CN105111422A - Preparation method for fully-biodegradable copolyester - Google Patents
Preparation method for fully-biodegradable copolyester Download PDFInfo
- Publication number
- CN105111422A CN105111422A CN201510596557.0A CN201510596557A CN105111422A CN 105111422 A CN105111422 A CN 105111422A CN 201510596557 A CN201510596557 A CN 201510596557A CN 105111422 A CN105111422 A CN 105111422A
- Authority
- CN
- China
- Prior art keywords
- acid
- polymerization reactor
- reactor
- preparation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method for fully-biodegradable copolyester. The preparation method comprises the steps that terephthalic acid, 1,4-butanediol, adipic acid, succinic acid and fumaric acid are added into a production reactor, the temperature is raised to 80-240 DEG C at atmospheric pressure, and the stirring speed is controlled to be 100-200 r/min so that esterification reaction can be performed; when distillate water of esterification reaction drains away, vacuumizing is started, and it is regarded that esterification reaction is completed when the distillate amount is larger than the theoretical distillate water amount; the materials in the production reactor is forcedly fed into a polymerization reactor via nitrogen gas, stirring is stopped, a catalyst is added, and then stirring is started; the polymerization reactor is heated after 10 minutes so that the temperature of the reactant can rise gradually, and at the same time, a vacuum pump is started so that the vacuum degree of the polymerization reactor can be gradually lowered for polymerization reaction; the internal pressure of the polymerization reactor is reduced to below 100 pa, the temperature is raised to 240-290 DEG C, and the reaction is stopped after 4-7 hours. The preparation method for the fully-biodegradable copolyester can adjust the strength, the flexibility and the degradation time of copolyester products, thereby being suitable for degradable polyester synthetic products of various purposes.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, be specifically related to a kind of preparation method of fully bio-degradable copolyesters.
Background technology
Along with the technical progress of China, the whole world is more and more paid attention to environmental issue, and the use of white pollution to conventional plastic has had increasing restriction, and especially require more strict at field of food, packaging industry, multiple province has been carried out taboo and moulded order.But existing Biodegradable Copolyester aggregates into thing existence and is difficult to degraded and complex manufacturing, has a strong impact on PE.
Summary of the invention
The object of the invention is the preparation method providing a kind of fully bio-degradable copolyesters, and the method can regulate intensity, snappiness, the degradation time of copolyesters product.
In order to achieve the above object, the present invention's utilization take titanium as the polyester catalyst of main component, adopts terephthalic acid, 1-4 butyleneglycol, hexanodioic acid, succinic acid, fumaric acid copolymerization component, the PBSATF polymkeric substance of synthesis high molecular, and concrete technical scheme is as follows:
The preparation method of fully bio-degradable copolyesters of the present invention, its step comprises: be equipped with in the type of production reactor of rectifying tower, condenser and receiving tank one and add terephthalic acid, 1,4-butyleneglycol, hexanodioic acid, succinic acid, fumaric acid, be warming up to 80-240 DEG C at ambient pressure, stirring velocity controls at 100-200 rev/min, carries out esterification; Start to vacuumize when the cut water of esterification goes out to the greatest extent, thing amount to be distillated is greater than and is considered as esterification when theory distillates the water yield and completes, material in type of production reactor is delivered in polymerization reactor with nitrogen pressure, stop starting after stirring adds catalyzer to stir, temperature of charge is made to increase gradually polymerization reactor heating after 10 minutes, unlatching vacuum pump gradually reduces polymerization reactor vacuum tightness and carries out polyreaction simultaneously, polymerization reactor internal drop is to below 100pa, temperature is increased to 240-290 DEG C, termination reaction after 4 hours;
The mass ratio of described terephthalic acid and succinic acid-hexanodioic acid-fumaric acid is 1:1-2.5:0.5-2:0.01-0.2, the quality sum of described succinic acid, terephthalic acid, hexanodioic acid, fumaric acid and 1, the mass ratio of 4-butyleneglycol is 1:1-1.5, and described catalyzer accounts for 0.1%-1.5% of total mass.
Described catalyzer is selected from tetrabutyl titanate, titanium isopropylate, magnesium acetate, stannic oxide, one or more in trimethyl phosphite 99, triethyl phosphate, reacting by heating is prepared from a solvent, described solvent accounts for 8.53%-57.20% of total mass, and Heating temperature is 80-200 DEG C of reaction 0.5-3h.
Described solvent is one or more in hexanaphthene, toluene, ethanol.
In technique scheme, the present invention's utilization take titanium as the polyester catalyst of main component, and this catalyzer has good catalytic activity, and impure group is few, and the polyester product form and aspect of synthesis are good, have stability, economy; Simultaneously, adopt terephthalic acid, hexanodioic acid, fumaric acid, succinic acid, 1,4-butyleneglycol copolymerization component, the existing good intensity of fully-degradable polyester product of synthesis, have again extraordinary flexibility, form and aspect are pure white, and ratios different in addition can meet various different blown film level and sheet material injection moulded products, realize the control of degradation time and product strength, become environment-friendly material best now.
Compared with prior art, tool has the following advantages in the present invention:
(1) this catalyzer is based on the stable liquid multicomponent catalyst of titanium, element silicon, directly can add or dilute in the raw material that adds for the synthesis of the ester or oligomer ester for the treatment of polycondensation for the synthesis of polyester;
(2), the while that catalyzer keeping highly active, the hue of chip of synthesis is good, good stability;
(3) Tc of polyester is obviously reduced;
(4) intensity of polyester product is significantly improved.
Embodiment
Below in conjunction with specific embodiment, the preparation method to fully bio-degradable copolyesters of the present invention is described further;
Embodiment 1
To stirrer is housed, rectifying tower, terephthalic acid 166kg is added in the type of production reactor of condenser and receiving tank, 1, 4-butyleneglycol 234kg, hexanodioic acid .116kg, succinic acid 23kg, fumaric acid 2kg., esterification is carried out under synthesis under normal pressure condition, until distilled effluent amount reach theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted a certain amount of catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 100pa, and temperature is increased to 255 DEG C, through 4 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains polyester grain through overcooling, dicing machine granulation.
Embodiment 2
In the type of production reactor that stirrer, rectifying tower, condenser and receiving tank be housed, add terephthalic acid 125kg, Isosorbide-5-Nitrae-butyleneglycol 180kg, hexanodioic acid 87kg, succinic acid 18kg, fumaric acid 2kg., be warming up to 240 DEG C at ambient pressure and carry out esterification.Start to take out rough vacuum when the cut water of esterification goes out to the greatest extent, thing amount to be distillated be greater than theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted a certain amount of catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 100pa, and temperature is increased to 250 DEG C, through 4 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains PBSTAF product through overcooling, granulation
Embodiment 3
To stirrer is housed, rectifying tower, terephthalic acid 166kg is added in the type of production reactor of condenser and receiving tank, 1, 4-butyleneglycol 234kg, hexanodioic acid .116kg, succinic acid 23kg, fumaric acid 2kg., esterification is carried out under synthesis under normal pressure condition, until distilled effluent amount reach theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted a certain amount of catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 100pa, and temperature is increased to 280 DEG C, through 4 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains polyester grain through overcooling, dicing machine granulation.
Embodiment 4
To stirrer is housed, rectifying tower, terephthalic acid 140kg is added in the type of production reactor of condenser and receiving tank, 1, 4-butyleneglycol 230kg, hexanodioic acid 150kg, succinic acid 23.kg, fumaric acid 2kg., esterification is carried out under synthesis under normal pressure condition, after 4 hours wait slip out thing amount reach theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted a certain amount of catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 100pa, and temperature is increased to 285 DEG C, through 5 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains polyester grain through overcooling, dicing machine granulation.
Embodiment 5
To stirrer is housed, rectifying tower, terephthalic acid 140kg is added in the type of production reactor of condenser and receiving tank, 1, 4-butyleneglycol .230kg, hexanodioic acid 150kg, succinic acid 23kg, fumaric acid 4kg., esterification is carried out under synthesis under normal pressure condition, after 4 hours wait slip out thing amount reach theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 1 mmhg, and temperature is increased to 285 DEG C, through 6 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains polyester grain through overcooling, dicing machine granulation.
Embodiment 6
To stirrer is housed, rectifying tower, terephthalic acid 140kg is added in the type of production reactor of condenser and receiving tank, 1, 4-butyleneglycol 230kg, hexanodioic acid 150.kg, succinic acid .23kg, fumaric acid .6kg., esterification is carried out under synthesis under normal pressure condition, after 4 hours wait slip out thing amount reach theory distillate the water yield time be considered as esterification and complete, material is delivered in polymerization reactor with nitrogen pressure, add diluted a certain amount of catalyzer and stir 10 minutes, make temperature of charge increase gradually reactor heating to open vacuum pump gradually to reduce reactor vacuum tightness and carry out polyreaction simultaneously.Vacuum tightness was down to below 100pa, and temperature is increased to 2290 DEG C, through 7 hours termination reactions.Material nitrogen pressurization in reactor discharged, polymkeric substance obtains polyester grain through overcooling, dicing machine granulation.
After testing, the fully-degradable polyester product form and aspect of being synthesized by the present invention are good, molecular weight is high, are the best environment-friendly materials producing film and agricultural film; Meanwhile, the method can simplify production technique, controllable operating, reduces production cost, is applicable to the fully bio-degradable copolyesters synthesis of industrial application.
Claims (3)
1. the preparation method of a fully bio-degradable copolyesters, its step comprises: in the type of production reactor that rectifying tower, condenser and receiving tank are housed, add terephthalic acid, 1,4-butyleneglycol, hexanodioic acid, succinic acid, fumaric acid stirring, be warming up to 80-240 DEG C at ambient pressure, stirring velocity controls at 100-200 rev/min, carries out esterification; Start to vacuumize when the cut water of esterification goes out to the greatest extent, thing amount to be distillated is greater than and is considered as esterification when theory distillates the water yield and completes, material in type of production reactor is delivered in polymerization reactor with nitrogen pressure, stop starting after stirring adds catalyzer to stir, temperature of charge is made to increase gradually polymerization reactor heating after 10 minutes, unlatching vacuum pump gradually reduces polymerization reactor vacuum tightness and carries out polyreaction simultaneously, polymerization reactor internal drop is to below 100pa, temperature is increased to 240-290 DEG C, termination reaction after 4-7 hours;
The mass ratio of described terephthalic acid and succinic acid-hexanodioic acid-fumaric acid is 1:1-2.5:0.5-2:0.01-0.2, the quality sum of described succinic acid, terephthalic acid, hexanodioic acid, fumaric acid and 1, the mass ratio of 4-butyleneglycol is 1:1-1.5, and described catalyzer accounts for 0.1%-1.5% of total mass.
2. the preparation method of the fully bio-degradable copolyesters according to claim 1 any one, it is characterized in that: described catalyzer is selected from tetrabutyl titanate, titanium isopropylate, magnesium acetate, stannic oxide, one or more in trimethyl phosphite 99, triethyl phosphate, reacting by heating is prepared from a solvent, described solvent accounts for 8.53%-57.20% of total mass, and Heating temperature is 80-200 DEG C of reaction 0.5-3h.
3. the preparation method of fully bio-degradable copolyesters according to claim 2, is characterized in that: described solvent is one or more in hexanaphthene, toluene, ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510596557.0A CN105111422A (en) | 2015-09-18 | 2015-09-18 | Preparation method for fully-biodegradable copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510596557.0A CN105111422A (en) | 2015-09-18 | 2015-09-18 | Preparation method for fully-biodegradable copolyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105111422A true CN105111422A (en) | 2015-12-02 |
Family
ID=54659559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510596557.0A Pending CN105111422A (en) | 2015-09-18 | 2015-09-18 | Preparation method for fully-biodegradable copolyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105111422A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1335049A (en) * | 1970-11-07 | 1973-10-24 | Mccall J D | Linear polyester method for its production and products obtainable therefrom |
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN103265668A (en) * | 2013-05-21 | 2013-08-28 | 山东宏信化工股份有限公司 | Preparation method of terephthalic type unsaturated polyester resin |
| CN103732684A (en) * | 2011-06-03 | 2014-04-16 | 吉顺科技有限公司 | Hydrolysis resistant and biodegradable aliphatic-aromatic copolyester resin composition |
-
2015
- 2015-09-18 CN CN201510596557.0A patent/CN105111422A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1335049A (en) * | 1970-11-07 | 1973-10-24 | Mccall J D | Linear polyester method for its production and products obtainable therefrom |
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN103732684A (en) * | 2011-06-03 | 2014-04-16 | 吉顺科技有限公司 | Hydrolysis resistant and biodegradable aliphatic-aromatic copolyester resin composition |
| CN103265668A (en) * | 2013-05-21 | 2013-08-28 | 山东宏信化工股份有限公司 | Preparation method of terephthalic type unsaturated polyester resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016173092A1 (en) | Liquid titanium catalyst and preparation method of polyester polymer using same | |
| CN104119518B (en) | The method of biological organic guanidinesalt catalysis method synthesis poly-(succinic acid-butanediol ester-altogether-tetramethylene adipate) | |
| CN101107287B (en) | Polyester polycondensation catalyst, and method for producing polyester resin using the polycondensation catalyst | |
| TWI577711B (en) | Method of manufacturing aliphatic polyesters | |
| CN102634174B (en) | Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine | |
| CN107513154A (en) | A kind of titanium series polyester catalyst and its method for producing copolyesters | |
| JP2018505278A5 (en) | ||
| CN113388100B (en) | Catalyst system for synthesizing aliphatic-aromatic copolyester and application thereof | |
| CN100572447C (en) | Polyester resin composition, manufacture method and moulding product | |
| CN102471471A (en) | Process for making polyethylene terephthalate | |
| CN105061744A (en) | Preparation method of PBS (poly butylenes succinate) | |
| CN109134832A (en) | A kind of new bio base PBAT synthetic method and its application | |
| JP2000143789A (en) | Production of polyester | |
| CN113896869B (en) | Method for preparing environment-friendly PET polyester with good hue quality on continuous polymerization device | |
| CN114891189A (en) | Preparation method of low-chroma PETG copolyester | |
| CN112851919A (en) | 1,4, 3, 6-diglycidyl hexaol modified PET polyester and semi-continuous preparation method thereof | |
| CN100439415C (en) | Method for producing aliphatic polyester and the aliphatic polyester | |
| CN114591496A (en) | Preparation method of rigid copolyester | |
| CN105111422A (en) | Preparation method for fully-biodegradable copolyester | |
| KR20100079504A (en) | Method for preparing polyester resin copolymerized with neopentyl glycol | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| CN102850534B (en) | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst | |
| CN114075330B (en) | Aluminum polyester catalyst and preparation method and application thereof | |
| TW201412817A (en) | Method of continuous production of biodegradable aliphatic polyester | |
| CN1800236A (en) | Highly transparent copolyester preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151202 |
|
| WD01 | Invention patent application deemed withdrawn after publication |