CN109553767A - A kind of high molecular polymer and preparation method thereof and purposes - Google Patents
A kind of high molecular polymer and preparation method thereof and purposes Download PDFInfo
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Abstract
The invention discloses a kind of high molecular polymer and preparation method thereof and purposes, are made using castor oil, polyadipate fourth diester and diethylene glycol divinyl ether as reactant reaction, castor oil, polyadipate fourth diester and toluene are mixed, mixed solution A is obtained；Then mixed solution A, p-methyl benzenesulfonic acid and tetrahydrofuran mixing, form mixed solution B；Diethylene glycol divinyl ether will be added dropwise again and be added in mixed solution B and react, final conversion ratio of the invention reaches as high as 90% or more；High molecular polymer obtained can be used in preparation engineering plastics；In the preparation, high molecular polymer and dimercapto reagent, initiator azodiisobutyronitrile and tetrahydrofuran are stirred, are put into reaction in baking oven and obtain engineering plastics.It is very friendly to environment since acid degradation can occur for engineering plastics of the invention；Engineering plastics tensile strength and bending strength with higher under normal operation at the same time can meet the needs of actual production life.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of high molecular polymer and preparation method thereof
With purposes.
Background technique
Engineering plastics refer to the plastics that can be used as engineering material and replace metal manufacture element part etc..And general-purpose plastics
Compare, engineering plastics mechanical performance, durability, corrosion resistance, in terms of can reach higher requirement, and process
More convenient and alternative metal material.Engineering plastics are widely used in the industries such as electronics, machinery, machinery, aerospace, with modeling
Dai Gang, international popular trend is had become to mould Dai Mu.It is most fast that engineering plastics have become growth rate in world today's plastics industry
Field, development supporting role not only is played to national pillar industry and modern high technology industry, while also push tradition
The adjustment of industry alteration and product structure.Engineering plastics mainly include polycarbonate, polyamide, polyformaldehyde, polyphenylene oxide, polyester
With the kinds such as polyphenylene sulfide, but existing engineering plastics are mostly non-degradable material, therefore the engineering plastics after a large amount of uses
It can only be handled, can not be recycled by burning or burying, resource utilization is extremely low, while also resulting in not to environment
Small injury, so that the pollution such as atmosphere is more acute.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of high molecular polymer and its preparation side
Method and purposes, which can be used as engineering plastics use, while can degrade in acid condition, very to environment
It is friendly.
To achieve the above object, the present invention provides the following technical scheme that a kind of high molecular polymer, molecular structural formula
Are as follows:
As a further improvement of the present invention, the high molecular polymer is by castor oil, polyadipate fourth diester and two
Ethylene glycol divinyl ether reacts to obtain；
The structural formula of the castor oil is
The structural formula of the polyadipate fourth diester is
The structural formula of the diethylene glycol divinyl ether isIts reaction equation are as follows:
As a further improvement of the present invention, the number-average molecular weight of the polyadipate fourth diester is 1000-4000；It is described
The number-average molecular weight of high molecular polymer is 10000-20000.
As a further improvement of the present invention, a kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: castor oil, polyadipate fourth diester and the first solvent being put into reaction vessel A and are stirred mixing,
Mixed solution A is obtained after mixing；
Step 2: mixed solution A, catalyst obtained in step 1 and the second solvent are put into reaction vessel B and stirred
Mixing, obtains mixed solution B after mixing；
Step 3: diethylene glycol divinyl ether is added in mixed solution B and is reacted；After fully reacting, it will mix
It closes solution B and carries out rotary evaporation and cooling and solidifying, obtain high molecular polymer.
As a further improvement of the present invention, first solvent is toluene；Second solvent is tetrahydrofuran.
As a further improvement of the present invention, the catalyst is p-methyl benzenesulfonic acid.
As a further improvement of the present invention, diethylene glycol divinyl ether is added to the tool of mixed solution B in step 3
It is 0 DEG C that body mode, which is in temperature, under the conditions of mixing speed is 800-1000rad/min, with the rate of addition of every five seconds clock 2-3 drop
Diethylene glycol divinyl ether is added drop-wise in mixed solution B.
As a further improvement of the present invention, when diethylene glycol divinyl ether is completely added to mixed solution in step 3
After B, 15-25 DEG C is set by reaction temperature, mixing speed is set as 800-1000rad/min, reaction time 4-6h.
As a further improvement of the present invention, a kind of application of high molecular polymer, the high molecular polymer is for making
Standby engineering plastics, the preparation method of the engineering plastics are by high molecular polymer, dimercapto reagent, initiator and tetrahydrofuran
It is added in reaction vessel and is stirred, stir 10-20min under the revolving speed of 200-400rad/min, obtain mixed solution；Then
Mixed solution is put into the baking oven that temperature is 40-60 DEG C and reacts 1-2h；After fully reacting, by mixed solution rotary evaporation and cold
But solidify, obtain engineering plastics.
As a further improvement of the present invention, the dimercapto reagent is bis- (2- mercaptoethyl) ethers, 1,2- dithioglycol
With any one in Isosorbide-5-Nitrae-succinimide mercaptans；The initiator is azodiisobutyronitrile.
Beneficial effects of the present invention: by using castor oil, polyadipate fourth diester and diethylene glycol divinyl ether as
Reactant reaction is made, and wherein castor oil is a kind of natural organic substance, and raw material is easy to get and cost is relatively low；As its of the invention
In an innovative point, be exactly first to be pre-processed to castor oil and polyadipate fourth diester, i.e., by castor oil, polyadipate fourth two
Ester and toluene mixing, obtain mixed solution A；The purpose for the arrangement is that possible improve forward rate of the invention, because castor oil,
Polyadipate fourth diester can be uniform be dispersed in toluene solvant, if castor oil and polyadipate fourth diester are directly put into four
In hydrogen THF solvent, dispersibility is general, is unable to fully be reacted between reactant, and reaction can not complete enough, conversion ratio
It is lower；Then mixed solution A is mixed with catalyst p-methyl benzenesulfonic acid and tetrahydrofuran, forms mixed solution B；As of the invention
Solution temperature will be first reduced to by another innovative point when that diethylene glycol divinyl ether will be added dropwise and be added to mixed solution B
0 DEG C, while needing to be slowly added dropwise, rate of addition is every five seconds clock 2-3 drop, this and is produced in order to avoid excessively high because of local concentration
Raw more side reaction, affects product quality and conversion ratio of the invention；When diethylene glycol divinyl ether is completely added to
After mixed solution B, then solution temperature risen to 15-25 DEG C, preferable temperature is 20 DEG C, and the reaction time is 4-6 hours, and preferably 5 is small
When；Conversion ratio and product quality must further be improved；Temperature is 15-25 DEG C, very mildly, and is carried out under normal pressure, and work is suitble to
Industry is manufactured；Final conversion ratio of the invention reaches as high as 90% or more；The high molecular polymer prepared simultaneously has had
Certain tensile strength, bending strength and impact strength；High molecular polymer obtained can be used in preparation engineering plastics,
When preparation engineering plastics, first high molecular polymer and dimercapto reagent, initiator azodiisobutyronitrile and tetrahydrofuran are stirred
Mixing, wherein dimercapto reagent is any one in bis- (2- mercaptoethyl) ethers, 1,2- dithioglycol and Isosorbide-5-Nitrae-succinimide mercaptans,
It is preferred that bis- (2- mercaptoethyl) ethers；It is put into baking oven and reacts after mixing, reaction temperature is 40-60 DEG C, preferable temperature 50
DEG C, the reaction time is 1-2 hours；Then engineering plastics are obtained by purifying.During the reaction, pass through azodiisobutyronitrile
Initiation, the sulfydryl in dimercapto reagent made polymerize with the double bond phase reaction in high molecular polymer, form fine and close sky
Between reticular structure, further increase the tensile strength, bending strength and impact strength of product；So that obtaining product can make
For engineering plastics use, the engineering plastics under normal operation (pH 7) when tensile strength and bending strength with higher, energy
Enough meet the needs of actual production life；Simultaneously because introduce acetal bonds in engineering plastics of the invention so that acidity compared with
It will degrade when (pH is less than 5) when weak, it is very friendly to environment, improve the utilization rate of resource, therefore its application range
It is relatively wide.
Detailed description of the invention
Fig. 1 is the nmr spectrum of embodiment 1 in the present invention；
Fig. 2 is the infrared spectrogram of embodiment 1 in the present invention；
Fig. 3 is the gel chromatography spectrogram of embodiment 1 in the present invention；
Fig. 4 is the molecular structural formula of high molecular polymer of the invention；
Fig. 5 is the chemical equation that high molecular polymer is formed in the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is described in more detail.
High molecular polymer of the invention, molecular structural formula are
Embodiment 1
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g castor oil, 20g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing is mixed, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtain mixed solution A:
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.6g diethylene glycol divinyl base
Ether is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 20 DEG C, stirring
Speed is arranged to 1000rad/min, reacts 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then
Cooling and solidifying, obtains high molecular polymer.
Embodiment 2
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2g castor oil, 23g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtains mixed solution A；
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.5g diethylene glycol divinyl base
Ether is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 15 DEG C, stirring
Speed is arranged to 1000rad/min, reacts 6 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then
Cooling and solidifying, obtains high molecular polymer.
Embodiment 3
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 4g castor oil, 18g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtains mixed solution A；
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 2g diethylene glycol divinyl ether
It is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 25 DEG C, stirring speed
Degree is arranged to 1000rad/min, reacts 4 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then cold
But solidify, obtain high molecular polymer.
Comparative example 1
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g castor oil, 20g polyadipate fourth diester, 0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put
Enter and be stirred in reaction vessel B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.6g diethylene glycol divinyl base
Ether is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 20 DEG C, stirring
Speed is arranged to 1000rad/min, reacts 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then
Cooling and solidifying, obtains high molecular polymer.
Comparative example 2
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g castor oil, 20g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing is mixed, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtain mixed solution A:
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: 1.6g diethylene glycol divinyl ether is added in mixed solution B；It is 20 DEG C in reaction temperature, stirring
Under conditions of speed is 1000rad/min, react 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；
Then it cools and solidifies, obtains high molecular polymer.
Reaction equation of the invention are as follows:
High molecular polymer obtained in embodiment 1-3 and comparative example 1-2 is weighed, conversion ratio is then calculated；
| Sample | Reactant gross mass/g | Product quality/g | Yield/% |
| Embodiment 1 | 24.5 | 22.45 | 91.6 |
| Embodiment 2 | 26.5 | 22.92 | 86.5 |
| Embodiment 3 | 24 | 20.26 | 84.4 |
| Comparative example 1 | 24.5 | 17.41 | 71.06 |
| Comparative example 2 | 24.5 | 15.74 | 64.2 |
Nuclear magnetic resonance test is carried out to high molecular polymer made from embodiment 1, to obtain nuclear magnetic resonance spectroscopy (figure
1)；
High molecular polymer made from embodiment 1 is detected with infrared spectrometer, to obtain infrared spectrogram (figure
2)；
High molecular polymer is made to embodiment 1 and carries out gel chromatography test, to obtain gel chromatography figure (Fig. 3).By
Known to Fig. 1:1H NMR (500MHz, CDCl3) wherein chemical shift be ethylidene ether structure at 4.094, which has acid degradation special
Property.
As shown in Figure 2, in 1132.5cm-1There is a strong absworption peak at place, hence it is evident that is ethylidene ether structure C-O-C absorption peak.It can by Fig. 3
Know that test result is Mn=13930, Mw=36894, PDI=2.648
Fig. 1 Fig. 2 Fig. 3, which is combined, demonstrates the successful synthesis of high molecular polymer obtained by embodiment 1.The structure of the substance
Formula are as follows:
Embodiment 4
A kind of preparation method of engineering plastics: by bis- (2- mercaptoethyl) ethers of 20g high molecular polymer, 3.6g, 1g azo
Bis-isobutyronitrile and 20ml tetrahydrofuran, which are added in reaction vessel, to be stirred, and is stirred 15min under the revolving speed of 300rad/min, is obtained
To mixed solution；Then mixed solution is put into the baking oven that temperature is 50 DEG C and reacts 1.5h；After fully reacting, by mixed solution
Rotary evaporation and cooling and solidifying, obtain engineering plastics.
Wherein high molecular polymer is made by embodiment 1.
Embodiment 5
A kind of preparation method of engineering plastics: by 20g high molecular polymer, 3.6g1,2- dithioglycol, 1g azo two are different
Butyronitrile and 20ml tetrahydrofuran, which are added in reaction vessel, to be stirred, and is stirred 15min under the revolving speed of 300rad/min, is mixed
Close solution；Then mixed solution is put into the baking oven that temperature is 50 DEG C and reacts 1.5h；After fully reacting, mixed solution is rotated
Evaporation and cooling and solidifying, obtain engineering plastics.
Wherein high molecular polymer is made by embodiment 1.
Embodiment 6
A kind of preparation method of engineering plastics: by 20g high molecular polymer, 3.6g1,4- succinimide mercaptans, 1g azo two are different
Butyronitrile and 20ml tetrahydrofuran, which are added in reaction vessel, to be stirred, and is stirred 15min under the revolving speed of 300rad/min, is mixed
Close solution；Then mixed solution is put into the baking oven that temperature is 50 DEG C and reacts 1.5h；After fully reacting, mixed solution is rotated
Evaporation and cooling and solidifying, obtain engineering plastics.
Wherein high molecular polymer is made by embodiment 1.
Comparative example 3
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g glycerine, 20g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing is mixed, at 160 DEG C, revolving speed stirs 15min under conditions of being 500tad/min, obtains mixed solution A；
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.6g diethylene glycol divinyl base
Ether is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 20 DEG C, stirring
Speed is arranged to 1000rad/min, reacts 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then
Cooling and solidifying, obtains high molecular polymer.
Bis- (2- mercaptoethyl) ethers of 20g high molecular polymer, 3.6g, 1g azodiisobutyronitrile and 20ml tetrahydrofuran are added
Enter in reaction vessel and be stirred, stirs 15min under the revolving speed of 300rad/min, obtain mixed solution；Then it will mix molten
Liquid, which is put into the baking oven that temperature is 50 DEG C, reacts 1.5h；After fully reacting, mixed solution rotary evaporation and cooling and solidifying obtain
Engineering plastics.
Comparative example 4
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g xylitol, 20g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing is mixed, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtains mixed solution A；
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.6g diethylene glycol divinyl base
Ether is added drop-wise in mixed solution B with the rate of addition that every five seconds clock 3 drips；After completion of dropwise addition, reaction temperature is risen to 20 DEG C, stirring
Speed is arranged to 1000rad/min, reacts 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then
Cooling and solidifying, obtains high molecular polymer.
Bis- (2- mercaptoethyl) ethers of 20g high molecular polymer, 3.6g, 1g azodiisobutyronitrile and 20ml tetrahydrofuran are added
Enter in reaction vessel and be stirred, stirs 15min under the revolving speed of 300rad/min, obtain mixed solution；Then it will mix molten
Liquid, which is put into the baking oven that temperature is 50 DEG C, reacts 1.5h；After fully reacting, mixed solution rotary evaporation and cooling and solidifying obtain
Engineering plastics.
Comparative example 5
A kind of preparation method of high molecular polymer, comprising the following steps:
Step 1: 2.9g castor oil, 20g polyadipate fourth diester and 20ml toluene are sequentially placed into reaction vessel A and are stirred
Mixing is mixed, at 160 DEG C, revolving speed stirs 15min under conditions of being 500rad/min, obtains mixed solution A；
Step 2: mixed solution A made from step 1,0.1g p-methyl benzenesulfonic acid and 50ml tetrahydrofuran are put into reaction and held
It is stirred in device B, at 80 DEG C, revolving speed stirs 20min under conditions of being 300rad/min, obtains mixed solution B；
Step 3: being 0 DEG C in temperature, under the conditions of mixing speed is 900rad/min, by 1.6g1,4 butanediol vinethenes with
The rate of addition that every five seconds clock 3 drips is added drop-wise in mixed solution B；After completion of dropwise addition, reaction temperature is risen to 20 DEG C, mixing speed
It is arranged to 1000rad/min, reacts 5 hours；After fully reacting, by mixed solution B rotary evaporation, solvent is removed；Then it cools down
Solidification, obtains high molecular polymer.
Bis- (2- mercaptoethyl) ethers of 20g high molecular polymer, 3.6g, 1g azodiisobutyronitrile and 20ml tetrahydrofuran are added
Enter in reaction vessel and be stirred, stirs 15min under the revolving speed of 300rad/min, obtain mixed solution；Then it will mix molten
Liquid, which is put into the baking oven that temperature is 50 DEG C, reacts 1.5h；After fully reacting, mixed solution rotary evaporation and cooling and solidifying obtain
Engineering plastics.
Sample made from embodiment 4-6 and comparative example 3-5 is subjected to Mechanics Performance Testing
From above-mentioned chart: sample made from embodiment 4 to 6 has biggish tensile strength, bending strength and impact
Intensity can be used as engineering plastics use；And tensile strength, bending strength and the impact strength of sample made from embodiment 3 to 5
It is all smaller, it can not be used as engineering plastics.
Sample made from embodiment 4-6 and comparative example 3-5 is put into the phosphate buffer solution of the 0.2mol/L of pH=7.0
In (PBS solution), after placing 24 hours, then Mechanics Performance Testing is carried out
As upper table it is found that sample made from embodiment 4-6 in normal circumstances (pH=7) place it is longer when after, group
It is smaller to beat up tensile strength, bending strength and impact strength variation, still can be used as engineering plastics use, it is non-degradable.
Sample made from 100g embodiment 4-6 is put into the phosphate buffer solution of the 0.2mol/L of pH=4.6, and (PBS is molten
Liquid) in, sample is taken out at regular intervals, constant mass is dried under vacuum under the conditions of 40 DEG C/1kPa, calculates sample mass damage
Mistake rate；
| Sample | After 5 days | After 10 days | After 20 days |
| Embodiment 4 | 5% | 20% | 50% |
| Embodiment 5 | 6% | 25% | 55% |
| Embodiment 6 | 8% | 30% | 60% |
| Comparative example 3 | 5% | 21% | 51% |
| Comparative example 4 | 6% | 26% | 57% |
| Comparative example 5 | 5% | 19% | 47% |
By above-mentioned chart it is found that after 20 days, engineering plastics made from embodiment 4-6 are sent out under conditions of pH is 4.6
Degradation is given birth to, and degradation rate is larger, 50% or more can be reached.
100g polyadipate fourth diester is put into the phosphate buffer solution (PBS solution) of the 0.2mol/L of pH=4.6,
Sample is taken out at regular intervals, constant mass is dried under vacuum under the conditions of 40 DEG C/1kPa, calculates polyadipate fourth diester matter
Amount loss rate；
| After 5 days | After 10 days | After 20 days | |
| Polyadipate fourth diester | 0.05% | 0.1% | 0.3% |
By above-mentioned chart it is found that after 20 days, there is no variations substantially for the quality of polyadipate fourth diester, therefore can
Think that polyadipate fourth diester is difficult to happen degradation under conditions of pH is 4.6；Because of the ester group in polyadipate fourth diester
It is very stable under conditions of pH is 4.6, it is difficult to be broken；And due to introducing acetal in engineering plastics produced by the present invention
Key, so that acetal bonds are broken, and corresponding aldehyde and alcohol, therefore engineering plastics are generated under conditions of pH is 4.6
It is easy to be degraded.More further the study found that the present invention be made engineering plastics be easy for dropping under conditions of pH is less than 5
Solution, (i.e. acetal bonds fracture)；And polyadipate fourth diester needs just start to degrade under conditions of pH is less than 2, but degradation rate according to
So less than 20%.
A kind of high molecular polymer of the invention and preparation method thereof and purposes, by with castor oil, polyadipate fourth two
Ester and diethylene glycol divinyl ether are made as reactant reaction, and wherein castor oil is a kind of natural organic substance, and raw material is easy
It obtains and cost is relatively low；It is exactly first to be carried out in advance to castor oil and polyadipate fourth diester as one of innovative point of the invention
Castor oil, polyadipate fourth diester and toluene are mixed, obtain mixed solution A by processing；The purpose for the arrangement is that possible mention
High forward rate of the invention because castor oil, polyadipate fourth diester can be uniform be dispersed in toluene solvant, if directly general
Castor oil and polyadipate fourth diester are put into tetrahydrofuran solvent, and dispersibility is general, are unable to fully carry out between reactant
Reaction, reaction can be not complete enough, and conversion ratio is relatively low；Then mixed solution A and catalyst p-methyl benzenesulfonic acid and tetrahydrofuran are mixed
It closes, forms mixed solution B；As another innovative point of the invention, will be added dropwise diethylene glycol divinyl ether be added to it is mixed
When closing solution B, solution temperature is first reduced to 0 DEG C, while needing to be slowly added dropwise, rate of addition is every five seconds clock 2-3 drop, this
It is to affect product quality and conversion ratio of the invention in order to avoid and generating more side reaction because local concentration is excessively high；
15-25 DEG C is risen to after diethylene glycol divinyl ether is completely added to mixed solution B, then by solution temperature, preferable temperature is
20 DEG C, the reaction time is 4-6 hours, preferably 5 hours；Conversion ratio and product quality must further be improved；Temperature is 15-25 DEG C,
It is very mild, and carry out under normal pressure, it is suitble to industrial production and manufacturing；Final conversion ratio of the invention reaches as high as 90% or more；
The high molecular polymer prepared simultaneously has had certain tensile strength, bending strength and impact strength；High score obtained
Sub- polymer can be used in preparation engineering plastics, in preparation engineering plastics, first by high molecular polymer and dimercapto reagent, draw
Hair agent azodiisobutyronitrile and tetrahydrofuran are stirred, and wherein dimercapto reagent is bis- (2- mercaptoethyl) ethers, 1,2- second two
Any one in mercaptan and Isosorbide-5-Nitrae-succinimide mercaptans, preferably bis- (2- mercaptoethyl) ethers；It is put into baking oven and reacts after mixing,
Reaction temperature is 40-60 DEG C, and preferable temperature is 50 DEG C, and the reaction time is 1-2 hours；Then engineering plastics are obtained by purifying.
During the reaction, by the initiation of azodiisobutyronitrile, the sulfydryl and high molecular polymer in dimercapto reagent that make
In double bond phase reaction polymerization, form fine and close space net structure, further increase the tensile strength of product, bending strength and
Impact strength；So that obtain product can be used as engineering plastics use, the engineering plastics under normal operation (pH 7) when
Tensile strength and bending strength with higher can meet the needs of actual production life；Simultaneously because engineering of the invention
Acetal bonds are introduced in plastics, so that will degrade when (pH is less than 5) when acid weaker, it is very friendly to environment, it mentions
The high utilization rate of resource, therefore its application range is wider.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of high molecular polymer, it is characterised in that: its molecular structural formula are as follows:
2. a kind of high molecular polymer according to claim 1, it is characterised in that: the high molecular polymer is by castor-oil plant
Oil, polyadipate fourth diester and diethylene glycol divinyl ether react to obtain；
The structural formula of the castor oil is
The structural formula of the polyadipate fourth diester is
The structural formula of the diethylene glycol divinyl ether is
Its reaction equation are as follows:
3. a kind of high molecular polymer according to claim 2, it is characterised in that: the number of the polyadipate fourth diester is equal
Molecular weight is 1000-4000；The number-average molecular weight of the high molecular polymer is 10000-20000.
4. according to claim 1 to a kind of preparation method of high molecular polymer described in 3 any one, it is characterised in that: packet
Include following steps:
Step 1: castor oil, polyadipate fourth diester and the first solvent being put into reaction vessel A and are stirred mixing, mixing
Mixed solution A is obtained after uniformly；
Step 2: mixed solution A, catalyst obtained in step 1 and the second solvent being put into reaction vessel B and are stirred,
Mixed solution B is obtained after mixing；
Step 3: diethylene glycol divinyl ether is added in mixed solution B and is reacted；After fully reacting, it will mix molten
Liquid B carries out rotary evaporation and cooling and solidifying, obtains high molecular polymer.
5. a kind of preparation method of high molecular polymer according to claim 4, it is characterised in that: first solvent is
Toluene；Second solvent is tetrahydrofuran.
6. a kind of preparation method of high molecular polymer according to claim 4, it is characterised in that: the catalyst is pair
Toluenesulfonic acid.
7. a kind of preparation method of high molecular polymer according to claim 4, it is characterised in that: diethyl two in step 3
Alcohol divinyl ether be added to mixed solution B concrete mode be in temperature be 0 DEG C, mixing speed 800-1000rad/min
Under the conditions of, diethylene glycol divinyl ether is added drop-wise in mixed solution B with the rate of addition of every five seconds clock 2-3 drop.
8. a kind of preparation method of high molecular polymer according to claim 7, it is characterised in that: work as diethyl in step 3
After divinyl ether is completely added to mixed solution B, 15-25 DEG C is set by reaction temperature, mixing speed is set as
800-1000rad/min, reaction time 4-6h.
9. according to claim 1 to a kind of method of high molecular polymer preparation engineering plastics described in 8 any one, feature
It is: high molecular polymer, dimercapto reagent, initiator and tetrahydrofuran is added in reaction vessel and are stirred, in 200-
10-20min is stirred under the revolving speed of 400rad/min, obtains mixed solution；Then mixed solution is put into temperature is 40-60 DEG C
1-2h is reacted in baking oven；After fully reacting, by mixed solution rotary evaporation and cooling and solidifying, engineering plastics are obtained.
10. a kind of method of high molecular polymer preparation engineering plastics according to claim 9, it is characterised in that: described
Dimercapto reagent is any one in bis- (2- mercaptoethyl) ethers, 1,2- dithioglycol and Isosorbide-5-Nitrae-succinimide mercaptans；The initiation
Agent is azodiisobutyronitrile.
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| JP2004149718A (en) * | 2002-10-31 | 2004-05-27 | Inoac Corp | Moisture absorbent composition for polyurethane |
| WO2006071813A2 (en) * | 2004-12-23 | 2006-07-06 | Massachusetts Institute Of Technology | Disposable medical supplies from hydrolytically biodegradable plastics |
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