CN101565509B - Method for preparing modified PBAT foaming material - Google Patents

Method for preparing modified PBAT foaming material Download PDF

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Publication number
CN101565509B
CN101565509B CN 200910051644 CN200910051644A CN101565509B CN 101565509 B CN101565509 B CN 101565509B CN 200910051644 CN200910051644 CN 200910051644 CN 200910051644 A CN200910051644 A CN 200910051644A CN 101565509 B CN101565509 B CN 101565509B
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butanediol ester
gathers
terephthalic acid
acid
foaming
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CN 200910051644
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CN101565509A (en
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林士全
杨斌
严洁峰
杨婧
赵亚平
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

A method for preparing a modified PBAT foaming material in the field of foaming material technology comprises the following steps of: step one: dissolving tristearin and PBAT in a chloroform, removing the chloroform by volatilizing at the temperature of 18-25 DEG C, thus preparing the modified PBAT material, wherein the weight of the tristearin is 0.1-10% of the weight of the PBAT; step two: arranging the modified PBAT material in a CO2 fluid of supercritical state to carry out swelling, depressurizing and foaming, thus obtaining the modified PBAT foaming material. The modified PBAT foaming material is a green plastic that can be completely bio-degraded and is a completely green foaming material.

Description

The preparation method of modified PBAT foaming material
Technical field
The present invention relates to a kind of preparation method of foam material technical field, specifically is the preparation method of a kind of modified PBAT (gathering hexanodioic acid-terephthalic acid-butanediol ester) foam material.
Background technology
Porous plastics is because its matrix contains a large amount of abscesses, thereby has light weight, sound-insulating and heat-insulating, can absorb shock load, saves material, characteristic such as reduce cost, and is widely used in departments such as packing, building, transportation, daily necessities.Porous plastics principal item has urethane, PS, Vilaterm three major types.But because urethane, PS, Vilaterm are Biodegradable materials not, and the whipping agent that uses in the foaming process is mainly chemical foaming agent, and environment is had pollution.Therefore, it is just particularly necessary to use environment amenable pneumatogen to prepare a kind of biodegradable expanded plastic.
With supercritical CO 2And N 2Deng pneumatogen is that main physical blowing method is paid attention to widely.Supercritical CO 2Have nontoxic, harmless, do not fire, characteristics such as pollution-free, easy recovery and reusable edible, be a kind of eco-friendly green reagent.Utilize supercritical CO 2Excellent and swelling and osmosis that regulate easily and control to polymer through injection molding, extrusion moulding or batch technology foaming, can obtain the cell density height, cell diameter is little and the high molecular foam material goods of even aperture distribution.Because these characteristics of foam structure make and utilize supercritical CO 2Many mechanical properties of the macromolecular material of technology foaming obviously are superior to common foam material and foam material not, for example its shock strength than foaming before 6～7 times of raisings, intensity and weight ratio can improve 5～7 times.Therefore, supercritical CO 2The foaming polymer material of technology preparation is more suitable for light weight in being applied in wrapping material, crash helmet, insulation and thermal insulation material, sports equipment and component etc. with high endergonic place, space flight and automotive industry.
In the preparation process of porous plastics, the adding additive carries out modification to macromolecular material or in foaming process, assists nucleation, and this structure and performance to final foam material has material impact.Select suitable additive can significantly improve porous plastics cell density, reduce cell diameter to reach the comprehensive physicals (shock resistance, antifatigue, dimensional stability and gas barrier property etc.) that increases macromolecular material, improve the material processing characteristics purpose of (processing temperature, tonnage, process period) simultaneously.
Literature search through to prior art is found; Chinese patent CN1544513 record; With several kinds of thermoplasticity and thermoset macromolecule material is base-material; Add filler such as lime carbonate, Mierocrystalline cellulose and relevant auxiliary agent and carry out modification, prepared a kind of modified foaming type macromolecular material and goods thereof of low-density and high-strength; Chinese patent CN1236901 record; In Biodegradable starch, having added Z 150PH is softening agent, and lime carbonate is nucleator, and Yelkin TTS is processing aid and other some functional additives; With water is whipping agent, through the microwave heating formation expansible foamed products of different step.But the product that aforesaid method obtains all can not be realized complete environmental friendliness.
Summary of the invention
The present invention is directed to the deficiency of prior art, a kind of preparation method of modified PBAT foaming material is provided.Modified PBAT foaming material of the present invention is a kind of green plastic that can complete biodegradable, is a kind of foam material of complete green.
The present invention realizes through following technical scheme, the present invention includes following steps:
Step 1 places trichloromethane to dissolve stearin and PBAT, and 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material; Stearin is 0.1%～10% of a PBAT weight;
Step 2 places the modified PBAT material CO of supercritical state 2Carry out swelling in the fluid, release, foaming obtains modified PBAT foaming material.
In the step 1, being shaped as of said modified PBAT material is granular, sheet or strip.
In the step 2, said CO 2Fluid, CO 2Temperature＞31.1 ℃, pressure＞7.4MPa.
In the step 2, said swelling, swelling time is 2 hours, and swelling temperature is 90 ℃, and swelling pressure is 8～20MPa.
In the step 2, said release is specially, and release speed is 5MPa/s, unloads and is depressed into normal atmosphere.
In the step 2, said foaming, temperature is 20～80 ℃.
In the step 2, said modified PBAT foaming material has uniform abscess, and cell diameter is 2.5～80.3 μ m, and cell density is 2.28 * 10 6～8.73 * 10 9Individual/cm 3
The present invention passes through the modified PBAT material at supercritical CO 2Middle swelling utilizes fast pressure relief to make it foaming then, thereby obtains cell diameter 2.5～80.3 μ m, cell density 2.28 * 10 6～8.73 * 10 9Individual/cm 3Modified PBAT foaming material.
The present invention has following beneficial effect: modified PBAT foaming material of the present invention is a kind of green plastic that can complete biodegradable, is a kind of foam material of complete green; Along with environment protection comes into one's own day by day, the prepared modified PBAT foaming material of the present invention will possess outstanding advantage in packaging field.
Description of drawings
Fig. 1 is the profile scanning Electronic Speculum figure that quenches of the modified PBAT foaming material of embodiment 1 preparation;
Fig. 2 is the profile scanning Electronic Speculum figure that quenches of the modified PBAT foaming material of embodiment 2 preparations.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
The analysis test method that following examples adopt is a scanning electron microscope analysis.
Adopt ESEM (SEM) to the modified PBAT foaming sample section analysis of quenching, big or small with the cell density of investigating modified PBAT foaming sample with cell diameter.Analytical instrument is the Japanese HitachiHigh-Technologies S-2150 of company type ESEM.Fig. 1 has indicated magnification and size for the profile scanning Electronic Speculum figure that quenches of the modified PBAT foaming material of embodiment 1 preparation among the figure.Statistics micropore number n is confirmed photo area A (cm from the SEM photo 2) and magnification M.Wherein cell diameter adopts following The Representation Equation:
D = Σ n i d i Σ n i
Cell density adopts document " V.Kumar; N.P.Suh.A Process for MakingMicrocellular Thermoplastic Parts.Polym.Eng.Sci.; 30 (20): 1323～1329 (1990) " disclosed Kumar method estimation; Because particle is approximately ball-type, therefore can suppose the abscess isotropic growth, then the unit volume cell density is:
N p = ( nM 2 A ) 3 2 .
Embodiment 1
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 0.1%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 14MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 20 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 62.1 μ m, and cell density is 7.92 * 10 6Individual/cm 3See that from cell morphology abscess is fully grown up, spherical in shape, as shown in Figure 1.Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 2
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 5%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 14MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 20 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 29.0 μ m, and cell density is 9.31 * 10 7Individual/cm 3See that from cell morphology abscess is fully grown up, spherical in shape, as shown in Figure 2.Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 3
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 10%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 14MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 20 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 32.2 μ m, and cell density is 7.76 * 10 7Individual/cm 3Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 4
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 5%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 20MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 20 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 2.5 μ m, and cell density is 8.73 * 10 9Individual/cm 3Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 5
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 5%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 8MPa, swelling 2 hours.Fast pressure relief to gauge pressure is a normal atmosphere then, and release speed is 5MPa/s.Take out sample, be placed on 20 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 80.3 μ m, and cell density is 2.28 * 10 6Individual/cm 3Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 6
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 5%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 14MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 50 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 38.5 μ m, and cell density is 7.40 * 10 7Individual/cm 3Experimental result such as cell diameter and cell density is listed in the table 1.
Embodiment 7
Place trichloromethane to dissolve additive stearin and PBAT, 18～25 ℃ of removal trichloromethanes that volatilize down prepare the modified PBAT material.Wherein in PBAT matrix weight, stearin content is 5%.
The modified PBAT material is placed in the autoclave, and wherein the volume of modified PBAT material is not more than 1/20th of autoclave volume, to guarantee the modified PBAT material enough space foamings can be arranged.Close autoclave, in still, charge into low pressure CO 2Purged the air in the displacement still several minutes.Autoclave placed in 90 ℃ the water-bath, with HPP with CO 2Charge into autoclave to pressure and reach 14MPa, swelling 2 hours, fast pressure relief to gauge pressure is a normal atmosphere then, release speed is 5MPa/s.Take out sample, be placed on 80 ℃ of foaming down, the foaming sample section of quenching is carried out scanning electron microscope analysis.The cell diameter of modified PBAT material foaming sample is 49.4 μ m, and cell density is 2.64 * 10 7Individual/cm 3Experimental result such as cell diameter and cell density is listed in the table 1.
Table 1
Embodiment Additive level (%) Swelling pressure (MPa) Blowing temperature (℃) Cell diameter (μ m) Cell density is (individual/cm 3)
1 0.1 14 20 62.1 7.92×10 6
2 5 14 20 29.0 9.31×10 7
3 10 14 20 32.2 7.76×10 7
4 5 20 20 2.5 8.73×10 9
5 5 8 20 80.3 2.28×10 6
6 5 14 50 38.5 7.40×10 7
7 5 14 80 49.4 2.64×10 7

Claims (7)

1. a modification gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, comprises the steps:
Step 1, with stearin with gather hexanodioic acid-terephthalic acid-butanediol ester and place trichloromethane to dissolve, 18～25 ℃ down volatilization remove trichloromethanes, preparing modification gathers hexanodioic acid-terephthalic acid-butanediol ester material; Stearin is to gather 0.1%～10% of hexanodioic acid-terephthalic acid-butanediol ester weight;
Step 2 is gathered hexanodioic acid-terephthalic acid-butanediol ester material with modification and is placed the CO of supercritical state 2Carry out swelling in the fluid, release, foaming obtains modification and gathers hexanodioic acid-terephthalic acid-butanediol ester foam material.
2. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, in the step 1, said modification gathers that being shaped as of hexanodioic acid-terephthalic acid-butanediol ester material is granular, sheet or strip.
3. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, and in the step 2, said CO 2Fluid, CO 2Temperature＞31.1 ℃, pressure＞7.4MPa.
4. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, and in the step 2, said swelling, swelling time is 2 hours, and swelling temperature is 90 ℃, and swelling pressure is 8～20MPa.
5. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, in the step 2, said release is specially, and release speed is 5MPa/s, unloads to be depressed into normal atmosphere.
6. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material, it is characterized in that, and in the step 2, said foaming, temperature is 20～80 ℃.
7. modification according to claim 1 gathers the preparation method of hexanodioic acid-terephthalic acid-butanediol ester foam material; It is characterized in that; In the step 2; Said modification gathers hexanodioic acid-terephthalic acid-butanediol ester foam material and has uniform abscess, and cell diameter is 2.5～80.3 μ m, and cell density is 2.28 * 10 6～8.73 * 10 9Individual/cm 3
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Publication number Priority date Publication date Assignee Title
CN102219986B (en) * 2011-05-16 2014-08-13 嘉兴博发新型塑料有限公司 Biodegradable poly(butylene adipate/terephthalate) hollow foamed particle and preparation method thereof
CN105602209B (en) * 2016-03-07 2017-02-08 天津金发新材料有限公司 PBAT resin composition
CN108484959B (en) * 2018-04-20 2020-09-22 中国科学院宁波材料技术与工程研究所 2, 5-furandicarboxylic acid based copolyester foam material and preparation method thereof
CN112694636A (en) * 2020-12-14 2021-04-23 浙江理工大学 Preparation method of soft PBAT-based biodegradable foam material
CN112708163A (en) * 2020-12-25 2021-04-27 安踏（中国）有限公司 Preparation method of high-resilience biodegradable polyester micro-foaming profiled bar
CN113956628A (en) * 2021-11-18 2022-01-21 广东舜天新材料有限公司 Preparation method and application of high-melting-point PBAT foam

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1169359A (en) * 1996-05-22 1998-01-07 纳幕尔杜邦公司 Foamed fluoropolymer
CN1817945A (en) * 2006-01-18 2006-08-16 中国石油化工股份有限公司 In situs polymerization and compatibilization blending method with microporous foaming polymer as matrix
CN101386685A (en) * 2008-10-30 2009-03-18 上海交通大学 Method for preparing poly hexane diacid-terephthalic acid-butylene terephthalate foaming material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1169359A (en) * 1996-05-22 1998-01-07 纳幕尔杜邦公司 Foamed fluoropolymer
CN1817945A (en) * 2006-01-18 2006-08-16 中国石油化工股份有限公司 In situs polymerization and compatibilization blending method with microporous foaming polymer as matrix
CN101386685A (en) * 2008-10-30 2009-03-18 上海交通大学 Method for preparing poly hexane diacid-terephthalic acid-butylene terephthalate foaming material

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