CN1219534A

CN1219534A - Preparation method for polymerized hindered amine light stabilizer monomer

Info

Publication number: CN1219534A
Application number: CN 97121993
Authority: CN
Inventors: 梁文忠
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 1997-12-12
Filing date: 1997-12-12
Publication date: 1999-06-16

Abstract

A process for preparing the monomer of polymeric hindered amine as optical stabilizer includes the ester exchange reaction between free nitrogen and oxygen radicals, 2,2,6,6-tetramethyl piperidinol, perspex and tetrabutyl phthalate as catalyst at 130-135 deg.C for 2-2.5 hr, separating with aqueous polar solvent and filtering, and features low consumption of raw materials and simple operation.

Description

The preparation method of polymerized hindered amine light stabilizer monomer

The present invention relates to a kind of preparation method of hindered amine, particularly a kind of preparation method of polymerized hindered amine light stabilizer monomer.

Photostabilizer is the indispensable additive of outdoor synthetic materials, and the high-molecular optical stablizer is better than low molecule photostabilizer.Polymerization is one of approach of preparation high-molecular optical stablizer, Intern.J.Polymeric Mater.1990,13,249, prepare the hindered amine monomer with chloride method, the productive rate of that method is 27%, the monomer fusing point is 57-58 ℃, chemistry circular 1980 (6), and 18 have reported ester-interchange method, with magnesium methylate is that catalyzer carries out methyl methacrylate and 2,2,6, the reaction of 6-tetramethylpiperidinol, the decompression of reaction back steams methacrylic acid--and 2,2,6,6-tetramethyl--4-piperidines ester (TMPM).During decompression, because of the product fusing point is higher than room temperature, the water in the prolong needs with the hot water that is higher than fusing point; What obtain in the receiving bottle is solid product, needs fusing again, condensation, pulverizing during use.

It is low to the objective of the invention is to overcome hindered amine monomer yield, and the separation that brings of high-melting-point and use the shortcoming of troublesome poeration, prepares the hindered amine monomer and adopt phthalandione four butyl ester catalyzer and set up a kind of dissolution precipitation separation method.56-58 ℃ of monomer fusing point.

Preparation method of the present invention carries out transesterify with the pure and mild alkene class of hindered amine ester by following.

R wherein ₁, R ₂, R ₃And R ₄Be CH partly or entirely ₃, C ₂H ₅R ₅Be H, CH ₃, comprising, but be not limited to, 2,2,6,6-tetramethylpiperidinol (TMP); R ₆Be H or CH ₃: R ₇Be CH ₃Or C ₂H ₅, comprising, but be not limited to methyl methacrylate (MMA); Wherein the mol ratio of TMP and MMA is 1.0: 0.9-4.0, be preferably 1.0: 1.5-3.6, optimum mole ratio is 1.0: 2.0-3.2, wherein catalyzer is that tetralkyl titanate comprises, but be not limited to, metatitanic acid orthocarbonate, tetrabutyl titanate or its mixture, the weight percent of itself and TMP is 1-6.0%; Stopper is low molecule or polymer nitroxyl free radical, comprise, but be not limited to, methacrylic acid-2,2,6, nitroxyl free radical or its mixture of the polymkeric substance of nitroxyl free radical (TMPM-NO) TMPM of 6-tetramethyl--4-piperidines ester (TMPM), the weight percent of itself and MMA is 0.005-0.05%.

Preparation method's of the present invention operation steps is as follows: in reaction flask, add the polymer nitroxyl free radical (nitroxyl free radical of homemade TMPM and cinnamic multipolymer, nitrogen content is 5.17%, oxygen level is 15.21%) or low dinitrogen oxyradical TMPM-NO, and TMP, MMA and tetrabutyl titanate are connected to the fractional column lower end with reaction flask, make the liquid level in the reaction flask consistent with the oil bath liquid level of heating usefulness; Make oil bath in half an hour, rise to 130 ℃; In 130-135 ℃ of reaction, the fractional column temperature is progressively transferred to 100 ℃ by 40 ℃, with the speed that distillates of control methyl alcohol; When methyl alcohol has heated up in a steamer soon, oil bath temperature is risen to 150 ℃, temperature rises to 115 ℃ in the post, distillates 2-5 milliliter MMA in 100 ℃.The entire reaction time is 2.0-2.5 hour.Get mixture of products.When changing fractional column into the Ke Shi still head, the reaction times is 3-4 hour.Going out product from mixture separation is following carrying out, and reaction flask is placed the water pump depressurized system, and in 46-48 ℃/13.3 thousand pools down, decompression steams MMA, but when having steamed near MMA, progressively gas clean-up steams residual volatile matter.When mixture does not solidify, add aqueous polar solvent,, destroy tetrabutyl titanate and make it be insoluble to solvent as industrial acetone, industrial methanol, industrial alcohol, 95% ethanol or its mixture, and lysate TMPM and TMP tell insolubles with this mixture with filtration or centrifugal separation; Filtrate water is settled out TMPM, and washing and drying obtains product, and its melting range is 59.3-59.8 ℃.With method of the present invention prepared TMPM and the styrene copolymerized photostabilizer of gained afterwards, the film of the 0.10mm that blows with 0.30% content and polyethylene blend, through atmospheric exposure after 15 months, the longitudinal fracture elongation retention is 101.6%, and GW's 540 is 12.5%, and Chimassorb's 944 is 90.0%.

This method productive rate height, raw material consumption is few, and is simple to operate.

Embodiment 1,

In reaction flask, add 0.0080 gram polymer nitroxyl free radical, 20.000 restrain 2,2,6,6-tetramethylpiperidinol (TMP), 31.748 gram methyl methacrylate (MMA), 0.882 gram tetrabutyl titanate is after mixing, with this reaction flask fractional column lower end of packing into, with oil bath reacting by heating thing to boiling.Regulate oil bath and fractional column temperature with the control reflux ratio, fractionate out methyl alcohol suitably heating up in a steamer under the speed; (reaction lasts 2 hours) changed receiving bottle and collected the MMA foreshot when the methyl alcohol fraction is intact soon, after so far the fraction boiling point is stablized, promptly stops fractionation.Reaction flask is packed under the depressurized system, and under 46-48 ℃/13.3 thousand pools, decompression steams MMA; When having steamed near MMA, progressively gas clean-up steams residue.When generating mixture and not solidifying, adds 30 milliliters of industrial acetones, dissolving mixt, leach insolubles after, wash insolubles three times with small amount of acetone.Under agitation, resultant solution is added in 100 ml waters slowly, product is separated out, and product is filtered washing, drying.Product weighs 25.765 grams, and productive rate is 89.9%; The product fusing point is 59.3-59.7 ℃, and results of elemental analyses contains C, 69.19%; H, 10.32%, N, 6.20%.Getting molecular weight product by mass spectrometric measurement is 225.Embodiment 2,

Experimental installation, step and nitroxyl free radical and TMP consumption all with embodiment 1 with, just MMA is with 25.366 grams, tetrabutyl titanate restrains with 0.836, product weighs 22.584 and restrains, productive rate is 78.8%; The product fusing point is 59.3-59.7 ℃; Results of elemental analyses: contain C, 69.18%; H, 10.27%; N, 6.20%.Embodiment 3,

Same with embodiment 1, just the MMA add-on is 14.054 grams, and tetrabutyl titanate is 0.234 gram.Product weighs 17.053 grams, and productive rate is 59.5%; The product fusing point is 59.3-59.7 ℃, and results of elemental analyses contains C, 69.26%; H, 10.15%, N, 6.24%.Embodiment 4,

Same with embodiment 1, just the MMA add-on is 14.498 grams, and tetrabutyl titanate is 0.827 gram.Product weighs 18.170 grams, and productive rate is that 63.4% product fusing point is 59.3-59.7 ℃, and results of elemental analyses contains C, and 69.23%; H, 10.18%, N, 6.18%.Embodiment 5,

Replace fractional column with the Ke Shi still head, other experimental installations, step and nitroxyl free radical and TMP consumption all with embodiment 1 with, just the MMA consumption is 14.4900 to restrain, tetrabutyl titanate is 0.9000 to restrain.Product weighs 15.677 grams, and productive rate is 54.7%; Fusing point is a 59.3-59.8 ℃ of results of elemental analyses: contain C, 69.20%; H, 10.23%, N, 6.19%.Embodiment 6,

With 20.000 gram MMA and 0.0015 gram 4-methacryloxy-2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical replaces MMA and the polymer nitroxyl free radical among the embodiment 1 to carry out embodiment 1 operation, after decompression steams MMA, replaces acetone to carry out embodiment 1 operation with 95% ethanol, the solution that must contain TMPM after the filtration under agitation, adds 80 ml waters wherein slowly, TMPM is all separated out, filter washing, drying, product weighs 23.16 grams, productive rate 80.8%, fusing point 59.5-59.8 ℃; Ultimate analysis: C, 69.23%; H, 10.22%; N, 6.15%.Embodiment 7,

With 40.000 gram MMA substitution embodiment 1, other raw material and consumption are constant, carry out 1 same operation with embodiment, and product is 25.391 grams, and productive rate 88.2%, fusing point are 59.5-59.8 ℃; Results of elemental analyses: contain C, 69.30%; H, 10.35%; N, 6,16%.

Claims

1, the preparation method of polymerized hindered amine light stabilizer monomer is characterized in that step is carried out in the following order:

(1) with nitroxyl free radical, 2,2,6,6-tetramethylpiperidinol TMP, methyl methacrylate MMA and phthalandione four butyl esters reacted 2-2.5 hour at 130-135 ℃ after mixing, and got mixture of products, wherein the mol ratio of TMP and MMA is 1.0: 0.9～4.0, the weight percent of phthalandione four butyl esters and TMP is 1-6%, and the weight percent of nitroxyl free radical and MMA is 0.005-0.05%

(2), steam MMA and residual volatile matter at 46-48 ℃

(3) adding contains aqueous polar solvent,

(4) insolubles is told in filtration

2, the preparation method of polymerized hindered amine light stabilizer monomer according to claim 1 is characterized in that described nitroxyl free radical is polymer or low dinitrogen oxyradical.

3, the preparation method of polymerized hindered amine light stabilizer monomer according to claim 1 is characterized in that described polar solvent is industrial acetone, industrial alcohol.