CN101735435A - Copolymer of aliphatic poly propylene carbonate-aromatic polyester and method for preparing same - Google Patents
Copolymer of aliphatic poly propylene carbonate-aromatic polyester and method for preparing same Download PDFInfo
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Abstract
The invention relates to a copolymer of aliphatic poly propylene carbonate-aromatic polyester and a method for preparing the same. The copolymer is formed by the random copolymerization of 6 to 120 dihydric alcohol monomers of the poly propylene carbonate, 10 to 200 monomers of aromatic diacid dimethyl ester and 10 to 200 aliphatic glycol monomers. The method for preparing the copolymer adopts the melt direct condensation polymerization, and particularly comprises the following steps of: adding raw materials of A, B and C and an esterifying catalyst into a reaction kettle for etherification reaction; and adding a condensation polymerization catalyst to perform an reaction to obtain the copolymer, wherein the raw material A is dimethyl terephthalate, isophthalic acid dimethyl ester, 1.4-naphthalic acid dimethyl ester or 2,6-naphthalic acid dimethyl ester, the raw material B is ethylene glycol, propylene glycol, butylene glycol, pentanediol or hexanediol, and the raw material C is poly ethylene carbonate glycol, poly propylene carbonate glycol or poly butylene carbonate glycol. The copolyester of the invention is high in molecular weight, is a raw material capable of being biologically degraded, and combines the heat resistant property of aromatics, and the copolymer can be widely applied to fiber materials and plastic products. The method for preparing the copolyester has a simple process and a low cost.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the copolyesters of a kind of aliphatic poly propylene carbonate and aromatic polyester, and the preparation method of this copolyesters.
Background technology
The polymerized thylene carbonate diol ester is a kind of macromolecular material that utilizes carbonic acid gas and synthesis of epoxy compounds to form, wherein aliphatics polymerized thylene carbonate diol ester has good biodegradability, and this kind polyester generally has good low-temperature kindliness, barrier properties for gases and transparency, makes carrier, film packing material, solid electrolyte, inorganic filler surface processing of its useful as drug slow-releasing system etc.But because the relatively poor thermostability of aliphatics polymerized thylene carbonate diol ester self has a strong impact on its practical application in every field.
In the research of aliphatics polymerized thylene carbonate diol ester, studying morely both at home and abroad has polymerized thylene carbonate glycol ester glycol, polymerized thylene carbonate butanediol ester glycol, the copolymerization of polymerized thylene carbonate propylene glycol ester glycol and other compounds, such as synthesizing polymerized thylene carbonate urethane elastomer (CN1865311A) by polymerized thylene carbonate ethyl ester and vulcabond, be the poly propylene carbonate type books elastomerics (Xie Xingyi that the synthetic class of raw material has premium properties for example again with the inferior ester dibasic alcohol of poly-own diamyl two carbonic acid, Liu's Singapore, the clock elecscreen. the biomedical engineering magazine, 1999,16:121-122), perhaps synthesize some solvent-proof aliphatic poly propylene carbonate type polyurethane elastomerics (Harris RF, Joseph MD, Avisdson CD er al.J Appl Polym Sci, 1990,41:487-507), perhaps with poly (propylene carbonate) and tolylene diisocyanate be raw material synthesized the poly (propylene carbonate) polyurethane elastomer (Peng Han etc. the synthetic and performance of poly (propylene carbonate) polyurethane elastomer, chemistry world, 1995,8:426-428).
Than the polymerized thylene carbonate diol ester, aromatic polyester then is a very detailed class superpolymer of research, as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT), they all have good thermotolerance, HDT temperature height, resistance to chemical attack, are the macromolecular materials of high comprehensive performance, have been widely used in fields such as fiber and film at present.Yet, the waste product huge amount after it uses and very strong to the resistivity of microorganism, having the cycle is 30～50 years, and environment is caused very big pollution.
In order to improve the degradation property of aromatic polyester, the investigator is carrying out a large amount of work aspect blend and the modification by copolymerization both at home and abroad.Aspect blend, blend result synthetic or natural polymer such as PET and PLA, PEG, starch, PCL shows that easily the degraded of degradable component can cause the part biological of material to destroy.(Polym.Int. 199639:83) adopts direct polycondensation method to prepare a series of PET-PEG multipolymers to Nagata etc., and experimental result shows that the introducing of PEG has reduced PET segmental regularity, has increased the wetting ability of polymkeric substance.In addition, there is the scholar to adopt ester-interchange method to prepare a series of multipolymers, as PET-PGA (Polish patent such as Niekraszewicz, 171 062 B1; Polym.Prepr., 198930:197), PET-PHB (Japanese patent such as Imu, 08217865A2), PET-BS (Pollimo. such as Kim, 199620:431), PET-PCL (Polym.Degrad.Stabil. such as Tokiwa, 199445:205), PET-PEA (J.Environ.Polym.Degrad. such as Heidary, 19942:19), yet this series reaction needs very high temperature of reaction, this can cause the degraded of aliphatic polyester, and transesterify efficient is lower.
On the main chain of aromatic polyester, introduce the structural unit of aliphatic polyester or the degradation property that segment can improve multipolymer, through the synthetic aliphatic-aromatic copolyester PBAT (Ecoflex of BASF and the Biomax of Dupont) that obtains of polycondensation, is a kind of polyester material of Wholly-degradable as butyleneglycol, hexanodioic acid and terephthalic acid.
In sum, the copolyesters of preparation aliphatic poly propylene carbonate and aromatic polyester both can solve the problem of aliphatic poly propylene carbonate poor heat resistance, can give the aromatic polymer biodegradability again, made copolyesters obtain the excellent comprehensive performance.So the copolyesters of development aliphatic poly propylene carbonate and aromatic polyester is highly significant.
Summary of the invention
The objective of the invention is provides a kind of biodegradable copolyesters at the above-mentioned state of the art, and the preparation method of a kind of technology this copolyesters simple, with low cost is provided.
Aliphatic poly propylene carbonate-aromatic polyester multipolymer of the present invention is formed by 6～120 dihydric alcohol monomers, 10～200 aromatic diacid dimethyl ester monomers, the random copolymerization of 10～200 aliphatic diol monomers, and molecular weight is 5000～60000g/mol; Wherein
The monomeric molecular formula of described aromatic diacid dimethyl ester is CH
3O-R
1-OCH
3
Radicals R
1For
In one or more;
The monomeric molecular formula of described aliphatic diol is HO-R
2-OH
Radicals R
2For
In m=2～6 one or more.
The molecular formula of described dihydric alcohol monomers is
Radicals R
3For
In one or more.
The method for preparing this copolyesters adopts the fusion direct polycondensation method, and concrete steps are:
With mole ratio is 0.01～19.8: 51.6～0.52: 77.4～0.62 reactant A, B, C add in the reactor with esterifying catalyst, carry out esterification under 140～260 ℃, 0.1～0.5MPa condition; Behind esterification 2～3.5h, add polycondensation catalyst, under 140～280 ℃, 0.1～300Pa, reacted 20～400 minutes, obtain high-molecular weight hypocrystalline aliphatic poly propylene carbonate-aromatic polyester multipolymer.
The add-on of described esterifying catalyst is reactant A, B, C total mass 0.001～10%, and the add-on of described polycondensation catalyst is reactant A, B, C total mass 0.001～10%.
Described reactant A is for being dimethyl terephthalate (DMT), dimethyl isophthalate, 1,4-naphthalene diformic acid dimethyl ester, 2, one or more in the 6-naphthalene diformic acid dimethyl ester.
Described reactant B is one or more in ethylene glycol, propylene glycol, butyleneglycol, pentanediol, the hexylene glycol.
Described reactant C is that weight-average molecular weight is one or more in the polymerized thylene carbonate ethyl ester glycol, poly (propylene carbonate) glycol, polymerized thylene carbonate butyl ester glycol of 1000～10000g/mol.
Described esterifying catalyst is one or more in compound zinc acetate, weisspiessglanz, manganese acetate, Cobaltous diacetate, the tin protochloride.
Described polycondensation catalyst is one or more of tetrabutyl titanate, titanium tetraisopropylate ester, titanium dioxide, zinc acetate, zinc oxide, antimony acetate, antimonous oxide, Cobaltous diacetate, tin protochloride, stannous octoate.
Copolyesters of the present invention is synthetic easily, the molecular weight height, can become a kind of can biodegradable material, in conjunction with aromatic resistance toheat, this multipolymer can be widely used in filamentary material and plastics.The preparation method of this copolyesters is that technology is simple, and is with low cost.
Description of drawings
Fig. 1 is the nuclear magnetic spectrogram of the copolyesters of the present invention's acquisition.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 0.15mol polymerized thylene carbonate ethyl ester glycol (molecular weight 1000g/mol), 1.35mol ethylene glycol and 0.0022g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 190 ℃ then, the 0.1MPa that keep-ups pressure, reaction 2.7h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.11g tetrabutyl titanate, mix after 5 minutes and heat up once more, temperature is risen to 230 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 0.1Pa, react 400min under this high vacuum condition, obtain intrinsic viscosity and be yellow poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-glycol ester polymkeric substance of 0.62, DSC records this compound does not have obvious exothermic peak.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 1.1mol polymerized thylene carbonate ethyl ester glycol (molecular weight 1500g/mol), 0.3mol poly (propylene carbonate) glycol (molecular weight 1000g/mol), 0.1mol propylene glycol and 0.506g weisspiessglanz drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 190 ℃ then, the 0.2MPa that keep-ups pressure, reaction 2.1h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the propylene glycol solution 20ml that contains 0.1g titanium tetraisopropylate ester, mix after 5 minutes and heat up once more, temperature is risen to 220 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 15Pa, react 3.5h under this high vacuum condition, obtain intrinsic viscosity and be light yellow poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-glycol ester polymkeric substance of 0.65, it is 201 ℃ that DSC records fusing point.
Under normal temperature with 0.1mol dimethyl isophthalate, 0.9mol dimethyl terephthalate (DMT), 1.3mol poly (propylene carbonate) glycol (molecular weight 2000g/mol), 0.2mol butyleneglycol and 0.55g manganese acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 260 ℃ then, 0.3MPa keep-ups pressure, reaction 2h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains 0.11g titanium dioxide, mix after 5 minutes and heat up once more, temperature is risen to 240 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 50Pa, react 20min under this high vacuum condition, obtain intrinsic viscosity and be the poly-m-phthalic acid of yellow-poly (propylene carbonate) glycol-glycol ester polymkeric substance of 0.41, it is 178 ℃ that DSC records fusing point.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 1.3mol poly (propylene carbonate) glycol (molecular weight 1200g/mol), 0.2mol pentanediol and 0.456g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 190 ℃ then, the 0.1MPa that keep-ups pressure, reaction 2.2h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.09g zinc acetate, mix after 5 minutes and heat up once more, temperature is risen to 140 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 1Pa, react 3.5h under this high vacuum condition, obtain intrinsic viscosity and be yellow poly terephthalic acid-poly (propylene carbonate) glycol-Diethylene Glycol ester polymer of 0.71, it is 208 ℃ that DSC records fusing point.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 1.2mol polymerized thylene carbonate ethyl ester glycol (molecular weight 3000g/mol), 0.3mol butyleneglycol, 12.5g pentanediol, 20.8g propylene glycol and 0.555g Cobaltous diacetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 200 ℃ then, the 0.1MPa that keep-ups pressure, reaction 2.7h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the propylene glycol solution 20ml that contains 0.11g zinc oxide, mix after 5 minutes and heat up once more, temperature is risen to 215 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 10Pa, react 3.0h under this high vacuum condition, obtain intrinsic viscosity and be tawny poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-propylene glycol ester polymkeric substance of 0.83, it is 165 ℃ that DSC records fusing point.The nuclear-magnetism spectrum of the copolyesters that obtains as shown in Figure 1.
G under normal temperature with the 1mol dimethyl isophthalate, 1.2mol polymerized thylene carbonate ethyl ester glycol (molecular weight 5000g/mol), 0.3mol hexylene glycol and 0.47g Cobaltous diacetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 140 ℃ then, the 0.1MPa that keep-ups pressure, reaction 3.0h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 130 ℃ after finishing, add the propylene glycol solution 20ml that contains the 0.09g antimony acetate, mix after 5 minutes and heat up once more, temperature is risen to 215 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 35Pa, react 3.0h under this high vacuum condition, obtain intrinsic viscosity and be yellow poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-propylene glycol ester polymkeric substance of 0.96, it is 211 ℃ that DSC records fusing point.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 0.3mol polymerized thylene carbonate ethyl ester glycol (molecular weight 6000g/mol), 1.0mol ethylene glycol, 0.2 butyleneglycol and 0.566g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 140 ℃ then, the 0.5MPa that keep-ups pressure, reaction 2.5h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is warming up to 160 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.11g antimonous oxide, mix after 5 minutes and heat up once more, temperature is risen to 170 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 25Pa, react 4.5h under this high vacuum condition, obtain intrinsic viscosity and be deep yellow poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-butanediol ester polymkeric substance of 0.74, it is 167 ℃ that DSC records fusing point.
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 1.1mol polymerized thylene carbonate ethyl ester glycol (molecular weight 10000g/mol), 0.4mol pentanediol and 0.484g tin protochloride drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 190 ℃ then, the 0.2MPa that keep-ups pressure, reaction 2.5h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.10g Cobaltous diacetate, mix after 5 minutes and heat up once more, temperature is risen to 180 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 100Pa, react 4h under this high vacuum condition, obtain intrinsic viscosity and be yellow poly terephthalic acid-polymerized thylene carbonate ethyl ester glycol-butanediol ester polymkeric substance of 0.68, it is 205 ℃ that DSC records fusing point.
Embodiment 9.
Under normal temperature with 0.8mol 1, the 4-naphthalene diformic acid dimethyl ester, 0.2mol dimethyl terephthalate (DMT), 0.2mol polymerized thylene carbonate ethyl ester glycol (molecular weight 500g/mol), 0.3mol poly (propylene carbonate) glycol (molecular weight 1000g/mol), 0.3mol polymerized thylene carbonate butyl ester glycol (molecular weight 10000g/mol), 0.7mol poly (propylene carbonate) glycol (molecular weight 5000g/mol) and 100g polymerized thylene carbonate butyl ester glycol (molecular weight 500g/mol), 60.8g propylene glycol, 0.554g tin protochloride and 0.002g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 150 ℃ then, 0.4MPa keep-ups pressure, reaction 2.0h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the propylene glycol solution 20ml that contains the 0.12g tin protochloride, mix after 5 minutes and heat up once more, temperature is risen to 190 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 55Pa, react 4.0h under this high vacuum condition, obtain intrinsic viscosity and be yellow poly terephthalic acid-poly (propylene carbonate) glycol-dipropylene glycol ester polymer of 0.91, it is 175 ℃ that DSC records fusing point.
Embodiment 10. poly terephthalic acids-poly (propylene carbonate) glycol-dipropylene glycol ester copolymer
Under normal temperature with the 1mol dimethyl terephthalate (DMT), 0.5mol poly (propylene carbonate) glycol (molecular weight 8000g/mol), 1mol hexylene glycol and 0.554g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 180 ℃ then, 0.2MPa keep-ups pressure, reaction 2.5h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the propylene glycol solution 20ml that contains the 0.12g stannous octoate, mix after 5 minutes and heat up once more, temperature is risen to 215 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 5Pa, react 3.4h under this high vacuum condition, obtain intrinsic viscosity and be khaki color poly terephthalic acid-poly (propylene carbonate) glycol-dipropylene glycol ester polymer of 0.99, it is 187 ℃ that DSC records fusing point.
Embodiment 11.
Under normal temperature, 1mol dimethyl isophthalate, 0.9mol polymerized thylene carbonate ethyl ester glycol (molecular weight 2000g/mol), 0.6mol polymerized thylene carbonate butyl ester glycol (molecular weight 1000g/mol), 0.4mol ethylene glycol, 0.2 butyleneglycol, 0.3 mole of hexylene glycol and 0.544g zinc acetate are dropped in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 190 ℃ then, 0.1MPa keep-ups pressure, reaction 3h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.16g tetrabutyl titanate and contain the 0.12g stannous octoate, mix after 5 minutes and heat up once more, temperature is risen to 220 ℃, beginning vacuumizes lentamente in the temperature-rise period, the about 40min of vacuum process, then vacuum tightness is brought up to 300Pa, under this high vacuum condition, react 6h, obtain intrinsic viscosity and be the poly-m-phthalic acid of deep yellow-polymerized thylene carbonate ethyl ester glycol-glycol ester polymkeric substance of 0.51, DSC records this compound does not have obvious exothermic peak.
Embodiment 12.
Under normal temperature with 1mol 1, the 4-naphthalene diformic acid dimethyl ester, 1mol polymerized thylene carbonate butyl ester glycol (molecular weight 1500g/mol), 0.5mol ethylene glycol and 10.24g weisspiessglanz, 0.12g tin protochloride and 0.012g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 170 ℃ then, 0.1MPa keep-ups pressure, reaction 2.5h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains 0.16g titanium tetraisopropylate ester, 0.20g titanium dioxide and 0.11g zinc acetate, mix after 5 minutes and heat up once more, temperature is risen to 250 ℃, beginning vacuumizes lentamente in the temperature-rise period, the about 40min of vacuum process, then vacuum tightness is brought up to 100Pa, under this high vacuum condition, react 6h, obtain intrinsic viscosity and be the poly-m-phthalic acid of deep yellow-polymerized thylene carbonate butyl ester glycol-glycol ester polymkeric substance of 0.50, DSC records this compound does not have obvious exothermic peak.
Embodiment 13.
Under normal temperature with 1mol 2, the 6-naphthalene diformic acid dimethyl ester, 1.0mol polymerized thylene carbonate ethyl ester glycol (molecular weight 2500g/mol), 0.35mol poly (propylene carbonate) glycol (molecular weight 5000g/mol), 0.15mol ethylene glycol and 22g zinc acetate drop in the 1L reactor, charge into nitrogen after vacuumizing displacement, be warming up to 180 ℃ then, 0.3MPa keep-ups pressure, reaction 3.5h collects methyl alcohol and is considered as esterification to 95% of theoretical amount and finishes; Esterification is cooled to 140 ℃ after finishing, add the ethylene glycol solution 20ml that contains the 0.16g tetrabutyl titanate, mix after 5 minutes and heat up once more, temperature is risen to 280 ℃, and beginning vacuumizes the about 40min of vacuum process lentamente in the temperature-rise period, then vacuum tightness is brought up to 210Pa, react 400min under this high vacuum condition, obtain intrinsic viscosity and be the poly-m-phthalic acid of deep yellow-polymerized thylene carbonate ethyl ester glycol-glycol ester polymkeric substance of 0.42, DSC records this compound does not have obvious exothermic peak.
Claims (4)
1. aliphatic poly propylene carbonate-aromatic polyester multipolymer, it is characterized in that: this multipolymer is formed by 6～120 dihydric alcohol monomers, 10～200 aromatic diacid dimethyl ester monomers, the random copolymerization of 10～200 aliphatic diol monomers, and molecular weight is 5000～60000g/mol; Wherein
The monomeric molecular formula of described aromatic diacid dimethyl ester is CH
3O-R
1-OCH
3
Radicals R
1For
In one or more;
The monomeric molecular formula of described aliphatic diol is HO-R
2-OH
Radicals R
2For
In m=2～6 one or more;
The molecular formula of described dihydric alcohol monomers is
Radicals R
3For
In one or more.
2. the method for preparing the aliphatic poly propylene carbonate-aromatic polyester multipolymer is characterized in that this method adopts the fusion direct polycondensation method, and concrete steps are:
With mole ratio is 0.01～19.8: 51.6～0.52: 77.4～0.62 reactant A, B, C add in the reactor with esterifying catalyst, carry out esterification under 140～260 ℃, 0.1～0.5MPa condition; Behind esterification 2～3.5h, add polycondensation catalyst, under 140～280 ℃, 0.1～300Pa, reacted 20～400 minutes, obtain high-molecular weight hypocrystalline aliphatic poly propylene carbonate-aromatic polyester multipolymer;
The add-on of described esterifying catalyst is reactant A, B, C total mass 0.001～10%, and the add-on of described polycondensation catalyst is reactant A, B, C total mass 0.001～10%;
Described reactant A is for being dimethyl terephthalate (DMT), dimethyl isophthalate, 1,4-naphthalene diformic acid dimethyl ester, 2, one or more in the 6-naphthalene diformic acid dimethyl ester;
Described reactant B is one or more in ethylene glycol, propylene glycol, butyleneglycol, pentanediol, the hexylene glycol;
Described reactant C is that weight-average molecular weight is one or more in the polymerized thylene carbonate ethyl ester glycol, poly (propylene carbonate) glycol, polymerized thylene carbonate butyl ester glycol of 1000～10000g/mol.
3. the method for preparing the aliphatic poly propylene carbonate-aromatic polyester multipolymer as claimed in claim 2 is characterized in that described esterifying catalyst is one or more in compound zinc acetate, weisspiessglanz, manganese acetate, Cobaltous diacetate, the tin protochloride.
4. the method for preparing the aliphatic poly propylene carbonate-aromatic polyester multipolymer as claimed in claim 2 is characterized in that described polycondensation catalyst is one or more of tetrabutyl titanate, titanium tetraisopropylate ester, titanium dioxide, zinc acetate, zinc oxide, antimony acetate, antimonous oxide, Cobaltous diacetate, tin protochloride, stannous octoate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102241815A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Aliphatic polycarbonate-aromatic polyester copolymer, and preparation method thereof |
| CN109721719A (en) * | 2018-12-10 | 2019-05-07 | 沈阳化工大学 | One kind 1,8- naphthalene anhydride is modified the third rouge of polymerized thylene carbonate preparation method |
| CN111440299A (en) * | 2020-04-27 | 2020-07-24 | 四川轻化工大学 | Polycarbonate diol copolyester and preparation method thereof |
| CN112126046A (en) * | 2020-09-17 | 2020-12-25 | 上海华峰新材料研发科技有限公司 | Carbon dioxide-based copolyester and preparation method and application thereof |
| CN114573799A (en) * | 2022-03-11 | 2022-06-03 | 宁波梅山保税港区丰邦企业管理合伙企业(有限合伙) | Biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol and preparation method thereof |
| CN116217905A (en) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | Preparation method and application of high-water-resistance high-transparency degradable resin |
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2009
- 2009-12-29 CN CN200910155895A patent/CN101735435A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241815A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Aliphatic polycarbonate-aromatic polyester copolymer, and preparation method thereof |
| CN109721719A (en) * | 2018-12-10 | 2019-05-07 | 沈阳化工大学 | One kind 1,8- naphthalene anhydride is modified the third rouge of polymerized thylene carbonate preparation method |
| CN111440299A (en) * | 2020-04-27 | 2020-07-24 | 四川轻化工大学 | Polycarbonate diol copolyester and preparation method thereof |
| CN112126046A (en) * | 2020-09-17 | 2020-12-25 | 上海华峰新材料研发科技有限公司 | Carbon dioxide-based copolyester and preparation method and application thereof |
| CN112126046B (en) * | 2020-09-17 | 2022-10-21 | 华峰集团有限公司 | Carbon dioxide-based copolyester and preparation method and application thereof |
| CN114573799A (en) * | 2022-03-11 | 2022-06-03 | 宁波梅山保税港区丰邦企业管理合伙企业(有限合伙) | Biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol and preparation method thereof |
| CN114573799B (en) * | 2022-03-11 | 2024-01-12 | 宁波梅山保税港区丰邦企业管理合伙企业(有限合伙) | Biodegradable carbon dioxide-based copolyester-carbonate dihydric alcohol and preparation method thereof |
| CN116217905A (en) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | Preparation method and application of high-water-resistance high-transparency degradable resin |
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