CN106700455A - Nano-Al2O3 modified biopolymer material and preparation method thereof - Google Patents
Nano-Al2O3 modified biopolymer material and preparation method thereof Download PDFInfo
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- CN106700455A CN106700455A CN201510779071.0A CN201510779071A CN106700455A CN 106700455 A CN106700455 A CN 106700455A CN 201510779071 A CN201510779071 A CN 201510779071A CN 106700455 A CN106700455 A CN 106700455A
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Abstract
The invention discloses a nano-Al2O3 modified biopolymer material and a preparation method thereof. The nano-Al2O3 modified biopolymer material is formed through mixing and extruding 3-20 parts of a modifying nano-Al2O3 material, 97-80 parts of P(3HB-co-4HB), 0.1-0.3 parts of a heat stabilizer and 0.1-0.3 parts of a lubricant. A biopolymer material poly(3-hydroxy butyrate-3-co-4-hydroxy butyrate) [P(3HB-co-4HB)] material is modified with nano-Al2O3 through a melt blending technology to improve the disadvantages of low crystallization rate, severe post-crystallization, low strength and poor toughness of the [P(3HB-co-4HB)] material, and the [P(3HB-co-4HB)] material has good biodegradability and biocompatibility, so the nano-Al2O3 modified biopolymer material has wide application prospect in the fields of biological and degradable materials.
Description
Technical field
The present invention relates to polypropylene technology field, and in particular to a kind of nanometer Al2O3Modification biological macromolecular material and preparation method thereof.
Background technology
It is poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] material be a kind of Microbe synthesis polymer copolymerization ester, received significant attention with good biodegradability and biocompatibility.Some performances are similar to thermoplastic simultaneously, and mechanical property is also similar in polypropylene material, will turn into the first-selection for substituting traditional material.But because its melt strength is low, crystalline rate is small, rear crystallization is serious, and chemical constitution is simply regular so that poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] material fragility is strong, fracture elongation is extremely low, hinders it to widely use.
The content of the invention
It is an object of the invention to provide nanometer Al2O3Modification biological macromolecular material and preparation method thereof.
A kind of nanometer Al2O3Modification biological macromolecular material, is prepared from by weight by following components：
P(3HB-co-4HB)
80-97 parts,
Coupling agent modified nanometer Al2O3Material3-20 parts,
Heat stabilizer
0.1-0.3 parts,
Lubricant
0.1-0.3 parts,
The P (3HB-co-4HB), coupling agent modified nanometer Al2O3Both's weight sum is 100 parts.
The coupling agent modified nanometer Al2O3Material is to be prepared by the following method：
By in titanate coupling agent addition isopropanol, ultrasonically treated 3-20min, supersonic frequency 60-90Hz form homogeneous solution, add nanometer Al2O3Reaction is filtered after 1-3 hours, is vacuum dried 8-20 hours under conditions of 25 DEG C -50 DEG C, obtains coupling agent modified nanometer Al2O3Material.
Described titanate coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters（TMC-201）.
Described titanate coupling agent is 1g with the w/v of isopropanol：（3-20）ML, titanate coupling agent and nanometer Al2O3Weight ratio be 1：10-30.
The heat stabilizer is one or more in phenolic thermostabilizers, amine heat stabilizer, phosphite ester type thermal stabilizing agent.
The lubricant is one or more in metal soap lubricant, stearic acid compound ester lubricant and acid amides series lubricant agent.
A kind of nanometer Al of the present invention2O3The preparation method of modification biological macromolecular material, it is by proportioning, by P (3HB-co-4HB), modified Nano Al2O3Material, heat stabilizer, lubricant are added in screw extruder, carry out melt blending, extruding pelletization and nanometer Al is obtained2O3Modification biological macromolecular material；The draw ratio of the screw extruder is 35-56:1, processing temperature is 130-160 DEG C.
The present invention uses inorganic nano Al2O3It is modified poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] material can improve the crystalline rate of the material, while playing activeness and quietness effect, effectively reduce the spherulite size of composite, proper amount of nano Al2O3It is dispersed in [P（3HB-co-4HB）] in material matrix, stronger interface binding power is formed, the intensity and toughness of material are substantially improved, can expand poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] material application field.
It is of the invention to have the following advantages that compared with prior art：
1. the present invention provides a kind of nanometer Al2O3It is modified poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] material method, the intensity and toughness of this biomaterial can be improved, significantly broadened the application field of this biomaterial；
2. nanometer Al2O3After titanate coupling agent surface graft modification, agglomeration improves, and can be dispersed in poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] in material substrate, stronger interface binding power is formed, so as to effectively improve material property；
3. method of modifying of the invention is simple and easy to apply, with industrial production prospect.
Specific embodiment
Heat stabilizer selects phenolic thermostabilizers 1010, phosphite ester type thermal stabilizing agent 168 in example below；
Lubricant selects calcium stearate, zinc stearate, glycol stearate, ethylene bis stearamide（EBS）, erucyl amide.
Embodiment
1
By 1g solid titanate coupling agents TMC-201 add 10mL isopropanols in, ultrasonically treated 10min（Supersonic frequency 80Hz）Homogeneous solution is formed, 15g nanometers of Al is added2O3Reaction is filtered after 2 hours, is vacuum dried 14 hours under conditions of 30 DEG C, obtains modified Nano Al2O3Material.
By 90kg P (3HB-co-4HB), 10kg modified Nanos Al2O3Material, 0.2
Kg phenolic thermostabilizers 1010,0.2kg Lubricate EBSs are 40 in draw ratio:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product a nanometer Al2O3Modification biological macromolecular material.Processing temperature during preparation is 150 DEG C.
Embodiment
2
By 2g solid titanate coupling agents TMC-201 add 40mL isopropanols in, ultrasonically treated 20min（Supersonic frequency 90Hz）Homogeneous solution is formed, 60g nanometers of Al is added2O3Reaction is filtered after 3 hours, is vacuum dried 20 hours under conditions of 50 DEG C, obtains modified Nano Al2O3Material.
By 80kgP (3HB-co-4HB), 20kg nanometers of Al2O3Material, 0.1kg lubricant stearic acids zinc, 0.1kg lubricant stearic acid calciums, 0.25 kg phenolic thermostabilizers 1010 are 56 in draw ratio:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product a nanometer Al2O3Modification biological macromolecular material.Processing temperature during preparation is 130 DEG C.
Embodiment
3
By 1g solid titanate coupling agents TMC-201 add 3mL isopropanols in, ultrasonically treated 3min（Supersonic frequency 60Hz）Homogeneous solution is formed, 10g nanometers of Al is added2O3Reaction is filtered after 1 hour, is vacuum dried 8 hours under conditions of 25 DEG C, obtains modified Nano Al2O3Material.
By 97kg polypropylene, 3kg nanometers of Al2O3Material, 0.3kg phenolic thermostabilizers 1010 and 0.3kg Lubricate EBSs, are 35 in draw ratio:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product a nanometer Al2O3Modification biological macromolecular material.Processing temperature during preparation is 160 DEG C.
Embodiment
4
By 1g solid titanate coupling agents TMC-201 add 15mL isopropanols in, ultrasonically treated 12min（Supersonic frequency 70Hz）Homogeneous solution is formed, 20g nanometers of Al is added2O3Reaction is filtered after 2 hours, is vacuum dried 18 hours under conditions of 40 DEG C, obtains modified Nano Al2O3Material.
By 85kgP (3HB-co-4HB), 15kg nanometers of Al2O3Material, 0.2kg phenolic thermostabilizers 168,0.15kg lubricant stearic acids glycol ester are 40 in draw ratio:Melting mixing dispersion in the double screw extruder of 1 550 sums, after all raw material blending extrusion granulations, obtains final product the nanometer Al of the present embodiment2O3Modification biological macromolecular material.Processing temperature during preparation is 136 DEG C.
Embodiment
5
By 1g solid titanate coupling agents TMC-201 add 5mL isopropanols in, ultrasonically treated 5min（Supersonic frequency 85Hz）Homogeneous solution is formed, 9g nanometers of Al is added2O3Reaction is filtered after 1.2 hours, is vacuum dried 10 hours under conditions of 45 DEG C, obtains modified Nano Al2O3Material.
By 91kgP (3HB-co-4HB), 9kg nanometers of Al2O3Material, 0.1kg phenolic thermostabilizers 1010,0.1kg lubricants erucyl amide are 40 in draw ratio:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product a nanometer Al2O3Modification biological macromolecular material.Processing temperature during preparation is 145 DEG C.
Comparative example
1
It is 40 in draw ratio by 90kg P (3HB-co-4HB), 0.2 kg phenolic thermostabilizers 1010,0.2kg Lubricate EBSs:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product unmodified bioabsorbable polymer material.Processing temperature during preparation is 150 DEG C.
Comparative example
2
It is 56 in draw ratio by 80kgP (3HB-co-4HB), 0.1kg lubricant stearic acids zinc, 0.1kg lubricant stearic acid calciums, 0.25 kg phenolic thermostabilizers 1010:Melting mixing dispersion in 1 double screw extruder, after all raw material blending extrusion granulations, obtains final product unmodified bioabsorbable polymer material.Processing temperature during preparation is 130 DEG C.
Bioabsorbable polymer material prepared by above-described embodiment 1-5 and comparative example 1, comparative example 2 is obtained standard batten, according to ISO527, ISO180 testing standard, test result such as following table：
As can be seen from Table 1, the present invention is obtained modified poly-（3 butyric ester-co-4 butyric esters）[P（3HB-co-4HB）] the more unmodified material of material compares, intensity and toughness are greatly improved.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be within protection scope of the present invention.
Claims (7)
1. one kind nanometer Al2O3Modification biological macromolecular material, it is characterised in that：It is prepared from by weight by following components：
80-97 parts of P (3HB-co-4HB),
Coupling agent modified nanometer Al2O3Material 3-20 parts,
Heat stabilizer 0.1-0.3 parts,
Lubricant 0.1-0.3 parts,
The P (3HB-co-4HB), coupling agent modified nanometer Al2O3Both's weight sum is 100 parts.
2. a kind of nanometer Al according to claim 12O3Modification biological macromolecular material, it is characterised in that：The coupling agent modified nanometer Al2O3Material is to be prepared by the following method：
By in titanate coupling agent addition isopropanol, ultrasonically treated 3-20min, supersonic frequency 60-90Hz form homogeneous solution, add nanometer Al2O3Reaction is filtered after 1-3 hours, is vacuum dried 8-20 hours under conditions of 25 DEG C -50 DEG C, obtains coupling agent modified nanometer Al2O3Material.
3. a kind of nanometer Al according to claim 22O3Modification biological macromolecular material, it is characterised in that：Described titanate coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters.
4. a kind of nanometer Al according to claim 22O3Modification biological macromolecular material, it is characterised in that：Described titanate coupling agent is 1g with the w/v of isopropanol：（3-20）ML, titanate coupling agent and nanometer Al2O3Weight ratio be 1：10-30.
5. a kind of nanometer Al according to claim 12O3Modification biological macromolecular material, it is characterised in that：The heat stabilizer is one or more in phenolic thermostabilizers, amine heat stabilizer, phosphite ester type thermal stabilizing agent.
6. a kind of nanometer Al according to claim 12O3Modification biological macromolecular material, it is characterised in that：The lubricant is one or more in metal soap lubricant, stearic acid compound ester lubricant and acid amides series lubricant agent.
7. a kind of nanometer Al as described in claim any one of 1-62O3The preparation method of modification biological macromolecular material, it is characterised in that：By proportioning, by P (3HB-co-4HB), coupling agent modified nanometer Al2O3Material, heat stabilizer, lubricant are added in screw extruder, carry out melt blending, extruding pelletization and nanometer Al is obtained2O3Modification biological macromolecular material；The draw ratio of the screw extruder is 35-56:1, processing temperature is 130-160 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395685A (en) * | 2018-03-21 | 2018-08-14 | 安徽江淮汽车集团股份有限公司 | A kind of high-performance PLA composite material and preparation methods |
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| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
| CN104788924A (en) * | 2015-05-04 | 2015-07-22 | 苏州汉丰新材料股份有限公司 | Heat-resistant completely biodegradable composite material for injection molded product and formula and preparation method of heat-resistant completely biodegradable composite material |
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2015
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Patent Citations (5)
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| US5646217A (en) * | 1992-11-06 | 1997-07-08 | Zeneca Limited | Polymer composition containing polyhydroxyalkanoate and metal compound |
| CN102295831A (en) * | 2010-06-23 | 2011-12-28 | 深圳市意可曼生物科技有限公司 | Special material for fully biodegradable rigid sheet and preparation method thereof |
| CN102675841A (en) * | 2012-02-22 | 2012-09-19 | 天津国韵生物材料有限公司 | Polylactic acid and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) nano modified composite |
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