CN115584002B - High-crystallinity polymethyl methacrylate polymer and preparation method thereof - Google Patents
High-crystallinity polymethyl methacrylate polymer and preparation method thereof Download PDFInfo
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- CN115584002B CN115584002B CN202211247333.5A CN202211247333A CN115584002B CN 115584002 B CN115584002 B CN 115584002B CN 202211247333 A CN202211247333 A CN 202211247333A CN 115584002 B CN115584002 B CN 115584002B
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Abstract
A polymethyl methacrylate polymer with high crystallinity and a preparation method thereof. The invention belongs to the field of polymethyl methacrylate polymers and preparation thereof. The invention aims to solve the technical problem of lack of high-crystallinity polymethyl methacrylate polymer and a preparation method thereof. The preparation method comprises the following steps: step 1: taking an amylose derivative containing a crystalline structure as an inducer, taking AIBN as an initiator, and inducing methyl methacrylate to carry out free radical polymerization under the condition of no solvent to obtain a mixture of a polymethyl methacrylate polymer and the amylose derivative containing the crystalline structure; step 2: and (3) after the polymerization in the step (1) is completed, cooling the system to room temperature, adding high-purity toluene, uniformly stirring for 12-24 hours, carrying out solid-liquid separation, and then carrying out rotary evaporation to remove the toluene, thereby obtaining the polymethyl methacrylate polymer with high crystallinity. The crystallinity of the obtained high crystallinity polymethyl methacrylate polymer is as high as 94 percent.
Description
Technical Field
The invention belongs to the field of polymethyl methacrylate polymers and preparation thereof, and particularly relates to a polymethyl methacrylate polymer with high crystallinity and a preparation method thereof.
Background
Crystalline polymers are of great interest due to their excellent mechanical and thermal properties. However, the lack of regularity and flexibility in the backbone of most polymers makes them spatially unordered to form an ordered lattice, which is greatly limited in its crystallization ability. Conventionally, polymethyl methacrylate (PMMA) obtained by free radical polymerization is a random polymer, and the α -methyl and ester bases in the side groups greatly hinder the regular arrangement of their backbone segments, resulting in the obtained polymethyl methacrylate being generally an amorphous polymer.
At present, a spiral chiral polymer amylose-tris (3, 5-dimethylphenylcarbamate) (ADMPC) is used as an inducer to induce a methyl methacrylate monomer to carry out free radical polymerization, so that the aim of improving the stereoregularity of polymethyl methacrylate (PMMA) is fulfilled, and polymethyl methacrylate with the isotacticity of up to 75% is obtained, but the polymethyl methacrylate is still an amorphous polymer. The irregular arrangement of the polymer chains is generally a major factor in hindering the crystallization of polymers, and crystalline polymers can be classified into two types at present, one type is polymers without stereoisomers, such as polyethylene; the other is a polymer of fully isotactic structure, such as isotactic polymethyl methacrylate. However, in the polymer crystallization process, in either of the above states, the molecular chain is inevitably curled and folded, so that the crystallinity of the resulting polymer is low. Therefore, how to improve the crystallinity of polymethyl methacrylate polymers is a problem to be solved in this field.
Disclosure of Invention
The invention aims to solve the technical problem of lack of a high-crystallinity polymethyl methacrylate polymer and a preparation method thereof, and provides the high-crystallinity polymethyl methacrylate polymer and the preparation method thereof.
One of the purposes of the invention is to provide a preparation method of a polymethyl methacrylate polymer with high crystallinity, which comprises the following steps:
step 1: taking an amylose derivative containing a crystalline structure as an inducer, taking Azobisisobutyronitrile (AIBN) as an initiator, and inducing methyl methacrylate to carry out free radical polymerization under the condition of no solvent to obtain a mixture of a polymethyl methacrylate polymer and the amylose derivative containing the crystalline structure;
step 2: and (3) after the polymerization in the step (1) is completed, cooling the system to room temperature, adding high-purity toluene, uniformly stirring for 12-24 hours, carrying out solid-liquid separation, and then carrying out rotary evaporation to remove the toluene, thereby obtaining the polymethyl methacrylate polymer with high crystallinity.
Further defined is the preparation of the amylose derivative containing crystalline structures of step 1: (1) Taking amylose as a matrix, taking 3, 5-dimethylphenyl isocyanate as a derivatization reagent for carbamate reaction, cooling to room temperature after the reaction is finished, then adding the mixture into absolute methanol at a constant speed dropwise for sedimentation, and washing a solid phase with the absolute methanol after solid-liquid separation; (2) The washed product is firstly dried for 1.5 hours under the condition of 20 ℃, the product is crushed into powder, and then dried for 24 hours under the condition of 60 ℃ under vacuum, and amylose-tri (3, 5-dimethylphenylcarbamate) containing crystalline structures is obtained, namely the amylose derivative containing crystalline structures is obtained.
Further defined, the molar ratio of amylose to 3, 5-dimethylphenyl isocyanate is 1: (5-7).
Further defined, the free radical polymerization process in step 1: after uniformly mixing methyl methacrylate and azobisisobutyronitrile, dropwise adding the mixture into an amylose derivative containing a crystalline structure under the protection of nitrogen and stirring, stopping stirring and polymerizing at 60 ℃ for 24 hours.
Further defined, the molar ratio of methyl methacrylate to azobisisobutyronitrile in step 1 is 100: (1-2).
Further defined, the molar ratio of methyl methacrylate to amylose derivative containing a crystalline structure in step 1 is 50: (3-4).
Further defined, the high purity toluene in step 2 is obtained by the following route: purifying the analytically pure toluene under nitrogen atmosphere by normal pressure distillation, and collecting the fraction at 109-112 ℃ to obtain the high-purity toluene.
Further defined, the volume ratio of high purity toluene to polymethyl methacrylate polymer and amylose derivative containing crystalline structure in step 2 is (50-60): 1.
it is another object of the present invention to provide a polymethyl methacrylate polymer having high crystallinity obtained by the above-mentioned production method.
Further defined, the high crystallinity polymethyl methacrylate polymer has a crystallinity of up to 94%.
Compared with the prior art, the invention has the remarkable effects that:
according to the invention, the amylose derivative with a regular structure and containing a crystalline structure is used as an inducer to induce and form the polymethyl methacrylate with a regular structure, further, the post-treatment is carried out on a post-polymerization reaction system, toluene is introduced, the influence of a side group in a polymethyl methacrylate polymer chain segment on a main chain is greatly weakened under the combined action of a non-covalent bond of toluene and intermolecular complexation of the amylose derivative, effective regulation and control on the stretching degree of a polymethyl methacrylate polymer molecular chain is realized, the crystallinity of the polymethyl methacrylate polymer is obviously improved, and the crystallinity of the obtained polymethyl methacrylate polymer is as high as 94%.
Drawings
FIG. 1 is a flow chart of the process for preparing the high crystallinity polymethyl methacrylate polymer of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of amylose-tris (3, 5-dimethylphenylcarbamate) having a crystalline structure obtained in example 1;
FIG. 3 is an X-ray diffraction pattern of amylose-tris (3, 5-dimethylphenylcarbamate) having a crystalline structure obtained in example 1;
FIG. 4 shows the polymerization-induced polymethyl methacrylate (PMMA-Oct) obtained in comparative example 1 and the crystalline polymethyl methacrylate obtained in example 1cPMMA) hydrogen nuclear magnetic resonance spectrum;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of polymethyl methacrylate (PMMA-Oct) obtained by non-induced polymerization of comparative example 1 and polymethyl methacrylate (PMMA-AD-Oct) obtained by comparative example 2;
FIG. 6 is an X-ray diffraction pattern of the high crystallinity polymethacrylate prepared in example 1 and the amorphous polymethacrylates prepared in comparative examples 1-2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
The first embodiment is as follows: the preparation method of the polymethyl methacrylate polymer with high crystallinity in the embodiment is carried out according to the following steps:
step 1:
preparation of amylose derivatives containing crystalline structures:
(1) Placing amylose in two bottles, heating to 120 ℃ and drying for 6 hours under a vacuum environment, then cooling the system to 105 ℃, adding anhydrous N, N-dimethylacetamide under the protection of nitrogen, stirring for 12 hours to fully swell the amylose, then cooling the system to room temperature, adding anhydrous lithium chloride under the protection of nitrogen, stirring for 2 hours to dissolve the amylose, then heating the system to 80 ℃, adding anhydrous pyridine under the protection of nitrogen, stirring for 4 hours to provide conditions for subsequent esterification reaction, keeping the temperature unchanged, adding 3, 5-dimethylphenyl isocyanate under the protection of nitrogen, stirring for 16 hours to fully react with the amylose, cooling the system to room temperature after the reaction is finished, dropwise adding the obtained mixture into anhydrous methanol at a uniform speed, stirring for 30 minutes to fully disperse the amylose, standing for 6 hours to precipitate the product, removing supernatant, centrifuging, and washing the product with anhydrous methanol; wherein the molar ratio of amylose to 3, 5-dimethylphenyl isocyanate is 1: (5-7);
(2) Placing the washed product in a vacuum drying oven for special drying treatment, wherein the main purpose is to avoid agglomeration and agglomeration of amylose derivatives and influence the crystal structure of the amylose derivatives, and the specific treatment method comprises the following steps: vacuum drying at 20deg.C for 1.5 hr, removing part of residual methanol, grinding the product into powder, and vacuum drying at 60deg.C for 24 hr to obtain amylose-tris (3, 5-dimethylphenylcarbamate) containing crystalline structure, i.e. amylose derivative containing crystalline structure.
Free radical polymerization:
(1) The prepared amylose-tri (3, 5-dimethyl phenyl carbamate) containing the crystalline structure is put into a two-mouth bottle, the temperature of the system is raised to 60 ℃, and the system is vacuumized and dried for 4 hours under the stirring condition, so that the amylose derivative containing the crystalline structure is fully dried;
(2) Uniformly mixing methyl methacrylate and azodiisobutyronitrile, dropwise adding the mixture into a reaction system under the protection of nitrogen and stirring, stopping stirring, and polymerizing at 60 ℃ for 24 hours in a standing state to obtain a mixture of a polymethyl methacrylate polymer and an amylose derivative containing a crystalline structure;
wherein the molar ratio of the methyl methacrylate to the azodiisobutyronitrile is 100: (1-2) the molar ratio of methyl methacrylate to amylose derivative containing a crystalline structure was 50: (3-4).
Step 2:
purification of toluene:
purifying the analytically pure toluene under nitrogen atmosphere by atmospheric distillation, removing hydrocarbon impurities with lower boiling point in toluene solvent, collecting fraction at 109-112 ℃ to obtain high-purity toluene, and preserving under nitrogen atmosphere for later use.
Preparation of high crystallinity polymethyl methacrylate polymer:
after the polymerization of the step 1 is completed, the temperature of the system is reduced to room temperature, then high-purity toluene is added, stirring is carried out at a constant speed for 12-24 hours, after the stirring is finished, solid-liquid separation is carried out through reduced pressure suction filtration, amylose-tris (3, 5-dimethylphenylcarbamate) containing crystalline structures is removed, toluene solution of polymethyl methacrylate polymer is obtained, rotary evaporation and decompression are carried out on the toluene solution of polymethyl methacrylate polymer in air at room temperature by using a rotary evaporator, when condensed small water drops appear on the outer wall of a reaction bottle, the reaction bottle is placed in a water bath, the temperature is raised to 30 ℃, redundant toluene solvent is removed, and the polymethyl methacrylate polymer is obtained, and is dried in vacuum for 24 hours at 60 ℃ to obtain the polymethyl methacrylate polymer with high crystallinity;
wherein the volume ratio of the high-purity toluene to the mixture of the polymethyl methacrylate polymer and the amylose derivative containing crystalline structure is (50-60): 1.
example 1: the preparation method of the high-crystallinity polymethacrylate comprises the following steps:
step 1:
preparation of amylose derivatives containing crystalline structures:
(1) Placing 1.0g of amylose in a two-mouth bottle, heating to 120 ℃ and drying for 6 hours under a vacuum environment, then adding anhydrous 40mLN, N-dimethylacetamide under the protection of nitrogen after the temperature of the system is reduced to 105 ℃, stirring for 12 hours to fully swell the amylose, then cooling the system to room temperature, adding 2.0g of anhydrous lithium chloride under the protection of nitrogen, stirring for 2 hours to dissolve the amylose, then heating the system to 80 ℃, adding 20mL of anhydrous pyridine under the protection of nitrogen, stirring for 4 hours to provide conditions for the subsequent esterification reaction, keeping the temperature unchanged, adding 5.2mL of 3, 5-dimethylphenyl isocyanate under the protection of nitrogen, stirring for 16 hours to fully react with the amylose, cooling the system to room temperature after the reaction is finished, adding the obtained mixture into 800mL of anhydrous methanol at a uniform speed dropwise, stirring for 30 minutes to fully disperse the amylose, settling the product, centrifuging after removing the supernatant, and washing the product 7 times with the anhydrous methanol;
(2) Placing the washed product in a vacuum drying oven for special drying treatment, wherein the main purpose is to avoid agglomeration and agglomeration of amylose derivatives and influence the crystal structure of the amylose derivatives, and the specific treatment method comprises the following steps: vacuum drying at 20deg.C for 1.5 hr, removing part of residual methanol, grinding the product into powder, and vacuum drying at 60deg.C for 24 hr to obtain amylose-tris (3, 5-dimethylphenylcarbamate) containing crystalline structure, i.e. amylose derivative containing crystalline structure. The yield was 80%. The nuclear magnetic resonance hydrogen spectrum (deuterated pyridine, 80 ℃,500 MHz) is shown in figure 2, and the synthesized derivative has regular structure and substitution degree reaching 98% as can be seen from figure 2. The X-ray diffraction pattern is shown in figure 3, and the synthesized derivative has a certain crystal structure as can be seen from figure 3.
Free radical polymerization:
(1) Taking 0.38g of the prepared amylose-tri (3, 5-dimethylphenyl carbamate) containing the crystalline structure in a two-mouth bottle, heating the system to 60 ℃, and vacuumizing and drying for 4 hours under the stirring condition to fully dry the amylose derivative containing the crystalline structure;
(2) 1mL of methyl methacrylate monomer and 15mg of azodiisobutyronitrile are taken and mixed uniformly, then added into a reaction system dropwise under the protection of nitrogen and stirring, stirring is stopped, and polymerization is carried out for 24 hours at 60 ℃ in a standing state, so as to obtain a mixture of polymethyl methacrylate and amylose derivative containing crystalline structure.
Step 2:
purification of toluene:
purifying the analytically pure toluene under nitrogen atmosphere by atmospheric distillation, removing hydrocarbon impurities with lower boiling point in toluene solvent, collecting fraction at 110 ℃ to obtain high-purity toluene, and preserving under nitrogen atmosphere for later use.
Preparation of high crystallinity polymethyl methacrylate polymer:
after the polymerization of the step 1 is completed, the system temperature is reduced to room temperature, 50mL of high-purity toluene is added, stirring is carried out at a constant speed for 24 hours, after the stirring is finished, solid-liquid separation is carried out through reduced pressure suction filtration, amylose-tris (3, 5-dimethylphenylcarbamate) containing crystalline structures is removed, a toluene solution of polymethyl methacrylate is obtained, rotary evaporation and decompression are carried out on the toluene solution of polymethyl methacrylate polymer in air at room temperature by using a rotary evaporator, when condensed small water drops appear on the outer wall of a reaction bottle, the reaction bottle is placed in a water bath, the temperature is increased to 30 ℃, excess toluene solvent is removed, polymethyl methacrylate is obtained, and vacuum drying is carried out for 24 hours at 60 ℃ to obtain polymethyl methacrylate with high crystallinity. The yield was 64%. The nuclear magnetic resonance hydrogen spectrum (deuterated chloroform, 35 ℃,500 MHz) is shown in fig. 4. The X-ray diffraction pattern is shown in fig. 6.
Comparative example 1: the difference between this comparative example and example 1 is that: the inducer amylose-tris (3, 5-dimethylphenylcarbamate) was not added. Other steps and parameters were the same as in example 1, and the obtained product was PMMA-Oct in 99% yield, and a nuclear magnetic resonance hydrogen spectrum (deuterated chloroform, 35 ℃,500 MHz) was shown in FIGS. 4 to 5. The X-ray diffraction pattern is shown in fig. 6.
Comparative example 2: the difference between this comparative example and example 1 is that: the amylose-tris (3, 5-dimethylphenyl carbamate) is obtained by drying at 60 ℃ in the whole process, namely, the amylose-tris (3, 5-dimethylphenyl carbamate) without a crystalline structure is obtained, meanwhile, the step 2 is omitted, the solid-liquid separation is carried out through reduced pressure suction filtration after the polymerization is completed, and the amylose-tris (3, 5-dimethylphenyl carbamate) is removed, so that polymethyl methacrylate is obtained. Other steps and parameters were the same as in example 1, and the obtained product was PMMA-AD-Oct in a yield of 32%, and a nuclear magnetic resonance hydrogen spectrum (deuterated chloroform, 35 ℃,500 MHz) was shown in FIG. 5. The X-ray diffraction pattern is shown in fig. 6.
As can be seen from FIG. 4, the crystalline amylose-tris (3, 5-dimethylphenylcarbamate) -containing structure prepared in example 1 was used to induce a cPMMA structure with mm/mr/rr=0.15/0.33/0.52, an isotacticity of 0.15 was achieved, and a PMMA-Oct structure with mm/mr/rr=0.07/0.37/0.56.
As can be seen from FIG. 5, the amorphous amylose-tris (3, 5-dimethylphenylcarbamate) prepared in comparative example 2 was used to induce a PMMA-AD-Oct structure with mm/mr/rr=0.19/0.30/0.51, and the isotacticity could reach 0.19.
As can be seen from FIG. 6, polymethyl methacrylate (PMMA-Oct) obtained in comparative example 1 without induction was an amorphous polymer, and PMMA-AD-Oct obtained in comparative example 2 was also an amorphous polymer. The polymethyl methacrylate (cPMMA) of example 1 of the present invention is crystalline polymer with a crystallinity of 94%.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (7)
1. A preparation method of a polymethyl methacrylate polymer with high crystallinity is characterized by comprising the following steps:
step 1: taking an amylose derivative containing a crystalline structure as an inducer, taking AIBN as an initiator, and inducing methyl methacrylate to carry out free radical polymerization under the condition of no solvent to obtain a mixture of a polymethyl methacrylate polymer and the amylose derivative containing the crystalline structure;
step 2: after the polymerization in the step 1 is completed, the temperature of the system is reduced to room temperature, then high-purity toluene is added, stirring is carried out at a constant speed for 12-24 hours, and after solid-liquid separation, toluene is removed by rotary evaporation, thus obtaining a polymethyl methacrylate polymer with high crystallinity;
the preparation process of the amylose derivative containing crystalline structure in the step 1: (1) Taking amylose as a matrix, taking 3, 5-dimethylphenyl isocyanate as a derivatization reagent for carbamate reaction, cooling to room temperature after the reaction is finished, then adding the mixture into absolute methanol at a constant speed dropwise for sedimentation, and washing a solid phase with the absolute methanol after solid-liquid separation; (2) Vacuum drying the washed product at 20deg.C for 1.5 hr, grinding the product into powder, and vacuum drying at 60deg.C for 24 hr to obtain amylose-tris (3, 5-dimethylphenylcarbamate) containing crystalline structure, i.e. amylose derivative containing crystalline structure; the molar ratio of amylose to 3, 5-dimethylphenyl isocyanate was 1: (5-7);
the high-purity toluene in the step 2 is obtained by the following way: purifying the analytically pure toluene under nitrogen atmosphere by atmospheric distillation, and collecting the fraction at 109-112 ℃ to obtain the high-purity toluene.
2. The method according to claim 1, wherein the free radical polymerization process in step 1: after uniformly mixing methyl methacrylate and AIBN, dropwise adding the mixture into an amylose derivative containing a crystalline structure under the protection of nitrogen and stirring, stopping stirring and polymerizing at 60 ℃ for 24 hours.
3. The process of claim 1, wherein the molar ratio of methyl methacrylate to AIBN in step 1 is 100: (1-2).
4. The method according to claim 1, wherein the molar ratio of methyl methacrylate to amylose derivative containing a crystalline structure in step 1 is 50: (3-4).
5. The method according to claim 1, wherein the volume ratio of high purity toluene to polymethyl methacrylate polymer and amylose derivative containing crystalline structure in step 2 is (50-60): 1.
6. a high crystallinity polymethyl methacrylate polymer produced by the method of any one of claims 1-5.
7. The high crystallinity polymethyl methacrylate polymer of claim 6 having crystallinity up to 94%.
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