CN111454548B - PHBV/HBP-CLs blend and preparation method thereof - Google Patents

PHBV/HBP-CLs blend and preparation method thereof Download PDF

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CN111454548B
CN111454548B CN202010212825.5A CN202010212825A CN111454548B CN 111454548 B CN111454548 B CN 111454548B CN 202010212825 A CN202010212825 A CN 202010212825A CN 111454548 B CN111454548 B CN 111454548B
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CN111454548A (en
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靳玉娟
黄健
翁云宣
吴悠
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Beijing Technology and Business University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract

The invention discloses a PHBV/HBP-CLs blend and a preparation method thereof, wherein the preparation method of the PHBV/HBP-CLs blend comprises the steps of mixing a PHBV resin and HBP-CLs, and carrying out melt blending to obtain the PHBV/HBP-CLs blend; the chemical structural formula of the HBP-CLs is shown as a formula (I), and the number n of repeating units on a grafting chain is an integer within the range of 5-30. The impact strength and the elongation at break of the PHBV/HBP-CLs blend prepared by the method are both greatly improved. When 3phrHBP-CLs is added into the PHBV/HBP-CLs blend, the impact strength is from 5.13KJ/m‑2Increased to 32.25KJ/m‑2The amplification reaches 528.65%, the elongation at break is increased from 1.62% to 4.22%, and the amplification reaches 160.49%.
Figure DDA0002423398610000011

Description

PHBV/HBP-CLs blend and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a PHBV/HBP-CLs blend and a preparation method thereof.
Background
With the increasing exhaustion of non-renewable resources such as petroleum and coal and the increasing severity of environmental problems such as white pollution and greenhouse effect, sustainable biomass resources are sought, and degradable products are developed to be more and more concerned by people all over the world.
Biobased and biodegradable materials, such as polylactic acid (PLA), Polyhydroxyalkanoates (PHAs), etc., have the characteristics of sustainable sources, degradable products, etc., and gradually become a hot spot of research in the industry and academia. Among them, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is one of PHAs, and is one of the most widely studied bio-based and biodegradable materials. PHBV has good application prospect in numerous fields such as biomedicine, automobiles, packaging, disposable tableware and the like, but has higher crystallinity and large crystal size and shows relatively brittle property. In order to widen the application range of the PHBV, the PHBV must be subjected to toughening modification.
Hyperbranched polymers (HBPs) are a novel high polymer material which appears in the last three decades and are a series of structurally similar polymers with continuously increased molecular mass, which are obtained by taking low molecules as growth points and gradually controlling repeated reactions. The hyperbranched polymer has three-dimensional highly branched structure, a large number of cavities, a large number of end groups, good solubility, low viscosity, high reactivity and other properties, and the use of the hyperbranched polymer to improve the performance of the resin is one of the research hotspots in recent years. The unique property of the hyperbranched polymer enables the hyperbranched polymer to be used as a novel processing aid, a rheology modifier, a compatibilizer and the like of thermoplastic resin and also can be used as a toughening modifier of thermosetting resin.
Disclosure of Invention
In the preparation method, HBP-CLs is adopted to toughen and modify PHBV resin, and the impact strength and the elongation at break of the prepared PHBV/HBP-CLs blend are both greatly improved on the premise that the tensile strength is slightly reduced.
Based on the aim, the preparation method of the PHBV/HBP-CLs blend is characterized in that PHBV resin and HBP-CLs are mixed and melt blended to obtain the PHBV/HBP-CLs blend;
the chemical structural formula of the HBP-CLs is shown as the formula (I):
Figure BDA0002423398590000021
wherein the number n of repeating units on the graft chain is an integer in the range of 5 to 30.
In some embodiments of the invention, the HBP-CLs are prepared using the following method: synthesizing HBPE by adopting a melt polycondensation one-step method under the action of a catalyst a from 2, 2-dimethylolpropionic acid (DMPA) and Trimethylolpropane (TMP), and then carrying out grafting reaction on the HBPE and epsilon-caprolactone to obtain HBP-CLs;
the chemical structural formula of the HBPE is shown as a formula (II):
Figure BDA0002423398590000031
in some embodiments of the invention, the step of synthesizing HBPE by melt polycondensation in a "one-step" method using 2, 2-dimethylolpropionic acid and trimethylolpropane in the presence of catalyst a comprises:
mixing 2, 2-dimethylolpropionic acid, trimethylolpropane and a catalyst a, preheating, heating, reacting under normal pressure under the protection of nitrogen when reactants are completely molten, then reacting under reduced pressure, and cooling.
In some embodiments of the invention, the step of grafting HBPE with epsilon-caprolactone to obtain HBP-CLs comprises:
and drying the prepared HBPE, then dropwise adding a catalyst b, simultaneously adding epsilon-caprolactone, heating, carrying out grafting reaction, and cooling to room temperature to obtain the HBP-CLs.
In some embodiments of the present invention, the catalyst a is p-toluenesulfonic acid, and the molar ratio of 2, 2-dimethylolpropionic acid to trimethylolpropane is (18-25): 1.
in some embodiments of the invention, the preheating is carried out at 115-125 ℃ for 5-15 min, the temperature is raised to 135-145 ℃, the time of the normal pressure reaction is 2-3 h, and the reduced pressure reaction is carried out at 95-105 Pa for 1.5-3 h.
In some embodiments of the invention, the mass ratio of HBPE to epsilon-caprolactone is 1: (20-25); catalyst b is stannous isooctanoate (Sn (Oct)2) (ii) a The drying is to carry out vacuum drying on the prepared HBPE for 5-7 h at 90-110 ℃, the dropwise adding of the catalyst b is to dropwise add 3-4 drops of stannous isooctoate, the temperature is raised to 100-120 ℃, and the grafting reaction is to carry out reaction for 15-25 h at the rotating speed of 100-150 rpm.
In the invention, 2-dimethylolpropionic acid (DMPA) and Trimethylolpropane (TMP) are used as raw materials, P-toluenesulfonic acid (P-TSA) is used as a catalyst, and HBPE with Trimethylolpropane (TMP) as a core is synthesized by a melt polycondensation one-step method, wherein a schematic diagram of a synthetic reaction route is as follows:
Figure BDA0002423398590000041
in the present invention, HBPE and epsilon-caprolactone are used in the presence of Sn (Oct)2The grafting reaction is carried out under the action of (1), HBP-CLs with different polymerization degrees can be synthesized by controlling the mass ratio of HBPE to epsilon-caprolactone, and the schematic diagram of the synthetic reaction route is as follows:
Figure BDA0002423398590000042
in some embodiments of the invention, the mass ratio of said PHBV resin to HBP-CLs is 100: (0-10), and the quality of HBP-CLs is not zero.
In some embodiments of the present invention, the temperature of the melt blending is 180 to 200 ℃, the rotation speed is 50 to 100rpm, and the time is 5 to 10 min.
Furthermore, the invention also provides the PHBV/HBP-CLs blend prepared by the preparation method of the PHBV/HBP-CLs blend.
As can be seen from the above, the PHBV/HBP-CLs blend is prepared by adopting a melt blending method, the PHBV resin is toughened and modified by adopting HBP-CLs in the melt blending method, and the impact strength and the elongation at break of the prepared PHBV/HBP-CLs blend are both greatly improved. When 3phr of HBP-CLs is added into the PHBV/HBP-CLs blend, the impact strength is controlled to be 5.13KJ/m-2Increased to 32.25KJ/m-2The increase reaches 528.65%, the elongation at break is increased from 1.62% to 4.22%, the increase reaches 160.49%, and the tensile strength is slightly reduced, which shows that the addition of HBP-CLs has better toughening effect on PHBV.
Drawings
FIG. 1 is a FT-IR diagram of HBPE and HBP-CLs in the present invention;
FIG. 2 shows HBP-CLs of the present invention1H-NMR chart and13C-NMR chart wherein FIG. 2(a) is of HBP-CLs1H-NMR chart, FIG. 2(b) is of HBP-CLs13C-NMR chart;
FIG. 3 is a DSC plot of PHBV and PHBV/HBP-CLs blends and HBP-CLs in example 4 of the present invention, wherein FIG. 3(a) is a plot during temperature reduction and FIG. 3(b) is a plot during second temperature increase;
FIG. 4 is a thermogravimetric plot of blends of PHBV and PHBV/HBP-CLs in example 4 of the present invention, wherein FIG. 4(a) is a plot of thermogravimetric plot of blends of PHBV and PHBV/HBP-CLs, and FIG. 4(b) is a plot of mass loss rate of blends of PHBV and PHBV/HBP-CLs;
FIG. 5 is a graph of mechanical properties of PHBV and PHBV/HBP-CLs in example 4 of the present invention, wherein FIG. 5(a) is a graph of impact strength of PHBV and PHBV/HBP-CLs, FIG. 5(b) is a graph of elongation at break of PHBV and PHBV/HBP-CLs, and FIG. 5(c) is a graph of tensile strength of PHBV and PHBV/HBP-CLs;
FIG. 6 is a scanning electron micrograph of a blend of PHBV and PHBV/HBP-CLs according to example 4 of the present invention, wherein FIG. 6(a) is a scanning electron micrograph of PHBV, FIG. 6(b) is a scanning electron micrograph of a blend of PHBV/HBP-CLs (1.0phr, mass ratio of PHBV to HBP-CLs of 100: 1), FIG. 6(c) is a scanning electron micrograph of a blend of PHBV/HBP-CLs (2.0phr, mass ratio of PHBV to HBP-CLs of 100: 2), FIG. 6(d) is a scanning electron micrograph of a blend of PHBV/HBP-CLs (3.0phr, mass ratio of PHBV to HBP-CLs of 100: 3), FIG. 6(e) is a scanning electron micrograph of a blend of PHBV/HBP-CLs (4.0phr, mass ratio of PHBV to HBP-CLs of 100: 4), FIG. 6(f) is a scanning electron micrograph of PHBV/HBP-CLs of 5. CLs of 100: 5, FIG. 6(g) is a scanning electron micrograph of a PHBV/HBP-CLs blend (6.0phr, mass ratio of PHBV to HBP-CLs 100: 6);
to illustrate, the meanings of 1.0phr, 2.0phr, 3.0phr, 4.0phr, 5.0phr and 6.0phr in FIGS. 3, 4 and 5 are the same as those in FIG. 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
The following examples relate to the main raw materials:
TMP (trimethylolpropane), p-TSA (p-toluenesulfonic acid), analytically pure, Shanghai Michelin Biochemical Co., Ltd;
DMPA (2, 2-dimethylolpropionic acid), Sn (Oct)2(stannous isooctanoate), ε -CL (ε -caprolactone), analytically pure, Shanghai Allantin Biotech Co., Ltd;
THF (tetrahydrofuran), MeOH (methanol), analytical grade, beijing chemical plant;
PHBV (poly (3-hydroxybutyrate-co-3-hydroxyvalerate)) resin, pellets, Ningbo Tianan biomaterial, Inc.
The following examples relate to the main equipment: vacuum drying oven, DZG-6050, Shanghai Sensin laboratory instruments, Inc.;
a heat collection type temperature control stirring device, DF-101s, Zhengzhou great wall science and trade Co., Ltd;
torque rheometer, XSS-300, Shanghai Korea rubber Co., Ltd;
fourier infrared spectrometer, Nicolet8700, thermo electron corporation, usa;
differential scanning calorimeter, Q100, TA instruments usa;
thermogravimetric analyzer, Q50, TA instruments inc;
an electronic universal tester, CMT6104, Shenzhen New Miss metering technology, Inc.;
a combined digital display impact tester, XJZ-50, Chengde tester, Inc.;
scanning electron microscope, Quanta FEG, FEI usa.
EXAMPLE 1 preparation of Flexible Long-chain hyperbranched polymers at the ends (HBP-CLs)
The first step is as follows: synthesizing a third-generation hydroxyl-terminated hyperbranched polymer (HBPE);
the HBPE with Trimethylolpropane (TMP) as a core is synthesized by adopting a melt polycondensation one-step method, the synthetic reaction route schematic diagram is shown as follows, and the specific reaction steps are as follows: into a three-necked flask were charged 42.21g of 2, 2-dimethylolpropionic acid (DMPA), 2.01g of Trimethylolpropane (TMP) and 25mg of p-toluenesulfonic acid (p-TSA); respectively connecting a stirrer, a reflux condenser tube and a thermometer into a three-neck flask, then putting the three-neck flask into an oil bath pot, preheating to 120 ℃ firstly, heating to 140 ℃ after preheating for 10min, starting timing when reactants in the flask are completely molten, and reacting for 2.5h under normal pressure under the protection of nitrogen; and then reducing the pressure (100Pa) by a water pump, reacting for 2.0h, stopping the reaction, and cooling to obtain a semitransparent solid, namely the target product.
Figure BDA0002423398590000071
The second step is that: and (3) carrying out grafting reaction on the epsilon-caprolactone and the HBPE.
2.57g of the HBPE prepared in the first step are weighed out and dried in vacuo at 100 ℃ for 6 h. 3-4 drops of stannous isooctanoate (Sn (Oct))2) 54.78g of epsilon-caprolactone (. epsilon. -CL) (n. 20) were added simultaneously and the temperature was raised to 110 ℃. After the reaction was carried out at 120rpm for 20 hours and the system became viscous, it was cooled to room temperature. Dissolving the system into 100mL Tetrahydrofuran (THF), adding cold methanol (MeOH), separating out white precipitate, and performing suction filtration to obtain white crystal powder, namely the target product HBP-CLs. The scheme for the synthesis of HBP-CLs is shown below:
Figure BDA0002423398590000072
EXAMPLE 2 preparation of Flexible Long-chain hyperbranched polymers at the ends (HBP-CLs)
The first step is as follows: synthesizing a third-generation hydroxyl-terminated hyperbranched polymer (HBPE);
the HBPE with Trimethylolpropane (TMP) as a core is synthesized by adopting a melt polycondensation one-step method, the synthetic reaction route schematic diagram is shown as follows, and the specific reaction steps are as follows: a three-necked flask was charged with 35.94g of 2, 2-dimethylolpropionic acid (DMPA), 2.01g of Trimethylolpropane (TMP) and 25mg of p-toluenesulfonic acid (p-TSA); respectively connecting a stirrer, a reflux condenser tube and a thermometer into a three-neck flask, then putting the three-neck flask into an oil bath pot, preheating to 120 ℃ firstly, heating to 136 ℃ after preheating for 10min, starting timing when reactants in the flask are completely molten, and reacting for 3 hours under normal pressure under the protection of nitrogen; and then reducing the pressure (105Pa) by a water pump to react for 1.5h, stopping the reaction, and cooling to obtain a translucent solid which is the target product.
Figure BDA0002423398590000081
The second step is that: and (3) carrying out grafting reaction on the epsilon-caprolactone and the HBPE.
2.57g of the HBPE prepared in the first step are weighed out and dried at 90 ℃ for 7h in vacuo. 3-4 drops of stannous isooctanoate (Sn (Oct))2) 49.30g of epsilon-caprolactone (. epsilon. -CL) (n. 18) were added simultaneously and the temperature was raised to 100 ℃. The reaction was carried out at 100rpm for 25h, and after the system became viscous, it was cooled to room temperature. Dissolving the system into 100mL Tetrahydrofuran (THF), adding cold methanol (MeOH), separating out white precipitate, and performing suction filtration to obtain white crystal powder, namely the target product HBP-CLs. The scheme for the synthesis of HBP-CLs is shown below:
Figure BDA0002423398590000082
EXAMPLE 3 preparation of Flexible Long-chain hyperbranched polymers at the ends (HBP-CLs)
The first step is as follows: synthesizing a third-generation hydroxyl-terminated hyperbranched polymer (HBPE);
the HBPE with Trimethylolpropane (TMP) as a core is synthesized by adopting a melt polycondensation one-step method, the synthetic reaction route schematic diagram is shown as follows, and the specific reaction steps are as follows: a three-necked flask was charged with 49.92g of 2, 2-dimethylolpropionic acid (DMPA), 2.01g of Trimethylolpropane (TMP) and 25mg of p-toluenesulfonic acid (p-TSA); respectively connecting a stirrer, a reflux condenser tube and a thermometer into a three-neck flask, then putting the three-neck flask into an oil bath pot, preheating to 120 ℃ firstly, heating to 145 ℃ after preheating for 10min, starting timing when reactants in the flask are completely molten, and reacting for 2h under normal pressure under the protection of nitrogen; and then reducing the pressure (95Pa) by a water pump to react for 3h, stopping the reaction, and cooling to obtain a semitransparent solid, namely the target product.
Figure BDA0002423398590000091
The second step: and (3) carrying out grafting reaction on the epsilon-caprolactone and the HBPE.
2.57g of the HBPE prepared in the first step are weighed out and dried in vacuo at 110 ℃ for 5 h. 3-4 drops of stannous isooctanoate (Sn (Oct))2) 68.48g of epsilon-caprolactone (. epsilon. -CL) (n. 25) were added simultaneously and the temperature was raised to 120 ℃. The reaction was carried out at 150rpm for 15h, and after the system became viscous, it was cooled to room temperature. Dissolving the system into 100mL Tetrahydrofuran (THF), adding cold methanol (MeOH), separating out white precipitate, and performing suction filtration to obtain white crystal powder, namely the target product HBP-CLs. The scheme for the synthesis of HBP-CLs is shown below:
Figure BDA0002423398590000092
the target compounds HBP-CLs prepared in examples 1 to 3 were characterized as follows:
1.1FT-IR
the FT-IR patterns of HBPEs and HBP-CLs are shown in FIG. 1. 3500cm-1Left and right: HBPE has dense terminal hydroxyl groups, is easy to form intramolecular and intermolecular hydrogen bonds, and has strong and wide absorption peaks; HBP-CLs, the introduction of caprolactone makes peripheral hydroxyl groups more dispersed, and hydrogen bonds are not easily formed, and the absorption peak is shown to be sharp and narrow. 731cm-1More than 4-CH appears on the left and right2-characteristic absorption peak, indicating that the long chain has been attached.
1.2NMR
Nuclear Magnetic Resonance (NMR) patterns of the molecules obtained by HBP-CLs are shown in FIGS. 2(a) and 2(b)1H-NMR of13C-NMR structural analysis also leads to the same conclusion that the terminal phenyl groups have been partially grafted onto the HBPE.
1H-NMR：1.40ppm，-CH2-CH2-CH2-；1.66ppm，-CH2-CH2-CO-O-；2.32ppm，-CH2-CO-O-；3.66ppm，-CH2-OH；4.08ppm，-CH2-O-CO-；7.28ppm，CDCl3。
13C-NMR：173.53ppm，-CO-；64.14ppm，-CH2-O-；25.54ppm，-CH2-CH2-CH2-；34.12ppm，-CH2-CO-O-；77.03ppm，CDCl3。
EXAMPLE 4 preparation of PHBV/HBP-CLs blends
4.1 formulation Table
Table 1 blend formula table
Figure BDA0002423398590000101
4.2 melt blending
Blending equipment: torque rheometer
Temperature: 190 deg.C
Rotating speed: 60rpm
Time: 8min
Mixing the PHBV resin and HBP-CLs according to the formula table, and carrying out melt blending to obtain the PHBV/HBP-CLs blend.
Example 5 Performance characterization of PHBV/HBP-CLs blends
5.1 thermal Properties
5.1.1 Differential Scanning Calorimetry (DSC)
The DSC test conditions for the samples were: before testing, the temperature is quickly raised to 200 ℃, the temperature is kept for 3min to eliminate the thermal history, then the temperature is reduced to-40 ℃ at the speed of 10 ℃/min, the temperature is kept for 3min, and then the temperature is raised to 200 ℃ at the speed of 10 ℃/min. A DSC curve was recorded in which the blend crystallinity (Xc) was calculated according to formula (1):
Figure BDA0002423398590000111
in formula (5): xc-the crystallinity of the PHBV phase in the blend system;
delta Hm is the melting enthalpy of the sample in the second temperature rise process, J/g;
w-mass percent of PHBV in the blend;
ΔHm0theoretical enthalpy of fusion of PHBV 100% crystallization (14)6J/g)。
The results of the DSC analysis are shown in FIG. 3 and Table 2.
TABLE 2 crystallization temperature, melting temperature and crystallinity of PHBV and PHBV/HBP-CLs blends and HBP-CLs
Figure BDA0002423398590000112
Wherein, 1phr, the mass ratio of PHBV to HBP-CLs is 100: 1, 2phr, the mass ratio of PHBV to HBP-CLs is 100: 2, 3phr, the mass ratio of PHBV to HBP-CLs is 100: 3, 4phr, the mass ratio of PHBV to HBP-CLs is 100: 4, 5phr, the mass ratio of PHBV to HBP-CLs is 100: 5, 6phr, the mass ratio of PHBV to HBP-CLs is 100: 6.
the cold crystallization temperature (Tc) and the melting temperature (T) of the blend are slightly reduced by DSC analysism) And the calculated maximum reduction amplitude of the crystallinity of the PHBV/HBP-CLs blend is about 10.2 percent, which shows that the addition of HBP-CLs provides possibility for toughening the PHBV.
5.1.2 thermogravimetric analysis (TGA)
The test conditions for sample TG were: the sample was heated from room temperature to 650 ℃ at a heating rate of 10 ℃/min under nitrogen.
The thermogravimetric curve and the mass loss rate are shown in fig. 4. The initial decomposition temperature and the decomposition rate of the blend are basically unchanged through TGA data analysis, which shows that the thermal stability of the blend is basically not influenced by the addition of the HBP-CLs.
5.2 analysis of mechanical Properties
The mechanical properties of PHBV and PHBV/HBP-CLs are shown in FIG. 5. From the mechanical data, it is known that the impact strength of the PHBV/HBP-CLs blend is from 5.13KJ/m when HBP-CLs is added in an amount of 3phr-2Increased to 32.25KJ/m-2The increase is 528.65% (reaching the maximum value), the elongation at break is increased from 1.62% to 4.22%, the increase is 160.49% (reaching the maximum value), and the tensile strength is slightly reduced, which shows that the addition of HBP-CLs has better toughening effect on PHBV on the premise of not obviously reducing the tensile strength of PHBV. The HBP-CLs can perform good toughening modification on PHBV mainly because: (1) HBP-CLThe end flexible long chain of s has strong physical entanglement with the PHBV molecular chain, and the hydroxyl (hydrogen atom) at the end of the end flexible long chain has hydrogen bond with the ester group (oxygen atom) in the PHBV molecular chain, so that the motion capability and the directional arrangement capability of the PHBV molecular chain are limited, and the crystallinity of the PHBV/HBP-CLs blend is reduced; (2) HBP-CLs molecules contain a large number of three-dimensional cavity structures, when an external force acts on the surface of a PHBV/HBP-CLs blend sample, the cavities in the HBP-CLs can absorb a part of energy, and the blend is toughened to a certain extent.
5.3 scanning Electron microscopy analysis (SEM)
The scanning electron micrograph of the blend of PHBV and PHBV/HBP-CLs is shown in FIG. 6. The microscopic appearance of the cross section is changed from smooth to rough as can be seen by observing the polymer by a scanning electron microscope, which is also a visual expression of toughening of the polymer.
As can be seen from the above, the PHBV/HBP-CLs blend is prepared by adopting a melt blending method, the PHBV resin is toughened and modified by adopting HBP-CLs in the melt blending method, and the impact strength and the elongation at break of the prepared PHBV/HBP-CLs blend are both greatly improved. When 3phr of HBP-CLs is added into the PHBV/HBP-CLs blend, the impact strength is controlled to be 5.13KJ/m-2Increased to 32.25KJ/m-2The increase reaches 528.65 percent, the elongation at break is increased from 1.62 percent to 4.22 percent, the increase reaches 160.49 percent, and the tensile strength is slightly reduced, which indicates that the addition of HBP-CLs has better toughening effect on PHBV.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A preparation method of a PHBV/HBP-CLs blend is characterized in that PHBV resin and HBP-CLs are mixed and melt blended to obtain the PHBV/HBP-CLs blend;
the chemical structural formula of the HBP-CLs is shown as the formula (I):
Figure FDA0002423398580000011
wherein the number n of repeating units on the graft chain is an integer in the range of 5 to 30.
2. The process for the preparation of a PHBV/HBP-CLs blend according to claim 1, wherein said HBP-CLs is prepared by the following process: synthesizing HBPE by adopting a melt polycondensation one-step method under the action of a catalyst a from 2, 2-dimethylolpropionic acid and trimethylolpropane, and then carrying out a grafting reaction on the HBPE and epsilon-caprolactone to obtain HBP-CLs;
the chemical structural formula of the HBPE is shown as a formula (II):
Figure FDA0002423398580000021
3. the process for preparing PHBV/HBP-CLs blend according to claim 2, wherein said step of synthesizing HBPE by melt polycondensation "one-step" of 2, 2-dimethylolpropionic acid and trimethylolpropane in the presence of catalyst a comprises:
mixing 2, 2-dimethylolpropionic acid, trimethylolpropane and a catalyst a, preheating, heating, reacting under normal pressure under the protection of nitrogen when reactants are completely molten, then reacting under reduced pressure, and cooling.
4. The method for preparing the PHBV/HBP-CLs blend according to claim 2, wherein the step of obtaining HBP-CLs by the grafting reaction of HBPE and epsilon-caprolactone comprises:
and drying the prepared HBPE, then dropwise adding a catalyst b, simultaneously adding epsilon-caprolactone, heating, carrying out grafting reaction, and cooling to room temperature to obtain the HBP-CLs.
5. The preparation method of the PHBV/HBP-CLs blend according to claim 2 or 3, wherein the catalyst a is p-toluenesulfonic acid, and the molar ratio of 2, 2-dimethylolpropionic acid to trimethylolpropane is (18-25): 1.
6. the preparation method of the PHBV/HBP-CLs blend according to claim 3, wherein the preheating is carried out at 115-125 ℃ for 5-15 min, the temperature rise is carried out to 135-145 ℃, the time of the normal pressure reaction is 2-3 h, and the reduced pressure reaction is carried out at 95-105 Pa for 1.5-3 h.
7. The process for the preparation of a PHBV/HBP-CLs blend according to claim 2 or 4, wherein the mass ratio of HBPE to epsilon-caprolactone is 1: (20-25); catalyst b is stannous isooctanoate; the drying is to carry out vacuum drying on the prepared HBPE for 5-7 h at 90-110 ℃, the dropwise adding of the catalyst b is to dropwise add 3-4 drops of stannous isooctoate, the temperature is raised to 100-120 ℃, and the grafting reaction is to carry out reaction for 15-25 h at the rotating speed of 100-150 rpm.
8. The process for the preparation of a PHBV/HBP-CLs blend according to claim 1, characterized in that the mass ratio of said PHBV resin to HBP-CLs is 100: (0-10), and the quality of HBP-CLs is not zero.
9. The preparation method of the PHBV/HBP-CLs blend according to claim 1, wherein the temperature of the melt blending is 180-200 ℃, the rotation speed is 50-100 rpm, and the time is 5-10 min.
10. The PHBV/HBP-CLs blend prepared by the method for preparing a PHBV/HBP-CLs blend according to any one of claims 1 to 9.
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