CN111500034B - PHBV/HBP-Bs blend and preparation method thereof - Google Patents
PHBV/HBP-Bs blend and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PHBV/HBP-Bs blend and a preparation method thereof, wherein the preparation method of the PHBV/HBP-Bs blend comprises the steps of mixing PHBV resin and HBP-Bs, and carrying out melt blending to obtain the PHBV/HBP-Bs blend; the chemical structural formula of the HBP-Bs is shown as a formula (I). In the melt blending method, HBP-Bs are adopted to toughen and modify the PHBV resin, and the impact strength and the elongation at break of the prepared PHBV/HBP-Bs blend are greatly improved. When 0.5phr HBP-Bs is added into the PHBV/HBP-Bs blend, the impact strength is from 7.41KJ/m ‑2 Increased to 19.25KJ/m ‑2 The increase is 159.78%, the elongation at break is increased from 0.91% to 4.55%, the increase is 400%, and the tensile strength is basically kept unchanged.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a PHBV/HBP-Bs 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 molecular material which appears in the last three decades and are a series of structurally similar polymers with growing 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 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-Bs is adopted to toughen and modify PHBV resin, and the impact strength and the elongation at break of the prepared PHBV/HBP-Bs blend are greatly improved on the premise of keeping the tensile strength unchanged.
Based on the aim, the preparation method of the PHBV/HBP-Bs blend provided by the invention comprises the steps of mixing the PHBV resin and the HBP-Bs, and carrying out melt blending to obtain the PHBV/HBP-Bs blend;
the chemical structural formula of the HBP-Bs is shown as the formula (I):
in some embodiments of the invention, the HBP-Bs are prepared using the following method: synthesizing HBPE by adopting a melt polycondensation one-step method under the action of a catalyst through 2, 2-dimethylolpropionic acid (DMPA) and Trimethylolpropane (TMP), and then carrying out grafting reaction on the HBPE and benzoyl chloride to obtain HBP-Bs;
the chemical structural formula of the HBPE is shown as a formula (II):
in some embodiments of the invention, the step of synthesizing HBPE by melt polycondensation in a "one-step" process using 2, 2-dimethylolpropionic acid and trimethylolpropane in the presence of a catalyst comprises:
mixing 2, 2-dimethylolpropionic acid, trimethylolpropane and a catalyst, 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 benzoyl chloride to obtain HBP-Bs comprises:
and adding an organic solvent into a system after the reaction for synthesizing the HBPE to dissolve the HBPE, and then adding alkali and benzoyl chloride to perform grafting reaction to obtain the HBP-Bs.
In the invention, 2-dimethylolpropionic acid and trimethylolpropane 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:
in the invention, the reaction system for synthesizing HBPE does not need post-treatment, the organic solvent is directly added into the system after the reaction is finished to dissolve HBPE, and then alkali and benzoyl chloride are added to carry out grafting reaction to obtain HBP-Bs, thereby simplifying the operation steps and improving the yield, and the schematic diagram of the synthetic reaction route is as follows:
in some embodiments of the invention, the catalyst 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 benzoyl chloride to 2, 2-dimethylolpropionic acid is 1: (2-4); the organic solvent is N, N-Dimethylformamide (DMF), the base is Triethylamine (TEA), and the volume ratio of the triethylamine to benzoyl chloride is (1-1.5): 1; the reaction time of the grafting reaction is 2-4 h.
In some embodiments of the invention, the mass ratio of said PHBV resin to HBP-Bs is 100: (0-1), and the quality of HBP-Bs 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-Bs blend prepared by the preparation method of the PHBV/HBP-Bs blend.
As can be seen from the above, the PHBV/HBP-Bs blend is prepared by adopting a melt blending method, the PHBV resin is toughened and modified by adopting the HBP-Bs in the melt blending method, and the impact strength and the elongation at break of the prepared PHBV/HBP-Bs blend are both greatly improved. When 0.5phr HBP-Bs is added into the PHBV/HBP-Bs blend, the impact strength is from 7.41KJ/m -2 Increased to 19.25KJ/m -2 The increase reaches 159.78 percent, the elongation at break is increased from 0.91 percent to 4.55 percent, the increase reaches 400 percent, and the tensile strength is basically kept unchanged, which shows that the addition of HBP-Bs has better toughening effect on PHBV on the premise of not losing the tensile strength of PHBV.
Drawings
FIG. 1 is a FT-IR chart of monomers DMPA and HBPE and HBP-Bs in the present invention, wherein FIG. 1(a) is a FT-IR chart of monomers DMPA and HBPE, and FIG. 1(b) is a FT-IR chart of HBPE and HBP-Bs;
FIG. 2 shows HBP-Bs of the present invention 1 H-NMR chart and 13 C-NMR chart in which FIG. 2(a) is of HBP-Bs 1 H-NMR chart, FIG. 2(b) is of HBP-Bs 13 C-NMR chart;
FIG. 3 is a DSC plot of blends of PHBV and PHBV/HBP-Bs 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-Bs in example 4 of the present invention, wherein FIG. 4(a) is a plot of thermogravimetric plot of blends of PHBV and PHBV/HBP-Bs, and FIG. 4(b) is a plot of mass loss rate of blends of PHBV and PHBV/HBP-Bs;
FIG. 5 is a photograph of a polarized light of a blend of PHBV and PHBV/HBP-Bs in example 4 of the present invention, wherein FIG. 5(a) is a photograph of a polarized light of PHBV, FIG. 5(b) is a photograph of a blend of PHBV/HBP-Bs (0.1phr, mass ratio of PHBV to HBP-Bs is 100: 0.1), FIG. 5(c) is a photograph of a blend of PHBV/HBP-Bs (0.2phr, mass ratio of PHBV to HBP-Bs is 100: 0.2), FIG. 5(d) is a photograph of a blend of PHBV/HBP-Bs (0.3phr, mass ratio of PHBV to HBP-Bs is 100: 0.3), FIG. 5(e) is a photograph of a blend of PHBV/HBP-Bs (0.4 phr), FIG. 5(f) is a photograph of a blend of PHBV/HBP-Bs (0.5 phr), mass ratio of PHBV to HBP-Bs (0.5) is a photograph of a photograph, FIG. 5(g) is a photograph of a PHBV/HBP-Bs blend (0.6phr, mass ratio of PHBV to HBP-Bs 100: 0.6), FIG. 5(h) is a photograph of a PHBV/HBP-Bs blend (0.7phr, mass ratio of PHBV to HBP-Bs 100: 0.7);
FIG. 6 is a graph showing the mechanical properties of PHBV and PHBV/HBP-Bs in example 4 of the present invention, wherein FIG. 6(a) is a graph showing the impact strengths of PHBV and PHBV/HBP-Bs, FIG. 6(b) is a graph showing the elongation at break of PHBV and PHBV/HBP-Bs, and FIG. 6(c) is a graph showing the tensile strengths of PHBV and PHBV/HBP-Bs;
FIG. 7 is a scanning electron micrograph of a blend of PHBV and PHBV/HBP-Bs in example 4 of the present invention, wherein FIG. 7(a) is a scanning electron micrograph of PHBV, FIG. 7(b) is a scanning electron micrograph of a blend of PHBV/HBP-Bs (0.1phr with a PHBV to HBP-Bs mass ratio of 100: 0.1), FIG. 7(c) is a scanning electron micrograph of a blend of PHBV/HBP-Bs (0.2phr with a PHBV to HBP-Bs mass ratio of 100: 0.2), FIG. 7(d) is a scanning electron micrograph of a blend of PHBV/HBP-Bs (0.3phr with a PHBV to HBP-Bs mass ratio of 100: 0.3), FIG. 7(e) is a scanning electron micrograph of a blend of PHBV/HBP-Bs (0.4phr with a PHBV to HBP-Bs mass ratio of 100: 0.4), FIG. 7(f) is a scanning electron micrograph of a blend of PHBV/HBP-B (0.5), FIG. 7(g) is a scanning electron micrograph of a PHBV/HBP-Bs blend (0.6phr, mass ratio of PHBV to HBP-Bs 100: 0.6), FIG. 7(h) is a scanning electron micrograph of a PHBV/HBP-Bs blend (0.7phr, mass ratio of PHBV to HBP-Bs 100: 0.7);
FIG. 8 is a diagram showing the mechanism of toughening of PHBV by HBP-Bs in the present invention;
to illustrate, the values of 0.1phr, 0.2phr, 0.3phr, 0.4phr, 0.5phr, 0.6phr and 0.7phr in FIGS. 3, 4 and 6 are the same as those in FIG. 5 or 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following 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), TEA (triethylamine), analytical grade, shanghai alatin biochemistry science and technology ltd;
DMF (N, N-dimethylformamide), 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 Sen 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.;
rotational rheometer, MARS, Thermo Scientific, usa;
scanning electron microscope, Quanta FEG, FEI usa.
EXAMPLE 1 preparation of hyperbranched Polymer of terminal phenyl type (HBP-Bs)
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 pan, preheating to 120 ℃ firstly, heating to 140 ℃ after preheating for 10min, 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 to react for 2.0h, stopping the reaction, and cooling to obtain a semitransparent solid, namely the target product.
The second step is that: the benzoyl chloride and HBPE are subjected to grafting reaction, and the preset grafting rate is 50%.
After the completion of the first-step reaction, 100mL of N, N-Dimethylformamide (DMF) was added to dissolve HBPE, and 14.27mL of Triethylamine (TEA) and 11.83mL of benzoyl chloride were added thereto and reacted for 3 hours. Then, triethylamine salt is filtered, and then the solvent, micromolecular byproducts and the like are extracted by a rotary evaporator to obtain orange viscous liquid, namely the target product HBP-Bs. The reaction scheme for the synthesis of HBP-Bs is shown below:
EXAMPLE 2 preparation of hyperbranched Polymer of terminal phenyl type (HBP-Bs)
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.
The second step is that: the benzoyl chloride and HBPE are subjected to grafting reaction, and the preset grafting rate is 50%.
After the first reaction, 100mL of N, N-Dimethylformamide (DMF) was added to the system to dissolve HBPE, and 9.65mL of Triethylamine (TEA) and 8.04mL of benzoyl chloride were added thereto and reacted for 2 hours. Then, triethylamine salt is filtered, and then the solvent, micromolecular byproducts and the like are extracted by a rotary evaporator to obtain orange viscous liquid, namely the target product HBP-Bs. The reaction scheme for the synthesis of HBP-Bs is shown below:
EXAMPLE 3 preparation of hyperbranched Polymer of terminal phenyl type (HBP-Bs)
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.
The second step is that: the benzoyl chloride and HBPE are subjected to grafting reaction, and the preset grafting rate is 50%.
After the completion of the first-step reaction, 100mL of N, N-Dimethylformamide (DMF) was added to dissolve HBPE, and 25.67mL of Triethylamine (TEA) and 18.45mL of benzoyl chloride were added thereto and reacted for 4 hours. Then, triethylamine salt is filtered, and then the solvent, micromolecular byproducts and the like are extracted by a rotary evaporator to obtain orange viscous liquid, namely the target product HBP-Bs. The reaction scheme for the synthesis of HBP-Bs is shown below:
the target compounds HBP-Bs prepared in examples 1-3 were characterized as follows:
1.1 FT-IR
for example, FIG. 1(a) and FIG. 1(b) show FT-IR diagrams of monomeric DMPA and HBPEs and FT-IR diagrams of HBPE and HBP-Bs, respectively. As shown in FIG. 1(a), the absorption peak was 1689cm -1 Conversion to 1732cm -1 Description of DMPA in monomerThe hydroxyl and carboxyl have undergone esterification reaction, namely the intermediate product HBPE is successfully synthesized; as shown in FIG. 1(b), the infrared absorption peak contrast between intermediate HBPE and target HBP-Bs is 715cm -1 And 1603cm -1 Is a characteristic absorption peak of a phenyl substituent, and is 3400cm -1 The peak at the hydroxyl group was weak, indicating that the phenyl group had been partially grafted onto the HBPE.
1.2 NMR
Nuclear Magnetic Resonance (NMR) patterns of HBP-Bs are shown in FIGS. 2(a) and 2(b), and the Nuclear Magnetic Resonance (NMR) patterns of HBP-Bs are shown by 1 H-NMR of 13 C-NMR structural analysis also leads to the same conclusion that the terminal phenyl groups have been partially grafted onto the HBPE.
1 H-NMR：1.0-1.3ppm，-CH 3 ；3.4-3.6ppm，-CH 2 OH；4.0-4.3ppm，-COOCH 2 -；7.3-8.1ppm，Ph-H；
13 C-NMR：17ppm，-CH 3 ；45-51ppm，C；62-66ppm，-CH 2 -；120-140ppm，-Ph；160-175ppm，-CO-。
1.3 hydroxyl value titration-graft Rate calculation
The hydroxyl value is used for titration, and the hydroxyl values before and after the end phenyl group grafting are respectively titrated, so that the grafting rate of the end phenyl group can be calculated, wherein the hydroxyl value of HBPE is calculated as formula (1), the hydroxyl value of HBP-Bs is calculated as formula (2), and the grafting rate is calculated as formula (3).
The graft of the terminal phenyl groups was calculated to be 43.6%.
1.4 GPC
The molecular weight and polydispersity data are shown in Table 1 by gel chromatography (GPC) analysis, and the number average molecular weight of the synthesized HBP-Bs was 3494 g/mol. According to the relation between the generation number of the hyperbranched polymer and the number of the monomers, etc., the generation number n is calculated by the formula (4) to be 3.13, which is consistent with the expected feeding ratio.
TABLE 1 relative molecular mass and polydispersity data tables for HBP-Bs
1.5 intrinsic viscosity
The intrinsic viscosity of HBP-Bs was measured by Ubbelohde viscometer method to be 0.014cm 3 ·g -1 。
Example 4 preparation of PHBV/HBP-Bs blend
4.1 formulation Table
Table 2 blend formula table
4.2 melt blending
Blending equipment: torque rheometer
Temperature: 190 deg.C
Rotating speed: 60rpm
Time: 8min
Mixing the PHBV resin and the HBP-Bs according to the formula table, and carrying out melt blending to obtain a PHBV/HBP-Bs blend.
Example 5 characterization of the Properties of PHBV/HBP-Bs 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 ℃, kept for 3min to eliminate thermal history, then lowered to-40 ℃ at the speed of 10 ℃/min, kept for 3min, and then raised to 200 ℃ at the speed of 10 ℃/min. Record DSC curve, wherein the blend crystallinity (Xc) is calculated according to equation (5):
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;
ΔHm 0 theoretical enthalpy of fusion (146J/g) of PHBV 100% crystallization.
The results of the DSC analysis are shown in FIG. 3 and Table 3.
TABLE 3 crystallization temperature, melting temperature and crystallinity of PHBV and PHBV/HBP-Bs blends
Wherein, 0.1phr, the mass ratio of PHBV to HBP-Bs is 100: 0.1, 0.2phr, the mass ratio of PHBV to HBP-Bs is 100: 0.2 and 0.3phr, the mass ratio of PHBV to HBP-Bs is 100: 0.3 and 0.4phr, the mass ratio of PHBV to HBP-Bs is 100: 0.4, 0.5phr, the mass ratio of PHBV to HBP-Bs is 100: 0.5 and 0.6phr, the mass ratio of PHBV to HBP-Bs is 100: 0.6 and 0.7phr, the mass ratio of PHBV to HBP-Bs is 100: 0.7.
analysis by DSC data reveals the cold crystallization temperature (T) of the blend c ) Slightly lower, melting temperature (T) m ) And the calculated maximum reduction amplitude of the crystallinity of the PHBV/HBP-Bs blend is about 14.5 percent, which shows that the addition of the HBP-Bs 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 from the analysis of TGA data, which shows that the addition of HBP-Bs has no influence on the thermal stability of the blend.
5.2 polarizing Electron microscopy analysis (POM)
The polarization photograph of the blend of PHBV and PHBV/HBP-Bs is shown in FIG. 5. As can be seen from the polarized photographs, the number of crystals of the PHBV/HBP-Bs blend system gradually decreased and the area of the crystalline domains gradually decreased as the amount of HBP-Bs added (less than 0.5phr) increased, wherein the number of crystals and the area of the crystalline domains of the PHBV/HBP-Bs blend system reached minimum and minimum, respectively, when the content of HBP-Bs was 0.5phr, indicating that the addition of HBP-Bs inhibited the formation of PHBV nuclei and decreased the crystallinity thereof. The reason for this phenomenon is that: (1) spherical HBP-Bs with a highly branched structure are uniformly dispersed in the PHBV, so that the directional arrangement of a PHBV molecular chain is influenced; (2) part of hydroxyl (hydrogen atoms) which is not grafted and modified in the HBP-Bs and ester groups (oxygen atoms) on a PHBV molecular chain generate hydrogen bonding action, and the motion of a PHBV molecular chain segment is limited, so that the crystallinity of a PHBV/HBP-Bs blending system is reduced. However, when the adding amount of the HBP-Bs is more than 0.5phr, the crystal quantity of a PHBV/HBP-Bs blending system starts to increase gradually, and the area of a crystal region starts to increase gradually, because excessive HBP-Bs are added, hydrogen bonding is generated among HBP-Bs molecules, so that the agglomeration of the HBP-Bs is caused, and the dispersion and modification effects of the HBP-Bs in the PHBV are influenced.
5.3 analysis of mechanical Properties
The mechanical properties of PHBV and PHBV/HBP-Bs are shown in FIG. 6. From the mechanical data, it is known that when the HBP-Bs is added in an amount of 0.5phr, the impact strength of the PHBV/HBP-Bs blended system is from 7.41KJ/m -2 Increased to 19.25KJ/m -2 The increase is 159.78% (reaching the maximum value), the elongation at break is increased from 0.91% to 4.55%, the increase is 400% (reaching the maximum value), and the tensile strength is basically kept unchanged, which shows that the addition of HBP-Bs has better toughening effect on the PHBV on the premise of not losing the tensile strength of the PHBV. HBP-Bs can be pairedThe good toughening modification of PHBV is mainly caused by the following reasons: (1) the addition of spherical HBP-Bs with a highly branched structure influences the motion capability and the directional arrangement capability of a PHBV molecular chain and reduces the crystallinity of the PHBV; (2) the HBP-Bs molecules contain a large number of three-dimensional cavity structures, when an external force acts on the surface of a PHBV/HBP-Bs blend sample, the cavities inside the HBP-Bs can absorb a part of energy, and the blend is toughened to a certain extent.
5.4 scanning Electron microscopy analysis (SEM)
The scanning electron micrograph of the blend of PHBV and PHBV/HBP-Bs is shown in FIG. 7. 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 a visual expression of the toughening of the polymer HBP-Bs.
5.5 toughening mechanism
Combining the above analyses, the mechanism of toughening of HBP-Bs can be summarized as shown in FIG. 8. The toughening effect can be explained mainly from three aspects: firstly, HBP-Bs are uniformly dispersed in a PHBV polymer, so that the arrangement of a PHBV molecular chain is influenced, the crystallinity of the PHBV molecular chain is reduced, and an amorphous area is increased; secondly, unreacted terminal hydroxyl at the peripheral part of HBP-Bs and ester groups in a PHBV molecular chain generate hydrogen bond action, so that the motion of the PHBV molecular chain is limited, and the PBHV/HBP-Bs blend is difficult to crystallize to a certain extent; finally, when the HBP-Bs is acted by external force, the cavity structure in the HBP-Bs absorbs partial energy, and the effect of toughening the blend is achieved. The PHBV toughness is greatly improved under the combined action of the three factors.
As can be seen from the above, the PHBV/HBP-Bs blend is prepared by adopting a melt blending method, the PHBV resin is toughened and modified by adopting the HBP-Bs in the melt blending method, and the impact strength and the elongation at break of the prepared PHBV/HBP-Bs blend are both greatly improved. When 0.5phr HBP-Bs is added into the PHBV/HBP-Bs blend, the impact strength is from 7.41KJ/m -2 Increased to 19.25KJ/m -2 The increase reaches 159.78 percent, the elongation at break is increased from 0.91 percent to 4.55 percent, the increase reaches 400 percent, and the tensile strength is basically kept unchanged, which shows that the PHBV has better effect on the PHBV under the premise of not losing the tensile strength of the PHBV due to the addition of HBP-BsThe toughening effect of (1).
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 which 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 (9)
1. A preparation method of a PHBV/HBP-Bs blend is characterized in that PHBV resin and HBP-Bs are mixed and melt blended to obtain the PHBV/HBP-Bs blend; the mass ratio of the PHBV resin to the HBP-Bs is 100: 0.5;
the chemical structural formula of the HBP-Bs is shown as the formula (I):
I。
2. the method for preparing PHBV/HBP-Bs blend according to claim 1, wherein said HBP-Bs are prepared by the following method: synthesizing HBPE by adopting a melt polycondensation one-step method under the action of a catalyst through 2, 2-dimethylolpropionic acid and trimethylolpropane, and then carrying out a grafting reaction on the HBPE and benzoyl chloride to obtain HBP-Bs;
the chemical structural formula of the HBPE is shown as a formula (II):
II。
3. the method for preparing PHBV/HBP-Bs blend according to claim 2, wherein the step of synthesizing HBPE by melt polycondensation of 2, 2-dimethylolpropionic acid and trimethylolpropane in one step under the action of catalyst comprises:
mixing 2, 2-dimethylolpropionic acid, trimethylolpropane and a catalyst, 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-Bs blend according to claim 2, wherein the step of obtaining HBP-Bs by grafting HBPE with benzoyl chloride comprises:
and adding an organic solvent into a system after the reaction for synthesizing the HBPE to dissolve the HBPE, and then adding alkali and benzoyl chloride to perform grafting reaction to obtain the HBP-Bs.
5. The preparation method of PHBV/HBP-Bs blend according to claim 2 or 3, wherein the catalyst 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-Bs blend according to claim 3, wherein 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, the pressure reduction reaction is carried out at 95-105 Pa, and the reaction time is 1.5-3 h.
7. The method for preparing PHBV/HBP-Bs blend according to claim 4, wherein the mass ratio of benzoyl chloride to 2, 2-dimethylolpropionic acid is 1: (2-4); the organic solvent is N, N-dimethylformamide, the alkali is triethylamine, and the volume ratio of the triethylamine to the benzoyl chloride is (1-1.5): 1; the reaction time of the grafting reaction is 2-4 h.
8. The method for preparing PHBV/HBP-Bs 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.
9. The PHBV/HBP-Bs blend prepared by the method for preparing PHBV/HBP-Bs blend according to any one of claims 1 to 8.
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