable branched co-polyester.
Embodiment
Provide embodiment below; But it is worthy of note that the present invention is not limited to these and implements example; The ordinary skill of this area to some nonessential change and adjustment that the present invention has done, still belongs to protection scope of the present invention according to the content of foregoing invention.
Embodiment 1
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2,4-trihydroxybutane ester
Take by weighing Succinic Acid 0.40mol and butyleneglycol 0.4224mol respectively, and 1,2,4-trihydroxybutane 0.0176mol adds reactor drum, wherein connects stirring flatly, connects nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 155 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 60min promptly obtains product under vacuum state.
Through detecting, the mol ratio of succinic acid-butanediol ester and Succinic Acid 1,2,4 trihydroxybutane esters is 96.2/3.8 in the product.25 ℃ following that intrinsic viscosity is 0.90dl/g.Fusing point is 105 ℃, and percent crystallinity is 43%.Weight-average molecular weight M
wBe 122000, tensile strength is 45MPa, and elongation at break is 36.8%, and the biodegradability of material is according to ASTMD5338 weightlessness 10% in a week.
Embodiment 2
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2-pinakon ester
Take by weighing Succinic Acid 0.40mol and butyleneglycol 0.396mol respectively, and 1,2-pinakon 0.044mol adds reactor drum, wherein connects stirring flatly, connects nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 200 ℃, keep simultaneously stirring fast, isothermal reaction 80min promptly obtains product under vacuum state.
Through detection, succinic acid-butanediol ester and Succinic Acid 1 in the product, it is 90.4/9.6 that 2-pinakon ester gets mol ratio.25 ℃ following that intrinsic viscosity is 0.74dl/g.Fusing point is 100 ℃, and percent crystallinity is 32%.Weight-average molecular weight M
wBe 111000, tensile strength is 36MPa, and elongation at break is 210%, and the biodegradability of material is according to ASTMD5338 weightlessness 12% in a week.
Embodiment 3
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1, the 2-pentadiol ester
Take by weighing Succinic Acid 0.40mol and 1 respectively, 2-pentanediol 0.066mol, and butyleneglycol 0.374mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 90min promptly obtains product under vacuum state.
Through detection, succinic acid-butanediol ester and Succinic Acid 1 in the product, the mol ratio of 2-pentadiol ester is 85.1/14.9.25 ℃ following that intrinsic viscosity is 0.70dl/g.Fusing point is 95 ℃, and percent crystallinity is 30%.Weight-average molecular weight M
wBe 111000, the biodegradability of material is according to ASTMD5338 weightlessness 15% in a week.
Embodiment 4
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2-decanediol ester
Take by weighing Succinic Acid 0.40mol and 1 respectively, 2-decanediol 0.10mol, and butyleneglycol 0.34mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detection, Succinic Acid fourth diester and Succinic Acid 1 in the product, it is 78.4/21.6 that 2-decanediol ester gets mol ratio.25 ℃ following that intrinsic viscosity is 0.60dl/g.Fusing point is 80 ℃, and percent crystallinity is 25%.Weight-average molecular weight M
wBe 102000, the biodegradability of material is according to ASTMD5338 weightlessness 15% in two weeks.
Embodiment 5
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid pinakon-common-Succinic Acid 1,2, the 3-glycerine ester
Take by weighing Succinic Acid 0.4mol and pinakon 0.02mol respectively, 1,2,3-USP Kosher 0.02mol, and butyleneglycol 0.4mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 160 ℃; Be warmed up to 240 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detection, succinic acid-butanediol ester, Succinic Acid pinakon ester and Succinic Acid 1,2 in the product, the mol ratio of 3-glycerine ester is 91: 4.5: 4.5.25 ℃ following that intrinsic viscosity is 1.5dl/g.Fusing point is 102 ℃, and percent crystallinity is 40%.Weight-average molecular weight Mw is 194000, and the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 6
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid pinakon-common-Succinic Acid 1,2-pinakon ester
Take by weighing Succinic Acid 0.4mol and pinakon 0.02mol respectively, 1,2-pinakon 0.02mol, and butyleneglycol 0.4mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detection, succinic acid-butanediol ester, Succinic Acid pinakon ester and Succinic Acid 1 in the product, the mol ratio of 2-pinakon alcohol ester is 91: 4.5: 4.5.25 ℃ following that intrinsic viscosity is 1.4dl/g.Fusing point is 103 ℃, and percent crystallinity is 40%.Weight-average molecular weight Mw is 183000, and the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 7
Present embodiment is a preparation poly-succinic acid-butanediol-altogether-2,2-dimethyl succinic acid butanediol ester
Take by weighing Succinic Acid 0.35mol and 2 respectively, 2-dimethyl succinic acid 0.05mol, and butyleneglycol 0.44mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 220 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detection, Succinic Acid fourth diester and 2 in the product, the mol ratio of 2-dimethyl succinic acid fourth diester is 88/12.Intrinsic viscosity under 25 ℃ is 0.90dl/g.Fusing point is 95 ℃, and percent crystallinity is 34%.Weight-average molecular weight M
wBe 122000, the biodegradability of material is according to ASTMD5338 weightlessness 14% in two weeks.
Embodiment 8
Present embodiment is preparation poly-succinic acid-butanediol-common-pyrovinic acid butanediol ester
Take by weighing Succinic Acid 0.36mol and pyrovinic acid 0.04mol respectively, and butyleneglycol 0.44mol, add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 90min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, to get mol ratio be 90.2/9.8 for Succinic Acid fourth diester and pyrovinic acid fourth diester in the product.25 ℃ following that intrinsic viscosity is 0.92dl/g.Fusing point is 98 ℃, and percent crystallinity is 36%.Weight-average molecular weight M
wBe 127000, the biodegradability of material is according to ASTMD5338 weightlessness 12% in two weeks.
Embodiment 9
Present embodiment is preparation poly-succinic acid-butanediol-common-trimesic acid butanediol ester
Take by weighing Succinic Acid 0.38mol and trimesic acid 0.02mol respectively, and butyleneglycol 0.44mol, add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, to get mol ratio be 95.3/4.7 for succinic acid-butanediol ester and trimesic acid butanediol ester in the product.25 ℃ following that intrinsic viscosity is 0.88dl/g.Fusing point is 106 ℃, and percent crystallinity is 45%.Weight-average molecular weight M
wBe 119000, the biodegradability of material is according to ASTMD5338 weightlessness 7% in two weeks.
Embodiment 10
Present embodiment is preparation poly-succinic acid-butanediol-common-mutual-phenenyl two acid bromide two alcohol ester
Take by weighing Succinic Acid 0.36mol and terephthalic acid 0.04mol respectively, and butyleneglycol 0.44mol, add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 220 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, succinic acid-butanediol ester and mutual-phenenyl two acid bromide two alcohol ester's mol ratio is 90.4/9.6 in the product.Intrinsic viscosity under 25 ℃ is 0.89dl/g.Fusing point is 110 ℃, and percent crystallinity is 46%.Weight-average molecular weight M
wBe 120000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 11
Present embodiment is preparation poly-succinic acid-butanediol-common-terephthalic acid butyleneglycol-common-tetramethylene adipate
Take by weighing Succinic Acid 0.36mol and terephthalic acid 0.02mol respectively, hexanodioic acid 0.02mol and butyleneglycol 0.44mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, the mol ratio of succinic acid-butanediol ester and mutual-phenenyl two acid bromide two alcohol ester and hexanodioic acid butyleneglycol is 90.5/4.7/4.8 in the product.Intrinsic viscosity under 25 ℃ is 0.86dl/g.Fusing point is 110 ℃, and percent crystallinity is 46%.Weight-average molecular weight M
wBe 118000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 12
Present embodiment is preparation poly-succinic acid-butanediol-common-trimesic acid butyleneglycol-common-tetramethylene adipate
Take by weighing Succinic Acid 0.36mol and trimesic acid 0.02mol respectively, hexanodioic acid 0.02mol and butyleneglycol 0.44mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, the mol ratio of succinic acid-butanediol ester, trimesic acid butanediol ester and hexanodioic acid butyleneglycol is 91.0/4.6/4.4 in the product.Intrinsic viscosity under 25 ℃ is 0.88dl/g.Fusing point is 110 ℃, and percent crystallinity is 46%.Weight-average molecular weight M
wBe 119000, the biodegradability of material is according to ASTMD5338 weightlessness 10% in two weeks.
Embodiment 13
Present embodiment is preparation poly-succinic acid-butanediol-common-Succinic Acid 1,2, the 3-glycerine ester
Take by weighing Succinic Acid 0.4mol and 1,2 respectively, 3-USP Kosher 0.0022mol, and butyleneglycol 0.4378mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 180 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 180 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detection, succinic acid-butanediol ester and Succinic Acid 1,2 in the product, it is 99.6/0.4 that the 3-glycerine ester gets mol ratio.25 ℃ following that intrinsic viscosity is 2.2dl/g.Fusing point is 112 ℃, and percent crystallinity is 49%.Weight-average molecular weight M
wBe 300000, the biodegradability of material is according to ASTMD5338 weightlessness 8% in two weeks.
Embodiment 14
Present embodiment is the atactic polyester of preparation (Succinic Acid, hexanodioic acid, butyleneglycol, 1,2,3-USP Kosher)
Take by weighing Succinic Acid 0.36mol and hexanodioic acid 0.04mol respectively, 1,2,3-USP Kosher 0.0022mol, and butyleneglycol 0.4378mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg mmHg, and be rapidly heated to 220 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
Through detecting, the intrinsic viscosity of 25 ℃ of following these atactic polyesters is 1.2dl/g.Fusing point is 103 ℃, and percent crystallinity is 45%.Weight-average molecular weight Mw is 16000, and the biodegradability of material is according to ASTMD5338 weightlessness 7% in two weeks.
Embodiment 15
Present embodiment is the atactic polyester of preparation (Succinic Acid, trimesic acid, butyleneglycol, 1,2,3-USP Kosher)
Take by weighing Succinic Acid 0.38mol and trimesic acid 0.02mol respectively, 1,2,3-USP Kosher 0.0022mol, and butyleneglycol 0.4378mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 155 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 80min up to the system thickness, the prepolymer that obtains no longer splashes 200 ℃ of following violent stirring.
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system.Stop to vacuumize and feeding nitrogen, add the about 0.001mol of mixture of titanium silicon coprecipitate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 100min under vacuum state promptly obtains product.
The intrinsic viscosity of this atactic polyester is 1.8dl/g under detecting 25 ℃.Fusing point is 103 ℃, and percent crystallinity is 45%.Weight-average molecular weight Mw is 253000, and the biodegradability of material is according to ASTMD5338 weightlessness 6% in two weeks.
Reference
[1]Zhao?J.B，Li?K.Y，Yang?W.T，Chain?extension?of?polybutylene?adipate?and?polybutylenesuccinate?with?adipoyl-and?terephthaloyl-biscaprolactamate，J?Appl?Polym?Sci，2007，106，590.
[2]Seidel?U，Eckert?T，New，highly?active?PET?catalyst?commercially?available?on?productionscale，Chem.Fibers?Int，1999，49，27.
[3]Kim?E.K，Bae?J.S，Preparation?and?properties?of?branched?polybutylenesuccinate，J?ApplPolym?Sci，2001，80，1388.
Claims (1)
1. the preparation method of a Biodegradable branched co-polyester is characterized in that, carries out according to following steps:
Take by weighing Succinic Acid 0.40mol and 1 respectively, 2-pentanediol 0.066mol, and butyleneglycol 0.374mol add reactor drum, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; Be warmed up to 200 ℃ with temperature-programmed mode behind the reaction 10min; Keep this thermotonus 100min up to the system thickness, the prepolymer that obtains extremely no longer splashes 200 ℃ of following violent stirring;
Esterification cools to 150 ℃ with system after finishing, and when continuing logical nitrogen, removes water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to below the 0.5mmHg, reaction 10min participates in the small molecules and remaining water of reaction in the removal system; Stop to vacuumize and feeding nitrogen; Mixture
0.001mol that adds tetrabutyl titanate and methyl ethyl diketone lanthanum, and triphenyl phosphite 0.001mol; Stir 10min and guarantee that catalyzer is dispersed in the reaction system; Stop logical nitrogen, be evacuated to below the 0.5mmHg, and be rapidly heated to 240 ℃, keep simultaneously stirring fast, isothermal reaction 90min promptly obtains product under vacuum state.
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| CN102850533B (en) * | 2011-07-01 | 2015-10-14 | 上海杰事杰新材料(集团)股份有限公司 | A kind of biodegradable polyesters and preparation method thereof |
| CN102344556B (en) * | 2011-08-08 | 2013-11-20 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
| KR20130027095A (en) * | 2011-09-02 | 2013-03-15 | 삼성정밀화학 주식회사 | Method of preparation for biodegradable co-polyester resin |
| CN103788348B (en) * | 2013-12-27 | 2016-02-03 | 上海华谊（集团）公司 | Prepare the method for modified butanediol ester poly succinic acid |
| CN107312165B (en) * | 2016-04-26 | 2020-04-24 | 中国科学院理化技术研究所 | Degradable thermoplastic polyester elastomer with side chain and preparation method thereof |
| CN109867921A (en) * | 2018-12-19 | 2019-06-11 | 长春工业大学 | A kind of PBS composite material and preparation method of the toughener containing PBST |
| CN111499849A (en) * | 2020-05-29 | 2020-08-07 | 陕西科技大学 | Polyhydroxy hydrophilic biodegradable material and preparation method and application thereof |
| CN113881198B (en) * | 2021-10-22 | 2024-03-01 | 汉中聚智达远环能科技有限公司 | Biodegradable material with polar groups for adhesive tape production and preparation method thereof |
| CN114133544B (en) * | 2021-12-13 | 2023-03-14 | 常州大学盱眙凹土研发中心 | Biodegradable hyperbranched modified PBS (Poly Butylene succinate) polyester and preparation method thereof |
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