A kind of preparation method who comprises the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base
Technical field
The invention belongs to the stopper technical field in the polyreaction, be specifically related to be used for esters of acrylic acid, methacrylic ester (following general designation propenoate) production process prevents that polymeric from comprising the preparation method of the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base.
Background technology
In the propenoate production process, because the carbon carbon unsaturated double-bond in vinylformic acid and the ester class formation thereof, the gelation of polymerization reaction take place, even generation easily, implode lead to industrial accident.Wherein, polymerization takes place than vinylformic acid in esters of acrylic acid more easily, how to prevent in process of production that therefore the polymerization of vinylformic acid and ester class thereof is very crucial.
Adding stopper is the polymeric effective means that prevents vinylformic acid and ester class thereof.Up to now, though it is of a great variety from the single variety to the compound system to be used for the stopper of propenoate, mainly be phenols, free radical type, amine stopper, and the composite polymerzation inhibitor of forming by free radical type stopper and phenol or amine stopper.Wherein phenols, amine stopper need work in the presence of oxygen molecule, and the solvability of metal-salt in system is relatively poor, and in the high temperature production process resistance to gather efficient low, make its industrial application receive certain restriction; The living free radical polymerization compounds is another kind of stopper, and they are remarkable to the polymerization inhibition effect of esters of acrylic acid, and efficient is high and need not lead to oxygen.Existing to 2,2,6, the research of 6-tetramethyl--4-hydroxy-piperdine NO free radical (TMHPO) shows, exists synergistic effect between the stopper of they and some other kind and its polymerization inhibition effect is significantly promoted.When TMHPO and phenolic inhibitor are composite, its consumption is reduced, resistance gathers time lengthening, and requires very little to oxygen level.
In traditional propenoate production technique; Esterification process is a homogeneous reaction, and vinylformic acid and ester class thereof are evenly distributed in the reactor drum, and the favorable solubility of small molecules stopper; Can be dispersed in the reaction system preferably, thereby reach the polymerization that prevents vinylformic acid and ester class thereof.But; What in the new production process of propenoate, adopt is the mobile mode of production of continuity; Effective catalyst loads on the fixation reaction bed, and the reaction product propenoate has a concentration distribution in system, higher near the regional concentration of catalyzer; Because the high polymerization activity of propenoate, polymerization takes place in this zone extremely easily.Therefore, the inhibitor concentration of these catalyst area requires also higher.If adopt traditional small molecules stopper to suppress the polyreaction in the total system, just must improve the inhibitor concentration demand that its consumption could satisfy catalyst area greatly, cause waste; And side reaction takes place easily; The stopper residual quantity is big, color burn, and quality product descends.Novel process requires the stopper macromoleization and can be fixed on the reaction bed, at the stopper of catalyst area distribution higher concentration, reaching the efficient inhibition to newly-generated propenoate, thereby reduces the usage quantity of whole system stopper.
About the small molecules stopper, U.S. Pat 3,666,794 proposed Resorcinol-phenol-oxygen system is used for acrylic ester monomer resistance gather, but must blast oxygen in addition, otherwise polymerization inhibition effect is relatively poor, and resistance to gather the time short, use difficulty.Chinese patent CN 86 1 03840 propose with phenol amine and the composite stopper of NO free radical, between two components synergistic effect is arranged, the effect of composite polymerzation inhibitor significantly improves with the concentration stock blend, and very little to the requirement of the oxygen level in the system.But this stopper only is applicable in traditional propenoate working method, and is powerless for the high local concentrations stopper that requires in the new production process.Do not see at present the report of relevant macromole polymerization inhibitor and preparation method thereof as yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who comprises the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base,, reach the good polymerization inhibition effect of propenoate production process to overcome the above-mentioned defective of prior art.
The present invention comprises the preparation method of the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base; It is characterized in that: be the polymethyl acrylate of p by the polymerization degree: phenolic cpd: the mol ratio of NO free radical compounds is 1: x: y is dissolved in the solvent, adds the catalyzer of pressing reaction mixture total mass 0.5-3.0wt%, at temperature 20-80 ℃; Under the 0.05-0.09MPa vacuum degree condition; React to phenolic cpd and NO free radical compounds concentration and no longer change (can adopt gc follow the tracks of), with reaction mixture sedimentation in water, and with promptly obtaining macromole polymerization inhibitor after the sediment drying; 0.1p≤x≤0.5p wherein; 0.1p≤y≤0.5p, 0.1p≤x+y≤0.5p, said polymerization degree p are the integer of 5-1000.
Said solvent is N, N-dimethyl--methane amide, N, N-dimethyl--ethanamide and/or methyl-sulphoxide.
Said catalyzer is sodium hydroxide, Pottasium Hydroxide, sodium methylate, sodium ethylate, yellow soda ash, salt of wormwood or hydrogenchloride.
Said phenolic cpd is following structure:
Wherein, R
2Base is hydroxyl, alkyl, alkoxyl group, halogen, haloalkyl, acyl group, acyloxy or carboxamido-group.Said NO free radical compounds is following structure:
Wherein, R
3, R
4Be respectively independently hydrogen, hydroxyl, alkyl, alkoxyl group, halogen, haloalkyl, acyl group, acyloxy or carboxamido-group.
With U.S. Pat 3; 666; Resorcinol-phenol of 794-oxygen system is compared, because macromole polymerization inhibitor of the present invention is incorporated into phenolic inhibitor and living free radical polymerization in the system simultaneously, can reduce the demand of system to oxygen level effectively; And both have synergistic effect, have improved resistance and have gathered efficient.Compare with the NO free radical compound polymerization inhibitor with the phenol amine that Chinese patent CN 86 1 03840 proposes; Though the latter's composite polymerzation inhibitor is owing to its effect of synergistic effect significantly improves with the concentration stock blend; Very little to the requirement of the oxygen level in the system, but this composite polymerzation inhibitor can't satisfy the requirement of the catalyst area high local concentrations stopper of new production process; Macromole polymerization inhibitor of the present invention not only has synergistic effect equally; Oxygen level requires low; And can be fixed on well near the supported catalyst zone of new production process, improve this regional inhibitor concentration greatly, stop the polymerization of product propenoate effectively; And reduced the usage quantity of whole system stopper, helped the raising of quality product.
The present invention adopts ester exchange method that phenols and NO free radical class stopper are attached in the same macromole, and raw material cheaply is easy to get, and reaction conditions is gentle, and is easy and simple to handle, helps large-scale industrial production.Macromole polymerization inhibitor provided by the invention comprises phenols simultaneously and the NO free radical resistance gathers group; Can effectively stop the polymerization in the product propenoate generative process, reduce oligomer in the product, reduce total stopper consumption; Improve the quality of products, the wide industrial application prospect is arranged.
Embodiment
Specify preparation method and the application in the propenoate industrial production thereof that the present invention comprises the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base with embodiment below.
Embodiment 1
In the three-necked bottle reactor drum of whipping appts is housed, add polymethylmethacrylate 200g, the p-Hydroxybenzylalcohol 62g, 2,2,6 of molecular weight 2000,6-tetramethyl--4-hydroxy-piperdine NO free radical 17.3g, catalyst n a
2CO
35.6g (2wt%) with solvent N, N-dimethyl--methane amide 800mL, stirring and dissolving is warming up to 40 ℃; Maintenance vacuum tightness is 0.09MPa, and reaction is extremely through gas chromatographic detection p-Hydroxybenzylalcohol and 2,2,6; The concentration of 6-tetramethyl--4-hydroxy-piperdine NO free radical no longer changes, and after the question response mixture cooling, pours sedimentation in the water of 2L into, filters and collects product; Vacuum-drying obtains white solid product, and called after MMIn 1, its productive rate are 88%.
In the infrared spectrum of products therefrom, 1167,1245cm
-1The place is the stretching vibration absorption peak of N-O co-ordination bond, 2882cm
-1The place is the stretching vibration absorption peak of C-N key, 1980-2400cm
-1The place is the stretching vibration absorption peak of phenyl ring;
In the nuclear magnetic spectrogram of products therefrom, 7.5-6.8ppm place multiplet ownership is Wasserstoffatoms on the phenyl ring, 4.2-4.0ppm place ownership is-and Wasserstoffatoms among the O-CH-, the 2.0-1.0ppm place is the Wasserstoffatoms of polymethacrylate backbone and pending methyl group.
Can know that by last analysis products therefrom MMIn 1 is the macromole polymerization inhibitor that comprises phenolic group and nitrogen oxygen base.
Embodiment 2
In the three-necked bottle reactor drum of whipping appts is housed, add polymethylmethacrylate 200g, the p-Hydroxybenzylalcohol 62g, 2,2 of molecular weight 8000,6; 6-tetramethyl--4-hydroxy-piperdine NO free radical 86.5g, catalyst n aOH5.2g (1.5wt%) and solvent N, N-dimethyl--ethanamide 1000mL, stirring and dissolving is warming up to 50 ℃; Maintenance vacuum tightness is 0.08MPa, and reaction is extremely through gas chromatographic detection p-Hydroxybenzylalcohol and 2,2; 6, the concentration of 6-tetramethyl--4-hydroxy-piperdine NO free radical no longer changes, after the cooling of question response mixture; Pour sedimentation in the water of 2L into, filter and collect product, vacuum-drying; Obtain white solid product, called after MMIn 2, its productive rate are 85%.
In the infrared spectrum of products therefrom, 1167,1245cm
-1The place is the stretching vibration absorption peak of N-O co-ordination bond, 2882cm
-1The place is the stretching vibration absorption peak of C-N key, 1980-2400cm
-1The place is the stretching vibration absorption peak of phenyl ring;
In the nuclear magnetic spectrogram of products therefrom, 7.5-6.8ppm place multiplet ownership is Wasserstoffatoms on the phenyl ring, 4.2-4.0ppm place ownership is-and Wasserstoffatoms among the O-CH-, the 2.0-1.0ppm place is the Wasserstoffatoms of polymethacrylate backbone and pending methyl group.
Can know that by last analysis products therefrom MMIn 2 is for comprising the macromole polymerization inhibitor of phenolic group and nitrogen oxygen base.
Embodiment 3
In existing Viscoat 295 (TMPTA) production process, with SO
4 2-/ TiO
2/ La
3+Be that solid super acid catalyst is fixed in the fixed-bed reactor, under 100 ± 10 ℃ of conditions, earlier TriMethylolPropane(TMP) and vinylformic acid direct esterification obtained TMPTA (original product).Be fixed on catalyzer the same area after macromole polymerization inhibitor MMIn 1 load that comprises phenolic group and nitrogen oxygen base with preparation among the invention described above embodiment 1 again, keep other condition of former technology constant, carry out the continuous production of TMPTA, products therefrom is a TMPTA product 1; The consumption that reduces the small molecules stopper is 1/2 in the former technology, keeps other working condition constant, and products therefrom is a TMPTA product 2.Their part physical properties and original product relatively be listed in the table below 1.
Table 1
Performance |
TMPTA product 1 |
TMPTA product 2 |
Original product |
Outward appearance |
Clear |
Clear |
Clear |
Ester content (%) |
98.8 |
98.7 |
98.0 |
Color APHA |
26 |
23 |
28 |
Viscosity (cps, 25 ℃) |
68 |
70 |
90 |
Moisture content (%) |
0.1 |
0.1 |
0.1 |
Acid number (mgKOH/g) |
0.4 |
0.4 |
0.4 |
Stopper (ppm) |
400 |
250 |
400 |
Can be known by the data in the table 1, compare with original product that TMPTA product 1 has improved fat content significantly with TMPTA product 2, has reduced the viscosity and the color of product, the latter has also reduced the residual quantity of stopper.
Embodiment 4
With being fixed on catalyzer the same area after above-mentioned macromole polymerization inhibitor MMIn 2 loads that comprise phenolic group and nitrogen oxygen base; Keep other condition of former technology constant; The consumption that reduces the small molecules stopper is 1/2 in the former technology, carries out the continuous production of TMPTA, and products therefrom is a TMPTA product 3; The consumption that reduces the small molecules stopper is 1/4 in the former technology, keeps other working condition constant, and products therefrom is a TMPTA product 4.Their part physical properties and original product relatively be listed in the table below 2.
Table 2
|
TMPTA product 3 |
TMPTA product 4 |
Outward appearance |
Clear |
Clear |
Ester content (%) |
99.2 |
99.0 |
Color APHA |
26 |
22 |
Viscosity (cps, 25 ℃) |
65 |
66 |
Moisture content (%) |
0.1 |
0.1 |
Acid number (mgKOH/g) |
0.4 |
0.4 |
Stopper (ppm) |
200 |
100 |
Can know by the data in the table 2, compare that TMPTA product 3 has improved fat content significantly with TMPTA product 4, has reduced the viscosity and the color of product, has reduced the residual quantity of stopper in the product simultaneously with original product.