CN109553767B - High molecular polymer and preparation method and application thereof - Google Patents
High molecular polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high molecular polymer and a preparation method and application thereof, wherein the high molecular polymer is prepared by taking castor oil, polybutylene adipate and diethylene glycol divinyl ether as reactants and reacting, and the castor oil, the polybutylene adipate and toluene are mixed to obtain a mixed solution A; then mixing the mixed solution A, p-toluenesulfonic acid and tetrahydrofuran to form a mixed solution B; then adding dropwise diethylene glycol divinyl ether into the mixed solution B for reaction, wherein the conversion rate of the method can reach more than 90% at most; the prepared high molecular polymer can be used for preparing engineering plastics; during preparation, the high molecular polymer, a dimercapto reagent, an initiator azodiisobutyronitrile and tetrahydrofuran are stirred and mixed, and the mixture is put into an oven to react to obtain the engineering plastic. The engineering plastic of the invention can be degraded by acid, thus being very environment-friendly; meanwhile, the engineering plastic has higher tensile strength and bending strength under normal conditions, and can meet the requirements of actual production and life.
Description
Technical Field
The invention relates to the field of high molecular materials, in particular to a high molecular polymer and a preparation method and application thereof.
Background
Engineering plastics refer to plastics that can be used as engineering materials and to replace metals for manufacturing machine parts and the like. Compared with general plastics, the engineering plastics can meet higher requirements on mechanical property, durability, corrosion resistance, heat resistance and the like, are more convenient to process and can replace metal materials. Engineering plastics are widely applied to industries such as electronics, electricity, machinery, aerospace and the like, and the international fashion trend of replacing steel with plastics and replacing wood with plastics is achieved. Engineering plastics become the fastest growing field in the plastic industry in the world nowadays, and the development of the engineering plastics not only plays a supporting role in the national pillar industry and the modern high and new technology industry, but also promotes the traditional industry to be modified and the product structure to be adjusted. Engineering plastics mainly include polycarbonate, polyamide, polyformaldehyde, polyphenyl ether, polyester and polyphenylene sulfide varieties, but most of the existing engineering plastics are non-degradable materials, so that a large amount of used engineering plastics can only be treated by burning or burying, cannot be recovered, has extremely low resource utilization rate, and causes no small damage to the environment, so that the pollution to the atmosphere and the like is more severe.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high molecular polymer, a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a high molecular polymer, the molecular structural formula of which is:
as a further improvement of the invention, the high molecular polymer is obtained by the reaction of castor oil, polybutylene adipate and diethylene glycol divinyl ether;
the structural formula of the castor oil is shown as
The polybutylene adipate has a structural formula of
The structural formula of the diethylene glycol divinyl ether is shown in the specification
The reaction formula is as follows:
as a further improvement of the invention, the number average molecular weight of the polybutylene adipate is 1000-4000; the number average molecular weight of the high molecular polymer is 10000-.
As a further improvement of the invention, the preparation method of the high molecular polymer comprises the following steps:
the method comprises the following steps: placing castor oil, polybutylene adipate and a first solvent into a reaction container A, stirring and mixing, and uniformly mixing to obtain a mixed solution A;
step two: putting the mixed solution A, the catalyst and the second solvent obtained in the step one into a reaction container B, stirring and mixing, and uniformly mixing to obtain a mixed solution B;
step three: adding diethylene glycol divinyl ether into the mixed solution B for reaction; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution B to obtain the high molecular polymer.
As a further improvement of the present invention, the first solvent is toluene; the second solvent is tetrahydrofuran.
As a further improvement of the invention, the catalyst is p-toluenesulfonic acid.
As a further improvement of the invention, the specific manner of adding the diethylene glycol divinyl ether into the mixed solution B in the step three is to add the diethylene glycol divinyl ether into the mixed solution B at the dropping speed of 2-3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 800-1000 rad/min.
As a further improvement of the invention, in the third step, after the diethylene glycol divinyl ether is completely added into the mixed solution B, the reaction temperature is set to be 15-25 ℃, the stirring speed is set to be 800-1000rad/min, and the reaction time is 4-6 h.
As a further improvement of the invention, the application of the high molecular polymer is used for preparing engineering plastics, and the preparation method of the engineering plastics comprises the steps of adding the high molecular polymer, a dimercapto reagent, an initiator and tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 10-20min at the rotating speed of 200-400rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 40-60 ℃ for reaction for 1-2 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
As a further improvement of the invention, the dimercapto reagent is any one of bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol and 1, 4-butanedithiol; the initiator is azobisisobutyronitrile.
The invention has the beneficial effects that: the castor oil is prepared by taking castor oil, polybutylene adipate and diethylene glycol divinyl ether as reactants for reaction, wherein the castor oil is a natural organic substance, and has the advantages of easily obtained raw materials and low cost; as one of the innovation points of the method, castor oil and polybutylene adipate are pretreated, namely, the castor oil, the polybutylene adipate and toluene are mixed to obtain a mixed solution A; the aim of doing so is to possibly improve the forwarding rate of the invention, because the castor oil and the polybutylene adipate can be uniformly dispersed in the toluene solvent, if the castor oil and the polybutylene adipate are directly put into the tetrahydrofuran solvent, the dispersibility is general, the reactants cannot fully react, the reaction is not complete enough, and the conversion rate is low; then mixing the mixed solution A with catalyst p-toluenesulfonic acid and tetrahydrofuran to form a mixed solution B; as another innovation point of the invention, when the dropwise adding diethylene glycol divinyl ether is added into the mixed solution B, the temperature of the solution is reduced to 0 ℃, and the solution is slowly dropwise added at the speed of 2-3 drops per 5 seconds, so that the problem that the local concentration is too high, so that a plurality of side reactions are generated, and the product quality and the conversion rate of the invention are influenced is avoided; when the diethylene glycol divinyl ether is completely added into the mixed solution B, raising the temperature of the solution to 15-25 ℃, preferably 20 ℃, and reacting for 4-6 hours, preferably 5 hours; further improving the conversion rate and the product quality; the temperature is 15-25 ℃, the temperature is very mild, the reaction is carried out under normal pressure, and the method is suitable for industrial production and manufacturing; finally, the conversion rate of the invention can reach more than 90 percent at most; meanwhile, the prepared high molecular polymer has certain tensile strength, bending strength and impact strength; the prepared high molecular polymer can be used for preparing engineering plastics, and when the engineering plastics are prepared, the high molecular polymer, a dimercapto reagent, an initiator azobisisobutyronitrile and tetrahydrofuran are stirred and mixed, wherein the dimercapto reagent is any one of bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol and 1, 4-butanedithiol, and preferably bis (2-mercaptoethyl) ether; uniformly mixing, putting into an oven for reaction, wherein the reaction temperature is 40-60 ℃, the preferred temperature is 50 ℃, and the reaction time is 1-2 hours; and purifying to obtain the engineering plastic. In the reaction process, through the initiation of azodiisobutyronitrile, the sulfydryl in a dimercapto reagent and the double bonds in the high molecular polymer react and polymerize to form a compact space network structure, so that the tensile strength, the bending strength and the impact strength of the product are further improved; therefore, the obtained product can be used as engineering plastic, and the engineering plastic has higher tensile strength and bending strength under normal conditions (pH is 7) and can meet the requirements of actual production and life; meanwhile, because the acetal bond is introduced into the engineering plastic, the engineering plastic can be degraded when the acidity is weak (the pH is less than 5), is environment-friendly, and improves the utilization rate of resources, so that the engineering plastic has a wide application range.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of example 1 of the present invention;
FIG. 2 is an infrared spectrum of example 1 of the present invention;
FIG. 3 is a gel chromatography spectrum of example 1 of the present invention;
FIG. 4 is a molecular structural formula of a high molecular polymer of the present invention;
FIG. 5 shows the chemical equation for forming a high molecular weight polymer according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The molecular structural formula of the high molecular polymer is shown in the specification
Example 1
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2.9g of castor oil, 20g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropping 1.6g of diethylene glycol divinyl ether into the mixed solution B at a dropping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 20 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 5 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Example 2
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2g of castor oil, 23g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at the temperature of 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropping 1.5g of diethylene glycol divinyl ether into the mixed solution B at a dropping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 15 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 6 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Example 3
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 4g of castor oil, 18g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at the temperature of 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropwise adding 2g of diethylene glycol divinyl ether into the mixed solution B at a dropwise adding speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 25 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 4 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Comparative example 1
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: placing 2.9g of castor oil, 20g of polybutylene adipate, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction container B, stirring and mixing, and stirring for 20min at 80 ℃ and the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropping 1.6g of diethylene glycol divinyl ether into the mixed solution B at a dropping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 20 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 5 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Comparative example 2
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2.9g of castor oil, 20g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: 1.6g of diethylene glycol divinyl ether was added to the mixed solution B; reacting for 5 hours at the reaction temperature of 20 ℃ and the stirring speed of 1000 rad/min; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
The reaction formula of the invention is as follows:
the high molecular polymers prepared in examples 1 to 3 and comparative examples 1 to 2 were weighed, and then the conversion rate was calculated;
| test specimen | Total mass of reactants/g | Product mass/g | Yield/%) |
| Example 1 | 24.5 | 22.45 | 91.6 |
| Example 2 | 26.5 | 22.92 | 86.5 |
| Example 3 | 24 | 20.26 | 84.4 |
| Comparative example 1 | 24.5 | 17.41 | 71.06 |
| Comparative example 2 | 24.5 | 15.74 | 64.2 |
The high molecular weight polymer obtained in example 1 was subjected to nmr measurement, whereby an nmr hydrogen spectrum (fig. 1) was obtained;
the high molecular polymer prepared in example 1 was detected by an infrared spectrometer to obtain an infrared spectrogram (fig. 2);
the high molecular weight polymer obtained in example 1 was subjected to a gel chromatography test, thereby obtaining a gel chromatogram (FIG. 3).
As can be seen from fig. 1:1H NMR(500MHz，CDCl3) Wherein the position with chemical shift of 4.094 is an acetal structure, and the structure has acid degradation characteristic.
As can be seen from FIG. 2, the distance is 1132.5cm-1A strong absorption peak is formed, which is obviously an acetal structure C-O-C absorption peak.
As shown in fig. 3, the results of the test were Mn 13930, Mw 36894, and PDI 2.648
FIG. 1 FIG. 2 FIG. 3 shows, in combination, the successful synthesis of the high molecular weight polymer obtained in example 1. The structural formula of the substance is as follows:
example 4
A preparation method of engineering plastics comprises the following steps: adding 20g of high molecular polymer, 3.6g of bis (2-mercaptoethyl) ether, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic. Wherein the high molecular weight polymer was obtained in example 1.
Example 5
A preparation method of engineering plastics comprises the following steps: adding 20g of high molecular polymer, 3.6g of 1, 2-ethanedithiol, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction container, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
Wherein the high molecular weight polymer was obtained in example 1.
Example 6
A preparation method of engineering plastics comprises the following steps: adding 20g of high molecular polymer, 3.6g of 1, 4-butanedithiol, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
Wherein the high molecular weight polymer was obtained in example 1.
Comparative example 3
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2.9g of glycerol, 20g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at the temperature of 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropping 1.6g of diethylene glycol divinyl ether into the mixed solution B at a dropping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 20 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 5 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Adding 20g of high molecular polymer, 3.6g of bis (2-mercaptoethyl) ether, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
Comparative example 4
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2.9g of xylitol, 20g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at the temperature of 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dropping 1.6g of diethylene glycol divinyl ether into the mixed solution B at a dropping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 20 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 5 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Adding 20g of high molecular polymer, 3.6g of bis (2-mercaptoethyl) ether, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
Comparative example 5
A preparation method of a high molecular polymer comprises the following steps:
the method comprises the following steps: sequentially putting 2.9g of castor oil, 20g of polybutylene adipate and 20ml of methylbenzene into a reaction container A, stirring and mixing, and stirring for 15min at 160 ℃ and the rotating speed of 500rad/min to obtain a mixed solution A;
step two: placing the mixed solution A prepared in the step one, 0.1g of p-toluenesulfonic acid and 50ml of tetrahydrofuran into a reaction vessel B, stirring and mixing, and stirring for 20min at 80 ℃ and at the rotating speed of 300rad/min to obtain a mixed solution B;
step three: dripping 1.6g of 1, 4-butanediol vinyl ether into the mixed solution B at the dripping speed of 3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 900 rad/min; after the dropwise addition, the reaction temperature is raised to 20 ℃, the stirring speed is set to 1000rad/min, and the reaction is carried out for 5 hours; after the reaction is completed, carrying out rotary evaporation on the mixed solution B, and removing the solvent; then cooling and solidifying to obtain the high molecular polymer.
Adding 20g of high molecular polymer, 3.6g of bis (2-mercaptoethyl) ether, 1g of azobisisobutyronitrile and 20ml of tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 15min at the rotating speed of 300rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 50 ℃ for reaction for 1.5 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
The samples obtained in examples 4 to 6 and comparative examples 3 to 5 were subjected to mechanical property testing
From the above chart, it can be seen that: the samples prepared in the examples 4 to 6 have higher tensile strength, bending strength and impact strength, and can be used as engineering plastics; on the other hand, the tensile strength, flexural strength and impact strength of the samples obtained in examples 3 to 5 were small and could not be used as engineering plastics.
The samples obtained in examples 4 to 6 and comparative examples 3 to 5 were placed in a 0.2mol/L phosphate buffer solution (PBS solution) having a pH of 7.0 and left for 24 hours, and then subjected to mechanical property testing
As can be seen from the above table, the samples prepared in examples 4 to 6 have small changes in group tensile strength, bending strength and impact strength after being left for a long time in a normal environment (pH 7), and can still be used as engineering plastics without degradation.
100g of the samples obtained in examples 4 to 6 were placed in a 0.2mol/L phosphate buffer solution (PBS solution) having a pH of 4.6, the samples were taken out at regular intervals, and the samples were vacuum-dried at 40 ℃/1kPa until the mass was constant, and the mass loss rate of the samples was calculated;
| test specimen | After 5 days | After 10 days | After 20 days |
| Example 4 | 5％ | 20％ | 50％ |
| Example 5 | 6％ | 25％ | 55％ |
| Example 6 | 8％ | 30％ | 60％ |
| Comparative example 3 | 5％ | 21％ | 51％ |
| Comparative example 4 | 6％ | 26％ | 57％ |
| Comparative example 5 | 5％ | 19％ | 47％ |
As can be seen from the above graphs, the engineering plastics prepared in examples 4 to 6 were degraded at pH 4.6 after 20 days, and the degradation rate was as high as 50% or more.
100g of polybutylene adipate is put into 0.2mol/L phosphate buffer solution (PBS solution) with the pH value of 4.6, samples are taken out at regular intervals, the samples are dried in vacuum under the condition of 40 ℃/1kPa until the mass is constant, and the mass loss rate of the polybutylene adipate is calculated;
| after 5 days | After 10 days | After 20 days | |
| Polybutylene adipate | 0.05％ | 0.1％ | 0.3％ |
As can be seen from the above graph, the quality of polybutylene adipate hardly changed after 20 days, and thus it is considered that polybutylene adipate hardly degraded under the condition of pH 4.6; because the ester group in polybutylene adipate is stable at a pH of 4.6, cleavage hardly occurs; the acetal bond is introduced into the engineering plastic prepared by the invention, so that the acetal bond is broken under the condition that the pH is 4.6 to generate corresponding aldehyde and alcohol, and the engineering plastic is easy to degrade. Further research shows that the engineering plastics prepared by the method are easy to degrade (namely acetal bond is broken) under the condition that the pH is less than 5; the polybutylene adipate needs to be degraded under the condition that the pH value is less than 2, but the degradation rate is still less than 20%.
The high molecular polymer and the preparation method and the application thereof are prepared by taking castor oil, polybutylene adipate and diethylene glycol divinyl ether as reactants for reaction, wherein the castor oil is a natural organic substance, the raw materials are easy to obtain and the cost is low; as one of the innovation points of the method, castor oil and polybutylene adipate are pretreated, namely, the castor oil, the polybutylene adipate and toluene are mixed to obtain a mixed solution A; the aim of doing so is to possibly improve the forwarding rate of the invention, because the castor oil and the polybutylene adipate can be uniformly dispersed in the toluene solvent, if the castor oil and the polybutylene adipate are directly put into the tetrahydrofuran solvent, the dispersibility is general, the reactants cannot fully react, the reaction is not complete enough, and the conversion rate is low; then mixing the mixed solution A with catalyst p-toluenesulfonic acid and tetrahydrofuran to form a mixed solution B; as another innovation point of the invention, when the dropwise adding diethylene glycol divinyl ether is added into the mixed solution B, the temperature of the solution is reduced to 0 ℃, and the solution is slowly dropwise added at the speed of 2-3 drops per 5 seconds, so that the problem that the local concentration is too high, so that a plurality of side reactions are generated, and the product quality and the conversion rate of the invention are influenced is avoided; when the diethylene glycol divinyl ether is completely added into the mixed solution B, raising the temperature of the solution to 15-25 ℃, preferably 20 ℃, and reacting for 4-6 hours, preferably 5 hours; further improving the conversion rate and the product quality; the temperature is 15-25 ℃, the temperature is very mild, the reaction is carried out under normal pressure, and the method is suitable for industrial production and manufacturing; finally, the conversion rate of the invention can reach more than 90 percent at most; meanwhile, the prepared high molecular polymer has certain tensile strength, bending strength and impact strength; the prepared high molecular polymer can be used for preparing engineering plastics, and when the engineering plastics are prepared, the high molecular polymer, a dimercapto reagent, an initiator azobisisobutyronitrile and tetrahydrofuran are stirred and mixed, wherein the dimercapto reagent is any one of bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol and 1, 4-butanedithiol, and preferably bis (2-mercaptoethyl) ether; uniformly mixing, putting into an oven for reaction, wherein the reaction temperature is 40-60 ℃, the preferred temperature is 50 ℃, and the reaction time is 1-2 hours; and purifying to obtain the engineering plastic. In the reaction process, through the initiation of azodiisobutyronitrile, the sulfydryl in a dimercapto reagent and the double bonds in the high molecular polymer react and polymerize to form a compact space network structure, so that the tensile strength, the bending strength and the impact strength of the product are further improved; therefore, the obtained product can be used as engineering plastic, and the engineering plastic has higher tensile strength and bending strength under normal conditions (pH is 7) and can meet the requirements of actual production and life; meanwhile, because the acetal bond is introduced into the engineering plastic, the engineering plastic can be degraded when the acidity is weak (the pH is less than 5), is environment-friendly, and improves the utilization rate of resources, so that the engineering plastic has a wide application range.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. A high-molecular polymer characterized by: the molecular structural formula is as follows:
2. a high molecular weight polymer according to claim 1, wherein: the high molecular polymer is obtained by the reaction of castor oil, polybutylene adipate and diethylene glycol divinyl ether;
the structural formula of the castor oil is shown as
The polybutylene adipate has a structural formula of
The structural formula of the diethylene glycol divinyl ether is shown in the specification
The reaction formula is as follows:
3. a high molecular weight polymer according to claim 2, wherein: the number average molecular weight of the polybutylene adipate is 1000-4000; the number average molecular weight of the high molecular polymer is 10000-.
4. A method for producing a high molecular weight polymer according to any one of claims 1 to 3, wherein: the method comprises the following steps:
the method comprises the following steps: placing castor oil, polybutylene adipate and a first solvent into a reaction container A, stirring and mixing, and uniformly mixing to obtain a mixed solution A;
step two: putting the mixed solution A, the catalyst and the second solvent obtained in the step one into a reaction container B, stirring and mixing, and uniformly mixing to obtain a mixed solution B;
step three: adding diethylene glycol divinyl ether into the mixed solution B for reaction; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution B to obtain the high molecular polymer.
5. A method for producing a high molecular weight polymer according to claim 4, wherein: the first solvent is toluene; the second solvent is tetrahydrofuran.
6. A method for producing a high molecular weight polymer according to claim 4, wherein: the catalyst is p-toluenesulfonic acid.
7. A method for producing a high molecular weight polymer according to claim 4, wherein: the specific way of adding the diethylene glycol divinyl ether into the mixed solution B in the third step is to dropwise add the diethylene glycol divinyl ether into the mixed solution B at the dropwise adding speed of 2-3 drops per 5 seconds under the conditions that the temperature is 0 ℃ and the stirring speed is 800-1000 rad/min.
8. A method for producing a high molecular weight polymer according to claim 7, wherein: in the third step, after the diethylene glycol divinyl ether is completely added into the mixed solution B, the reaction temperature is set to be 15-25 ℃, the stirring speed is set to be 800-1000rad/min, and the reaction time is 4-6 h.
9. The method for preparing engineering plastics from high molecular polymer according to any one of claims 1 to 3, wherein: adding a high molecular polymer, a dimercapto reagent, an initiator and tetrahydrofuran into a reaction vessel, stirring and mixing, and stirring for 10-20min at the rotating speed of 200-400rad/min to obtain a mixed solution; then putting the mixed solution into an oven with the temperature of 40-60 ℃ for reaction for 1-2 h; and after the reaction is completed, carrying out rotary evaporation and cooling solidification on the mixed solution to obtain the engineering plastic.
10. The method for preparing engineering plastic from high molecular polymer according to claim 9, wherein: the dimercapto reagent is any one of bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol and 1, 4-butanedithiol; the initiator is azobisisobutyronitrile.
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| JP2004149718A (en) * | 2002-10-31 | 2004-05-27 | Inoac Corp | Moisture absorbent composition for polyurethane |
| WO2006071813A3 (en) * | 2004-12-23 | 2006-10-12 | Abraham J Domb | Disposable medical supplies from hydrolytically biodegradable plastics |
| AU2007218990A1 (en) * | 2006-02-24 | 2007-08-30 | Phb Industrial S.A. | Environmentally degradable polymeric blend and process for obtaining an environmentally degradable polymeric blend |
| CN107556452A (en) * | 2017-09-15 | 2018-01-09 | 华南农业大学 | A kind of castor oil-base hydrophilic chain extender and its preparation method and application |
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| JP2004149718A (en) * | 2002-10-31 | 2004-05-27 | Inoac Corp | Moisture absorbent composition for polyurethane |
| WO2006071813A3 (en) * | 2004-12-23 | 2006-10-12 | Abraham J Domb | Disposable medical supplies from hydrolytically biodegradable plastics |
| AU2007218990A1 (en) * | 2006-02-24 | 2007-08-30 | Phb Industrial S.A. | Environmentally degradable polymeric blend and process for obtaining an environmentally degradable polymeric blend |
| CN107556452A (en) * | 2017-09-15 | 2018-01-09 | 华南农业大学 | A kind of castor oil-base hydrophilic chain extender and its preparation method and application |
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