CN106987100A - One kind is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）The preparation method of ester group composite - Google Patents
One kind is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）The preparation method of ester group composite Download PDFInfo
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- CN106987100A CN106987100A CN201710159232.5A CN201710159232A CN106987100A CN 106987100 A CN106987100 A CN 106987100A CN 201710159232 A CN201710159232 A CN 201710159232A CN 106987100 A CN106987100 A CN 106987100A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of poly- (terephthalic acid (TPA) butanediol co adipic acids butanediol) ester group composite, this method passes through chloroform soln blending method, the nucleator voluntarily synthesized, i.e. phosphenylic acid zinc is added in poly- (terephthalic acid (TPA) butanediol co adipic acids butanediol) ester biological degradable material, is made after chloroform volatilization is dried completely and in 40 DEG C of vacuum tanks.The beneficial effects of the invention are as follows：Obtained composite, crystallization temperature and crystalline rate are greatly improved, and crystallization time is greatly shortened, and have been greatly saved the material processing and forming time.This method technique is simple, and method is ripe, prepare it is with low cost, can large-scale application in the production and processing of the products such as biodegradable agricultural mulching, disposable garbage bag, disposable container.
Description
Technical field
The invention belongs to technical field of composite materials, particularly a kind of poly- (terephthalic acid (TPA) butanediol-co- adipic acid fourths
Glycol) ester (PBAT) based composites preparation method.
Background technology
The conventional petroleum based high molecular material (polyethylene, polypropylene, polystyrene etc.) gone out of use can not degrade, to environment
Cause serious pollution.It is general to be handled with the method buried or burned.The method of burial is cured the symptoms, not the disease, it is impossible to from root
Its pollution on the environment is eliminated on this.The toxic gas produced after burning can cause more serious atmosphere pollution.Biology drop
Solving polyester material can be degraded by microorganism or esterase, and the final product (carbon dioxide and water) of degraded is Plant Light and effect
Raw material.In addition, the mechanical performance of some polyester materials can compare favourably with conventional plastic.Therefore polyester material is expected to replace traditional modeling
Expect and as green material, be developed and be widely used in the fields such as agricultural, environmental protection, medical science.
Poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) material is BASF Aktiengesellschaft's exploitation
The copolyesters that is made up of polybutylene terephthalate (PBT) (PBT) and poly adipate succinic acid ester (PBA) of one kind, be processed
Into products such as agricultural mulching, environment-friendly shopping bag, preservative films.Because its crystalline rate is slow, its machine-shaping and machine have been had a strong impact on
Tool performance.The method that addition nucleator prepares composite into high polymer material is industrially used for improving its crystallinity always
Energy, heat endurance, mechanical performance, transparency etc., because this method cost is low, process is simple, material short preparation period, change
Property effect is obvious.Currently used for the nucleator being modified to PBAT materials, modified effect has much room for improvement, or nucleator used
There is certain side effect to environment or organism.
Phosphenylic acid zinc (zinc phenylphosphonate, PPZn) good biocompatibility and preparation method is simple.According to
Report, PPZn is expected to cure for preparing a variety of biologies for having application potential as a kind of good nucleator of modified effect or additive
Use material.Therefore, the present invention prepares a kind of environmental protection composite with PBAT and PPZn, PPZn is greatly improved PBAT's
Crystalline rate and crystallization temperature, shorten the process-cycle, save processing cost.
The content of the invention
The present invention is directed to the problem of being proposed in technical background, it is proposed that a kind of raw material are cheap and preparation method is simple and easy to apply
A kind of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite preparation method, the preparation method can
Improve polyester material crystalline rate and crystallization temperature.
Technical scheme：
A kind of preparation method of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite, including under
State step：
1) phosphenylic acid is added in deionized water, the amount ratio of phosphenylic acid and deionized water is 0.1mol：200mL,
Stirring and dissolving obtains phosphenylic acid solution；Zinc halide is added in deionized water, the amount ratio of zinc halide and deionized water is
0.1mol：100mL, stirring and dissolving obtains halogenation zinc solution；Zinc halide is mixed and is sufficiently stirred for phosphenylic acid solution, is obtained
Mixed liquor；
2) alkaline solution that concentration is 0.1mol/L is added dropwise in above-mentioned mixed liquor while stirring and adjusts pH to 5-6, the alkali
Property solution be sodium hydroxide solution or potassium hydroxide solution, the rate of addition of alkaline solution is 2-5 mL/min, by what is be collected into
Precipitation is added in deionized water, and the amount ratio of precipitation and deionized water is 1g:100mL, stirs 3 days at a temperature of 50 DEG C, obtains
Sediment；
3) it after above-mentioned sediment deionized water rinsing, will be put into 40 DEG C of vacuum tank and dry 1 day, be subsequently placed in
Sloughed in 180-250 DEG C of vacuum tank and combine water, obtain being dehydrated phosphenylic acid zinc (PPZn) powder；
4) with mortar PPZn powder is further fine ground, cross 100 mesh sieves, obtain it is fine ground after PPZn it is standby；
5) by it is above-mentioned it is fine ground after PPZn powder and poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester
(PBAT) plastics are mixed, and PPZn mass percent is 0.1-0.5% in mixture, then add chloroform, mixture with
The amount ratio of chloroform is 1g:100mL, is placed in fume hood and is sufficiently stirred for 1 day to ensure that PBAT dissolvings divide with PPZn completely
Dissipate uniform, after after chloroform volatilization completely, obtain PBAT/PPZn composite membranes；
6) above-mentioned PBAT/PPZn composite membranes are placed in 40 DEG C of vacuum tank and vacuumized 10 hours, is completely dried
The PBAT group compound films that crystalline rate and crystallization temperature are greatly improved.
The step 1) in zinc halide be zinc chloride, zinc fluoride or zinc bromide；Phosphenylic acid and zinc halide in mixed liquor
Mol ratio is 1:1.
The step 5) in poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) molecular weight for not
Less than 50000 dalton；Polyadipate fourth two in poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT)
The molar content of alcohol ester (PBA) is not higher than 65%.
The beneficial effects of the invention are as follows：
Composite crystallization temperature prepared by this method is greatly improved, and the crystallization temperature than pure PBAT improves nearly 20 DEG C,
The isothermal crystal time greatly reduces, and shortens the material processing and forming cycle；Composite technology prepared by this method is simple, cost
Cheap, process time is short, easy popularization and application.
Brief description of the drawings
Fig. 1 is PPZn XRD.
Fig. 2 is pure PBAT and PBAT/PPZn nonisothermal crystallization DSC curve.
Fig. 3 is isothermal crystal DSC curves of the pure PBAT and PBAT/PPZn at 70 DEG C.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It will be appreciated that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.
Embodiment 1：
A kind of preparation method of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite, including under
State step：
Phosphenylic acid 0.1mol phosphenylic acids and 0.1mol zinc chloride is taken to be dissolved in 200mL and 100 mL deionizations respectively
In water, it is sufficiently stirred for after 30min, phosphenylic acid solution is poured into liquor zinci chloridi, stirred, while with 2mL/min's
The pH to 5.0 for the sodium hydroxide solution mixed liquor that speed is added dropwise plus concentration is 0.1mol/L.
Precipitation is collected, will be precipitated after continuing stirring 3 days with 50 DEG C of deionized water, obtained sediment is true at 40 DEG C
Preliminarily dried 1 day in empty van, is subsequently placed in slough in 180 DEG C of vacuum tank and combines water, obtains being dehydrated phosphenylic acid zinc
(PPZn) powder；100 mesh sieves (particle diameter is less than or equal to 0.15mm) are crossed, the PPZn powder of sieving are remained standby.
0.999 gram of PBAT and 0.001 gram of PPZn is added in the beaker equipped with 100mL chloroform solns, wherein poly-
The molecular weight of (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) is 66000 dalton；Poly- (terephthalic acid (TPA)
Butanediol-co- adipic acids butanediol) molar content of poly adipate succinic acid ester (PBA) in ester (PBAT) is 58%,
Stir, until chloroform volatilizees completely.In the vacuum tank that the composite membrane for being deposited on beaker bottom is placed in 40 DEG C
Dry 10h, the PBAT/PPZn composites being completely dried.
Fig. 1 is PPZn XRD.
Fig. 2 is pure PBAT and PBAT/PPZn nonisothermal crystallization DSC curve.Show in figure：PBAT/0.1%PPZn's
Crystallization temperature improves 14 DEG C than the crystallization temperature of pure PBAT materials.
Fig. 3 is isothermal crystal DSC curves of the pure PBAT and PBAT/PPZn at 70 DEG C.Show in figure：In 70 DEG C of isothermal knots
Under the conditions of crystalline substance, 0.1%PPZn allows PBAT crystallization times to shorten 52 minutes.
Embodiment 2：
A kind of preparation method of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite, including under
State step：
0.1mol phosphenylic acid and 0.1mol zinc fluoride is taken to be dissolved in respectively in 200mL and 100mL deionized waters, fully
Stir after 30min, phosphenylic acid solution is poured into fluorination zinc solution, stirred, while being added dropwise with 3ml/min speed dense
The potassium hydroxide solution spent for 0.1mol/L adjusts the pH to 5.5 of mixed liquor.
Precipitation is collected, will be precipitated after continuing stirring 3 days with 50 DEG C of deionized water, obtained sediment is true at 40 DEG C
Preliminarily dried 1 day in empty van, is subsequently placed in slough in 200 DEG C of vacuum tank and combines water, obtains being dehydrated phosphenylic acid zinc
(PPZn) powder；100 mesh sieves are crossed, the PPZn powder of sieving are remained standby.
0.997 gram of PBAT and 0.003 gram of PPZn is added in the beaker equipped with 100mL chloroform solns, wherein poly-
The molecular weight of (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) is 74100；Poly- (terephthalic acid (TPA) fourth two
Alcohol-co- adipic acids butanediol) molar content of poly adipate succinic acid ester (PBA) in ester (PBAT) is that molecular weight is
61%, stir, until chloroform volatilizees completely.The composite membrane for being deposited on beaker bottom is placed in 40 DEG C of vacuum
10h, the PBAT/PPZn composites being completely dried are dried in case.
Fig. 2 is pure PBAT and PBAT/PPZn nonisothermal crystallization DSC curve.Show in figure：PBAT/0.3%PPZn's
Crystallization temperature improves 17 DEG C than the crystallization temperature of pure PBAT materials.
Fig. 3 is isothermal crystal DSC curves of the pure PBAT and PBAT/PPZn at 70 DEG C.Show in figure：In 70 DEG C of isothermal knots
Under the conditions of crystalline substance, 0.3%PPZn allows PBAT crystallization times to shorten 58 minutes.
Embodiment 3：
A kind of preparation method of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite, including under
State step：
0.1mol phosphenylic acid and 0.1mol zinc bromide is taken to be dissolved in respectively in 200mL and 100mL deionized waters, fully
Stir after 30min, then phosphenylic acid solution is poured into fluorination zinc solution, stir, while being added dropwise with 5ml/min speed
Concentration adjusts the pH to 6 of mixed liquor for 0.1mol/L sodium hydroxide solution.
Precipitation is collected, will be precipitated after continuing stirring 3 days with 50 DEG C of deionized water, obtained sediment is true at 40 DEG C
Preliminarily dried 1 day in empty van, is subsequently placed in slough in 220 DEG C of vacuum tank and combines water, obtains being dehydrated phosphenylic acid zinc
(PPZn) powder；100 mesh sieves are crossed, the PPZn powder of sieving are remained standby.
0.995 gram of PBAT and 0.005 gram of PPZn is added in the beaker equipped with 100mL chloroform solns, wherein poly-
The molecular weight of (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) is 88300；Poly- (terephthalic acid (TPA) fourth two
Alcohol-co- adipic acids butanediol) molar content of poly adipate succinic acid ester (PBA) in ester (PBAT) is 64%,
Stir, until chloroform volatilizees completely.In the vacuum tank that the composite membrane for being deposited on beaker bottom is placed in 40 DEG C
Dry 3h, the PBAT/PPZn composites being completely dried.
Fig. 2 is pure PBAT and PBAT/PPZn nonisothermal crystallization DSC curve.Show in figure：PBAT/0.5%PPZn's
Crystallization temperature improves 20 DEG C than the crystallization temperature of pure PBAT materials.
Fig. 3 is isothermal crystal DSC curves of the pure PBAT and PBAT/PPZn at 70 DEG C.Show in figure：In 70 DEG C of isothermal knots
Under the conditions of crystalline substance, 0.5%PPZn allows PBAT crystallization times to shorten 60 minutes.
Claims (3)
1. a kind of preparation method of poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite, its feature exists
In comprising the steps：
1) phosphenylic acid is added in deionized water, the amount ratio of phosphenylic acid and deionized water is 0.1mol：200mL, stirring
Dissolving obtains phosphenylic acid solution；Zinc halide is added in deionized water, the amount ratio of zinc halide and deionized water is 0.1mol：
100mL, stirring and dissolving obtains halogenation zinc solution；Zinc halide is mixed and is sufficiently stirred for phosphenylic acid solution, mixed liquor is obtained；
2) alkaline solution that concentration is 0.1mol/L is added dropwise in above-mentioned mixed liquor while stirring and adjusts pH to 5-6, the alkalescence is molten
Liquid is sodium hydroxide solution or potassium hydroxide solution, and the rate of addition of alkaline solution is 2-5mL/min, and the precipitation being collected into is added
Enter in deionized water, the amount ratio of precipitation and deionized water is 1g:100mL, stirs 3 days at a temperature of 50 DEG C, obtains sediment；
3) it after above-mentioned sediment deionized water rinsing, will be put into 40 DEG C of vacuum tank and dry 1 day, be subsequently placed in 180-
Sloughed in 250 DEG C of vacuum tank and combine water, obtain being dehydrated phosphenylic acid zinc (PPZn) powder；
4) with mortar PPZn powder is further fine ground, cross 100 mesh sieves, obtain it is fine ground after PPZn it is standby；
5) by it is above-mentioned it is fine ground after PPZn powder and poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) mould
PPZn mass percent is 0.1-0.5% in material mixing, mixture, then adds chloroform, mixture and chloroform
Amount ratio be 1g:100mL, is placed in fume hood and is sufficiently stirred for 1 day to ensure that PBAT dissolvings are uniformly dispersed with PPZn completely, treat
After chloroform volatilization completely, PBAT/PPZn composite membranes are obtained；
6) above-mentioned PBAT/PPZn composite membranes are placed in 40 DEG C of vacuum tank the crystallization for vacuumizing 10 hours, being completely dried
The PBAT group compound films that speed and crystallization temperature are greatly improved.
2. the preparation of (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite poly- according to claim 1
Method, it is characterised in that：The step 1) in zinc halide be zinc chloride, zinc fluoride or zinc bromide；In mixed liquor phosphenylic acid and
The mol ratio of zinc halide is 1:1.
3. the preparation of (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester group composite poly- according to claim 1
Method, it is characterised in that：The step 5) in poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) point
Son amount is not less than 50000 dalton；In poly- (terephthalic acid (TPA) butanediol-co- adipic acids butanediol) ester (PBAT) gather oneself two
The molar content of sour butanediol ester (PBA) is not higher than 65%.
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| CN201710159232.5A CN106987100A (en) | 2017-03-17 | 2017-03-17 | One kind is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）The preparation method of ester group composite |
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| CN201710159232.5A CN106987100A (en) | 2017-03-17 | 2017-03-17 | One kind is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）The preparation method of ester group composite |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351181A (en) * | 2021-06-15 | 2021-09-07 | 青岛科技大学 | Multi-adsorption biodegradable foam with oil-water separation function |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804855A (en) * | 2012-11-08 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | High-strength copolyester and preparation method thereof |
| EP2251378A4 (en) * | 2008-03-03 | 2014-09-17 | Unitika Ltd | Biodegradable polyester resin composition and molded body composed of the same |
| CN106220889A (en) * | 2016-08-24 | 2016-12-14 | 合肥学院 | A kind of phenyl-phosphonic acid zinc nucleator, preparation method, morphological control method and application |
-
2017
- 2017-03-17 CN CN201710159232.5A patent/CN106987100A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2251378A4 (en) * | 2008-03-03 | 2014-09-17 | Unitika Ltd | Biodegradable polyester resin composition and molded body composed of the same |
| CN103804855A (en) * | 2012-11-08 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | High-strength copolyester and preparation method thereof |
| CN106220889A (en) * | 2016-08-24 | 2016-12-14 | 合肥学院 | A kind of phenyl-phosphonic acid zinc nucleator, preparation method, morphological control method and application |
Non-Patent Citations (2)
| Title |
|---|
| 王国全: "《聚合物改性》", 30 June 2000 * |
| 韩倩: "苯基磷酸锌和多酰胺成核剂对聚乳酸结晶动力学影响的对比研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351181A (en) * | 2021-06-15 | 2021-09-07 | 青岛科技大学 | Multi-adsorption biodegradable foam with oil-water separation function |
| CN113351181B (en) * | 2021-06-15 | 2023-08-11 | 青岛科技大学 | Biodegradable foam with multiple adsorption and oil-water separation functions |
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Application publication date: 20170728 |