CN115232451A - Polyhydroxyalkanoate material or product capable of being crystallized rapidly and preparation method thereof - Google Patents
Polyhydroxyalkanoate material or product capable of being crystallized rapidly and preparation method thereof Download PDFInfo
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- CN115232451A CN115232451A CN202210809117.9A CN202210809117A CN115232451A CN 115232451 A CN115232451 A CN 115232451A CN 202210809117 A CN202210809117 A CN 202210809117A CN 115232451 A CN115232451 A CN 115232451A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C08K5/16—Nitrogen-containing compounds
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- C08K5/24—Derivatives of hydrazine
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a polyhydroxyalkanoate material with a rapid crystallization characteristic and a preparation method thereof. The invention provides a polyhydroxyalkanoate material or product, and the polyhydroxyalkanoate material or product comprises the following raw materials: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds. The invention selects the specific crystallization regulator, and the product is processed in the conventional forming processing equipment through simple melt blending, so that the crystallization rate can be obviously improved, and the obtained product has high crystallinity and complete crystallization.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyhydroxyalkanoate material with a rapid crystallization characteristic and a preparation method thereof.
Background
At present, the polymer materials used by human beings in large quantities are basically petroleum-based and non-biodegradable, which not only aggravates the problems of carbon emission and shortage of petrochemical resources, but also causes huge pollution to the ecological environment after being discarded, so that the development of biodegradable polymer materials taking biomass resources as raw materials is receiving more and more attention. Polyhydroxyalkanoates (PHAs) are bio-based biodegradable polymers with great development potential, are aliphatic copolyesters directly synthesized by microorganisms through fermentation of various bio-based carbon sources (such as vegetable oil, fatty acid, starch and the like), and can be completely biodegraded into carbon dioxide and water in natural environments such as soil, water and the like.
As the only green low-carbon bioplastic capable of being completely biosynthesized, PHAs also have excellent biocompatibility, mechanical property, optical activity, barrier property, piezoelectricity and the like, are applied to high-added-value fields such as tissue engineering, medical drugs, cosmetics and the like, and show wide application prospects in the fields of packaging, agriculture and the like. There are many kinds of PHAs, including homopolyphas composed of monomers having different chain lengths and copolymers composed of different kinds of monomers. Among them, poly beta-hydroxybutyrate (PHB) is a kind of PHAs which is the most widely studied and has the greatest application potential, but due to the regular structure and high crystallinity, the toughness is poor, and the processing window is narrow (the decomposition temperature and the melting temperature are close), so that the forming processing and the application are very challenging. To overcome these disadvantages, a series of copolymers such as poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P3 HB4 HB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx), and the like were prepared by copolymerization with other monomers. However, since the molecular chain regularity is destroyed by copolymerization, the crystallization rate of copolymers such as PHBHHx is significantly reduced, which results in slow solidification rate and long molding cycle in the melt processing molding process, and the obtained product has low crystallinity and large post-shrinkage caused by secondary crystallization (the glass transition temperature lower than room temperature causes the molecular chain not crystallized in the product to crystallize during storage and use), thus severely limiting the large-scale commercial application thereof. Therefore, the crystallization regulation of PHAs becomes the key for widening the application of PHAs, and has extremely important application value.
To solve the above problems, the induction of crystallization of PHAs by the addition of a nucleating agent has been studied. At present, nucleating agents which are reported in literatures and can be used for regulating and controlling PHAs crystallization mainly comprise three types of inorganic nanoparticles (superfine talcum powder and BN), natural organic small molecules (L-phenylalanine and cytosine) and high-molecular nucleating agents (chitin, chitosan-g-PCL and cellulose nanocrystals). However, the existing nucleating agents generally have weak ability to regulate and control PHAs crystallization, and have very limited effect on improving the crystallization rate, so that crystallization still cannot be completed under the rapid cooling condition in the conventional melt processing and molding process. Therefore, the development of a novel crystallization regulator with low cost and high nucleation efficiency is extremely important for preparing novel PHAs materials with rapid crystallization characteristics, and can provide opportunities for preparing high-performance PHAs products.
Disclosure of Invention
In view of the above-mentioned problems, the present invention provides a method for preparing polyhydroxyalkanoate material or article capable of rapid crystallization by adding an organic crystallization modifier with high efficiency.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a polyhydroxyalkanoate material or product, which comprises the following raw materials: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds. The obtained material or product can meet the requirement of rapid crystallization and solidification in conventional melt processing and molding, and solves the problems of post shrinkage, warping and the like caused by secondary crystallization.
Further, the amide compound is selected from: aromatic amides, aliphatic amides, and the like; preferably an aryldicarboxamide.
Further, the phenylphosphonate is selected from the group consisting of: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate, aluminum phenylphosphonate, and the like.
Further, the hydrazide compound is selected from: adipic acid diphenyldihydrazide or sebacic acid diphenyldihydrazide, and the like.
Further, the polyhydroxyalkanoate is selected from: the copolymer is any one of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P3 HB4 HB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) or poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx), and the monomer content (the comonomer is 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid) in the copolymer is 0 to 12mol%.
Preferably, the proportion of each raw material is as follows: 99.8 to 99.5 weight percent of polyhydroxyalkanoate and 0.2 to 0.5 weight percent of crystallization regulator.
The second technical problem to be solved by the present invention is to provide a method for preparing the above polyhydroxyalkanoate material or product, wherein the method comprises: and carrying out melt blending on the polyhydroxyalkanoate and the crystallization regulator, and then processing and forming to obtain the polyhydroxyalkanoate material or the product.
Further, the melt blending temperature is 160-180 ℃, and the melt blending time is 4-6 min.
Furthermore, before melt blending, the raw materials are physically premixed
Further, the melt mixer may be one of an extruder, open mill, torque rheometer, micro-mix rheometer, or other polymer blending device
Further, the molding process adopts methods such as injection molding, mold pressing or plastic suction.
The third technical problem to be solved by the invention is to provide a method for improving the crystallization rate of polyhydroxyalkanoate, which comprises the following steps: introducing a crystallization regulator into the polyhydroxyalkanoate, and then carrying out melt blending and processing molding on the polyhydroxyalkanoate and the polyhydroxyalkanoate; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds.
Further, the ratio of the introduced crystallization modifier in the polyhydroxyalkanoate is as follows: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator.
Further, the amide compound is selected from: aromatic amides, aliphatic amides, and the like; preferably an aryldicarboxamide.
Further, the phenylphosphonate salt is selected from: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate, aluminum phenylphosphonate, and the like.
Further, the hydrazide compound is selected from: adipic acid diphenyldihydrazide or sebacic acid diphenyldihydrazide, and the like.
The fourth technical problem to be solved by the invention is to indicate the application of the phenylphosphonate, the hydrazide compound or the amide compound in improving the crystallization rate of the polyhydroxyalkanoate.
Compared with the prior art, the invention has the following advantages:
(1) The invention selects the specific crystallization regulator, and the product is processed in the conventional forming processing equipment through simple melt blending, so that the crystallization rate can be obviously improved, and the obtained product has high crystallinity and complete crystallization.
(2) The polyhydroxyalkanoate material or the product prepared by the invention can meet the requirement of rapid crystallization and solidification in conventional melt processing and molding, so that the problems of post shrinkage, warping and the like caused by secondary crystallization of the product are inhibited, and the application scene can be greatly widened.
(3) The material system of the invention has simple composition and wide application range, can realize the rapid crystallization of the polyhydroxyalkanoate material or the product through the crystallization regulator, and can adapt to various molding methods.
(4) The preparation method provided by the invention is simple and efficient, is easy to operate, can be used for batch and continuous production, and is easy to realize large-scale industrial production.
Drawings
FIG. 1 is a differential scanning calorimeter curve of polyhydroxyalkanoates prepared by the present invention in a nitrogen atmosphere.
FIG. 2 is a polarizing microscope photograph showing isothermal crystallization of polyhydroxyalkanoate prepared by the present invention at 100 ℃.
Detailed Description
The invention can prepare a polyhydroxyalkanoate material or product which can be quickly crystallized by adopting the following preparation method: firstly, the polyhydroxyalkanoate and the crystallization regulator are physically mixed by a high-speed stirrer, then the components are melted and blended in a melting mixer, and then the obtained mixed material is made into a product by the forming processing methods of injection molding, mould pressing, plastic suction and the like. The melt mixer used in the above process may be one of a polymer blending device such as an extruder, open mill, torque rheometer, micro-mixing rheometer, and the like.
The polyhydroxyalkanoate material or product capable of being crystallized quickly can meet the requirement of quick crystallization and solidification in conventional melt processing and forming (the product is crystallized completely, and the problems of post shrinkage and the like caused by secondary crystallization are avoided), so that the application of polyhydroxyalkanoate in food packaging, agricultural products and the like is greatly widened.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Comparative example 1
PHBHHx (HHx mol% =6 mol%) was added to a micro-mixing rheometer (model Minilab-II, thermoFisher, USA) and melt blended for 5min at 170 ℃.
Example 1
0.05 part of aryldiformamide and 99.95 parts of PHBHHx (HHx mol% = 6) are stirred and mixed evenly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃; the aryldicarboxamide used in the examples of the present invention is N, N' -dicyclohexyl-2, 6-naphthalenedicarboxamide having the structural formula
Example 2
0.1 part of aryldiformamide and 99.9 parts of PHBHHx (HHx mol% = 6) are stirred and mixed evenly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 3
0.2 part of aryldiformamide and 99.8 parts of PHBHHx (HHx mol% = 6) are stirred and mixed evenly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 4
0.3 part of aryldiformamide and 99.7 parts of PHBHHx (HHx mol% = 6) are stirred and mixed evenly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 5
0.5 part of aryldiformamide and 99.5 parts of PHBHHx (HHx mol% = 6) are stirred and mixed evenly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 6
1.0 part of aryldiformamide and 99.0 parts of PHBHHx (HHx mol% = 8) are stirred and mixed uniformly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 7
2.0 parts of aryldiformamide and 98.0 parts of PHBHHx (HHx mol% = 12) are stirred and mixed evenly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 8
Stirring and mixing 0.5 part of zinc phenylphosphonate and 99.5 parts of PHBHHx (HHx mol% = 6) uniformly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 9
0.5 part of sebacic acid diphenyl dihydrazide and 99.5 parts of PHBHHx (HHx mol% = 6) are stirred and mixed uniformly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 10
Stirring and uniformly mixing 0.5 part of ethylene bis-12-hydroxystearamide and 99.5 parts of PHBHHx (HHx mol% = 6); adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 11
Stirring and uniformly mixing 0.5 part of aryldicarboxamide and 99.5 parts of P3HB4HB (4 HB mol% = 3); adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 12
1.0 part of aryldicarboxamide and 99.0 parts of P3HB4HB (4 HB mol% = 5) are stirred and mixed uniformly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 13
2.0 parts of aryldicarboxamide and 98.0 parts of P3HB4HB (4 HB mol% = 10) are stirred and mixed uniformly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 14
0.5 part of aryldicarboxamide and 99.5 parts of PHBV (HV mol% = 2) are stirred and mixed evenly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 15
1.0 part of aryldicarboxamide and 99.0 parts of PHBV (HV mol% = 7) are stirred and mixed evenly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Example 16
2.0 parts of aryldiformamide and 98.0 parts of PHBV (HVmol% = 12) are stirred and mixed evenly; adding the mixed materials into a micro-mixing rheometer, and melting and blending for 5min at the temperature of 170 ℃.
Example 17
2.0 parts of benzamide and 98.0 parts of PHBHHx (HHx mol% = 6) are stirred and mixed uniformly; adding the mixture into a micro-mixing rheometer, and melting and blending for 5min at 170 ℃.
Testing and characterization
Differential Scanning Calorimeter (DSC)
The non-isothermal crystallization and melting behavior of the samples obtained in the above examples and comparative examples were investigated using a differential scanning calorimeter model DSC800 of Perkin Elmer, USA; the following test method was used, after calibration with indium as the standard in a 20ml/min nitrogen atmosphere, to place approximately 5mg of sample in an aluminum crucible, raise the temperature of the sample from-10 ℃ to 170 ℃, hold the temperature for 3min to remove the thermal history, then lower the temperature to-10 ℃ at different rates, hold the temperature for 1min, then raise the temperature again to 170 ℃, with a rate of temperature rise of 10 ℃/min.
Polarizing microscope (POM)
The crystal morphology of the product was observed using a polarizing microscope (BX-1, model) equipped with a temperature-controlled hot stage (Linkam, UK, model THMS 600); the specific procedure is as follows, the heat history is eliminated after 5min of isothermal temperature at 170 ℃, and the crystal morphology evolution is observed after isothermal crystallization at 100 ℃ and min.
FIG. 1 is a DSC curve of non-isothermal crystallization at a cooling rate of 100 ℃/min and subsequent re-heating in comparative example 1, example 5, example 8, example 9 and example 10 in accordance with the present invention. It is found from the figure that the crystallization ability of the matrix is improved to different degrees after adding crystallization modifiers of zinc phenylphosphonate, diphenyl hydrazide sebacate, ethylene bis-12-hydroxystearamide and aryl dimethylamide. The improvement degree of the crystallization capacity of the blend added with the zinc phenylphosphonate, the sebacic acid diphenylhydrazide and the ethylene bis-12-hydroxystearamide is limited, the crystallization capacity of a matrix is greatly improved by adding the aryldimethylamide, and when the addition amount of the aryldimethylamide is 0.5wt%, the appearance of a cold crystallization exothermic peak of a secondary heating DSC curve of the blend can be found, so that the crystallization regulator can quickly complete the crystallization of the polyhydroxyalkanoate copolymer under the condition of a very high cooling rate.
FIG. 2 is a photograph showing the polarization of the inventive examples 1, 4, 8, and 9 after 2.5min of isothermal crystallization at 100 ℃. As can be seen from the figure, comparative example 1 and example 10 are typical spherulite morphologies, and the maltese cross extinction phenomenon is clearly visible; the presence of fine crystals was observed with the addition of a blend of 0.3wt% aryldicarboxamide and 0.5wt% zinc phenylphosphonate, indicating that these two nucleating agents have an effect on the crystal size of the matrix.
The crystallization properties of the polyhydroxyalkanoate materials obtained in the above examples and comparative examples at different cooling rates are shown in table 1. As can be seen from Table 1: after adding crystallization regulators such as zinc phenylphosphonate, sebacic acid diphenylhydrazide, ethylene bis-12-hydroxystearamide and aryl diformylamide, the crystallization capacity of the matrix is improved to different degrees; the addition of the aryldimethylamide greatly improves the crystallization capacity of a matrix, and when the addition amount of the aryldimethylamide is 0.5wt%, the secondary temperature rise of the blend can be found without the occurrence of cold crystallization for the copolymer with low copolymerization content, which shows that the crystallization regulator selected by the invention can quickly finish crystallization of the polyhydroxyalkanoate copolymer under the condition of extremely high temperature reduction rate (the temperature reduction rate is more than or equal to 40 ℃/min), and realizes the cooling rate equivalent to that in the industrial processing process.
TABLE 1 crystallization Properties of polyhydroxyalkanoate materials obtained in examples and comparative examples at different cooling rates
Claims (10)
1. A polyhydroxyalkanoate material or article, wherein the polyhydroxyalkanoate material or article comprises: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds.
2. A polyhydroxyalkanoate material or article of manufacture as claimed in claim 1, wherein the amide compound is selected from: aromatic amides or aliphatic amides, etc.; preferably an aryldicarboxamide;
further, the phenylphosphonate is selected from the group consisting of: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate or aluminum phenylphosphonate;
further, the hydrazide compound is selected from: adipic acid diphenyl dihydrazide or sebacic acid diphenyl dihydrazide.
3. A polyhydroxyalkanoate material or article as claimed in claim 1 or claim 2, wherein the polyhydroxyalkanoate is selected from: the copolymer is any one of poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) or poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and the monomer content in the copolymer is 0-12 mol%.
4. A polyhydroxyalkanoate material or article as claimed in any one of claims 1 to 3, wherein the proportions of the starting materials are: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator.
5. A method of producing a polyhydroxyalkanoate material product of any one of claims 1 to 4, wherein the method comprises: the polyhydroxyalkanoate and the crystallization regulator are subjected to melt blending and then are processed and formed.
6. The method of claim 5, wherein the melt blending temperature is 160-180 ℃ and the melt blending time is 4-6 min.
7. A method for increasing the crystallization rate of polyhydroxyalkanoate, the method comprising: introducing a crystallization regulator into the polyhydroxyalkanoate, and then carrying out melt blending and processing molding on the polyhydroxyalkanoate and the polyhydroxyalkanoate; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds.
8. The method of claim 7, wherein the polyhydroxyalkanoate is incorporated with the crystallization modifier in a ratio of: 98-99.95 wt% of polyhydroxyalkanoate and 0.05-2.0 wt% of crystallization regulator.
9. The method for increasing the crystallization rate of polyhydroxyalkanoate according to claim 7 or 8, wherein the amide compound is selected from the group consisting of: aromatic or aliphatic amides; preferably an aryldicarboxamide;
further, the phenylphosphonate is selected from the group consisting of: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate or aluminum phenylphosphonate;
further, the hydrazide compound is selected from: adipic acid diphenyl dihydrazide or sebacic acid diphenyl dihydrazide.
10. Use of a phenylphosphonate, hydrazide or amide compound to increase the crystallization rate of polyhydroxyalkanoates.
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