CN115232451B - Polyhydroxyalkanoate material or product capable of being rapidly crystallized and preparation method thereof - Google Patents
Polyhydroxyalkanoate material or product capable of being rapidly crystallized and preparation method thereof Download PDFInfo
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- CN115232451B CN115232451B CN202210809117.9A CN202210809117A CN115232451B CN 115232451 B CN115232451 B CN 115232451B CN 202210809117 A CN202210809117 A CN 202210809117A CN 115232451 B CN115232451 B CN 115232451B
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- 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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- C08L2205/24—Crystallisation aids
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a polyhydroxyalkanoate material with a characteristic of rapid crystallization and a preparation method thereof. The invention provides a polyhydroxyalkanoate material or product, which comprises the following raw materials: 98 to 99.95 weight percent of polyhydroxyalkanoate and 0.05 to 2.0 weight percent of crystallization regulator; wherein the crystallization regulator is at least one of phenylphosphonate, hydrazide compounds or amide compounds. The invention selects specific crystallization regulator, and the product can be processed into a product in conventional molding 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 characteristic of rapid crystallization and a preparation method thereof.
Background
At present, the polymer materials used by a large amount of human beings are basically petroleum-based and non-biodegradable, which not only aggravates the problems of carbon emission and shortage of petrochemical resources, but also causes great pollution to the ecological environment after being abandoned, so that the development of biodegradable polymer materials taking biomass resources as raw materials is receiving more and more attention. Polyhydroxyalkanoates (PHAs) are a type of bio-based and biodegradable polymer 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 which can be completely biosynthesized, PHAs also have excellent biocompatibility, mechanical property, optical activity, barrier property, piezoelectricity and the like, have been applied to the fields of high added value such as tissue engineering, medical drugs, cosmetics and the like, and have wide application prospects in the fields of packaging, agriculture and the like. PHAs are of various types, including homo-PHAs composed of monomers of different chain lengths and copolymers composed of monomers of different types. Among them, poly-beta-hydroxybutyrate (PHB) is one of the most widely studied and most widely used PHAs, but molding processing and application are very challenging due to its regular structure, high crystallinity, poor toughness, and narrow processing window (near decomposition and melting temperatures). 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), and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) have been prepared by copolymerization with other monomers. However, the crystallization rate of the PHBHHx and other copolymers is remarkably slow due to the fact that the regularity of molecular chains is damaged by copolymerization, so that the solidification rate is slow in the melt processing and forming process, the forming processing period is long, the crystallinity of the obtained product is low, the post shrinkage rate caused by secondary crystallization (crystallization occurs in the storage and use processes of uncrystallized molecular chains in the product due to the glass transition temperature lower than room temperature) is relatively large, and the large-scale commercial application of the product is severely limited. Therefore, the crystallization regulation of PHAs becomes a key for widening the application of PHAs, and has extremely important application value.
To solve the above problems, there have been studies to induce PHAs crystallization by adding a nucleating agent. Currently, nucleating agents reported in the literature to be used for regulating and controlling PHAs crystallization mainly comprise three types of inorganic nano particles (superfine talcum powder and BN), natural small organic molecules (L-phenylalanine and cytosine) and high molecular nucleating agents (chitin, chitosan-g-PCL and cellulose nanocrystalline). However, these existing nucleating agents generally have weak capability of regulating and controlling PHAs crystallization, and have very limited effect of improving crystallization rate, so that crystallization still cannot be completed under the condition of rapid cooling in conventional melt processing molding. Therefore, the development of novel crystallization regulators 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-described problems, the present invention provides a method for preparing polyhydroxyalkanoate materials or articles that can be rapidly crystallized by adding an efficient organic crystallization modifier.
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 to 99.95 weight percent of polyhydroxyalkanoate and 0.05 to 2.0 weight percent 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 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 or aliphatic amides, and the like; aryl dimethylamides are preferred.
Further, the phenylphosphonate salt is selected from the group consisting of: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate, or aluminum phenylphosphonate, and the like.
Further, the hydrazide compound is selected from: adipic acid diphenyl dihydrazide or sebacic acid diphenyl dihydrazide, and the like.
Further, the polyhydroxyalkanoate is selected from the group consisting of: the monomer content (comonomer is 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid) in the copolymer is 0 to 12mol% in any of the copolymers such as poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P3 HB4 HB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx).
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 modifier.
The second technical problem to be solved by the invention is to provide a preparation method of the polyhydroxyalkanoate material or the polyhydroxyalkanoate product, which comprises the following steps: and (3) carrying out melt blending on the polyhydroxyalkanoate and the crystallization regulator, and then carrying out processing molding to obtain the polyhydroxyalkanoate material or product.
Further, the temperature of the melt blending is 160-180 ℃, and the melt blending time is 4-6 min.
Further, each raw material is physically premixed before melt blending
Further, the melt mixer may be one of polymer blending devices such as an extruder, an open mill, a torque rheometer, a micro-mixing rheometer, etc
Further, the molding process adopts injection molding, mould pressing or plastic sucking and other methods.
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 polyhydroxyalkanoate, and performing 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 proportion of the crystallization modifier incorporated in the polyhydroxyalkanoate is: 98 to 99.95 weight percent of polyhydroxyalkanoate and 0.05 to 2.0 weight percent of crystallization modifier.
Further, the amide compound is selected from: aromatic amides, aliphatic amides, and the like; aryl dimethylamides are preferred.
Further, the phenylphosphonate salt is selected from the group consisting of: zinc phenylphosphonate, sodium phenylphosphonate, calcium phenylphosphonate, or aluminum phenylphosphonate, and the like.
Further, the hydrazide compound is selected from: adipic acid diphenyl dihydrazide or sebacic acid diphenyl dihydrazide, and the like.
The fourth technical problem to be solved by the invention is to point out the application of phenylphosphonate, hydrazide compounds or amide compounds in improving the crystallization rate of polyhydroxyalkanoate.
Compared with the prior art, the invention has the following advantages:
(1) The invention selects specific crystallization regulator, and can obviously improve the crystallization rate by simple melt blending and processing into products in conventional molding processing equipment, so that the obtained products have high crystallinity and complete crystallization.
(2) The polyhydroxyalkanoate material or product prepared by the invention can meet the requirement of rapid crystallization and solidification in conventional melt processing 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 polyhydroxyalkanoate materials or products by 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 realize batch and continuous production, and is easy to realize large-scale industrial production.
Drawings
FIG. 1 is a differential scanning calorimeter curve of polyhydroxyalkanoate prepared according to the present invention in a nitrogen atmosphere.
FIG. 2 is a polarized light microscope photograph of isothermal crystallization of polyhydroxyalkanoate prepared according to the present invention at 100 ℃.
Detailed Description
The invention can prepare a polyhydroxyalkanoate material or product capable of crystallizing rapidly by adopting the following preparation method: the polyhydroxyalkanoate and crystallization modifier are firstly physically mixed by a high-speed stirrer, then are melt blended in a melt mixer, and then the obtained mixture is manufactured into products by molding processing methods such as injection molding, mould pressing, plastic suction and the like. The melt mixer used in the above method may be one of polymer blending devices such as an extruder, an open mill, a torque rheometer, a micro-mixing rheometer, and the like.
The polyhydroxyalkanoate material or product capable of being rapidly crystallized can meet the requirement of rapid crystallization and solidification in conventional melt processing molding (the product is completely crystallized, the problems of post-shrinkage and the like caused by secondary crystallization are avoided), and further the application of polyhydroxyalkanoate in the aspects of 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 for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Comparative example 1
PHBHHx (HHHx mol% = 6 mol%) was added to a micro-mixer rheometer (model Minilab-II, thermo Fisher Co., U.S.A.), and melt blended at a temperature of 170℃for 5min.
Example 1
0.05 part of aryldimethylamide and 99.95 parts of PHBHHx (HHx mol% =6) are stirred and mixed uniformly; adding the mixed material into a micro-mixing rheometer, and melt blending for 5min at 170 ℃; the aryl dicarboxamide used in the embodiment of the invention is N, N' -dicyclohexyl-2, 6-naphthalene dicarboxamide, and the structural formula is as follows
Example 2
0.1 part of aryldimethylamide and 99.9 parts of PHBHHx (HHx mol% =6) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 3
0.2 part of aryldimethylamide and 99.8 parts of PHBHHx (HHx mol% =6) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 4
0.3 part of aryldimethylamide and 99.7 parts of PHBHHx (HHx mol% =6) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 5
0.5 part of aryldimethylamide and 99.5 parts of PHBHHx (HHx mol% =6) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 6
1.0 part of aryldimethylamide and 99.0 parts of PHBHHx (HHx mol% =8) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 7
2.0 parts of aryldimethylamide and 98.0 parts of PHBHHx (HHx mol% = 12) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 8
Uniformly stirring and mixing 0.5 part of zinc phenylphosphonate and 99.5 parts of PHBHHx (HHx mol% =6); the mixture was added to a micro-mixing rheometer and melt blended for 5min at 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; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 10
Uniformly stirring and mixing 0.5 part of ethylene bis-12-hydroxystearamide and 99.5 parts of PHBHHx (HHx mol% =6); the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 11
Uniformly stirring and mixing 0.5 part of aryldimethylamide and 99.5 parts of P3HB4HB (4 HB mol% =3); the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 12
1.0 part of aryldimethylformamide and 99.0 parts of P3HB4HB (4 HB mol% =5) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 13
2.0 parts of aryldimethylformamide and 98.0 parts of P3HB4HB (4 HB mol% =10) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 14
0.5 part of aryl dimethylformamide and 99.5 parts of PHBV (HV mol% =2) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 15
1.0 part of aryldimethylamide and 99.0 parts of PHBV (HV mol% =7) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 16
2.0 parts of aryl dimethylamide and 98.0 parts of PHBV (HVmol% = 12) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended for 5min at 170 ℃.
Example 17
2.0 parts of benzamide and 98.0 parts of PHBHHx (HHx mol% = 6) are stirred and mixed uniformly; the mixture was added to a micro-mixing rheometer and melt blended 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 studied using a Perkin Elmer DSC model 800 differential scanning calorimeter in the United states; after calibration with indium as a standard under a nitrogen atmosphere of 20ml/min, about 5mg of the sample was placed in an aluminum crucible, the sample was warmed up from-10 ℃ to 170 ℃ and kept for 3min to remove the heat history, then cooled down to-10 ℃ at different rates and kept for 1min, and then warmed up again to 170 ℃ with a warming rate of 10 ℃/min.
Polarizing microscope (POM)
The crystal morphology of the product was observed using a polarizing microscope (model BX-1, olympus, japan) equipped with a temperature-controlled heat stage (model THMS600, linkam, england); the specific procedure is as follows, the heat history is eliminated at 170 ℃ for 5min, the temperature is reduced to 100 ℃ at a speed of 100 ℃ per min, and the isothermal crystallization is observed to observe the crystal morphology evolution.
FIG. 1 shows DSC curves of the non-isothermal crystallization of comparative example 1, example 5, example 8, example 9 and example 10 according to the present invention after the non-isothermal crystallization at a cooling rate of 100 ℃/min. From the figure, it is found that the crystallization ability of the matrix is improved to different degrees after the crystallization regulator zinc phenylphosphonate, diphenyl hydrazide sebacate, ethylene bis-12-hydroxystearamide and aryl dimethylamide are added. The blend with zinc phenylphosphonate, diphenyl hydrazide sebacate and ethylene bis-12-hydroxystearamide has limited crystallization capability improvement, the crystallization capability of the matrix is greatly improved by adding aryl dicarboxamide, and when the addition amount of the aryl dicarboxamide is 0.5wt%, the secondary temperature rise DSC curve of the blend can be found to have no cold crystallization exothermic peak, which indicates that the crystallization regulator can enable the polyhydroxyalkanoate copolymer to rapidly complete crystallization under the condition of extremely high cooling rate.
FIG. 2 is a polarized light picture of comparative example 1, example 4, example 8, example 9 of the present invention after isothermal crystallization at 100℃for 2.5 min. From the figures, it can be seen that comparative example 1 and example 10 are typical spherulitic morphology, and the maltese cross extinction phenomenon is clearly seen; the presence of fine crystals was observed with the addition of a blend of 0.3wt% aryldimethylamide and 0.5wt% zinc phenylphosphonate, indicating that both 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: the crystallization capacity of the matrix is improved to different degrees after the crystallization regulator zinc phenylphosphonate, sebacic acid diphenyl hydrazide, ethylene bis-12-hydroxystearamide and aryl dicarboxamide are added; the addition of aryl dicarboxamide greatly improves the crystallization capacity of a matrix, and when the addition amount of aryl dicarboxamide is 0.5wt%, the copolymer with low copolymerization content can be found that no cold crystallization occurs when the secondary temperature rise of the blend, which indicates that the crystallization regulator selected by the invention can enable the polyhydroxyalkanoate copolymer to rapidly complete crystallization under the condition of extremely high cooling rate (the cooling rate is more than or equal to 40 ℃/min), and the cooling rate is 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 (3)
1. A method for increasing the crystallization rate of polyhydroxyalkanoates, said method comprising: introducing a crystallization regulator into polyhydroxyalkanoate, and performing melt blending and processing molding on the polyhydroxyalkanoate and the polyhydroxyalkanoate; wherein the crystallization regulator is N, N' -dicyclohexyl-2, 6-naphthalimide; the proportion of the crystallization modifier introduced into the polyhydroxyalkanoate is as follows: 98-99.95 wt% of polyhydroxyalkanoate and 0.5-1 wt% of crystallization regulator; the mass sum of the polyhydroxyalkanoate and the crystallization modifier is 100%.
2. A method of increasing the crystallization rate of a polyhydroxyalkanoate according to claim 1, wherein said polyhydroxyalkanoate is selected from the group consisting of: any one of poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) or poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) with a monomer content of 0-12 mol% in the copolymer.
3. The method for improving the crystallization rate of polyhydroxyalkanoate according to claim 1 or 2, wherein the melt blending temperature is 160-180 ℃ and the melt blending time is 4-6 min.
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| JP4455413B2 (en) * | 2004-06-11 | 2010-04-21 | キヤノン株式会社 | Polyhydroxyalkanoic acid having vinyl group, ester group, carboxyl group and sulfonic acid group and method for producing the same |
| US7301000B2 (en) * | 2004-09-15 | 2007-11-27 | The Procter & Gamble Company | Nucleating agents for polyhydroxyalkanoates |
| US9340660B2 (en) * | 2011-09-30 | 2016-05-17 | Nissan Chemical Industries, Ltd. | Poly(3-hydroxyalkanoate) resin composition |
| CN104194293B (en) * | 2014-09-02 | 2015-11-25 | 江南大学 | Biological poly ester composition of a kind of rapid crystallization and preparation method thereof |
| WO2016058097A1 (en) * | 2014-10-15 | 2016-04-21 | Terraverdae Bioworks Inc. | Biodegradable polymer filament |
| CN106519610A (en) * | 2016-11-02 | 2017-03-22 | 江南大学 | Method for rapid crystallization of polymer at high temperature |
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