CN103788352B - A kind of poly-barkite and preparation method thereof - Google Patents
A kind of poly-barkite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses poly-barkite and preparation method thereof, comprise the following steps: barkite, carbonatoms, under bulk polymerization conditions, are aliphatic dihydroxy alcohol and the mass polymerization catalyst exposure of 2-14, obtain barkite prepolymer by (1); (2) under vacuum state or protection of inert gas, the pre-crystallized rear granulation of barkite prepolymer step (1) obtained, obtains barkite prepolyer granule; (3) under vacuum state or inert gas exist, at solid phase polymerization conditions, make the polycondensation of barkite prepolyer granule, obtain poly-barkite.The molecular weight of poly-barkite provided by the invention is high.
Description
Technical field
The present invention relates to a kind of poly-barkite and preparation method thereof.
Background technology
Oxalic acid is the simplest diprotic acid, and industrial oxalic acid can use wood chip for waste, also can be obtained by starch or glucose mother liquid oxidation.Oxalic acid is a kind of raw material of biomass source, has cost lower, wide material sources and reproducible advantage.On chemical industry, oxalic acid is in order to manufacture the intermediate of tetramethylolmethane, cobalt oxalate, nickelous oxalate, alkalescent light green and various chemosynthesis, iron and steel, soil analysis reagent set etc., but application in polymer is few.
Poly-barkite is a kind of Biodegradable polyester, the feature such as there is fusing point high (higher than 100 DEG C), good static heat stability, second-order transition temperature is relatively low, temperature process window is wider, therefore poly-barkite has the potentiality becoming general-purpose plastics, can as the masterbatch of general-purpose plastics, also can as material of main part and thermoplastic starch, poly(lactic acid) etc. blended, make biodegradable plastic.Barkite material finds comparatively early, but does not have product development so far out, and current research is based on Japan.
Poly-barkite has biodegradable character, but comes out to now from being synthesized in laboratory for the first time, and research and the report of barkite are but quite few.Barkite polymkeric substance (polyoxalate, POX) can be synthesized by ester exchange method, also can by glycol (as ethylene glycol, 1,3-PD, 1,4-butyleneglycol) to synthesize with oxalic acid (or oxalyl chloride), the method is implemented simple, but is difficult to the barkite polymkeric substance obtaining high molecular.Polycondensation later stage typical temperature can reach more than 200 DEG C, and under this temperature, the reactions such as a series of decarboxylation, oxidation, degraded can occur oxalic acid, cause the molecular weight of polyester to reduce, color blackening etc.
At present poly-barkite polymerization adopts melt phase polycondensation usually, and during melt phase polycondensation, necessary high temperature can bring the reaction such as a series of decarboxylation, oxidation, degraded of polycondensation deuterogenesis under high temperature, causes the molecular weight of polyester to reduce, color blackening etc.
Method for solid phase polymerization is one of common method obtaining high quality and high average molecular weight polyester and polymeric amide, and it refers to a kind of polymerization process carried out higher than its second-order transition temperature at the fusing point lower than prepolymer.Be characterized in that polymerization temperature is low, the polymerization side reactions because thermolysis and thermooxidizing bring can be reduced significantly, effectively improve molecular weight, improve the transformation efficiency of monomer.Solid state polymerization, as a kind of traditional polymerization process, at nylon, has obtained extremely successful application in the material produce such as PET, PC, but there is not yet report in the polymerization of barkite.
Summary of the invention
The object of the invention is to adopt melt phase polycondensation to prepare in the process of poly-barkite to overcome in prior art, the thermolysis during high temperature during melt phase polycondensation can bring poly-barkite to be polymerized and the shortcoming of thermooxidizing, provide a kind of poly-barkite and preparation method thereof.
The invention provides a kind of preparation method of poly-barkite, the method comprises the following steps:
(1) under bulk polymerization conditions, be aliphatic dihydroxy alcohol and the mass polymerization catalyst exposure of 2-14 by barkite, carbonatoms, obtain barkite prepolymer;
(2) under vacuum state or nitrogen protection, the pre-crystallized rear granulation of barkite prepolymer step (1) obtained, obtains barkite prepolyer granule;
(3) under vacuum state or inert gas exist, at solid phase polymerization conditions, make the polycondensation of barkite prepolyer granule, obtain poly-barkite.
Present invention also offers the poly-barkite that a kind of aforesaid method prepares.
Method of the present invention uses method for solid phase polymerization, prepares the poly-barkite of high molecular, overcomes thermolysis and the thermooxidizing resolution problem of the high temperature generation in melt phase polycondensation process.Through the poly-barkite of present method synthesis, molecular weight is high, may be used for plastic processes, such as, extrude, blowing, injection and other courses of processing and application.
Embodiment
According to the preparation method of poly-barkite of the present invention, the method comprises the following steps:
(1) under bulk polymerization conditions, be aliphatic dihydroxy alcohol and the mass polymerization catalyst exposure of 2-14 by barkite, carbonatoms, obtain barkite prepolymer;
(2) under vacuum state or nitrogen protection, the pre-crystallized rear granulation of barkite prepolymer step (1) obtained, obtains barkite prepolyer granule;
(3) under vacuum state or inert gas exist, at solid phase polymerization conditions, make the polycondensation of barkite prepolyer granule, obtain poly-barkite.
According to the present invention, the present invention is not particularly limited described bulk polymerization condition, can be that the routine of this area is selected.As a rule, described bulk polymerization condition comprises temperature, pressure and time.Wherein, described temperature, time and pressure all can carry out selecting and changing in wider scope, in order to more be conducive to the carrying out of polyreaction, described bulk polymerization conditions comprises two stages of carrying out successively, the temperature of first stage is 110-210 DEG C, pressure is 0.07-0.2MPa, the time is 1-4 hour, preferably, described temperature is 140-200 DEG C, pressure is 0.1-0.12MPa, the time is 1-2 hour; The temperature of subordinate phase is 160-220 DEG C, pressure is 200-3000Pa, the time is 0.5-4 hour, and preferably, described temperature is 170-220 DEG C, pressure is 1500-2500Pa, the time is 0.5-3 hour.
According to the present invention, described barkite, carbonatoms are that the aliphatic dihydroxy alcohol of 2-14 and the weight ratio of mass polymerization catalyzer can carry out selecting and adjusting in wider scope, such as, the weight ratio of described barkite, dibasic alcohol and mass polymerization catalyzer can be 100:50-200:0.05-0.5, is preferably 100:80-120:0.05-0.5.
According to the present invention, although the kind of the present invention to dibasic alcohol does not have particular requirement, as long as can carry out reacting the prepolymer forming barkite with barkite, preferably, described dibasic alcohol is selected from ethylene glycol, 1,3-PD, 1,4-butyleneglycol and 1, one or more in 6-hexylene glycol, are preferably BDO and/or ethylene glycol.
By controlling the weight ratio of bulk polymerization conditions and barkite, dibasic alcohol and mass polymerization catalyzer, making poly-barkite prepolymer limiting viscosity number be 0.15-0.80dL/g, being preferably 0.3-0.64dL/g.Described limiting viscosity number is by viscosimetry method, records under 30 DEG C of conditions.
Known in those skilled in the art, the prepolymer obtained by mass polymerization usually needed to carry out pre-crystallized and granulation process before carrying out solid state polymerization.By pre-crystallized, the hydroxyl of barkite prepolymer and carboxyl are all arranged in plane of crystal, barkite prepolymer local end group concentration is comparatively large, adds speed of reaction.
According to the present invention, the pre-crystallized isothermal crystal that usually adopts in a crystallizer carries out.The present invention is not particularly limited described pre-crystallized condition, can be that the routine of this area is selected.As a rule, described pre-crystallized condition comprises temperature and time.Described pre-crystallized condition comprises: temperature is 80-170 DEG C, the time is 0.5-10 hour; Preferably, described temperature is 110-150 DEG C, the time is 1-3 hour.By pre-crystallized, the degree of crystallinity of barkite prepolymer is made to reach between 25-70%, preferred 35-45%.
In order to strengthen the body surface area of prepolymer, thus quickening speed of reaction, usual needs are pre-crystallized by carrying out after the granulation of poly-barkite prepolymer, the granular size that the present invention gathers barkite prepolymer is not particularly limited, consider from the speed of reaction of solid state polymerization, preferably, the particle diameter of the poly-barkite prepolymer after granulation can be under 200 orders, is preferably 4-160 order.The particle diameter of described barkite prepolymer adopts the laser particle analyzer be purchased from the new powder testing apparatus company limited of Chengdu essence to measure, and is volume average particle size.
According to the present invention, solid state polymerization is generally the condensation reaction completed at a lower temperature, and solid state polymerization directly reacts increase molecular weight often through end group.The present invention is not particularly limited described solid-phase polymerization condition, can be that the routine of this area is selected.As a rule, described solid-phase polymerization condition comprises temperature, pressure and time.Wherein, described temperature, time and pressure all can carry out selecting and changing in wider scope, in order to more be conducive to the carrying out of polyreaction, in a kind of embodiment, described solid state polymerization carries out under vacuum conditions, and the condition of solid state polymerization comprises that temperature is 60-180 DEG C, absolute pressure is 0-2000Pa, the time is 1-50 hour; Preferably, described temperature is 110-150 DEG C, absolute pressure is less than 1000Pa, the time is 10-30 hour.In another kind of embodiment, described solid state polymerization carries out under inert gas exists, and the mass ratio of described inert gas and barkite prepolyer granule is 0.1-3:1, is preferably 0.3-1:1; The condition of solid state polymerization comprises that temperature is 60-180 DEG C, pressure is 0.03-0.3MPa, and the time is 1-50 hour; Preferably, described temperature is 110-150 DEG C, pressure is 0.07-0.2MPa, and the time is 10-30 hour; Further preferably, described temperature is 130-150 DEG C, pressure is 0.1-0.2MPa, and the time is 20-30 hour.In the method for the invention, described rare gas element refers to that various is inactive gas under polymerization conditions, such as: nitrogen, neutral element gas (as argon gas).
According to the present invention, when solid state polymerization carries out in the reactor, such as, when adopting continuation method to carry out in fixed-bed reactor or flowing bed reactor, the flow direction of the present invention to rare gas element and barkite prepolyer granule does not specially require, the flow direction of rare gas element and the flow direction of barkite prepolyer granule can be and flow, also can be adverse current, be preferably adverse current, effectively to take the by product that solid state polymerization produces out of reactor.
According to the present invention, preferably, the solid state polymerization of step (3) carries out under the existence of solid phase polymerization catalyst, to accelerate the speed of response of solid state polymerization.
According to the present invention, the present invention to the special requirement of the consumption of solid phase polymerization catalyst, preferably, with the weight of barkite prepolyer granule for benchmark, the consumption of described solid phase polymerization catalyst is 0.01-5 % by weight, more preferably 0.1-1.5 % by weight, more preferably 1-1.5 % by weight.
According to the present invention, the kind of the present invention to mass polymerization catalyzer and solid phase polymerization catalyst does not specially require, described mass polymerization catalyzer and solid phase polymerization catalyst can be identical or different, be selected from metal oxide, metal-salt and organic sulfonic acid class catalyzer independently of one another one or more, wherein, described metal is the metal of IIA, IIIA, IVA, IVB race be selected from the periodic table of elements; Preferred described mass polymerization catalyzer and solid phase polymerization catalyst are one or more in stannous octoate, antimonous oxide, sodium hypophosphite, tetrabutyl titanate, zinc oxide and Dibutyltin oxide.
According to the present invention, preferably, the method is also included in step (3), adds chainextender to increase the speed of reaction of end group, improves the molecular weight of product.The kind of the present invention to chainextender does not specially require, and only having bifunctional can react with barkite prepolymer.Preferably, described chainextender be selected from comprise in two or more epoxide groups, the compound of isocyanate groups, two oxazoline or organic acid acid anhydrides one or more, the functional group that can comprise in chainextender can be, but not limited to into;-N=S=O,
-N=C=O,
further preferred described chainextender is at least one in vulcabond, Tetra hydro Phthalic anhydride, pyromellitic dianhydride, two oxazoline and epoxy resin, more preferably 2,6-tolylene diisocyanates.
According to poly-barkite prepared by aforesaid method of the present invention.
The invention effect of this patent is described below in conjunction with embodiment, and the testing method that the present invention relates to is as follows.
(1) the limiting viscosity number viscosimetry of poly-barkite measures: adopt Ubbelohde viscometer during measurement, solvent is chloroform, and temperature is 30 DEG C, and polymer concentration is 0.01g/mL.According to the glutinous number of the elution time estimated performance of the elution time and solvent of measuring gained.Formula used is
In formula, C is polymer solution concentration, η
spfor wheat starch, [η] is limiting viscosity number.
(2) degree of crystallinity: be on the DSC of DSC6000 being purchased from the model of PE company, measure the degree of crystallinity of barkite prepolymer, wherein, degree of crystallinity is relative crystallinity, and after 100% degree of crystallinity is measured by wide-angle x-ray method, extrapolation obtains.
(3) particle diameter adopts the laser particle analyzer being purchased the smart new powder testing apparatus company limited from Chengdu to measure the median size of poly-barkite prepolyer granule, is volume average particle size.
Embodiment 1
(1) preparation of barkite prepolymer
Be furnished with to 1L in the four-hole bottle of thermometer, mechanical stirring and nitrogen ingress pipe and add oxalic acid diethyl ester 146 grams, BDO 125 grams, tetrabutyl titanate 0.2 gram, is progressively warmed up to 200 DEG C, under 0.1MPa, make oxalic acid diethyl ester and BDO pre-polymerization 2 hours, obtain oligomer.After most of ethanol is discharged, the temperature of reaction system is down to 170 DEG C, under 2000Pa, starts polycondensation, and be progressively warmed up to 200 DEG C, continue polycondensation 1 hour, obtain poly-barkite prepolymer Y1.The limiting viscosity number recording Y1 is 0.41dL/g.
(2) preparation of barkite prepolyer granule
Being pulverized by Y1 and being a granulated into median size is 10 object barkite prepolyer granules.Get the Y1 particle of 15 grams in a crystallizer in 130 DEG C, isothermal crystal is after 2 hours, and degree of crystallinity is 36% after measured.
(3) preparation of poly-barkite
0.1 gram of stannous octoate is mixed into by the barkite prepolyer granule 10 grams of step (2), then adding in rotatable reactor, be heated to 150 DEG C, is 2000Pa(absolute pressure in vacuum tightness) under reaction 20 hours, reactor rotating speed is 100 turns/min, the poly-barkite P1 obtained.Employing viscosimetry measures, and the limiting viscosity number recording P1 is 0.94dL/g.
Embodiment 2-6
Basic repetition embodiment 1, unlike, the catalyst type of embodiment 2-6 solid state polymerization changes, and the kind of the catalyzer that embodiment 1-6 is used is as shown in table 1 below with the result of the limiting viscosity number of the barkite polymkeric substance prepared.
Embodiment 7
(1) preparation of barkite prepolymer
The preparation of the barkite prepolymer in basic repetition embodiment 1, unlike, most of ethylene glycol is progressively warmed up to 220 DEG C after discharging, and continues polycondensation 3 hours.Obtain poly-barkite prepolymer Y7.The limiting viscosity number recording Y7 is 0.64dL/g.
(2) preparation of barkite prepolyer granule
Being pulverized by Y7 and being a granulated into median size is 4 object barkite prepolyer granules, and get the Y7 particle of 50.0 grams, in a crystallizer in 130 DEG C, isothermal crystal 2 hours, degree of crystallinity is 40% after measured.
(3) preparation of poly-barkite
Be mixed into 0.1 gram of stannous octoate by the barkite prepolyer granule 10 grams of step (2), then add in rotatable reactor.Being heated to 150 DEG C, is 2000Pa(absolute pressure in vacuum tightness) under reaction 20 hours, reactor rotating speed is 100 turns/min, the poly-barkite P7 obtained.The limiting viscosity number recording P7 is 1.16dL/g.
Embodiment 8
Basic repetition embodiment 7, unlike, in the preparation process of the poly-barkite of step (3), reaction carries out in nitrogen atmosphere, and the mass ratio of described inert gas and barkite prepolyer granule is 0.3:1; The temperature of solid state polymerization is 130 DEG C, pressure is 0.1MPa, and the time is 30 hours, the poly-barkite P8 obtained.The glutinous number of the polymer property obtained recording P8 is 0.98dL/g.
Embodiment 9
Basic repetition embodiment 7, unlike, in the preparation process of the poly-barkite of step (3), after adding 0.1 gram of stannous octoate, add 0.1 gram of 2,6-tolylene diisocyanate, the poly-barkite P9 obtained.The limiting viscosity number recording P9 is 1.08dL/g.
Comparative example 1
Be furnished with to 1L in the four-hole bottle of thermometer, mechanical stirring and nitrogen ingress pipe and add oxalic acid diethyl ester 146 grams, BDO 125 grams, tetrabutyl titanate 0.2 gram, is progressively warmed up to 200 DEG C, under 0.1MPa, make oxalic acid diethyl ester and BDO pre-polymerization 2 hours, obtain oligomer.When most of ethanol is discharged, be cooled to 170 DEG C, under 2000Pa, start polycondensation, and be progressively warmed up to 220 DEG C in 1 hour, continue pressure to reduce to 500Pa, and 220 DEG C stop 4 hours, obtain poly-barkite.The limiting viscosity number recording B1 is 0.72dL/g.
Table 1
From the data of table 1, use method for solid phase polymerization, effectively can improve the molecular weight of poly-barkite.Wherein, when adopting method of the present invention to prepare poly-barkite, the molecular weight of the poly-barkite prepolymer prepared is larger, then the final molecular weight of the poly-barkite obtained is larger.
Claims (16)
1. a preparation method for poly-barkite, the method comprises the following steps:
(1) under bulk polymerization conditions, be aliphatic dihydroxy alcohol and the mass polymerization catalyst exposure of 2-14 by barkite, carbonatoms, obtain barkite prepolymer;
(2) under vacuum state or protection of inert gas, the pre-crystallized rear granulation of barkite prepolymer step (1) obtained, obtains barkite prepolyer granule;
(3) under vacuum state or inert gas exist, at solid phase polymerization conditions, make the polycondensation of barkite prepolyer granule, obtain poly-barkite;
Wherein, the volume average particle size of the barkite prepolymer after step (2) granulation is 4-160 order;
Wherein, the solid state polymerization of step (3) carries out under the existence of solid phase polymerization catalyst, and with the weight of barkite prepolyer granule for benchmark, the consumption of described solid phase polymerization catalyst is 0.11-1.5 % by weight;
Wherein, described mass polymerization catalyzer and described solid phase polymerization catalyst identical or different, be one or more in stannous octoate, sodium hypophosphite, tetrabutyl titanate, zinc oxide and Dibutyltin oxide independently of one another.
2. method according to claim 1, wherein, described bulk polymerization conditions comprises two stages of carrying out successively, and the temperature of first stage is 110-210 DEG C, pressure is 0.07-0.2MPa, the time is 1-4 hour; The temperature of subordinate phase is 160-220 DEG C, pressure is 200-3000Pa, the time is 0.5-4 hour.
3. method according to claim 2, wherein, the temperature of first stage is 140-200 DEG C, pressure is 0.1-0.12MPa, the time is 1-2 hour; The temperature of subordinate phase is 170-220 DEG C, pressure is 1500-2500Pa, the time is 0.5-3 hour.
4. method according to claim 1, wherein, in step (1), barkite, carbonatoms are the aliphatic dihydroxy alcohol of 2-14 and the weight ratio of mass polymerization catalyzer is 100:50-200:0.05-0.5.
5. the method according to claim 1 or 4, wherein, in step (1), described carbonatoms be the aliphatic dihydroxy alcohol of 2-14 be selected from ethylene glycol, 1,3-PD, BDO and 1,6-hexylene glycol one or more.
6. method according to claim 5, wherein, described carbonatoms is the aliphatic dihydroxy alcohol of 2-14 is BDO and/or ethylene glycol.
7. method according to claim 1, wherein, described pre-crystallized condition comprises: temperature is 80-170 DEG C, the time is 0.5-10 hour.
8. method according to claim 1, wherein, described pre-crystallized condition comprises: described temperature is 110-150 DEG C, the time is 1-3 hour.
9. method according to claim 1, wherein, described solid state polymerization carries out under vacuum conditions, and the condition of solid state polymerization comprises: temperature is 60-180 DEG C, absolute pressure is 0-2000Pa, the time is 1-50 hour.
10. method according to claim 9, wherein, the condition of solid state polymerization comprises: temperature is 110-150 DEG C, absolute pressure is less than 1000Pa, the time is 10-30 hour.
11. methods according to claim 1, wherein, described solid state polymerization carries out under inert gas exists, and the mass ratio of described inert gas and barkite prepolyer granule is 0.1-3:1; The condition of solid state polymerization comprises: temperature is 60-180 DEG C, pressure is 0.03-0.3MPa, and the time is 1-50 hour.
12. methods according to claim 11, wherein, the mass ratio of described inert gas and barkite prepolyer granule is 0.3-1:1; The condition of solid state polymerization comprises: described temperature is 110-150 DEG C, pressure is 0.07-0.2MPa, and the time is 10-30 hour.
13. methods according to claim 1, wherein, the method is also included in step (3), adds chainextender.
14. methods according to claim 13, wherein, described chainextender be selected from the compound containing two or more epoxide group, the compound containing two or more isocyanate groups, two oxazoline and acid anhydrides one or more.
15. methods according to claim 14, wherein, described chainextender is at least one in vulcabond, Tetra hydro Phthalic anhydride, pyromellitic dianhydride, two oxazoline and epoxy resin.
The poly-barkite that in 16. claim 1-15 prepared by method described in any one.
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| CN105315445B (en) * | 2015-11-20 | 2017-06-16 | 宁波浙铁大风化工有限公司 | A kind of poly- oxalate synthesis technique |
| CN113372542A (en) * | 2021-05-17 | 2021-09-10 | 俏东方生物燃料集团有限公司 | Preparation method of bio-based polyethylene glycol oxalate resin |
| CN115477742B (en) * | 2021-10-19 | 2023-12-15 | 源创核新(北京)新材料科技有限公司 | Preparation method of terminal group modified polyoxalate |
| CN115785416B (en) * | 2022-07-04 | 2024-01-19 | 新倍斯(杭州)材料科技有限公司 | Poly (ethylene glycol-co-diethylene glycol) oxalate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327460A (en) * | 1999-07-09 | 2001-12-19 | 三井化学株式会社 | Process for producing aliphatic polyester |
| CN101486790A (en) * | 2009-02-20 | 2009-07-22 | 中国石化仪征化纤股份有限公司 | Method for producing high molecular weight polyester |
| CN102718948A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Method for preparing aliphatic polyoxalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327460A (en) * | 1999-07-09 | 2001-12-19 | 三井化学株式会社 | Process for producing aliphatic polyester |
| CN101486790A (en) * | 2009-02-20 | 2009-07-22 | 中国石化仪征化纤股份有限公司 | Method for producing high molecular weight polyester |
| CN102718948A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Method for preparing aliphatic polyoxalate |
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