CN113683731A - Method for effectively improving grafting rate of MAH in compatilizer based on DES system - Google Patents
Method for effectively improving grafting rate of MAH in compatilizer based on DES system Download PDFInfo
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Abstract
The invention discloses a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system, which comprises the following steps: s1: dissolving choline chloride in ethylene glycol, heating, cooling the mixed solution to room temperature, and standing for 20-28h to obtain a uniform DES solvent; s2: and placing the MAH at the bottom of the spray reactor, heating the MAH to sublimate the MAH to rise to the middle of the spray reactor, adding a DES solvent at the top end of the spray reactor to enable the MAH to fall in a mist form at the top end of the spray reactor, fully and uniformly mixing the MAH gas with the middle of the spray reactor, and returning to the top end to continue reacting to obtain a DES-MAH initial product. And putting the obtained DES-MAH initial product into a three-neck flask, heating, condensing and refluxing to obtain a DES-MAH final product. S3: and (3) mixing the DES-MAH obtained in the step (S2) with polyethylene, adding an initiator, uniformly mixing by using a mixer, performing melt extrusion by using a double-screw extruder, and performing wire drawing, air drying and grain cutting to obtain the compatilizer. The grafting rate of MAH in the invention is improved by about 31.4%.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system.
Background
The adhesive resin is widely used in industry because of its low price, environmental protection and low requirement for equipment. At present, MAH is mostly selected as a polar monomer grafted polyolefin synthetic compatilizer in industry to prepare adhesive resin. However, MAH is very volatile during melt extrusion and the grafting rate of MAH in most compatibilizers in the industry is less than 1%. Therefore, increasing the grafting ratio of MAH in the compatibilizer is an urgent need in the industry.
At present, methods for improving the grafting rate of the compatilizer mainly comprise: the Chinese patent with publication number CN105037635A adds a second monomer in the raw material to improve the utilization efficiency of MAH, thereby improving the grafting rate of the compatilizer; the Chinese patent with publication number CN103436193B utilizes the electron-donating effect, introduces an electron donor to reduce the gel content in the melting process, thereby achieving the purpose of improving the grafting rate of the compatilizer. However, these methods only increase the MAH-graft ratio by about 10% compared to the conventional MAH-grafted polyolefin.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system. The method is green and environment-friendly, has low cost, and can overcome the problems of easy sublimation and low grafting rate of MAH in the existing compatilizer.
The invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system, which comprises the following steps:
s1: preparation of DES solvents
Dissolving choline chloride in ethylene glycol, heating, cooling the mixed solution to room temperature, and standing for 20-28h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
And (2) placing the MAH at the bottom of a spray reactor, heating the MAH to sublimate and raise the MAH to the middle of the reactor, adding the DES solvent obtained in the step S1 to the top of the spray reactor, enabling the mixture to fall in a mist form at the top of the reactor, fully and uniformly mixing the MAH gas with the MAH gas in the middle of the reactor, returning to the top to continue reacting, continuing reacting for 2-3h to obtain an initial product of DES-MAH, placing the obtained initial product of DES-MAH into a three-mouth flask, heating, condensing and refluxing to obtain a final product of DES-MAH.
S3: preparation of the compatibilising agent
And (3) mixing the DES-MAH obtained in the step (S2) with polyethylene, adding an initiator, uniformly mixing by using a mixer, performing melt extrusion by using a double-screw extruder, and performing wire drawing, air drying and grain cutting to obtain the compatilizer.
Preferably, the mole ratio of the ethylene glycol to the choline chloride in the S1 is 1-3: 1.
Preferably, the heating condition in S1 is 50-85 ℃, and the heating time is 10-30 min.
Preferably, the mass ratio of DES to MAH in S2 is 0.3-3: 1.
Preferably, the temperature of the MAH heated at the bottom of the spray reactor in S2 is 120-180 ℃.
Preferably, the flow rate of DES solvent at the top of the spray reactor in S2 is 2-5m3H; the pressure of a nozzle at the top of the spray reactor is 5-20 MPa.
Preferably, the temperature of the condensation reflux in the S2 is 55-90 ℃ and the time is 3-4 h.
Preferably, the mass ratio of DES-MAH, polyethylene and initiator in S3 is 1:90-110: 0.04-0.06.
Preferably, the working conditions of the twin-screw extruder in S3 are as follows: the temperature is 180 ℃ and 200 ℃, and the rotating speed is 250 ℃ and 350 r/min.
The compatilizer prepared by the method is provided by the invention.
Mechanism of action
The main causes of gel generation:
DES solvent mechanism of action:
advantageous technical effects
(1) The DES-MAH preparation process uses a spray reactor in combination with a condensing reflux. In order to enable the MAH to be sublimated and volatilized in a large amount, the middle part of the reactor is fully and uniformly mixed with the vaporous DES solvent, and the bottom of the spray reactor is heated to 120-180 ℃. And then the DES and the MAH are mixed more fully by condensing and refluxing for 3 to 4 hours at the temperature of between 55 and 90 ℃, and the volatilization of the MAH in the process is avoided.
(2) The reason why the DES-MAH is selected as the polar grafting monomer for the compatilizer is that the DES solution has higher viscosity and can be coated when being compounded with the MAH, so that the DES-MAH cannot be volatilized in a large amount when being melted and extruded in a double-screw extruder, the utilization efficiency of the MAH is improved, and the aim of increasing the grafting rate is fulfilled.
(3) In addition, because the DES system has a very strong electron-donating effect, a large amount of electron donors in the melting reaction process can stop the reaction of macromolecular free radicals before the reaction, so that the crosslinking phenomenon of the MAH in the reaction process can be inhibited, and the grafting rate is improved.
Drawings
Fig. 1 is an IR diagram of (a) a pure DES sample, (b) a pure MAH sample, (c) DES: MAH ═ 1:3 sample, (d) DES: MAH ═ 1:1 sample, (e) DES: MAH ═ 3:1 sample, proposed by the present invention;
FIG. 2 is a schematic structural view of a spray reactor according to the present invention;
FIG. 3 is a schematic diagram of the hydrogen bond ball-stick model formed by (a) pure MAH, (b) pure choline chloride, (c) pure ethylene glycol, and (d) DES and MAH.
In the figure: 1-DES solvent storage tank, 2-pressure type nozzle, 3-MAH heating plate, 4-valve, 5-delivery pump.
Detailed Description
The raw materials in the examples of the invention are all commercially available; the twin-screw extruder was model TSE-20/600-5.5-48 (Nanjing Ruia extrusion machinery manufacturing Co., Ltd.); the initiator is di-tert-butylperoxydiisopropylbenzene (BIBP).
Example 1
The invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system, which comprises the following steps:
s1: preparation of DES solvents
Weighing a certain amount of ethylene glycol in a round-bottom flask, adding choline chloride into the round-bottom flask, putting the round-bottom flask on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 1:1, the heating temperature is 50 ℃, the heating time is 10min, cooling the mixed solution to room temperature, and standing for 20h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
33g of MAH was weighed out and placed at the bottom of the spray reactor, and heated at 120 ℃ to sublime the MAH up to the middle of the reactor, and 100g of DES solvent from S1 was added to the top of the spray reactor at a pressure of 5MPa and a flow rate of 2m3And/h, the mixture falls in a mist form at the top end of the reactor, is fully and uniformly mixed with MAH gas in the middle of the reactor, returns to the top end to continue to react, and continues to react for 2h to obtain an initial product of DES-MAH, and the obtained initial product of DES-MAH is put into a three-neck flask, heated to 55 ℃ and subjected to condensation reflux for 3h to obtain a final product of DES-MAH.
S3: preparation of the compatibilising agent
And (2) mixing 10g of DES-MAH obtained in S2 with 900g of polyethylene, adding 0.4g of initiator, uniformly mixing by using a mixer, pouring the mixed material into a double-screw extruder with the temperature set to 180 ℃ and the rotating speed set to 250r/min, and carrying out wire drawing, air drying and grain cutting to obtain the compatilizer with high grafting rate.
Example 2
The invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system, which comprises the following steps:
s1: preparation of DES solvents
Weighing a certain amount of ethylene glycol in a round-bottom flask, adding choline chloride into the round-bottom flask, putting the round-bottom flask on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 2:1, the heating temperature is 70 ℃, the heating time is 20min, cooling the mixed solution to room temperature, and standing for 24h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
100g of MAH was weighed out and placed at the bottom of the spray reactor, and heated at 150 ℃ to sublime the MAH up to the middle of the reactor, and 100g of DES solvent from S1 was added to the top of the spray reactor at a pressure of 10MPa and a flow rate of 3m3And/h, the mixture falls in a mist form at the top end of the reactor, is fully and uniformly mixed with MAH gas in the middle of the reactor, returns to the top end to continue to react, and continues to react for 2 hours to obtain an initial product of DES-MAH, and the obtained initial product of DES-MAH is put into a three-neck flask, heated to 70 ℃ and subjected to condensation reflux for 3 hours to obtain a final product of DES-MAH.
S3: preparation of the compatibilising agent
And (2) mixing 10g of DES-MAH obtained in S2 with 1000g of polyethylene, adding 0.5g of initiator, uniformly mixing by using a mixer, pouring the mixed material into a double-screw extruder with the temperature set to 190 ℃ and the rotating speed set to 300r/min, and carrying out wire drawing, air drying and grain cutting to obtain the compatilizer with high grafting rate.
Example 3
The invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system, which comprises the following steps:
s1: preparation of DES solvents
Weighing a certain amount of ethylene glycol in a round-bottom flask, adding choline chloride into the round-bottom flask, putting the round-bottom flask on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 3:1, the heating temperature is 85 ℃, the heating time is 30min, cooling the mixed solution to room temperature, and standing for 28h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
Weighing 300g of MAH, placing at the bottom of a spray reactor, heating at 180 deg.C to sublimate MAH, adding 100g of DES solvent obtained in S1 at the top of the spray reactor, and allowing to flow at 5m under 20MPa3The mixture falls in the form of fog at the top end of the reactor, is fully and uniformly mixed with MAH gas in the middle of the reactor, and is heavyAnd (3) returning to the top end again to continue the reaction, continuing the reaction for 3 hours to obtain an initial product of DES-MAH, putting the obtained initial product of DES-MAH into a three-neck flask, heating to 90 ℃, and carrying out condensation reflux for 4 hours to obtain a final product of DES-MAH.
S3: preparation of the compatibilising agent
And (2) mixing 10g of DES-MAH obtained in S2 with 1100g of polyethylene, adding 0.6g of initiator, uniformly mixing by using a mixer, pouring the mixed material into a double-screw extruder with the temperature set to be 200 ℃ and the rotating speed set to be 350r/min, and carrying out wire drawing, air drying and grain cutting to obtain the compatilizer with high grafting rate.
Comparative example
A preparation method of a DES-solvent-free compatilizer comprises the following steps:
s1: weighing 10g of MAH and 0.5g of initiator in a beaker, adding a small amount of acetone solution, continuously stirring, and standing for 1h after the MAH in the beaker is completely dissolved.
S2: slowly pouring the mixed solution into 1kg of polyethylene, uniformly mixing by a high-speed mixer, pouring the mixed material into a double-screw extruder with the temperature set to 190 ℃ and the rotating speed set to 300r/min, and carrying out wire drawing, air drying and grain cutting to obtain the compatilizer.
The grafting ratios of the adhesive resins prepared in examples 1 to 3 and comparative example were measured by an acid-base titration method, which specifically comprises the following steps: 1.0 part of the compatibilizer was weighed in an analytical balance, placed in a 250mL three-necked flask, 100mL of xylene was added to the flask, clamped with a test tube, placed in a constant temperature oil bath, and opened to reflux. Starting an oil bath for heating, raising the temperature to about 150 ℃, heating for 2 hours, and stopping heating after the graft in the three-neck flask is completely dissolved. And then the three-neck flask is removed from the oil bath, is naturally cooled to about 70 ℃, and is quickly poured into a large beaker filled with 150mL of acetone, so that the product is precipitated. Vacuum filtering the graft; the column was washed with 150mL of acetone, and the upper solid sample was collected by suction filtration. The samples were transferred to glassware and dried in an oven at 80-100 ℃ for 1 h. And (3) drying the purified graft in an oven at 100 ℃ for 1h, and taking out.
Accurately weighing 0.5g (to 0.001g)The purified sample, designated M, was placed in an erlenmeyer flask containing 100mL of xylene and allowed to reflux by condensation for 1.5 h. The conical flask is taken out of the oil bath, cooled for 5min (about 70 ℃), added with 10mL potassium hydroxide-ethanol solution accurately measured by a pipette, heated and refluxed for 15min, taken off the conical flask, added with 3 drops of phenolphthalein indicator, titrated by prepared acetic acid-xylene solution to change the color of the solution from red to white, and the volume V of the acid consumed is recorded1. Weighing blank sample according to the same steps, and titrating the acid volume V consumed by the blank sample0。
In the formula: g-grafting ratio (G MAH/100G graft); v0-volume of acetic acid-xylene solution consumed in titration of the blank, mL; v1Volume of acetic acid-xylene solution consumed at the time of sample titration after purification, mL; c-concentration of acetic acid-xylene solution, mol/L.
The results are shown in Table 1.
TABLE 1 measurement results of graft ratio of adhesive resin
| Group of | DES:MAH | Percent of grafting% | Rate of increase/%) |
| Example 1 | 3:1 | 0.88 | 25.7 |
| Example 2 | 1:1 | 0.92 | 31.4 |
| Example 3 | 1:3 | 0.82 | 17.1 |
| Comparative example | No DES | 0.70 | / |
As can be seen from table 1, the graft ratio of the adhesive resin obtained by the method of the present application was improved by 17.1% or more, and when DES: MAH was 1:1, the growth rate was as high as 31.4%, as compared to the adhesive resin without DES.
In order to prove the mechanism of improving the grafting rate, infrared spectrum measurement is carried out on each sample, the result is shown in figure 1, and 3320cm appears in the infrared spectrum-1Nearby hydroxyl characteristic absorption peak, and obvious 1720cm appeared in infrared spectrum after adding MAH-1Nearby characteristic absorption peaks for MAH. Characteristic absorption peak with pure MAH 1790cm-1Compared with DES-MAH, the characteristic absorption peak of DES-MAH is obviously shifted, and the characteristic peak of hydroxyl is also shifted, which indicates that a new chemical bond is generated between MAH and DES, the bonding between the MAH and DES is tighter, and MAH is more difficult to sublimate during melting reaction.
FIG. 2 is a schematic view of the DES-MAH preparation equipment structure, the DES solvent is sprayed and pressed into a mist water drop in a storage tank through a pressure type nozzle, the MAH is sublimated and volatilized at high temperature on a heating plate, and is pressed into the DES storage tank again through a water pump after fully reacting with the mist DES, and the DES-MAH is sprayed and pressed again for reaction. After reacting for 2-3h, stopping heating, closing the water pump, opening the valve, and collecting the DES-MAH primary product.
Fig. 3 is a schematic view of a ball stick model, and it can be seen from (d) of fig. 3 that hydrogen bonds are formed between H of choline chloride and Cl, hydrogen bonds are formed between H of ethylene glycol and Cl of choline chloride, and hydrogen bonds are formed between O of maleic anhydride and Cl of choline chloride, so that it can be shown that mixing between DES and MAH is not only simple physical mixing, but also is connected through hydrogen bonds, and thus MAH and DES solvents are combined, and sublimation of themselves in a melt grafting process is greatly reduced.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for effectively improving the grafting rate of MAH in the compatilizer based on the DES system is characterized by comprising the following steps:
s1: preparation of DES solvents
Dissolving choline chloride in ethylene glycol, heating, cooling the mixed solution to room temperature, and standing for 20-28h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
The MAH was placed at the bottom of the spray reactor and heated to sublime the MAH up to the middle of the reactor, and the DES solvent from S1 was added at the top of the spray reactor to drop in mist form at the top of the reactor. And after fully and uniformly mixing the mixture with the MAH gas in the middle of the reactor, returning to the top end for continuous reaction, and continuously reacting for 2-3h to obtain a DES-MAH initial product. And putting the obtained DES-MAH initial product into a three-neck flask, heating, condensing and refluxing to obtain a DES-MAH final product.
S3: preparation of the compatibilising agent
And (3) mixing the DES-MAH obtained in the step (S2) with polyethylene, adding an initiator, uniformly mixing by using a mixer, performing melt extrusion by using a double-screw extruder, and performing wire drawing, air drying and grain cutting to obtain the compatilizer.
2. The method for effectively increasing the grafting rate of MAH in the compatilizer according to claim 1, wherein the molar ratio of ethylene glycol to choline chloride in S1 is 1-3: 1.
3. The method for effectively increasing the grafting rate of MAH in the compatilizer based on DES system as claimed in claim 1, wherein the heating in S1 is performed under the condition of 50-85 ℃ for 10-30 min.
4. The method for effectively improving the grafting rate of MAH in the compatilizer based on the DES system as claimed in claim 1, wherein the mass ratio of DES to MAH in S2 is 0.3-3: 1.
5. The method for effectively increasing the grafting rate of MAH in the compatilizer according to the DES system as claimed in claim 1, wherein the temperature for heating MAH at the bottom of the spray reactor in S2 is 120-180 ℃.
6. The method for effectively increasing the grafting rate of MAH in compatilizer based on DES system as claimed in claim 1, wherein the flow rate of DES solvent at the top of the spray reactor in S2 is 2-5m3H; the pressure of a nozzle at the top of the spray reactor is 5-20 MPa.
7. The method for effectively increasing the grafting rate of MAH in the compatilizer based on DES system as claimed in claim 1, wherein the temperature of the condensing reflux in S2 is 55-90 ℃ for 3-4 h.
8. The method for effectively improving the grafting rate of MAH in the compatilizer based on DES system as claimed in claim 1, wherein the mass ratio of DES-MAH, polyethylene and initiator in S3 is 1:90-110: 0.04-0.06.
9. The method for effectively increasing the grafting rate of MAH in the compatilizer based on DES system as claimed in claim 1, wherein the working conditions of the twin-screw extruder in S3 are as follows: the temperature is 180 ℃ and 200 ℃, and the rotating speed is 250 ℃ and 350 r/min.
10. A compatibilizer made by the process of any of claims 1-9.
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