CN1088590A - A kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer - Google Patents
A kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer Download PDFInfo
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- CN1088590A CN1088590A CN 92114759 CN92114759A CN1088590A CN 1088590 A CN1088590 A CN 1088590A CN 92114759 CN92114759 CN 92114759 CN 92114759 A CN92114759 A CN 92114759A CN 1088590 A CN1088590 A CN 1088590A
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Abstract
The present invention relates to a kind of being used as on the side chain of photostabilizer and have 2,2,6, the preparation method of the multipolymer of 6-tetramethyl-piperidyl (hindered amine), it is by 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine and α-vinyl monomer make by free radical precipitation process for copolymerization.Owing in copolymerization, replaced the aromatics organic solvent with aliphatics straight chain or naphthenic hydrocarbon, not only eliminate the pollution of aromatic hydrocarbons, and simplified technology, improved yield.The high-molecular optical stablizer that makes with the inventive method has outstanding light stability to multiple synthetic polymer, particularly polyolefine.
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, thereby be subjected to general attention.
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.
The 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
3
It 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.
DE2748362 once adopted (I) and α-vinyl monomer the photostabilizer of solution polymerization process polymeric multipolymer as various synthetic high polymers.
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.
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 DT 2748362 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 DT 2748362 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 with the inventive method, 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.).
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, vinyl acetate, acrylamide, maleic anhydride, vinyl cyanide etc.
Polymer photostabilizer of the present invention is by monomer (I) (M
1) and 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 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 1) 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
| 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 | -1000 gram sherwood oils | 〉95％ 70％ | Simple very complicated |
M
1: monomer (I), M
2: vinyl acetate M
2/ M
1=60/40
Polymerization temperature: 80 ℃ of polymerization times: 8 hours
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 | Monomer | Consumption (gram) | N% |
| M 1?M 2 | M 1?M 2 | ||
| 2 3 4 | (I) methyl methacrylate (I) methacrylic acid rate ester (I) methacrylic acid hexadecyl ester | 6.8 13.5 11.3 44.6 37.9 37.9 | 2.66 1.25 0.69 |
Embodiment 5
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
| Photostabilizer | Content (%) | After tanning by the sun 62 days | After tanning by the sun 103 days | ||
| Stretching strength retentivity (%) | Extension at break conservation rate (%) | Stretching strength retentivity (%) | Extension at break conservation rate (%) | ||
| Blank embodiment 1 Tinuvin 622 | － 0.2 0.2 | 23 47 26 | 58 103 75 | Can't take a sample and 18 can't take a sample | Can't take a sample and 5 can't take a sample |
Annotate: 1, thickness of sample 13 μ (LLDPE Daqing Petrochemical head factory DFDA-7042)
2, tan by the sun the place: Guangzhou, throwing try May 22 date
3, Tinmvin 622, are Ciba-Geigy company commodity
The various photostabilizers of table 4 are to the comparison of polyacrylic light stability
| Photostabilizer | Content | Photoxidation inductive phase (hour) | The light stable factor |
| Blank embodiment 234 | － 4×10 －5Ml/10gpp is the same | 28 76 114 168 | 1 2.7 4 6 |
Annotate: 1, sample thickness 100 μ
2, be light source (＜2900 with the 500w high voltage mercury lamp
Elimination) carries out artificial accelerated aging.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 Tinuvin 622.But its light stability is better than 622, and the result has fully shown photostabilizer excellent light stability energy of the present invention.
Claims (6)
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, described photostabilizer is by monomer 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine (M
1) and α-vinyl monomer (M
2) in the presence of radical initiator copolymerization make α-vinyl monomer (M
2) be the acrylic or methacrylic esters of gallic acid:
C
1-18Alkyl; Vinyl acetate; Acrylamide; Vinyl cyanide, described monomer ratio (weight %) M
2: M
1=90-5: 10-95, it is characterized in that adopting the free radical precipitation polymerization process, with inert solvent as reaction medium, polymerization temperature and time are respectively 50-90 ℃ and 6-10 hour, 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, and described inert solvent is meant the aliphatics straight chain hydrocarbon, also can be alicyclic hydrocarbon, described α-vinyl monomer (M
2) can also be maleic anhydride, described radical initiator is azo compound and organo-peroxide.
2, the preparation method of photostabilizer as claimed in claim 1, the optimum amount that it is characterized in that described radical initiator is the 0.8-1.5% of reaction-ure mixture.
3, as the preparation method of claim 1,2 described photostabilizers, it is characterized in that described aliphatics straight chain hydrocarbon is meant any in hexane, heptane, the sherwood oil, described alicyclic hydrocarbon is meant hexanaphthene, any in the suberane.
4, as the preparation method of photostabilizer as described in the claim 3, it is characterized in that described radical initiator azo-compound is a Diisopropyl azodicarboxylate, any in the 2,2'-Azobis(2,4-dimethylvaleronitrile).
5, the preparation method of photostabilizer as claimed in claim 3 is characterized in that described radical initiator organo-peroxide is a dilauroyl peroxide.
6,, it is characterized in that described best polymerization temperature is 60-70 ℃ as the preparation method of claim 4,5 described photostabilizers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114759A CN1036998C (en) | 1992-12-24 | 1992-12-24 | Making method for hidered amine side group containing copolymer used as light stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Publication Number | Publication Date |
|---|---|
| CN1088590A true CN1088590A (en) | 1994-06-29 |
| CN1036998C CN1036998C (en) | 1998-01-14 |
Family
ID=4947086
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|---|---|---|---|
| CN92114759A Expired - Fee Related 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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|---|---|
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Cited By (5)
| 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 |
| CN109517108A (en) * | 2018-10-22 | 2019-03-26 | 保定市乐凯化学有限公司 | Prepare maleimide/alpha olefin copolymer method |
| CN111808225A (en) * | 2020-06-22 | 2020-10-23 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| CN116003680A (en) * | 2022-12-26 | 2023-04-25 | 天集化工助剂（沧州）有限公司 | Polymeric anti-light aging multifunctional additive and preparation method and application thereof |
Families Citing this family (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 |
Family Cites Families (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 |
| DE2920918A1 (en) * | 1979-05-23 | 1980-11-27 | Hoechst Ag | COPOLYMERS SUBSTITUTED PIPERIDINE, THEIR PRODUCTION 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
Cited By (8)
| 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 |
| CN109517108A (en) * | 2018-10-22 | 2019-03-26 | 保定市乐凯化学有限公司 | Prepare maleimide/alpha olefin copolymer method |
| 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 |
| CN111808225A (en) * | 2020-06-22 | 2020-10-23 | 宿迁联盛科技股份有限公司 | High molecular weight polymeric light stabilizer and preparation method thereof |
| 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 |
| CN116003680A (en) * | 2022-12-26 | 2023-04-25 | 天集化工助剂（沧州）有限公司 | Polymeric anti-light aging multifunctional additive and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036998C (en) | 1998-01-14 |
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