CN105601792A - Preparation method of controllable molecular weight copolymerized hindered amine light stabilizer - Google Patents
Preparation method of controllable molecular weight copolymerized hindered amine light stabilizer Download PDFInfo
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- CN105601792A CN105601792A CN201610041900.XA CN201610041900A CN105601792A CN 105601792 A CN105601792 A CN 105601792A CN 201610041900 A CN201610041900 A CN 201610041900A CN 105601792 A CN105601792 A CN 105601792A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Hydrogenated Pyridines (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of a controllable molecular weight copolymerized hindered amine light stabilizer. The method comprises: according to the principle of reversible addition-fragmentation chain transfer free-radical polymerization, adding polymerizable hindered amine with methyl methacrylate, azodiisobutyronitrile and a chain transfer agent into a solvent, and stirring well for dissolving; under hydrogen protection, reacting at 70-85 DEG C for 4-12 hours, and ending reaction; pouring a precipitating agent into reacted material for precipitation, and drying precipitate to obtain a final product. By controlling the ratio and reaction time of reaction materials, it is possible to prepare the copolymerized hindered amine light stabilizer with predictable molecular weight; it is possible to effectively reduce physical loss of a processing process and transfer volatilization of the hindered amine light stabilizer in use, thus providing persistent and effective light stabilization.
Description
Technical field
The present invention relates to the auxiliary agent field of macromolecule material product, relate in particular a kind of system of light stabilizerPreparation Method.
Background technology
Macromolecular material is in use subject to the impact of photooxidation, can make outward appearance and the physical machine of material productTool performance worsens, and loses gradually use value, is to prevent that photooxidation is the most square and add light stabilizerJust be also one of the most effective approach. Light stabilizer kind is a lot, and wherein, hindered amine as light stabilizer is because of its toolStandby light stability efficiently, has become a current range of application class light stabilizer the most widely. And allow matrixMaterial in use possesses the prerequisite of photooxidation resistant, is exactly that light stabilizer can steady in a long-term being present inIn matrix material. But mostly the hindered amine as light stabilizer product of going on the market is in early days taking hindered piperidine as functional groupLow molecular weight compound, they because of the shortcomings such as volatile, easy extracting cannot be long-term for material provides protection,Therefore the HMW of hindered amine changes into one of important directions into hindered amine new varieties. But then,Macromolecule quantizes to have hindered again hindered amine as light stabilizer to spread in polymer, is unfavorable for hindered amine as light stabilizerMolecule is had more supplementary to surface by goods inside, affect giving full play to of its light stabilizing active. Therefore,Size how to control light stabilizer molecular weight just seems most important. In CN105153121A, utilize N-The reaction of (2,2,6,6-tetramethyl-4-piperidyl) amine and Cyanuric Chloride obtains intermediate, recycling intermediate withN, N '-bis-[N-(2,2,6,6-tetramethyl-4-piperidyl)]-1-hexamethylene diamine reaction, and further at the work of catalystWith under obtain polymer, building-up process is comparatively complicated; In CN1088590A, utilize 4-(methyl) acryloyl-oxyBase-2,2,6,6-tetramethyl piperidine and α-vinyl monomer carry out free radical precipitation process for copolymerization and make, process solventUse lessly, process is simple. These achievements in research can both obtain the aggretion type light stabilizer of HMW,But both are not mentioned molecular weight how to control products therefrom all. Traditional radical polymerization is produced for controllingThing molecular weight comparatively bothers, and particularly how to change reaction condition and obtain the polymer of predictable molecular weight,And reversible addition-fragmentation chain transfer free radical polymerization (RAFT) is to have development in Controlled Living Radical Polymerization mostOne of active free radical polymerization method of prospect, it can control the mean molecule quantity of polymer effectively, andReversible addition-fragmentation chain transfer free radical polymerization not only has the advantage of other controlled living polymerization but also applicableMonomeric species is many, needed polymeric reaction condition gentleness, and therefore reversible addition-fragmentation chain transfer free radical is poly-Close and there is wide prospects for commercial application.
Summary of the invention
The object of the invention is to utilize reversible addition-fragmentation chain transfer free radical polymerization method, provide a kind of controlled pointThe preparation method of the copoly type hindered amine as light stabilizer of son amount.
The preparation method of the copoly type hindered amine as light stabilizer of controllable molecular weight of the present invention, mainly comprises following stepRapid:
1) polymerizable type hindered amine and methyl methacrylate, azodiisobutyronitrile and chain-transferring agent are added to solventIn, fully stirring and dissolving;
2) under the protection of nitrogen, at 70 DEG C-85 DEG C, reaction 4-12 hour, cessation reaction;
3) reactant is poured in precipitating reagent and is carried out precipitation process, then sediment is dried and obtained end product.
In preparation method of the present invention, the mol ratio of polymerizable type hindered amine, chain-transferring agent and radical initiatorFor: 30-200:1:0.1-0.5.
In preparation method of the present invention, polymerizable type hindered amine and methyl methacrylate mol ratio are 0.1～2.
In preparation method of the present invention, the hindered amine of described polymerizable type, is 4-acryloxy-1,2,2,6,6-Pentamethyl piperidines or 4-methacryloxy-1,2,2,6,6-pentamethyl piperidines.
In preparation method of the present invention, described chain-transferring agent is dithiobenzoic acid ester class transfer agent or three sulfo-sCarbonates transfer agent.
In preparation method of the present invention, described dithiobenzoic acid ester class transfer agent is dithiobenzoic acid isopropylPhenyl ester, dithio benzyl benzoate or dithiobenzoic acid-1-ethoxycarbonyl-n-propyl.
In preparation method of the present invention, described trithiocarbonate class transfer agent is S, S '-bis-(α, α '-methyl-α " acetic acid)Trithiocarbonate, S, S '-bis-(α-acetophenone) trithiocarbonate, S, S '-dipropionic acid trithiocarbonate or S-propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate.
Solvent described in preparation method of the present invention is dioxane, and the addition of dioxane is 0.5-1ml/gMonomer.
In preparation method of the present invention, the reaction time is 6-8 hour.
In preparation method of the present invention, described precipitating reagent is methyl alcohol or methyl alcohol and water 1:1 volume ratio mixed liquor.
The copoly type hindered amine as light stabilizer molecular weight of controllable molecular weight of the present invention is 103-2*104Between.
The present invention has following beneficial effect:
The present invention, by reversible addition-fragmentation chain transfer free radical polymerization, works as reversible addition-fragmentation chain transfer free radicalWhen polymerization reaction monomer reaches same conversion, the ratio of monomer and chain-transferring agent is larger, its polymerizate reasonOpinion molecular weight will become large thereupon; In the situation that monomer is identical with chain-transferring agent ratio, along with polymerisationTime increases, and it is large that monomer conversion becomes, and polymer molecular weight also can become greatly thereupon, but reaches when the reaction timeTo a certain extent, it is maximum that monomer conversion reaches, and its polymer molecular weight again can be along with time increaseIncrease; Therefore, control reaction raw materials ratio and reaction time, can make measurable molecular size rangeCopoly type hindered amine as light stabilizer.
The copoly type hindered amine as light stabilizer of controllable molecular weight of the present invention, the methacrylate segment energy in segmentEnough promote the compatibility of described light stabilizer and matrix material, can effectively reduce the physics in processThe migration of hindered amine stabilizer volatilization in loss and use procedure, can have light stabilization in permanent continuingEffect.
No coupling product in process of the present invention, reaction condition gentleness, simple to operate, clean environment firendly, does not have dirt substantiallyDye, catalyst amount is few.
Brief description of the drawings
Fig. 1 is the structural formula of the copoly type hindered amine as light stabilizer of controllable molecular weight of the present invention. Wherein R is hydrogenOr methyl.
Fig. 2 is the infrared spectrum of the copoly type hindered amine as light stabilizer of controllable molecular weight of the present invention.
Detailed description of the invention
By the following examples the present invention is further described specifically. Be necessary this be pointed out that withLower embodiment, only for the present invention is described further, can not be interpreted as the limit to protection domain of the present inventionSystem, this art skilled person makes some nonessential improvement according to the invention described above content to the present inventionAnd adjustment, still belong to protection scope of the present invention.
Embodiment 1
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 2.86g, methyl methacrylate 2.5g, azoBis-isobutyronitrile 0.021g, chain-transferring agent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate 0.353gAdd in 5.5ml dioxane, fully stirring and dissolving; By mixture under the protection of nitrogen, rising reaction temperatureDegree, to 70 DEG C, reacts 12 hours, after having reacted, the product mixed liquor obtaining is poured in methanol/water and is carried outPrecipitation process, suction filtration, oven dry can be waited until end product. Products therefrom number-average molecular weight is 1581.
According to its infrared spectrum, wherein 2969cm-1Place is the stretching vibration peak of methyl, in ester group functional groupThe peak of C=O stretching vibration appears at 1733cm-1Place, at 1380～1360cm-1There are one two in scopePeak, this be by hindered amine group peculiar-C (CH3)2The asymmetric bending vibration of structure causes, is to be obstructedThe characteristic absorption peak of amine groups. Therefore can judge and access hindered amine monomer in polymer architecture.
Embodiment 2
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 2.86g, methyl methacrylate 2.5g, azoBis-isobutyronitrile 0.025g, chain-transferring agent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate 0.212g adds 3mlDioxane in, fully stirring and dissolving; By mixture under the protection of nitrogen, rising reaction temperature to 85DEG C, react 4 hours, after having reacted, the product mixed liquor obtaining is poured into and in methanol/water, carried out precipitation process,Suction filtration, oven dry can be waited until end product. Products therefrom number-average molecular weight is 2592.
Embodiment 3
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 5.632g, methyl methacrylate 1.25g, evenNitrogen bis-isobutyronitrile 0.025g, chain-transferring agent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate 0.216g addsIn the dioxane of 5.5ml, fully stirring and dissolving; By mixture under the protection of nitrogen, rising reaction temperatureTo 85 DEG C, react 8 hours, after having reacted, the product mixed liquor obtaining is poured in 1:1 methanol/waterRow precipitation process, suction filtration, oven dry can be waited until end product. Products therefrom number-average molecular weight is 2132.
Embodiment 4
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 2.86g, methyl methacrylate 2.5g, azoBis-isobutyronitrile 0.012g, chain-transferring agent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate 0.106g adds 5.5mlDioxane in, fully stirring and dissolving; By mixture under the protection of nitrogen, rising reaction temperature to 85DEG C, react 12 hours, after having reacted, the product mixed liquor obtaining is poured into and in methanol/water, carried out precipitation process,Suction filtration, oven dry can be waited until end product. Products therefrom number-average molecular weight is 7346.
Embodiment 5
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 2.86g, methyl methacrylate 2.5g, azoBis-isobutyronitrile 0.015g, chain-transferring agent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate 0.053g adds 3mlDioxane in, fully stirring and dissolving; By mixture under the protection of nitrogen, rising reaction temperature to 85DEG C, react 12 hours, after having reacted, the product mixed liquor obtaining is poured into and in methanol/water, carried out precipitation process,Suction filtration, oven dry can be waited until end product. Products therefrom number-average molecular weight is 15563.
Embodiment 6
By 4-acryloxy-1,2,2,6,6-pentamethyl piperidines 2.86g, methyl methacrylate 2.5g, azoBis-isobutyronitrile 0.025g, chain-transferring agent dithiobenzoic acid isopropyl phenyl ester 0.204g adds 5.5ml dioxaneIn, fully stirring and dissolving; By mixture, under the protection of nitrogen, rising reaction temperature to 85 DEG C, reacts 12Hour, after having reacted, the product mixed liquor obtaining to be poured in methanol/water and carried out precipitation process, suction filtration, driesDo and can wait until end product. Products therefrom number-average molecular weight is 2869.
The molecular size range of the hindered amine as light stabilizer that embodiment 1-6 obtains and profile exponent thereof adopt Japan eastThe HLC-8320GPC of Cao Co., Ltd. gel permeation chromatograph is measured. Chromatographic column is TSKgelsuperHZM-M (6.0*150mm) and TSKgelSuperHZ3000 (6.0*150mm) two root chromatogram column stringsConnection differential refraction detector, taking oxolane as mobile phase, flow velocity is 0.6 ml/min, temperature is 40 DEG C.
Application examples
In order to investigate the light stable modification of controllable molecular weight copoly type light stabilizer macromolecular material of the present inventionEffect, the present invention selects the poor macromolecular material of a kind of anti-ultraviolet aging---polyformaldehyde (POM)As modification object. First adding the product in embodiment 2 in the present invention's preparation to polyformaldehyde according to 1% stirsMix and mix, then put on double screw extruder and extrude blend, granulation, finally injection moulding on injection machineBecome standard specimen. And through ultraviolet light, (irradiation level is 3.0W/m by this standard specimen (application examples), pure polyformaldehyde2)After irradiation 800 hours, according to its tensile property of GB1040-92 standard test, draw speed 50mm/min,According to its impact property of GB1843-96 standard test, its test result is as shown in the table.
Claims (10)
1. a preparation method for the copoly type hindered amine as light stabilizer of controllable molecular weight, mainly comprises following stepRapid:
1) polymerizable type hindered amine and methyl methacrylate, azodiisobutyronitrile and chain-transferring agent are added to solventIn, fully stirring and dissolving;
2) under the protection of nitrogen, at 70 DEG C-85 DEG C, reaction 4-12 hour, cessation reaction;
3) reactant is poured in precipitating reagent and is carried out precipitation process, then sediment is dried and obtained end product.
2. according to preparation method claimed in claim 1, it is characterized in that, wherein, described polymerizable type is subject toThe mol ratio of resistance amine, chain-transferring agent and radical initiator is: 30-200:1:0.1-0.5.
3. according to preparation method claimed in claim 1, it is characterized in that, wherein, described polymerizable type is subject toResistance amine and methyl methacrylate mol ratio are 0.1～2.
4. according to preparation method claimed in claim 1, it is characterized in that, wherein, described polymerizable typeHindered amine is 4-acryloxy-1,2,2,6,6-pentamethyl piperidines or 4-methacryloxy-1,2,2,6,6-fiveMethyl piperidine.
5. according to preparation method claimed in claim 1, it is characterized in that, wherein, described chain-transferring agent isDithiobenzoic acid ester class transfer agent or trithiocarbonate class transfer agent.
6. according to preparation method claimed in claim 1, it is characterized in that, wherein, described solvent is dioxy sixRing, the addition of dioxane is 0.5-1ml/g monomer.
7. according to preparation method claimed in claim 5, it is characterized in that, wherein, two described thio phenyl firstEsters of gallic acid transfer agent is dithiobenzoic acid isopropyl phenyl ester, dithio benzyl benzoate or dithiobenzoic acid-1-Ethoxycarbonyl-n-propyl.
8. according to preparation method claimed in claim 5, it is characterized in that, wherein, described trithiocarbonic acidEster class transfer agent is S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate, S, S '-bis-(α-acetophenone) trithiocarbonic acidEster, S, S '-dipropionic acid trithiocarbonate or S-propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate.
9. according to preparation method claimed in claim 1, it is characterized in that, wherein, reaction time 6-8 hour.
10. according to preparation method claimed in claim 1, it is characterized in that, wherein, described precipitating reagent is firstAlcohol or methyl alcohol and water 1:1 volume ratio mixed liquor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413096A (en) * | 1981-04-13 | 1983-11-01 | Ciba-Geigy Corporation | α-Olefin copolymers containing pendant hindered amine groups |
| CN1084183A (en) * | 1992-09-09 | 1994-03-23 | 中国科学院化学研究所 | A kind of preparation method with high-molecular optical stablizer of auto-synergistic effect |
| CN1088590A (en) * | 1992-12-24 | 1994-06-29 | 中国科学院化学研究所 | A kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer |
| CN104371053A (en) * | 2014-09-11 | 2015-02-25 | 四川大学 | Hindered amine light stabilizer with characteristics of high molecular weight and narrow molecular weight distribution, and preparation method thereof |
-
2016
- 2016-01-21 CN CN201610041900.XA patent/CN105601792A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413096A (en) * | 1981-04-13 | 1983-11-01 | Ciba-Geigy Corporation | α-Olefin copolymers containing pendant hindered amine groups |
| CN1084183A (en) * | 1992-09-09 | 1994-03-23 | 中国科学院化学研究所 | A kind of preparation method with high-molecular optical stablizer of auto-synergistic effect |
| CN1088590A (en) * | 1992-12-24 | 1994-06-29 | 中国科学院化学研究所 | A kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer |
| CN104371053A (en) * | 2014-09-11 | 2015-02-25 | 四川大学 | Hindered amine light stabilizer with characteristics of high molecular weight and narrow molecular weight distribution, and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20160525 |