CN1036998C - Making method for hidered amine side group containing copolymer used as light stabilizer - Google Patents
Making method for hidered amine side group containing copolymer used as light stabilizer Download PDFInfo
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- CN1036998C CN1036998C CN92114759A CN92114759A CN1036998C CN 1036998 C CN1036998 C CN 1036998C CN 92114759 A CN92114759 A CN 92114759A CN 92114759 A CN92114759 A CN 92114759A CN 1036998 C CN1036998 C CN 1036998C
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001412 amines Chemical class 0.000 title claims abstract description 11
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 9
- 229920001577 copolymer Polymers 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 150000003254 radicals Chemical class 0.000 claims abstract description 19
- -1 2, 2, 6, 6-tetramethyl piperidyl Chemical group 0.000 claims abstract description 11
- JMVRUDUIARAACU-UHFFFAOYSA-N (2,2,4,6,6-pentamethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1CC(C)(C)N(OC(=O)C=C)C(C)(C)C1 JMVRUDUIARAACU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 238000012673 precipitation polymerization Methods 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 7
- 150000003053 piperidines Chemical class 0.000 claims description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 10
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229920001059 synthetic polymer Polymers 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- RALRVIPTUXSBPO-UHFFFAOYSA-N 4-[4-chloro-3-(trifluoromethyl)phenyl]piperidin-4-ol Chemical class C=1C=C(Cl)C(C(F)(F)F)=CC=1C1(O)CCNCC1 RALRVIPTUXSBPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010023321 Factor VII Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- CCRIVCWOXSIYEP-UHFFFAOYSA-N methyl prop-2-enoate;hydrochloride Chemical compound Cl.COC(=O)C=C CCRIVCWOXSIYEP-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000003351 photoxidation Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The present invention relates to a method for preparing copolymers used as light stabilizers. Side chains of the copolymers have 2, 2, 6, 6-tetramethyl piperidyl (hindered amine). The copolymers are prepared from 4-(methyl) acrylyl oxy-2, 2, 6, 6-tetramethyl piperidine and alpha-alkene monomers in a free radical precipitation copolymerization method. Because fatty group straight chains or cyclane replaces aryl group organic solvent in the copolymerization, the aromatic hydrocarbon pollution is eliminated, the process is simplified, and the yield is improved. The high molecular light stabilizers prepared by the method of the present invention have excellent light stability quality on various synthetic polymers, particularly polyolefin.
Description
The present invention relates to a kind of preparation method of polymer hindered amine light stabilizer
Along with the fast development of macromolecular material industry, not only its output has obtained quick growth, and its application is also constantly enlarged, no matter be in industry, much more more and more agricultural still in national defence, has all used macromolecular material or goods in science and technology and the daily life.
But, most synthesized polymer materials all can because of be heated, the effect of light etc. destroyed, the forfeiture physical and mechanical properties, make it lose use value, wherein especially with the infringement of light for, no matter be outdoor directing light, still the effect of indoor casual light all can make the aging at leisure embrittlement of synthetic materials, how preventing the aging of macromolecular material, is one of development macromolecular material key issue that need solve.
The main method that prevents the macromolecule material aging deterioration is to add a certain amount of photostabilizer therein, photostabilizer commonly used has energy quencher type, uv-absorbing type and radical termination type etc., substituted piperidine (hindered amine) compounds is a radical termination type efficiency light stablizer, so demonstrate excellent especially light stability because it has thermo oxidative aging concurrently and can regenerate in the anti-photooxidation process.
The usefulness that is added on the photostabilizer in the macromolecular material except that the molecular structure that depends on it, also depend on it macromolecular material or goods in processing and use because of thermolysis, volatilize and extracting etc. is former thereby the loss that causes, thereby improved its usefulness.
4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine (I) are the unsaturated vinyl monomers that contains the substituted piperidine base that everybody is familiar with.
R wherein
1For H or-CH
3It can pass through (methyl) acrylate chloride and 4-hydroxyl-2,2,6,6-tetramethyl piperidine reaction or with (methyl) methyl acrylate and 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine carries out permutoid reaction and makes.
DT2748362 once adopted the photostabilizer of solution polymerization process polymeric multipolymer as various synthetic high polymers with (I) with α-vinyl monomer.
But the preparation method who is proposed in above-mentioned patent exists following defective at least:
1, in the polymerization of carrying out monomer (I) or copolymerization, used monomer total amount 1.5-8 poisonous aromatic solvent doubly as reaction medium.
2, reaction at the end will come precipitation polymers with quantity of solvent 4-8 sherwood oil doubly.
3,15-40 solvent and precipitation agent and that be the monomer total amount doubly.Obviously, for solvent is separated with precipitant mix liquid, purifying and recovery must increase facility investment and cost.
4, temperature of reaction height, the time is long, and productive rate is low.
USP4308362 discloses the technology of the multipolymer of the sour unsaturated dicarboxylic acid substituted piperidine of rich horse (or Malaysia) alcohol ester as photostabilizer, described manufacture method complexity, need high pressure to react for a long time, or make the sour lower member ester of rich horse (or Malaysia) earlier, carry out transesterification reaction with substituted piperidine alcohol again, need this moment to use poisonous organic solvent, and yield is low.
The objective of the invention is to have proposed a kind of improved synthesis technique in order to overcome the shortcoming of above-mentioned patent method therefor.Thereby the multipolymer of synthon (I) and various α-vinyl monomers successfully, they are various synthesized polymer materials, especially polyolefinic good photostabilizer.
The monomer (I) that patent DT2748362 inventors once pointed out to contain the substituted piperidine base is extremely difficult polymeric, and they play inhibition when carrying out copolymerization with α-vinyl monomer, become stopper.They attempt to prolong the reaction times with improving temperature of reaction in above-mentioned patent, and ways such as increasing initiator amount overcome this point.Though obtained certain success, do not obtain well-content result, because use solvent and precipitation agent in large quantities, complicated operations technology and lower productive rate make this invention be difficult to put into practice aborning.
The defective that the present invention is directed to DT2748362 has proposed improved new synthesis process.Novel method of the present invention is characterised in that and has adopted the undissolvable inert solvent of multipolymer that generates as reaction medium, that is to say that the present invention synthesizes the multipolymer that contains substituted piperidine monomer (I) and α-vinyl monomer with the free radical precipitation polymerization method.
Another feature of the inventive method is when carrying out the free radical precipitation polymerization, and the consumption of inert solvent only is 1-2 a times of monomer total amount, and copolymerization is to carry out under higher material concentration.
Because reaction medium can not dissolve the multipolymer of generation, so in polyreaction is carried out, precipitation is separated out voluntarily when copolymer molecule increases and reaches the certain molecular weight value, thereby can reduce the reaction that is in the chain free radical in the growth in this part piperidyl and the solution, suppressed their inhibition.Also, the inventive method under high reacting material concentration, carries out copolymerization, so have higher speed of response owing to having adopted.Therefore, produce monomer (I) and α-vinyl monomer multipolymer, although under demulcent reaction conditions relatively, also can realize satisfactory results under (as lower temperature of reaction, short reaction times and needn't use excessive initiator etc.) with the inventive method.
Free radical precipitation polymerization method of the present invention is characterized in that carrying out in the process in copolymerization, and copolymer molecule precipitates segregation voluntarily when molecular weight increases above certain value.So after reaction finishes, needn't come the precipitating multipolymer with a large amount of precipitation agents.Reaction finishes the back as long as with the reaction solution cooling, leave standstill, multipolymer promptly voluntarily sedimentation separate fully with solvent.
Polymer hindered amine as light stabilizer of the present invention mainly is meant the multipolymer of monomer (I) and α-vinyl monomer, and described α-vinyl monomer is meant:
The acrylic or methacrylic esters of gallic acid:
R wherein
2For H or-CH
3, R
3For containing the alkyl of 1-18 carbon.Described α-vinyl monomer can also be a vinyl acetate, acrylamide, maleic anhydride, vinyl cyanide etc.
Polymer photostabilizer of the present invention is by monomer M
1And α-vinyl monomer (M
2) copolymerization makes.Two kinds of monomeric proportionings (weight %) are M
2: M
1=90-5: 10-95.With 70-20: 30-80 is better, and its best proportioning (weight %) is 65: 35.
Polymer photostabilizer of the present invention is by M
1With M
2Make by free radical copolymerization, used radical polymerization initiator is superoxide such as dilauroyl peroxide etc.; Also can be azo-compound, they be 2,2'-Azobis(2,4-dimethylvaleronitrile), a kind of in the Diisopropyl azodicarboxylate.The 0.1-7% of total monomer weight was advisable with 0.5-5% when their consumption was generally reaction, and its optimum amount is 0.8-1.5%.
When producing the polymer photostabilizer with the inventive method, principal character is to have adopted the free radical precipitation polymerization process to synthesize required multipolymer.With the reaction medium of inert solvent as the copolymerization of free radical precipitation.Its inert solvent is the aliphatics straight chain hydrocarbon, and they are hexanes, heptane, any in the sherwood oil; Also can be alicyclic hydrocarbon, they be hexanaphthenes, any in the suberane.Their consumption is generally 1-2 times of monomer total amount.
The number-average molecular weight of the polymer photostabilizer that makes with the inventive method is 10
3-2 * 10
4Between, can regulate according to service requirements.
The technology that free radical precipitation polymerization method of the present invention is produced the polymer photostabilizer is: take by weighing M by required ratio of components
1And M
2Monomer.With them and solvent, add people's radical polymerization initiator, polymerization under agitation then, temperature and time is respectively 50-90 ℃ and 6-10 hour, and best polymerization temperature is 60-70 ℃.Room temperature is at the end left standstill reactant and be cooled in reaction, divides then and removes supernatant liquid, will promptly get product after the gained multipolymer drying, productive rate＞95%.
Adopt free radical precipitation polymerization process of the present invention to synthesize the polymer photostabilizer that side chain has the substituted piperidine base, can avoid using a large amount of noxious solvents; And can save the step of coming precipitation polymers with a large amount of solvents, also can economize and desolvate and the separating of precipitation agent, the retrieving arrangement of purifying, thereby can simplify technology, and the product purity height, than the productive rate height (table 2) of original solution polymerization process, owing to reduced facility investment, save energy consumption, reduced cost.
The comparison of table 1, the inventive method and prior art
M
1: monomer (I), M
2: vinyl acetate M
2/ M
1=60/40 polymerization temperature: 80 ℃ of polymerization times: 8 hours
| Method | Solvent | Precipitation agent productive rate processing step | |
| Title | Amount (gram) | ||
| Precipitation polymerization process solvents for polymerization polymerization process of the present invention polymerization | Sherwood oil benzene | 200 200 | -＞95% simple 1000 gram sherwood oils, 70% very complicated |
The macromolecule stabilizer that makes with the inventive method can be used as the photostabilizer of multiple synthetic polymer, as polyolefine and multipolymer thereof: polyethylene, polypropylene, polybutene-1, polyhutadiene and b-propylene copolymer etc.; Vinylbenzene and multipolymer thereof; The homopolymerization of acrylic or methacrylic acid esters or multipolymer.Polymer hindered amine as light stabilizer of the present invention can with multiple other auxiliary agent such as uv-absorbing agent, quencher, oxidation inhibitor, antifogging agent and various filler, pigment matches, its suitable consumption is the 0.2-0.5% of weight resin.
Embodiment 1
4-methacryloxy-2,2,6, the preparation of 6-tetramethyl piperidine and vinyl acetate copolymer.
At one reflux exchanger is housed, adds 86 gram vinyl acetates in the reactor of stirring motor, 55 gram 4-methacryloxies-2,2,6, the 6-tetramethyl piperidine, 200 gram sherwood oils and 1.42 gram α, α '-Diisopropyl azodicarboxylate stirs and is mixed with homogeneous solution.Place 80 ℃ of thermostatic baths to carry out copolymerization reactor, temperature is remained on 80 ℃, under agitation reacted 9 hours.Reaction at the end stops to stir, and reaction solution is left standstill be cooled to room temperature.Treat that multipolymer divides and remove supernatant liquid after the complete precipitating of reactor bottom.Gained multipolymer drying and crushing is promptly got white powdery solid product.Yield＞95%, number-average molecular weight is about 1.5 * 10
4, the product ultimate analysis shows that nitrogen content is 2.14%.
Get a certain amount of product and be made into benzole soln, use then＞10 times the amount sherwood oils carry out the reprecipitation purifying.Dried reprecipitation sample is carried out ultimate analysis, and nitrogen content is 2.23%.This shows that the high-molecular optical stablizer that makes with the inventive method has higher purity, need not to be further purified, so can simplify technology.Embodiment 2-4
4-methacryloxy-2,2,6, the preparation of 6-tetramethyl piperidine and alkylmethacrylate polymer.
With method similarly to Example 1: produced 4-methacryloxy-2,2,6 by the listed prescription of table 1, the multipolymer of 6-tetramethyl piperidine and methyl acrylic ester, initiator amount are 1% of monomer total amount, and solvent load is 2 times of monomer total amount.Last is the nitrogen content of product in the table 2.
Table 2
Embodiment 5
| Embodiment | Monomer | Consumption (gram) | N％ |
| M 1 M 2 | M 1 M 2 | ||
| 2 3 4 | (I) methyl methacrylate (I) Octyl methacrylate (I) methacrylic acid hexadecyl ester | 6.8 13.5 11.3 44.6 37.9 37.9 | 2.66 1.25 0.69 |
Contain 4-methacryloxy-2,2,6, the light stability test of the high-molecular optical stablizer of 6-tetramethyl piperidine.
To add in the polyolefine by finite concentration by the polymer hindered amine as light stabilizer of gained among the embodiment 1-4 and make film.Carry out exposure to weather(ing) or artificial accelerated aging test then, the results are shown in table 2 and the table 3.
Table 3, various photostabilizer are to the comparison of poly light stability
Annotate: 1, thickness of sample 13 μ (LLDPE Daqing Petrochemical head factory DFDA-7042)
| Photostabilizer | Content (%) | Tan by the sun tan by the sun 103 days after 62 days after |
| Tensile strength extension at break tensile strength extension at break conservation rate (%) conservation rate (%) conservation rate (%) conservation rate (%) | ||
| Blank embodiment 1 Tinuvin 622 | 0.2 0.2 | 23 58 can't take a sample can't take a sample and 47 103 18 5 26 75 can't take a sample and can't take a sample |
2, tan by the sun the place: Guangzhou, throwing try May 22 date
3, Tinmvin 622, are Ciba-Geiqy company commodity
The various photostabilizers of table 4 are to the comparison photostabilizer content photoxidation light inductive phase stable factor of polyacrylic light stability
(hour) blank-28 1 embodiment 24 * 10
-5Mol/10gpp 76 2.7
3 the same 114 4
4 the same 168 6
Annotate: 1, the sample thickness 100
2, be that light source (＜2900A is elimination) carries out artificial accelerated aging with the 500w high voltage mercury lamp.With infrared tracking 1710cm
-1Place's carbonyl absorption, when the carbonyl absorption value reaches 0.01 as the oxidation induction period of sample.
Although the effective piperidyl content of polymer hindered amine as light stabilizer of the present invention as seen from Table 2 is lower than Tinuvin622.But its light stability is better than 622, and the result has fully shown photostabilizer excellent light stability energy of the present invention.
Claims (10)
1, the preparation method who has the polymer hindered amine as light stabilizer of substituted piperidine base (hindered amine HA) on a kind of side chain is characterized in that described photostabilizer is by monomer 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine M
1And α-vinyl monomer M
2In the presence of radical initiator, adopt the free radical precipitation polymerization process to make described α-vinyl monomer M
2Be methyl acrylic ester or vinyl acetate, described monomer ratio (weight %) M
2: M
1=90-5: 10-95, as reaction medium, polymerization temperature and time are respectively 50-90 ℃ and 6-10 hour with inert solvent, and the radical initiator consumption is the 0.1-7% of reaction-ure mixture, and the inert solvent consumption is 1-2 a times of reactant consumption.
2, the preparation method of photostabilizer according to claim 1 is characterized in that described inert solvent is aliphatics straight chain hydrocarbon or alicyclic hydrocarbon.
3, the preparation method of photostabilizer according to claim 1 is characterized in that described α-vinyl monomer M
2Be maleic anhydride, acrylamide or vinyl cyanide.
4, the preparation method of photostabilizer according to claim 1 is characterized in that described radical initiator is azo compound or organo-peroxide.
5, the preparation method of photostabilizer according to claim 1 is characterized in that described radical initiator is the 0.8-1.5% of reaction-ure mixture.
6, the preparation method of photostabilizer according to claim 2 is characterized in that described aliphatics straight chain hydrocarbon is meant any in hexane, heptane, the sherwood oil.
7, the preparation method of photostabilizer according to claim 2 is characterized in that described alicyclic hydrocarbon is a hexanaphthene, any in the suberane.
8,, it is characterized in that described radical initiator azo-compound is a Diisopropyl azodicarboxylate, any in the 2,2'-Azobis(2,4-dimethylvaleronitrile) according to the preparation method of the described photostabilizer of claim 4.
9, the preparation method of photostabilizer according to claim 4 is characterized in that described radical initiator organo-peroxide is a dilauroyl peroxide.
10, the preparation method of photostabilizer according to claim 1 is characterized in that described polymerization temperature is 60-70 ℃.
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| CN92114759A CN1036998C (en) | 1992-12-24 | 1992-12-24 | Making method for hidered amine side group containing copolymer used as light stabilizer |
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| CN92114759A CN1036998C (en) | 1992-12-24 | 1992-12-24 | Making method for hidered amine side group containing copolymer used as light stabilizer |
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| CN1088590A CN1088590A (en) | 1994-06-29 |
| CN1036998C true CN1036998C (en) | 1998-01-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432160C (en) * | 2004-12-16 | 2008-11-12 | 汕头大学 | Water-based reaction type hindered amine use, formula and method for in-situ photostabilization of coating layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601792A (en) * | 2016-01-21 | 2016-05-25 | 四川大学 | Preparation method of controllable molecular weight copolymerized hindered amine light stabilizer |
| CN108484833A (en) * | 2018-03-07 | 2018-09-04 | 乐凯胶片股份有限公司 | A kind of functional resin, polyolefine material, and its preparation method and application |
| CN109517108B (en) * | 2018-10-22 | 2021-04-02 | 乐凯化学材料有限公司 | Process for preparing maleimide/alpha-olefin copolymer |
| CN111808225B (en) * | 2020-06-22 | 2023-01-20 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| CN116003680B (en) * | 2022-12-26 | 2024-07-09 | 天集化工助剂（沧州）有限公司 | Polymeric anti-light aging multifunctional additive and preparation method and application thereof |
| CN117186621A (en) * | 2023-09-11 | 2023-12-08 | 胡燕 | A thermoplastic elastomer composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2748362A1 (en) * | 1977-10-28 | 1979-05-03 | Hoechst Ag | POLYMERS SUBSTITUTED PIPERIDINE, THEIR PRODUCTION AND USE |
| US4308362A (en) * | 1979-05-23 | 1981-12-29 | Hoechst Aktiengesellschaft | Copolymers of substituted piperidines, their manufacture and use |
| US5047489A (en) * | 1990-02-14 | 1991-09-10 | Ciba-Geigy Corporation | Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties, and polymers, copolymers and stabilized compositions |
-
1992
- 1992-12-24 CN CN92114759A patent/CN1036998C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2748362A1 (en) * | 1977-10-28 | 1979-05-03 | Hoechst Ag | POLYMERS SUBSTITUTED PIPERIDINE, THEIR PRODUCTION AND USE |
| US4308362A (en) * | 1979-05-23 | 1981-12-29 | Hoechst Aktiengesellschaft | Copolymers of substituted piperidines, their manufacture and use |
| US5047489A (en) * | 1990-02-14 | 1991-09-10 | Ciba-Geigy Corporation | Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties, and polymers, copolymers and stabilized compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432160C (en) * | 2004-12-16 | 2008-11-12 | 汕头大学 | Water-based reaction type hindered amine use, formula and method for in-situ photostabilization of coating layer |
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| CN1088590A (en) | 1994-06-29 |
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