CN105061971A - Method for preparing completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate) - Google Patents
Method for preparing completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate) Download PDFInfo
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- 229920000379 polypropylene carbonate Polymers 0.000 title abstract 3
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 38
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- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
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- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The present invention discloses a method for preparing a completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate), wherein 50-95 parts by mass of degradable poly(propylene carbonate), 0.1-10 parts by mass of an acid anhydride and 5-50 parts by mass of microcrystalline cellulose are subjected to melt mixing to form a master batch of a completely-degradable composite material, and mold pressing molding is performed to obtain the sample. According to the present invention, the completely-degradable composite material prepared through the method has characteristics of good mechanical property and good thermal stability, and the processing stability and the mechanical property of the prepared product can be effectively improved.
Description
Technical Field
The invention relates to the technical field of preparation of polymer composite materials, in particular to a method for preparing a fully-degradable composite material by using anhydride and microcrystalline cellulose synergistically modified polymethyl ethylene carbonate.
Background
The polymethyl ethylene carbonate (PPC) is prepared from carbon dioxide (CO)2) Can be completely biodegraded by using the epoxy propane as raw material, and can be used for large-scale comprehensive utilization of CO2To open up a path. By using CO2The PPC is synthesized as a raw material, so that the dependence of plastics on petroleum resources can be reduced; on the other hand, a material which can be fully biodegraded can be obtained, the greenhouse effect can be relieved to a certain extent, and the reduction of white pollution is facilitated. Moreover, the polymethyl ethylene carbonate has excellent gas barrier property, biocompatibility and easy processability, and is an environment-friendly material with great development prospect. In practical application, however, due to the existence of ether bonds in the PPC, the chain segments are easy to rotate around the ether bonds, the flexibility of the chain is increased, and the PPC has a lower glass transition temperature; and the terminal hydroxyl (-OH) is an active point of a PPC molecular chain, can induce and decompose zipper-releasing degradation, and reduces the thermal stability of the PPC. Thus, the poor thermodynamic properties of PPC limit its applications. In order to expand the range of applications of PPC, it must be modified.
The reports of blending modification of PPC at present are mainly divided into the following three categories: PPC/synthetic polymer blend, PPC/inorganic particle composite material, PPC/natural polymer composite material. The natural polymer material has various varieties, low price and reproducibility, and can be completely degraded under various natural conditions. And the general natural polymer materials contain a large amount of hydroxyl, and can generate interaction with carbonyl in the PPC through hydrogen bonds, so that the mechanical property and the heat resistance of the PPC are improved, and the fully biodegradable PPC-based composite material is obtained. The plant fiber and the derivatives thereof are the most abundant varieties of natural polymer materials, and the plant fiber is used as a reinforcement to prepare the PPC-based composite material.
The PPC/cotton fiber composite material is prepared by mixing cotton fiber and PPC through a mixer in the coke-building industry of Zhongshan university, the tensile strength of the PPC is effectively improved, however, the compatibility of the cotton fiber and the PPC is poor, the effect of improving the thermal stability of the composite material is not obvious, and the application range of the composite material is limited.
Li et al prepared fiber reinforced composites using melt blending of indian hildegardhiapapulifolia fiber with PPC and the results of the study showed: with the addition of the fibers, the tensile strength of the composite increases, but the elongation at break of the PPC decreases significantly.
The invention application with the publication number of CN103571166A discloses a cellulose, microcrystalline cellulose and polymethyl ethylene carbonate composition and a preparation method thereof, wherein a composite material prepared by using a plurality of auxiliary agents such as an end-capping reagent, a lubricant, an antioxidant, a plasticizer and the like according to a certain proportion improves the mechanical strength of the polymethyl ethylene carbonate.
The results of practical studies of the above various treatment methods show that the method for modifying PPC by using plant fibers still has the defects of insufficient heat resistance and obviously reduced toughness of PPC.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a fully-degradable composite material by using anhydride and microcrystalline cellulose to synergistically modify polymethyl ethylene carbonate.
The technical scheme of the invention is as follows: a method for preparing a fully-degradable composite material by using anhydride and microcrystalline cellulose to synergistically modify polymethyl ethylene carbonate is characterized in that degradable polymethyl ethylene carbonate, anhydride and microcrystalline cellulose are melted and mixed to form master batch of the fully-degradable composite material, and then the master batch is molded into a sample;
wherein the mass ratio of the polymethyl ethylene carbonate, the acid anhydride and the microcrystalline cellulose is as follows:
polymethyl ethylene carbonate: 50 to 95 parts of a water-soluble polymer,
microcrystalline cellulose: 5 to 50 parts of (A) a water-soluble polymer,
acid anhydride: 0.1-10 parts.
The polymethyl ethylene carbonate is used as a matrix of the fully degradable composite material, the acid anhydride is used as an end-capping reagent and a compatibilizer, and the microcrystalline cellulose is used as a filling material.
The number average molecular weight of the polymethyl ethylene carbonate is 10000-100000.
The acid anhydride is one or a mixture of more of acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, pyromellitic dianhydride or mellitic anhydride.
The microcrystalline cellulose is prepared by acidolysis of natural plant fibers.
The particle size of the microcrystalline cellulose is 20-100 mu m.
The specific process of melt mixing the polymethyl ethylene carbonate, the anhydride and the microcrystalline cellulose is as follows:
(1) weighing polymethyl ethylene carbonate, anhydride and microcrystalline cellulose according to weight percentage, drying for 12-36 h at 40-80 ℃, and then mechanically mixing to form premix;
(2) and putting the premix into mixing equipment for melt mixing to obtain the master batch of the fully-degradable composite material.
The mechanical mixing adopts a high-speed mixer, and the mechanical mixing time is 0.5-3 min.
The mixing equipment is a single-screw extruder, a double-screw extruder, an internal mixer or an open mill, the melting and mixing temperature in the mixing equipment is 110-150 ℃, the die head temperature in the mixing equipment is 110-170 ℃, the rotating speed of the mixing equipment is 10-200 r/min, and the blending time in the mixing equipment is 3-10 min.
In the method for preparing the fully-degradable composite material by using the anhydride and microcrystalline cellulose synergistically modified polymethyl ethylene carbonate, the mechanism is shown in figure 1, and the method specifically comprises the following steps: based on the activity of the surface hydroxyl of microcrystalline cellulose (MCC) and the active hydroxyl at the tail end of the PPC, various acid anhydrides are added to serve as a compatibilizer, the PPC is modified by utilizing the synergistic effect of the acid anhydrides and the MCC, and a simple and easy method is adopted to prepare the fully-degradable PPC-based composite material. The anhydride bond is broken under the heating condition to form carboxyl, and the carboxyl can be subjected to esterification reaction with hydroxyl of PPC and MCC, so that the PPC and MCC are not only simply physically blended but also have chemical interaction, the interaction between the filler and the matrix is enhanced, and in addition, the anhydride can also be used as a capping reagent to cap the PPC, so that the tensile strength and the mechanical property of the PPC are improved.
Compared with the prior art, the invention has the following beneficial effects:
the degradable polymethyl ethylene carbonate resin is used as a composite material matrix, acid anhydride is used as an end-capping agent, and microcrystalline cellulose with degradation performance is added as a filling material at the same time, so that the composite material is prepared by melt blending. The microcrystalline cellulose with small size, complete crystal structure, excellent mechanical property and high reactivity is used as the filler, and the problems of interface and dispersion of the cellulose in the matrix polymethyl ethylene carbonate are solved. After microcrystalline cellulose is added into a copolymer system of the anhydride-terminated polymethyl ethylene carbonate and blended, the thermal stability and the mechanical property of the material can be improved, and the microcrystalline cellulose and the base material can be degraded, so that the prepared composite material can be naturally degraded finally, and the composite material is a novel composite material capable of being continuously developed. The microcrystalline cellulose has the advantages of rich source, low price, full degradation and the like, and the production cost of the material is greatly reduced. The product prepared by the method also has the advantages of safety, environmental protection, low cost, good processing performance and the like.
Drawings
FIG. 1 is a mechanism diagram of the preparation of fully degradable composite material by using the anhydride and microcrystalline cellulose to synergistically modify polymethyl ethylene carbonate.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The number average molecular weight of the PPC used was 5.91X 104Mixing the dried PPC and Maleic Anhydride (MA) according to the mass ratio of 100:0.5, 100:1, 100:3 and 100:5 respectively to form a premix of 4 parts of samples, and then respectively putting the premix into a double-screw extruder to prepare the maleic anhydride end-capped PPC, wherein the screw rotation speed is 80r/min, the die head temperature of the extruder is 120 ℃, and the products are respectively marked as PPC-MA0.5, PPC-MA1, PPC-MA3 and PPC-MA 5.
A sample of pure PPC without MA was also prepared as a blank and labeled as pure PPC.
Selecting the same amount of sample obtained by extrusion, observing with infrared scanner, and determining the spectrum of PPC-MA1 at 1640cm-1A distinct absorption peak appears indicating that MA successfully capped PPC.
Selecting the same amount of sample obtained by extrusion, performing TG analysis by using a thermogravimetric analyzer in a nitrogen environment at a heating rate of 10 ℃/min in the whole process, and performing T of each PPC-MA when pure PPC and different MA addition amounts are adopted-5％、T-50％、T-95％(i.e., temperatures corresponding to 5%, 50%, and 95% reduction in total mass) are shown in Table 1.
TABLE 1 thermal decomposition temperature values for pure PPC and MA different contents of PPC-MA
As can be seen from Table 1, the improvement of the thermal stability of PPC-MA is closely related to the MA content, and the thermal stability of the product is improved along with the increase of the MA content; wherein, when the adding amount of the MA is 1phr, the grafting ratio of the PPC-MA is the maximum, and T-5％The highest is achieved, 264.8 ℃. The reason is that the MA and the PPC terminal hydroxyl have end-capping reaction, and the 'unzipping' degradation of the PPC is inhibited.
Example 2
The number average molecular weight of the PPC used was 9.17X 104Respectively mixing the dried PPC with Maleic Anhydride (MA), Phthalic Anhydride (PA) and pyromellitic dianhydride (PMDA) according to a mass ratio of 100:1 to form a premix of 3 parts of samples, and then respectively putting the premix into a double-screw extruder to prepare three different types of anhydride-terminated PPC, wherein the screw rotation speed is 80r/min, the die head temperature of the extruder is 120 ℃, and products are respectively marked with PPC-MA1, PPC-PA1 and PPC-PMDA 1.
A sample of pure PPC without added anhydride was also prepared as a blank and labeled as pure PPC.
The same amount of 4 samples obtained by extrusion was selected and subjected to thermal stability analysis in the same manner as in example 1 to obtain T's of pure PPC, PPC-MA1, PPC-PA1 and PPC-PMDA1-5％、T-50％、T-95％As shown in table 2.
TABLE 2 thermal decomposition temperature values for pure PPC, PPC-MA1, PPC-PA1, PPC-PMDA1
As can be seen from Table 2, the T of pure PPC was obtained after the addition of the three anhydrides MA, PA and PMDA-5％There are various degrees of improvement. Wherein,t of PPC-PMDA1-5％The highest is 26.3 ℃. This is because PMDA is an aromatic dianhydride, and contains not only benzene rings but also a large number of carbonyl groups in its molecular structure, and therefore can more effectively improve the thermal stability of PPC.
Example 3
The number average molecular weight of the PPC used was 9.17X 104Respectively mixing the dried PPC with Maleic Anhydride (MA), Phthalic Anhydride (PA) and pyromellitic dianhydride (PMDA) according to a mass ratio of 100:1 to form a premix of 3 parts of samples, and then respectively putting the premix into a double-screw extruder to prepare three different types of anhydride-terminated PPC, wherein the screw rotation speed is 80r/min, the die head temperature of the extruder is 120 ℃, and products are respectively marked with PPC-MA1, PPC-PA1 and PPC-PMDA 1.
A sample of pure PPC without added anhydride was also prepared as a blank and labeled as pure PPC.
Four identical extrusion samples were dried under vacuum at 60 ℃ for 24 hours, and then placed in a flat vulcanizing press for compression molding, and tested for mechanical properties according to the IOS527-2 and IOS179-1982 standards, with the results shown in Table 3.
TABLE 3 values of mechanical properties of pure PPC, PPC-MA1, PPC-PA1, PPC-PMDA1
As is clear from Table 3, the tensile strengths of PPC-MA1, PPC-PA1 and PPC-PMDA1 were improved to different degrees compared with the tensile strength of pure PPC. Wherein, the maximum PPC-PMDA1 is improved by 4.15MPa compared with the pure PPC. The reason is that the intrinsic viscosity of PPC-PMDA1 is the greatest, and therefore the tensile strength is also the greatest.
Example 4
The number average molecular weight of the PPC used was 9.17X 104Adding the dried PPC into an internal mixer, mixing at 160 ℃ for 3min at a certain rotating speed, adding microcrystalline cellulose (MCC) powder after the PPC is fully melted, and mixing for 10min, wherein the mass ratio of the PPC to the MCC is as follows: 95:5, 90:10, 85:15, 80:20, forming 4 parts of PPC/MCC composite material (noted as PPC/MCC-5, PPC/MCC-10, PPC/MCC-15, PPC/MCC-20, respectively). And the obtained 4 parts of composite material was subjected to press molding by a press vulcanizer. MCC was dried before experiment and the powder was filtered through 200 mesh screen.
Meanwhile, pure PPC pressed sample strips without MCC were prepared as a blank, and mechanical property tests were performed according to the IOS527-2 and IOS179-1982 standards, and the results are shown in Table 4.
TABLE 4 mechanical Properties of the pure PPC and PPC/MCC composites
As can be seen from table 4, the tensile strength of the composite increased first and then decreased with increasing MCC content, and both were greater than pure PPC. Wherein, the tensile strength of the composite material added with 15 percent MCC is increased to the highest degree, and is increased to 7.12MPa from the original 5.11MPa, and is increased by 39.33 percent. This is due to the fact that MCC is able to efficiently carry loads and stresses in PPC resin matrices.
Example 5
The number average molecular weight of the PPC used was 9.17X 104Respectively mixing the dried PPC with Maleic Anhydride (MA), Phthalic Anhydride (PA) and pyromellitic dianhydride (PMDA) according to a mass ratio of 100:1 to form a premix of 3 parts of samples, and then respectively putting the premix into a double-screw extruder to prepare three different types of anhydride-terminated PPC, wherein the screw rotation speed is 80r/min, the die head temperature of the extruder is 120 ℃, and products are respectively marked with PPC-MA1, PPC-PA1 and PPC-PMDA 1.
A sample of pure PPC without added anhydride was also prepared as a blank and labeled as pure PPC.
Four extrusion experiment samples with the same amount are taken and dried for 24 hours in vacuum at 60 ℃, the dried extrusion samples are added into an internal mixer, and are mixed for 3 minutes at 160 ℃ at a certain rotating speed, after the samples are fully melted, MCC powder is added and mixed for 10 minutes, the mass ratio of each sample to the MCC is 85:15, and 4 parts of composite materials (respectively marked as PPC/MCC-15, PPC-MA1/MCC-15, PPC-PA1/MCC-15 and PPC-PMDA1/MCC-15) are formed. MCC was dried before experiment and the powder was filtered through 200 mesh screen.
The 4 parts of the composite material thus obtained were pressed into tablets by a press vulcanizer and subjected to mechanical property tests in accordance with the IOS527-2 and IOS179-1982 standards, the results of which are shown in Table 5.
TABLE 5 values of mechanical Properties of PPC/MCC and three anhydride-terminated PPC/MCC composites
As is clear from Table 5, the tensile strengths of PPC-MA1/MCC-15, PPC-PA1/MCC-15, and PPC-PMDA1/MCC-15 were improved to different degrees as compared with the tensile strength of PPC/MCC. Wherein, the maximum PPC-PMDA1/MCC-1 is 34.5 percent higher than that of PPC-PMDA 1.
Example 6
The number average molecular weight of the PPC used was 9.17X 104Respectively mixing the dried PPC with Maleic Anhydride (MA), Phthalic Anhydride (PA) and pyromellitic dianhydride (PMDA) according to a mass ratio of 100:1 to form a premix of 3 parts of samples, and then respectively putting the premix into a double-screw extruder to prepare three different types of anhydride-terminated PPC, wherein the screw rotation speed is 80r/min, the die head temperature of the extruder is 120 ℃, and products are respectively marked with PPC-MA1, PPC-PA1 and PPC-PMDA 1.
A sample of pure PPC without added anhydride was also prepared as a blank and labeled as pure PPC.
Four extrusion experiment samples with the same amount are taken and dried for 24 hours in vacuum at 60 ℃, the dried extrusion samples are added into an internal mixer, and are mixed for 3 minutes at 160 ℃ at a certain rotating speed, after the samples are fully melted, MCC powder is added and mixed for 10 minutes, the weight ratio of each sample to the MCC is 85:15, and 4 parts of composite materials (respectively marked as PPC/MCC-15, PPC-MA1/MCC-15, PPC-PA1/MCC-15 and PPC-PMDA1/MCC-15) are formed. MCC was dried before experiment and the powder was filtered through 200 mesh screen.
Taking samples with the same amount for 4 parts of composite materials, performing TG analysis by using a thermogravimetric analyzer in a nitrogen environment in the whole process at the temperature rise rate of 10 ℃/min, and performing T analysis-5％、T-50％、T-95％(i.e., temperatures corresponding to 5%, 50%, and 95% reduction in total mass) are shown in Table 6.
TABLE 6 thermal decomposition temperature values for PPC/MCC and three anhydride-terminated PPC/MCC composites
As can be seen from Table 6, when pure PPC was added with 15 wt% MCC, the T of the material was-5％The temperature increased from 210.5 ℃ to 239.6 ℃, which was 29.1 ℃.
Comparing Table 2 with Table 6, it can be seen that the thermal stability of the composite material is greatly improved when MCC is added to the anhydride-terminated PPC system, for example, composite material T is added to the PPC-PMDA1 system-5％The temperature is increased from 236.8 ℃ to 257.3 ℃ and is increased by 20.5 ℃. This is because the MCC has many hydroxyl groups on its surface, which can enhance the interaction with the molecular chain of PPC and inhibit the thermal degradation of PPC. Compared with the thermal decomposition temperature of the PPC/MCC composite material, the three anhydride-terminated PPC/MCC composite material T-5％There are various degrees of improvement. The interaction between PPC and MCC in the composite material is enhanced due to the addition of the anhydride, and the anhydride can generate esterification reaction with hydroxyl of the PPC and MCC after being heated, so that the MCC and a PPC matrix are chemically combined, and the improvement is thatThe thermal stability of PPC is high.
From the above examples 2 to 6, it can be seen that when the end-capping reagent anhydride is PMDA and the mass ratio of PPC, PMDA and microcrystalline cellulose is 85:15:1, the PPC-PMDA1/MCC-15 composite material has the best mechanical and thermal stability. Therefore, the modification method of the polymethyl ethylene carbonate has the advantages of simple process, low cost, complete degradation, good mechanical property and high thermal stability, and greatly widens the application of carbon dioxide-based compounds.
As mentioned above, the present invention can be better realized, and the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; all equivalent changes and modifications made according to the present disclosure are intended to be covered by the scope of the claims of the present invention.
Claims (9)
1. The method for preparing the fully-degradable composite material by using the acid anhydride and the microcrystalline cellulose to synergistically modify the polymethyl ethylene carbonate is characterized in that degradable polymethyl ethylene carbonate, acid anhydride and microcrystalline cellulose are melted and mixed to form master batch of the fully-degradable composite material, and then the master batch is molded into a sample by compression;
wherein the mass ratio of the polymethyl ethylene carbonate, the acid anhydride and the microcrystalline cellulose is as follows:
polymethyl ethylene carbonate: 50 to 95 parts of a water-soluble polymer,
microcrystalline cellulose: 5 to 50 parts of (A) a water-soluble polymer,
acid anhydride: 0.1-10 parts.
2. The method for preparing the fully-degradable composite material by using the anhydride and the microcrystalline cellulose for synergistically modifying the polymethyl ethylene carbonate as the claim 1, wherein the polymethyl ethylene carbonate is used as a matrix of the fully-degradable composite material, the anhydride is used as an end-capping agent and a compatibilizer, and the microcrystalline cellulose is used as a filling material.
3. The method for preparing the fully degradable composite material by using the anhydride and the microcrystalline cellulose for synergistic modification of the polymethyl ethylene carbonate according to claim 1, wherein the number average molecular weight of the polymethyl ethylene carbonate is 10000-100000.
4. The method for preparing fully degradable composite material by using the anhydride and microcrystalline cellulose to synergistically modify the polymethyl ethylene carbonate according to claim 1, wherein the anhydride is one or more of acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, pyromellitic dianhydride or mellitic anhydride.
5. The method for preparing the fully-degradable composite material by using the anhydride and the microcrystalline cellulose to synergistically modify the polymethyl ethylene carbonate, which is characterized in that the microcrystalline cellulose is prepared by acidolysis of natural plant fibers.
6. The method for preparing the fully degradable composite material by the anhydride and microcrystalline cellulose synergistic modification of the polymethyl ethylene carbonate according to claim 1, wherein the grain size of the microcrystalline cellulose is 20-100 μm.
7. The method for preparing the fully degradable composite material by the acid anhydride and microcrystalline cellulose synergistic modification of the polymethyl ethylene carbonate according to claim 1, wherein the specific process of melt mixing the polymethyl ethylene carbonate, the acid anhydride and the microcrystalline cellulose is as follows:
(1) weighing polymethyl ethylene carbonate, anhydride and microcrystalline cellulose according to weight percentage, drying for 12-36 h at 40-80 ℃, and then mechanically mixing to form premix;
(2) and putting the premix into mixing equipment for melt mixing to obtain the master batch of the fully-degradable composite material.
8. The method for preparing the fully-degradable composite material from the anhydride and the microcrystalline cellulose synergistically modified polymethyl ethylene carbonate according to claim 7, wherein the equipment for mechanical mixing is a high-speed mixer, and the time for mechanical mixing is 0.5-3 min.
9. The method for preparing the fully-degradable composite material from the anhydride and the microcrystalline cellulose synergistically modified polymethyl ethylene carbonate, according to claim 7, wherein the mixing equipment is a single screw extruder, a double screw extruder, an internal mixer or an open mill, the melt mixing temperature in the mixing equipment is 110-150 ℃, the die head temperature in the mixing equipment is 110-170 ℃, the rotation speed of the mixing equipment is 10-200 r/min, and the mixing time in the mixing equipment is 3-10 min.
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