CN113683731B - Method for effectively improving MAH grafting rate in compatilizer based on DES system - Google Patents
Method for effectively improving MAH grafting rate in compatilizer based on DES system Download PDFInfo
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Abstract
The invention discloses a method for effectively improving MAH grafting rate in a compatilizer based on a DES system, which comprises the following steps: s1: dissolving choline chloride in glycol, heating, cooling the mixed solution to room temperature, and standing for 20-28h to obtain a uniform DES solvent; s2: and (3) placing the MAH at the bottom of a spray reactor, heating the MAH to sublimate and rise the MAH to the middle of the reactor, adding a DES solvent at the top end of the spray reactor to enable the DES solvent to drop in a mist form at the top end of the reactor, fully and uniformly mixing the MAH gas in the middle of the reactor, and returning to the top end again to continuously react to obtain the initial product of the DES-MAH. And (3) placing the obtained initial product of the DES-MAH into a three-neck flask, and heating, condensing and refluxing to obtain the final product of the DES-MAH. S3: mixing the DES-MAH obtained in the step S2 with polyethylene, adding an initiator, uniformly mixing by a mixer, performing melt extrusion by a double-screw extruder, and performing wiredrawing, air drying and granulating 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 low cost and environmental protection and low requirement on equipment. Currently, MAH is mostly selected as a polar monomer grafted polyolefin synthetic compatibilizer in industry so as to prepare the adhesive resin. However, MAH is extremely volatile during melt extrusion and the grafting rate of MAH in large industrial multi-phase compatibilizers is less than 1%. Therefore, increasing the grafting rate of MAH in compatibilizers is an urgent need in the current industry.
At present, the method for improving the grafting rate of the compatilizer mainly comprises the following steps: the Chinese patent with publication number of CN105037635A adds a second monomer into the raw material to improve the utilization efficiency of MAH, thereby improving the grafting rate of the compatilizer; the Chinese patent with publication number of CN103436193B utilizes electron donating effect, and introduces electron donor to reduce gel content in melting process, thereby achieving the purpose of improving grafting rate of 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 technology, the invention provides a method for effectively improving the grafting rate of MAH in a compatilizer based on a DES system. The method is environment-friendly and low in cost, and can overcome the problems that MAH in the existing compatilizer is easy to sublimate and the grafting rate is low.
The method for effectively improving the MAH grafting rate in the compatilizer based on the DES system comprises the following steps:
s1: preparation of DES solvent
Dissolving choline chloride in 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
Placing MAH at the bottom of a spray reactor, heating the MAH to sublimate and rise the MAH to the middle of the reactor, adding the DES solvent obtained by S1 at the top end of the spray reactor to enable the DES solvent to drop in a mist shape at the top end of the reactor, fully and uniformly mixing the MAH gas in the middle of the reactor, returning to the top end to continue the reaction after fully mixing the MAH gas with the MAH gas, continuing the reaction for 2-3h to obtain an initial product of the DES-MAH, placing the initial product of the DES-MAH into a three-neck flask, heating, condensing and refluxing to obtain a final product of the DES-MAH.
S3: preparation of compatibilizing agents
Mixing the DES-MAH obtained in the step S2 with polyethylene, adding an initiator, uniformly mixing by a mixer, performing melt extrusion by a double-screw extruder, and performing wiredrawing, air drying and granulating to obtain the compatilizer.
Preferably, the molar ratio of the glycol to the choline chloride in the S1 is 1-3:1.
Preferably, the heating condition in the step S1 is 50-85 ℃ and the heating time is 10-30min.
Preferably, the mass ratio of DES to MAH in S2 is 0.3-3:1.
Preferably, the temperature of heating MAH at the bottom of the spray reactor in S2 is 120-180 ℃.
Preferably, the flow rate of DES solvent at the top of the spraying reactor in the step S2 is 2-5m 3 /h; the nozzle pressure at the top of the spray reactor is 5-20MPa.
Preferably, the temperature of the condensed reflux in the S2 is 55-90 ℃ for 3-4 hours.
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 180-200 ℃ and the rotating speed is 250-350r/min.
The compatilizer prepared by the method provided by the invention.
Mechanism of action
The main cause of gel generation is:
DES solvent mechanism of action:
beneficial technical effects
(1) The DES-MAH preparation process uses a spray reactor in combination with a condensed reflux. In order to enable the MAH to sublimate and volatilize in a large amount, the MAH and the mist DES solvent are fully and uniformly mixed in the middle part of the reactor, and the bottom part of the spraying reactor is heated to 120-180 ℃. And then condensing and refluxing for 3-4 hours at 55-90 ℃ so as to ensure that DES and MAH are mixed more fully and avoid volatilization of MAH in the process.
(2) The DES-MAH is selected as the polar grafting monomer of the compatilizer because the DES solution has high viscosity and can be coated when being compounded with the MAH, so that the DES-MAH cannot volatilize 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, since the DES system has very strong electron donating effect, a large amount of electron donors in the melting reaction process can stop the macromolecular free radicals before the reaction, so that the crosslinking phenomenon of 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) a DES: mah=1:3 sample, (d) a DES: mah=1:1 sample, (e) a DES: mah=3:1 sample, according to the present invention;
FIG. 2 is a schematic diagram of a spray reactor according to the present invention;
fig. 3 is a schematic diagram of a hydrogen bond club model formed by (a) pure MAH, (b) pure choline chloride, (c) pure ethylene glycol, and (d) DES and MAH according to the present invention.
In the figure: 1-DES solvent storage tank, 2-pressure nozzle, 3-MAH hot plate, 4-valve, 5-feed pump.
Detailed Description
The raw materials in the examples of the present invention are all commercially available; the twin screw extruder was TSE-20/600-5.5-48 (Nanjing Ruiya extrusion machinery Co., ltd.); the initiator is bis-tert-butyldiisopropylbenzene peroxide (BIBP).
Example 1
The method for effectively improving the grafting rate of MAH in the compatilizer based on the DES system comprises the following steps:
s1: preparation of DES solvent
Weighing a certain amount of ethylene glycol into a round-bottom flask, adding choline chloride into the round-bottom flask, placing the mixture on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 1:1, heating the mixture at 50 ℃ for 10min, cooling the mixture to room temperature, and standing the mixture for 20h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
33g of MAH was weighed and sprayedHeating the mist reactor at 120deg.C to sublimate MAH to the middle of the reactor, adding 100g of DES solvent obtained by S1 at the top of the mist reactor, and maintaining the pressure at 5MPa and flow rate at 2m 3 And/h, making the mixture drop in a mist form at the top end of the reactor, fully and uniformly mixing the mixture with MAH gas in the middle of the reactor, returning to the top end for continuous reaction, continuously reacting for 2h to obtain an initial product of DES-MAH, putting the obtained initial product of DES-MAH into a three-neck flask, heating to 55 ℃, condensing and refluxing for 3h, and obtaining a final product of DES-MAH.
S3: preparation of compatibilizing agents
Mixing 10g of DES-MAH obtained in the step S2 with 900g of polyethylene, adding 0.4g of initiator, uniformly mixing by a mixer, pouring the mixed material into a double-screw extruder with the temperature set at 180 ℃ and the rotating speed set at 250r/min, and obtaining the compatilizer with high grafting rate through wiredrawing, air drying and granulating.
Example 2
The method for effectively improving the MAH grafting rate in the compatilizer based on the DES system comprises the following steps:
s1: preparation of DES solvent
Weighing a certain amount of ethylene glycol into a round-bottom flask, adding choline chloride into the round-bottom flask, placing the mixture on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 2:1, heating the mixture at 70 ℃ for 20min, cooling the mixture to room temperature, and standing the mixture for 24h to obtain a uniform DES solvent;
s2: preparation of DES-MAH
Weighing 100g of MAH, placing at the bottom of a spray reactor, heating at 150deg.C to sublimate MAH to the middle of the reactor, adding 100g of DES solvent obtained by S1 at the top of the spray reactor, and maintaining the pressure at 10MPa and flow rate at 3m 3 And/h, making the mixture drop in a mist form at the top end of the reactor, fully and uniformly mixing the mixture with MAH gas in the middle of the reactor, returning to the top end for continuous reaction, continuously reacting for 2h to obtain an initial product of DES-MAH, putting the obtained initial product of DES-MAH into a three-neck flask, heating to 70 ℃, condensing and refluxing for 3h, and obtaining a final product of DES-MAH.
S3: preparation of compatibilizing agents
Mixing 10g of DES-MAH obtained in the step S2 with 1000g of polyethylene, adding 0.5g of initiator, uniformly mixing by a mixer, pouring the mixed material into a double-screw extruder with the temperature set at 190 ℃ and the rotating speed set at 300r/min, and obtaining the compatilizer with high grafting rate through wiredrawing, air drying and granulating.
Example 3
The method for effectively improving the MAH grafting rate in the compatilizer based on the DES system comprises the following steps:
s1: preparation of DES solvent
Weighing a certain amount of ethylene glycol into a round-bottom flask, adding choline chloride into the round-bottom flask, placing the mixture on a heating sleeve, wherein the molar ratio of the ethylene glycol to the choline chloride is 3:1, heating the mixture at 85 ℃ for 30min, cooling the mixture to room temperature, and standing the mixture 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 180deg.C to sublimate MAH to the middle of the reactor, adding 100g of DES solvent obtained by S1 at the top of the spray reactor, and maintaining the pressure at 20MPa and flow rate at 5m 3 And/h, making the mixture drop in a mist form at the top end of the reactor, fully and uniformly mixing the mixture with MAH gas in the middle of the reactor, returning to the top end for continuous reaction, continuously reacting for 3h to obtain an initial product of DES-MAH, putting the obtained initial product of DES-MAH into a three-neck flask, heating to 90 ℃, condensing and refluxing for 4h, and obtaining a final product of DES-MAH.
S3: preparation of compatibilizing agents
Mixing 10g of DES-MAH obtained in the step S2 with 1100g of polyethylene, adding 0.6g of initiator, uniformly mixing by a mixer, pouring the mixed material into a double-screw extruder with the temperature set at 200 ℃ and the rotating speed set at 350r/min, and obtaining the compatilizer with high grafting rate through wiredrawing, air drying and granulating.
Comparative example
A preparation method of a compatilizer without a DES solvent comprises the following steps:
s1: 10g of MAH and 0.5g of initiator are weighed into a beaker, a small amount of acetone solution is added for continuous stirring, and the mixture is left stand 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 at 190 ℃ and the rotating speed set at 300r/min, and obtaining the compatilizer through wiredrawing, air drying and granulating.
The grafting ratio of the adhesive resins prepared in examples 1 to 3 and comparative example was measured by an acid-base titration method, and the specific operation method was as follows: 1.0 of compatilizer is weighed in an analytical balance, placed in a 250mL three-neck flask, 100mL of xylene is added into the flask, clamped by a test tube clamp, placed in a constant-temperature oil bath, and opened for condensation reflux. And (3) starting oil bath heating, heating to about 150 ℃, heating for 2 hours, and stopping heating after the grafts in the three-neck flask are completely dissolved. And then the three-neck flask is removed from the oil bath, naturally cooled to about 70 ℃, and quickly poured into a large beaker filled with 150mL of acetone to precipitate a product. Vacuum filtering the graft; then, the mixture 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 1h. The purified graft was dried in an oven at 100℃for 1h and removed.
0.5g (to 0.001 g) of the purified sample, designated M, was accurately weighed and placed in an Erlenmeyer flask containing 100mL of xylene, and condensed and refluxed for 1.5 hours. The conical flask was removed from the oil bath, cooled for 5min (about 70 ℃), 10mL of potassium hydroxide-ethanol solution accurately measured with a pipette was added, heated and refluxed for 15min, the conical flask was removed, 3 drops of phenolphthalein indicator were added, titration was performed with the prepared acetic acid-xylene solution to turn the color of the solution from red to white, and the volume V of acid consumed was recorded 1 . Weighing blank sample according to the same procedure, and titrating out the acid volume V consumed by the blank sample 0 。
Wherein: g-grafting ratio (G MAH/100G graft); v (V) 0 BlankVolume of acetic acid-xylene solution consumed during sample titration, mL; v (V) 1 -volume of acetic acid-xylene solution, mL, consumed upon dropping of the sample after purification; c-acetic acid-xylene solution concentration, mol/L.
The results are shown in Table 1.
TABLE 1 grafting yield measurement results of adhesive resins
| Group of | DES:MAH | Grafting rate/% | Growth rate/% |
| 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 | DES-free | 0.70 | / |
As can be seen from table 1, the grafting ratio of the adhesive resin obtained by the method of the present application was improved by 17.1% or more, and the increase rate was as high as 31.4% when DES: mah=1:1, compared to the adhesive resin without DES added.
To demonstrate the mechanism of improving the grafting rate, infrared spectrum measurement is carried out on each sample, and the result is shown in figure 1, wherein 3320cm appears in the infrared spectrum -1 Characteristic absorption peaks of nearby hydroxyl groups, and when MAH was added, 1720cm of infrared spectrum appeared clearly -1 The nearby MAH features absorption peaks. Characteristic absorption peak of 1790cm from pure MAH -1 Compared with DES-MAH, the characteristic absorption peak of DES-MAH is significantly shifted, and the characteristic peak of hydroxyl is also shifted, which indicates that new chemical bonds are generated between MAH and DES, the combination between the two is tighter, and MAH is more difficult to sublimate during the melting reaction.
FIG. 2 is a schematic diagram of an apparatus for producing DES-MAH, in which a DES solvent is sprayed into mist by a pressure nozzle in a tank, and drops down, MAH is sublimated and volatilized at high temperature on a heating plate, and after fully reacting with mist DES, the solution is pressed into the DES tank again by a water pump, and the sprayed solution is again reacted. After 2-3 hours of the reaction, the heating is stopped, the water pump is closed, the valve is opened, and the initial product of DES-MAH is collected.
Fig. 3 is a schematic view of a club model, in which (d) in fig. 3, H of choline chloride forms a hydrogen bond with Cl, H of ethylene glycol forms a hydrogen bond with Cl of choline chloride, and O of maleic anhydride forms a hydrogen bond with Cl of choline chloride, so that it can be shown that the mixing between DES and MAH is not only simple physical mixing, but also is connected through a hydrogen bond, and therefore, MAH is combined with DES solvent, thereby greatly reducing sublimation of MAH during melt grafting.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The method for 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 solvent
Dissolving choline chloride in 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
Placing MAH at the bottom of a spray reactor, heating the MAH to sublimate and rise the MAH to the middle part of the reactor, and adding the DES solvent obtained in the step S1 at the top end of the spray reactor to enable the DES solvent to fall in a mist form at the top end of the reactor; fully and uniformly mixing the middle part of the reactor with MAH gas, returning to the top end again for continuous reaction, and continuously reacting for 2-3h to obtain a primary product of DES-MAH; placing the obtained initial product of the DES-MAH into a three-neck flask, and heating, condensing and refluxing to obtain the final product of the DES-MAH;
s3: preparation of compatibilizing agents
Mixing the DES-MAH obtained in the step S2 with polyethylene, adding an initiator, uniformly mixing by a mixer, performing melt extrusion by a double-screw extruder, and performing wiredrawing, air drying and granulating to obtain the compatilizer.
2. The method of claim 1, wherein the molar ratio of ethylene glycol to choline chloride in S1 is 1-3:1.
3. The method for increasing the grafting yield of MAH in a compatibilizer based on a DES system according to claim 1, wherein the heating condition in S1 is 50-85℃and the heating time is 10-30min.
4. The method of claim 1, wherein the mass ratio of DES to MAH in S2 is 0.3-3:1.
5. The method for increasing the grafting yield of MAH in a compatibilizer based on a DES system according to claim 1 wherein the temperature of heating MAH at the bottom of the spray reactor in S2 is 120-180 ℃.
6. The method for increasing MAH grafting in a compatibilizer based on a DES system of claim 1, wherein the flow of DES solvent at the top of the spray reactor in S2 is 2-5m 3 /h; the nozzle pressure at the top of the spray reactor is 5-20MPa.
7. The method for increasing the grafting yield of MAH in a compatibilizer based on a DES system of claim 1 wherein the reflux in S2 is performed at a temperature of 55-90℃for 3-4 hours.
8. The method for increasing MAH grafting rate in a compatibilizer based on a DES system of 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 increasing the grafting ratio of MAH in a compatibilizer based on a DES system according to claim 1, wherein the operation conditions of the twin screw extruder in S3 are: the temperature is 180-200 ℃ and the rotating speed is 250-350r/min.
10. A compatibilizer prepared by the method of any one of claims 1 to 9.
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