CN114316543A - Polyhydroxyalkanoate particles and preparation method thereof - Google Patents
Polyhydroxyalkanoate particles and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of plastic processing, and discloses polyhydroxyalkanoate particles and a preparation method thereof. The polyhydroxyalkanoate particles comprise the following components: polyhydroxyalkanoate, anionic starch, and a thickener. The preparation method comprises the following steps: mixing polyhydroxyalkanoate powder, anionic starch and a thickening agent, and then pressing at 5-40 ℃ by adopting a pressure of 40-120kN to prepare polyhydroxyalkanoate granules. The PHA granules are prepared at normal temperature by selecting the components, using anionic starch matched with a thickening agent and adopting a pressure granulation mode. The prepared PHA particles have smooth surfaces and high particle forming degree, and are not easy to loose and break; and the degradation of the polyhydroxyalkanoate can be reduced, and the secondary processing and subsequent use of the polyhydroxyalkanoate are facilitated.
Description
Technical Field
The invention belongs to the technical field of plastic processing, and particularly relates to polyhydroxyalkanoate particles and a preparation method thereof.
Background
Polyhydroxyalkanoate (PHA), an intracellular polyester synthesized by many microorganisms, is a natural high molecular biomaterial. The material exists mainly as a carbon source and an energy source in an organism, and has many excellent properties such as physicochemical properties similar to those of synthetic plastics, biodegradability, biocompatibility, optical activity, piezoelectricity, gas barrier property, and the like which synthetic plastics do not have. The polyhydroxyalkanoate has wide application prospect in biodegradable packaging materials, tissue engineering materials, slow release materials, electrical materials and medical materials.
PHA is used as a bio-based completely degradable bioplastic and is produced by microbial fermentation, and the product is mainly in a powdery form and is very unfavorable for later processing and use. The current common granulation method still depends on the processing mode of the traditional plastics, mainly uses a single-screw or double-screw extruder, achieves the melting point by heating, and extrudes, cools and granulates after melting. The PHA particles are prepared by an extruder, and the PHA is degraded to form oligomer and monomer compounds due to the influence of temperature in the extrusion process, so that the molecular weight is reduced, and the PHA particles are corrosive to equipment; and due to the existence of oligomer and monomer compounds, the physical properties of the PHA are seriously influenced, and further the secondary processing and subsequent use of the PHA are influenced.
Therefore, it is desirable to provide a method for preparing polyhydroxyalkanoate particles, which can reduce the degradation of polyhydroxyalkanoate and is beneficial to secondary processing and subsequent use of polyhydroxyalkanoate.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of polyhydroxyalkanoate particles, which can reduce the degradation of polyhydroxyalkanoate and is beneficial to secondary processing and subsequent use of polyhydroxyalkanoate.
In a first aspect, the present invention provides a polyhydroxyalkanoate particle.
Specifically, the polyhydroxyalkanoate particles comprise the following components: polyhydroxyalkanoate, anionic starch, and a thickener.
Preferably, the anionic starch is starch with anionic groups obtained after chemical treatment. Further preferably, the anionic starch is selected from at least one of carboxymethyl starch, starch sulfate, starch succinate monoester, starch phosphate or starch acetate.
Preferably, the thickener is a cellulose-based substance or a polysaccharide-based substance. Further preferably, the thickener is selected from at least one of xanthan gum, pectin, agar, hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium hydroxypropyl methylcellulose, or methylcellulose.
Preferably, the thickening agent comprises carboxymethylcellulose and/or sodium hydroxymethylcellulose, which not only has a thickening effect, but also improves the smoothness of the surface of the PHA granules.
More preferably, the thickener comprises methylcellulose and hydroxypropylmethylcellulose sodium.
Preferably, the polyhydroxyalkanoate has a weight average molecular weight of 5 to 80 ten thousand Da. Such as 5 ten thousand Da, 10 ten thousand Da, 15 ten thousand Da, 20 ten thousand Da, 25 ten thousand Da, 30 ten thousand Da, 35 ten thousand Da, 40 ten thousand Da, 45 ten thousand Da, 50 ten thousand Da, 55 ten thousand Da, 60 ten thousand Da, 65 ten thousand Da, 70 ten thousand Da, 75 ten thousand Da, 80 ten thousand Da.
Preferably, the Polyhydroxyalkanoates (PHAs) include, but are not limited to, poly-beta-hydroxybutyrate (PHB), copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV), copolyesters of 3-hydroxybutyrate with 3-hydroxyhexanoate (PHBHHx), and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P34 HB).
Preferably, the mass ratio of the polyhydroxyalkanoate to the anionic starch is (2-20): 1; further preferably, the mass ratio of the polyhydroxyalkanoate to the anionic starch is (3-19) to 1; more preferably, the mass ratio of the polyhydroxyalkanoate to the anionic starch is (5-15): 1.
Preferably, the mass ratio of the polyhydroxyalkanoate to the thickener is (5-35): 1; further preferably, the mass ratio of the polyhydroxyalkanoate to the thickener is (6.5-32): 1; more preferably, the mass ratio of the polyhydroxyalkanoate to the thickener is (10-25): 1.
In a second aspect, the invention provides a method for preparing polyhydroxyalkanoate particles.
Specifically, the preparation method of the polyhydroxyalkanoate particles comprises the following steps:
mixing polyhydroxyalkanoate powder, anionic starch and a thickening agent, and then pressing at 5-40 ℃ by using a pressure of 40-120kN to obtain the polyhydroxyalkanoate granules.
PHA is a high molecular polymer, and its melting point is between 80-180 deg.C depending on the monomers to be polymerized. The granulation by using a twin-screw extruder is to melt the PHA by heating at the melting point of the PHA, then extrude the PHA by using the shearing force of the twin-screw extruder, cool the extruded PHA and cut the PHA granules to form PHA granules. The method can lead PHA to be degraded to form monomer compounds such as 3-hydroxybutyric acid and other oligomers, thus leading the molecular weight of PHA to be reduced, and the physical properties of PHA to be obviously changed, thereby having adverse effect on subsequent use.
The invention adds anionic starch and thickening agent into polyhydroxyalkanoate powder, and prepares PHA granules at normal temperature (5-40 ℃) by utilizing a pressure granulation mode. The anionic starch can balance cations in the polyhydroxyalkanoate powder and reduce the rejection among the polyhydroxyalkanoate powder, and the anionic starch is matched with a thickening agent for use, particularly methylcellulose and sodium carboxymethylcellulose, so that the prepared polyhydroxyalkanoate particles not only have smooth particle surfaces and high smoothness, but also do not fall off powder, have high particle forming degree and are not easy to loose or break; and can effectively reduce the degradation of the polyhydroxyalkanoate.
Preferably, the polyhydroxyalkanoate powder is obtained by sieving through a 40-mesh sieve.
Preferably, the polyhydroxyalkanoate powder has a moisture content of less than 4%; further preferably, the polyhydroxyalkanoate powder has a moisture content of less than 2%. The subsequent preparation of the polyhydroxyalkanoate particles is facilitated by controlling the moisture content.
Preferably, the pressing process is carried out at 5-35 ℃ and with the pressure of 40-100 kN; further preferably, the pressing is performed at 15-35 ℃ with a pressure of 60-90 kN.
Preferably, the time of said pressing is between 5 and 90 s; such as 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90 s.
Preferably, the weight of each of the polyhydroxyalkanoate particles is 0.1 to 1.0 grams; further preferably, the weight of each of the polyhydroxyalkanoate particles is 0.2 to 0.8 grams.
More specifically, a preparation method of polyhydroxyalkanoate particles comprises the following steps:
the polyhydroxyalkanoate powder, the anionic starch and the thickening agent are fully mixed in a mixer, and then the weight of each single particle is controlled to be 0.2-0.8 g, and the single particle is pressed for 5s-90s at the temperature of 5-40 ℃ by adopting the pressure of 40kN-120kN, so as to prepare the polyhydroxyalkanoate particle.
Compared with the prior art, the invention has the following beneficial effects:
the method prepares PHA granules at normal temperature (5-40 ℃) by selecting components, using anionic starch matched with a thickening agent and adopting a pressure granulation mode, and the prepared PHA granules have smooth and bright surfaces and high granule forming degree and are not easy to loose or break; and through the selection of the components and the selection of the granulation mode, the degradation of the polyhydroxyalkanoate can be reduced, the molecular weight of the polyhydroxyalkanoate in the PHA granules is almost unchanged, and the polyhydroxyalkanoate is beneficial to secondary processing and subsequent use.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The polyhydroxyalkanoate powder (PHA powder) used in the following examples and comparative examples was poly (3-hydroxybutyrate-co-4-hydroxybutyrate), and all the raw materials, reagents or devices were obtained from a conventional commercial route or were obtained by a conventionally known method unless otherwise specified.
Example 1
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of carboxymethyl starch, 2 parts of methyl cellulose and 2 parts of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, and carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding into a three-dimensional mixer, and mixing for 24 hours till being fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 70kN for 10s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The weight average molecular weight of the PHA particles was analyzed by GPC, and was still about 10 ten thousand Da, with little change. And the PHA particles have smooth surfaces and do not fall off.
Similar effects can be obtained by preparing polyhydroxyalkanoate granules using other PHA powders such as PHB, PHBV and phbhfx.
Example 2
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 90 parts of polyhydroxyalkanoate, 5 parts of carboxymethyl starch, 2 parts of methylcellulose and 1 part of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, and carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding into a three-dimensional mixer, and mixing for 24 hours till being fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 70kN for 10s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The PHA particles were analyzed by GPC for a weight average molecular weight of about 9.8 ten thousand Da. The PHA particles have smooth surfaces and do not fall off.
Example 3
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 110 parts of polyhydroxyalkanoate, 5 parts of carboxymethyl starch, 2 parts of methylcellulose and 1 part of sodium carboxymethylcellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, and carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding into a three-dimensional mixer, and mixing for 24 hours till being fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 70kN for 10s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The PHA particles were analyzed by GPC for a weight average molecular weight of about 9.7 ten thousand Da. The PHA particles have smooth surfaces and do not fall off.
Example 4
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of carboxymethyl starch, 2 parts of methyl cellulose and 2 parts of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, and carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding into a three-dimensional mixer, and mixing for 24 hours till being fully mixed; PHA granules were then prepared by pressing at a temperature of 40 ℃ and a pressure of 70kN for 10s, using a die having a size of 6mm by 4mm, controlling the weight of the individual granules to be 0.3 g.
The PHA particles were analyzed by GPC for a weight average molecular weight of about 9.5 ten thousand Da. The PHA particles have smooth surfaces and do not fall off.
Example 5
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of carboxymethyl starch, 2 parts of methyl cellulose and 2 parts of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, and carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding into a three-dimensional mixer, and mixing for 24 hours till being fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 110kN for 10s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The PHA particles were analyzed by GPC for a weight average molecular weight of about 9.8 ten thousand Da. PHA particles have smooth surfaces and do not fall off powder, but during the pressing process, the granulation of the material is poor and cracked particles can appear.
Example 6
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of starch sulfate, 2 parts of hydroxyethyl cellulose and 2 parts of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 37 ten thousand Da, starch sulfate, hydroxyethyl cellulose and sodium carboxymethyl cellulose, adding the PHA powder, the starch sulfate, the hydroxyethyl cellulose and the sodium carboxymethyl cellulose into a three-dimensional mixer, and mixing for 24 hours till the mixture is fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 80kN for 12s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The weight average molecular weight of the PHA particles was analyzed by GPC, and was still about 37 million Da, with little change. The particle surface is smooth and does not fall off; but loose particles may occur.
Example 7
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 85 parts of polyhydroxyalkanoate, 8 parts of starch succinic acid monoester, 2 parts of methylcellulose, 2 parts of sodium carboxymethylcellulose and 1 part of hydroxypropyl methylcellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 52 ten thousand Da, starch succinic acid monoester, methylcellulose, sodium carboxymethylcellulose and hydroxypropyl methylcellulose, adding the mixture into a three-dimensional mixer, and mixing for 24 hours till the mixture is fully mixed; PHA granules were then prepared by pressing at a temperature of 15 ℃ and a pressure of 50kN for 30s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
Analysis of the weight-average molecular weight of the PHA granules by GPC, the weight-average molecular weight was still about 52 ten thousand Da, with little variation; and the surface of the particles is smooth and does not fall off.
Example 8
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of carboxymethyl starch, 2 parts of methyl cellulose and 2 parts of xanthan gum.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of: weighing PHA powder (passing through a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand Da, carboxymethyl starch, methylcellulose and xanthan gum, adding the PHA powder, the carboxymethyl starch, the methylcellulose and the xanthan gum into a three-dimensional mixer, and mixing for 24 hours till the PHA powder and the carboxymethyl starch are fully mixed; PHA granules were then prepared by pressing at a temperature of 20 ℃ and a pressure of 70kN for 10s, using a die having a size of 6mm by 4mm, with the weight of the individual granules controlled at 0.3 g.
The weight average molecular weight of the PHA particles was analyzed by GPC, and was still about 10 ten thousand Da, with little change. However, the PHA granules were not as smooth as those prepared in example 1, and the PHA granules had a non-smooth surface and were easily dusted.
Comparative example 1
The polyhydroxyalkanoate particles comprise the following components in parts by weight: 86 parts of polyhydroxyalkanoate, 8 parts of carboxymethyl starch, 2 parts of methyl cellulose and 2 parts of sodium hydroxymethyl cellulose.
A method for preparing polyhydroxyalkanoate particles, comprising the steps of:
weighing PHA powder (sieved by a 40-mesh sieve) with the water content of 0.4 percent and the weight-average molecular weight of about 10 ten thousand, carboxymethyl starch, methylcellulose and sodium carboxymethylcellulose, adding the PHA powder, the carboxymethyl starch, the methylcellulose and the sodium carboxymethylcellulose into a three-dimensional mixer, and mixing for 24 hours to obtain a mixture for later use;
preheating a double-screw extruder: and turning on a power supply, setting the temperature of each temperature zone of the extruder to be 135 ℃, and starting to heat up. And starting a cooling circulating water refrigerating system, and setting the water temperature to be 15 ℃. When the temperature reached 135 ℃, the temperature was kept constant for 30 minutes. Then cooling water circulation is started, and the mixture is put into a double-screw extruder. After the mixture reaches a molten state through different temperature zones, extruding the mixture in a linear shape from an outlet; the extruded linear PHA is cooled by cooling water and then is drawn to a granulator by a tractor, and the granular PHA is cut by the granulator to obtain PHA granules.
The weight average molecular weight of the PHA granules analyzed by GPC, the weight average molecular weight of the PHA granules prepared in comparative example 1 was reduced to about 4 ten thousand Da, which was reduced by more than half compared to the weight average molecular weight of the raw PHA powder.
Comparative example 2
Comparative example 2 differs from example 1 in that 4 parts of methylcellulose and 4 parts of sodium carboxymethylcellulose are used instead of carboxymethyl starch, and the remaining components and preparation method are the same as in example 1.
The weight average molecular weight of the PHA particles was analyzed by GPC, and was still about 10 ten thousand Da, with little change. However, PHA particles are poor in formability and easy to loosen, and the phenomena of block falling and particle breaking occur in the placement process.
Comparative example 3
Comparative example 3 differs from example 1 in that PHA granules were produced by pressing at a temperature of 20 ℃ and a pressure of 35kN for 30s, the composition of the PHA granules and the remaining production method were the same as in example 1.
The weight average molecular weight of the PHA particles was analyzed by GPC, and was still about 10 ten thousand Da, with little change. However, PHA particles are poor in formability and easy to loosen, and the phenomena of block falling and particle breaking occur in the placement process.
Claims (10)
1. A polyhydroxyalkanoate particle, comprising the following components: polyhydroxyalkanoate, anionic starch, and a thickener.
2. The polyhydroxyalkanoate particles of claim 1, wherein the anionic starch is selected from at least one of carboxymethyl starch, starch sulfate, starch succinate monoester, starch phosphate, or starch acetate.
3. The polyhydroxyalkanoate pellet of claim 1, wherein the thickener is a cellulose-based material or a polysaccharide-based material.
4. Polyhydroxyalkanoate particles according to claim 3, wherein the thickener is selected from at least one of xanthan gum, pectin, agar, hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium hydroxypropyl methylcellulose or methylcellulose.
5. Polyhydroxyalkanoate particles according to claim 1, characterized in that the polyhydroxyalkanoate has a weight average molecular weight of 5-80 ten thousand Da.
6. The polyhydroxyalkanoate particles of claim 1, wherein the mass ratio of polyhydroxyalkanoate to anionic starch is (2-20): 1.
7. The polyhydroxyalkanoate particles of claim 1, wherein the mass ratio of polyhydroxyalkanoate to the thickener is (5-35): 1.
8. The method for producing polyhydroxyalkanoate particles of any one of claims 1 to 7, comprising the steps of:
mixing polyhydroxyalkanoate powder, anionic starch and a thickening agent, and then pressing at 5-40 ℃ by using a pressure of 40-120kN to obtain the polyhydroxyalkanoate granules.
9. The method according to claim 8, wherein the polyhydroxyalkanoate powder has a moisture content of less than 4%.
10. The method of claim 8, wherein the pressing is performed at 5 to 35 ℃ for 5 to 90 seconds using a pressure of 40 to 100 kN.
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