CN106565899B - Controllable molecular weight benzotriazole styrol copolymer and its preparation method and application - Google Patents
Controllable molecular weight benzotriazole styrol copolymer and its preparation method and application Download PDFInfo
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- benzotriazole
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- 239000012964 benzotriazole Substances 0.000 title claims abstract description 50
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920001577 copolymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004611 light stabiliser Substances 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000000047 product Substances 0.000 claims description 31
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012989 trithiocarbonate Substances 0.000 claims description 14
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 3
- -1 dithiobenzoic acid isopropyl phenyl ester Chemical class 0.000 claims description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 2
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N Benzyl benzoate Natural products C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229960002903 benzyl benzoate Drugs 0.000 claims 1
- 125000004396 dithiobenzyl group Chemical group 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
- 238000013467 fragmentation Methods 0.000 abstract description 6
- 238000006062 fragmentation reaction Methods 0.000 abstract description 6
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- PZJQZQQFGDNUGY-UHFFFAOYSA-N 2h-benzotriazole;styrene Chemical compound C=CC1=CC=CC=C1.C1=CC=C2NN=NC2=C1 PZJQZQQFGDNUGY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- 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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of controllable molecular weight benzotriazole styrol copolymers and its preparation method and application, the present invention utilizes reversible addition-fragmentation chain transfer free radical polymerization method, by polymerizable type benzotriazole, styrene, azodiisobutyronitrile, chain-transferring agent, by controlling reaction raw materials ratio, it is gradually added in the amount of the reaction temperature in the stage of reaction each stage and the control in reaction time and chain-transferring agent, the benzotriazole styrol copolymer of controllable molecular size range, narrow ditribution is made；Controllable molecular weight narrow ditribution benzotriazole styrol copolymer of the invention is used as the light stabilizer in high molecular material, can effectively reduce the physical deterioration in process and the migration volatilization in use process, enable the continuous and effective that light stabilization is permanent.
Description
Technical field
The present invention relates to the auxiliary agent field of macromolecule material product, more specifically to a kind of light stabilizer benzotriazole
Styrol copolymer, the invention further relates to the preparation methods and purposes of a kind of benzotriazole styrol copolymer.
Background technique
High molecular material is influenced by photooxidation in use, can make the appearance and Physical Mechanical of material product
It can deteriorate, gradually lose use value, and adding light stabilizer is that prevent photooxidation most convenient be also most effective
One of approach.There are many light stabilizer type, wherein benzotriazole light stabilizer has become because it has efficient light stability
For the widest a kind of light stabilizer of current application range.And before allowing basis material to have photooxidation resistant work in use
It mentions, is exactly that light stabilizer steady in a long-term can be present in basis material.But the benzotriazole light stabilizer being put on sale in early days
Product is mostly alkyl-substituted phenols derivative, they because the disadvantages of volatile, easy extracting can not be that material provides protection for a long time, because
The molecular weight of this benzotriazole becomes one of the important directions of benzotriazole new varieties.But then, macromolecule
Quantization hampers benzotriazole light stabilizer again and spreads in the polymer, is unfavorable for benzotriazole light stabilizer molecule by product
Portion is effectively supplemented to surface, influences giving full play to for its light stabilizing active.Therefore, light stabilizer molecular weight how is controlled
Size just seems most important.Traditional free radical polymerization is more troublesome control molecular weight of product, the reaction condition of polymerization
Also it is difficult to control, in particular how changes reaction condition and obtain the polymer of predictable molecular weight, it is often unavailable preparatory
The molecular weight of design, and the molecular weight distribution of product is wider, if the molecular weight distribution of light stabilizer is wider, low molecular weight part
It is volatile, easily extract；And high molecular weight moieties are difficult to spread in the polymer, are unfavorable for playing a role.And reversible addition is disconnected
Splitting chain tra nsfer free radical polymerization is one of active free radical polymerization method most promising in Controlled Living Radical Polymerization,
It can efficiently control the average molecular weight of polymer, and obtained polymer molecular weight narrow distribution, and reversible addition
Fragmentation chain transfer free radical polymerization polymerization not only has the advantages that other controllable living polymerizations but also applicable monomeric species are more, institute
The polymeric reaction condition needed is mild, therefore synthesizes controllable molecular weight using reversible addition-fragmentation chain transfer free radical polymerization method
Benzotriazole polymerization has wide prospects for commercial application.
Summary of the invention
The purpose of the present invention is utilizing reversible addition-fragmentation chain transfer free radical polymerization method, a kind of controllable molecular weight is synthesized
Benzotriazole styrol copolymer.The benzotriazole styrene that another object of the present invention provides a kind of controllable molecular weight is total
The benzotriazole styrol copolymer of the preparation method of polymers, another object of the present invention controllable molecular weight is stablized as light
The purposes of agent.
The preparation method of controllable molecular weight benzotriazole styrol copolymer of the invention, mainly comprises the steps that
A. by polymerizable type benzotriazole, styrene, azodiisobutyronitrile, the 1/3 of chain-transferring agent total amount, reactor is added
In be dissolved in dioxane, dissolution is sufficiently stirred at normal temperature；The 2/3 of another container Chain transfer agent total amount, is dissolved in two
In six ring of oxygen；
B. under the protection of nitrogen, the first stage, starts initial reaction, time 0.5-2.0 hour by 50-60 DEG C of temperature；Second
60-70 DEG C of phase temperature, remaining 2/3 chain-transferring agent solution is added dropwise in reactor, the reaction was continued, time 1.0-4.0 hour,
Phase III is added dropwise after the completion of chain-transferring agent, heats up 70-90 DEG C, reaction time 2.5-6.0 hour；
C. after the reaction was completed, product mixture is poured into methanol or methanol and water 1:1 volume ratio mixed liquor and is precipitated, and is taken out
Filter, drying obtain product, a small amount of tetrahydrofuran of product are dissolved, then pour into methanol or methanol and water 1:1 volume ratio mixed liquor
In precipitated, repeat above step obtain final product for several times.
In preparation method of the invention, polymerizable type benzotriazole, the molar ratio of chain-transferring agent and radical initiator are as follows:
30-200:1:0.1-0.5。
In preparation method of the invention, polymerizable type benzotriazole and styrene molar ratio are 0.1~2.
In preparation method of the invention, the benzotriazole of the polymerizable type is 2- (2 '-propionyloxies -5 '-methylbenzene
Base) benzotriazole.
In preparation method of the invention, the chain-transferring agent is dithiobenzoic acid isopropyl phenyl ester, dithiobenzoic acid
Benzyl ester, dithiobenzoic acid -1- ethoxycarbonyl-n-propyl, S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate, S,
S '-two (α-acetophenone) trithiocarbonate, S, S '-dipropionic acid trithiocarbonate or S- propionic acid-S '-(Alpha-Methyl-α '-second
Acid) trithiocarbonate.
The additive amount of dioxane is 0.5-2ml/g monomer in preparation method of the invention.
Controllable molecular weight benzotriazole styrol copolymer of the invention, molecular weight is 1 × 103-2×104Between；Molecule
Amount is distributed between 1.05-1.3.
The benzotriazole styrol copolymer of controllable molecular weight narrow ditribution of the invention is preventing high score as light stabilizer
The application of sub- material light aging.
The invention has the following advantages:
The present invention is by reversible addition-fragmentation chain transfer free radical polymerization method, by controlling reaction raw materials ratio, anti-
The amount of the reaction temperature and the control in reaction time and chain-transferring agent of answering each stage in stage is gradually added, and can be made can
The benzotriazole styrol copolymer of predicted molecular weight size, narrow ditribution；Principle is to work as reversible addition-fragmentation chain transfer free radical
When polymerization reaction monomer reaches same conversion, the ratio of monomer and chain-transferring agent is bigger, and polymerizate theoretical molecular weight is just
It can become larger therewith；Under monomer and the identical situation of chain-transferring agent ratio, as polymerization reaction time increases, monomer conversion becomes
Greatly, polymer molecular weight can also become larger therewith, but when reacted between reache a certain level, monomer conversion reaches maximum,
Polymer molecular weight can not increase as the time increases again；Predictable molecular size range narrow ditribution benzotriazole can be made
Styrol copolymer.
Benzotriazole styrol copolymer of the invention, the styrene segment in segment be able to ascend the light stabilizer with
The compatibility of basis material can effectively reduce benzotriazole in physical deterioration and the use process in process and stablize
The migration of agent is volatilized, and the continuous and effective that light stabilization is permanent is enable.
No coupling product in process of the present invention, reaction condition is mild, easy to operate, and clean and environmental protection does not pollute substantially.
Detailed description of the invention
Fig. 1 is the structural formula of controllable molecular weight benzotriazole styrol copolymer of the present invention.
Fig. 2 is the infrared spectroscopy of controllable molecular weight benzotriazole styrol copolymer of the present invention.
Specific embodiment
The present invention is further described specifically by the following examples.It is necessarily pointed out that following implement
Example is served only for that the present invention is described further, should not be understood as limiting the scope of the invention, the field technology is ripe
Practice personnel and some nonessential modifications and adaptations are made to the present invention according to aforementioned present invention content, still falls within protection of the invention
Range.
Embodiment 1
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 3,36g, styrene 2.5g, azodiisobutyronitrile
Reaction is added in the 1/3 of 0.021g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.353g total amount
It is dissolved in dioxane in device, dissolution is sufficiently stirred at normal temperature；The 2/3 of another container Chain transfer agent total amount 0.353g,
It is dissolved in dioxane.
It is added in 10ml dioxane, dissolution is sufficiently stirred；By mixture under the protection of nitrogen, reaction temperature is increased extremely
60 DEG C, the first stage, beginning initial reaction, the time 1.0 hours；Remaining 2/3 chain-transferring agent is added dropwise in second stage temperature 70 C
Solution is in reactor, and the reaction was continued, and the reaction time 2.0 hours, the phase III was added dropwise after the completion of chain-transferring agent, heats up 90 DEG C,
Reaction time 2.5 hours.
After the reaction was completed, product mixture is poured into methanol or methanol and water 1:1 volume ratio mixed liquor and is precipitated, and is taken out
Filter, drying obtain product, a small amount of tetrahydrofuran of product are dissolved, then pour into methanol or methanol and water 1:1 volume ratio mixed liquor
In precipitated, repeat above step obtain final product for several times.Products therefrom number-average molecular weight is 1822, and molecular weight distribution is
1.086。
According to its infrared spectrum, wherein 3060cm-1Place for=C-H stretching vibration peak, in addition, 1610cm-1, 1570cm-1, 1510cm-1There is the skeletal vibration absorption peak of phenyl ring in place, these are all the characteristic absorption peaks of benzotriazole monomer.Therefore it can
To determine to have accessed benzotriazole monomer in polymer architecture.
Embodiment 2
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 3,36g, styrene 2.5g, azodiisobutyronitrile
0.025g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.212g, the 1/3 of total amount, it is added anti-
It answers and is dissolved in device in 10ml dioxane, dissolution is sufficiently stirred at normal temperature；Another container Chain transfer agent total amount 0.212g
2/3, be dissolved in dioxane.
It is added in 10ml dioxane, dissolution is sufficiently stirred；By mixture under the protection of nitrogen, reaction temperature is increased extremely
50 DEG C, the first stage, beginning initial reaction, the time 2.0 hours；65 DEG C of second stage temperature, remaining 2/3 chain-transferring agent is added dropwise
Solution is in reactor, and the reaction was continued, and the reaction time 4.0 hours, the phase III was added dropwise after the completion of chain-transferring agent, heats up 90 DEG C,
Reaction time 6.0 hours.
After the reaction was completed, product mixture is poured into methanol or methanol and water 1:1 volume ratio mixed liquor and is precipitated, and is taken out
Filter, drying obtain product, a small amount of tetrahydrofuran of product are dissolved, then pour into methanol or methanol and water 1:1 volume ratio mixed liquor
In precipitated, repeat above step obtain final product for several times.Products therefrom number-average molecular weight is 2760, and molecular weight distribution is
1.175。
Embodiment 3
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 6.72g, styrene 1.25g, azodiisobutyronitrile
Reaction is added in the 1/3 of 0.025g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.216g total amount
It is dissolved in device in 15ml dioxane, dissolution is sufficiently stirred at normal temperature；Another container Chain transfer agent total amount 0.216g's
2/3, it is dissolved in dioxane.
By mixture under the protection of nitrogen, reaction temperature is increased to 50 DEG C, the first stage starts initial reaction, time
0.5 hour；Remaining 2/3 chain-transferring agent solution is added dropwise in reactor in second stage temperature 70 C, and the reaction was continued, when reaction
Between 3.0 hours, the phase III, be added dropwise chain-transferring agent after the completion of, heat up 85 DEG C, the reaction time 2.5 hours.
After the reaction was completed, product mixture is poured into methanol or methanol and water 1:1 volume ratio mixed liquor and is precipitated, and is taken out
Filter, drying obtain product, a small amount of tetrahydrofuran of product are dissolved, then pour into methanol or methanol and water 1:1 volume ratio mixed liquor
In precipitated, repeat above step obtain final product for several times.Products therefrom number-average molecular weight is 2132, and molecular weight distribution is
1.202。
Embodiment 4
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 3.36g, styrene 2.5g, azodiisobutyronitrile
Reaction is added in the 1/3 of 0.012g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.106g total amount
It is dissolved in device in 10ml dioxane, dissolution is sufficiently stirred at normal temperature；The 2/3 of another container Chain transfer agent total amount, it is molten
Solution is in dioxane.
By mixture under the protection of nitrogen, reaction temperature is increased to 55 DEG C, starts first stage initial reaction, time
1.5 hour；65 DEG C of second stage temperature, remaining 2/3 chain-transferring agent solution is added dropwise in reactor, the reaction was continued, when reaction
Between 4.0 hours, the phase III, be added dropwise chain-transferring agent after the completion of, heat up 85 DEG C, the reaction time 5.0 hours.
Obtained product mixture is poured into after the reaction was completed and carries out precipitation process in methanol, is filtered, drying can wait until
Final product.Products therefrom number-average molecular weight is 6456, molecular weight distribution 1.127.
Embodiment 5
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 13.44g, styrene 10g, azodiisobutyronitrile
Reaction is added in the 1/3 of 0.015g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.053g total amount
It is dissolved in device in 15ml dioxane, dissolution is sufficiently stirred at normal temperature；The 2/3 of another container Chain transfer agent total amount, it is molten
Solution is in dioxane.
By mixture under the protection of nitrogen, reaction temperature is increased to 60 DEG C, starts first stage initial reaction, time
2.0 hour；Remaining 2/3 chain-transferring agent solution is added dropwise in reactor in second stage temperature 70 C, and the reaction was continued, when reaction
Between 3.0 hours, the phase III, be added dropwise chain-transferring agent after the completion of, heat up 85 DEG C, the reaction time 5.0 hours.
Obtained product mixture is poured into after the reaction was completed and carries out precipitation process in methanol, is filtered, drying can wait until
Final product.Products therefrom number-average molecular weight is 18928, molecular weight distribution 1.255.
Embodiment 6
By 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole 3.36g, styrene 2.5g, azodiisobutyronitrile
Reaction is added in the 1/3 of 0.025g, chain-transferring agent S, S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate 0.204g total amount
It is dissolved in device in 10ml dioxane, dissolution is sufficiently stirred at normal temperature；The 2/3 of another container Chain transfer agent total amount, it is molten
Solution is in dioxane.
By mixture under the protection of nitrogen, reaction temperature is increased to 55 DEG C, starts first stage initial reaction, time
1.5 hour；Remaining 2/3 chain-transferring agent solution is added dropwise in reactor in second stage temperature 70 C, and the reaction was continued, when reaction
Between 3.5 hours, the phase III, be added dropwise chain-transferring agent after the completion of, heat up 85 DEG C, the reaction time 4.0 hours.
Obtained product mixture is poured into after the reaction was completed and carries out precipitation process in methanol, is filtered, drying can wait until
Final product.Products therefrom number-average molecular weight is 3657, molecular weight distribution 1.146.
The molecular size range and its profile exponent for the benzotriazole light stabilizer that embodiment 1-6 is obtained are using Japanese Tosoh strain
Formula commercial firm HLC-8320GPC gel permeation chromatograph measures.Chromatographic column is TSK gel super HZM-M (6.0*
150mm) and two root chromatogram column of TSK gel SuperHZ3000 (6.0*150mm) connect differential refraction detector, with tetrahydrofuran
For mobile phase, flow velocity is 0.6 ml/min, and temperature is 40 DEG C.
Application examples
Change to investigate the light stabilization of the copoly type light stabilizer high molecular material of controllable molecular weight narrow ditribution of the invention
Property effect, the present invention selects a kind of high molecular material that anti-ultraviolet aging is poor --- polyformaldehyde is as modified object.
The product in present invention preparation in embodiment 2 is first added to polyformaldehyde according to 1% to be uniformly mixed, is then placed in double spiral shells
It squeezes out and is blended on bar extruder, be granulated, standard sample is finally molded on injection molding machine.And by the standard sample (application examples),
Through ultraviolet light, (irradiation level is 3.0W/m to pure polyformaldehyde2) after irradiation 800 hours, according to its draftability of GB1040-92 standard test
Can, tensile speed 50mm/min, according to its impact property of GB1843-96 standard test, test result is as follows shown in table.
Claims (5)
1. a kind of preparation method of controllable molecular weight benzotriazole styrol copolymer, mainly comprises the steps that
A. by polymerizable type benzotriazole, styrene, azodiisobutyronitrile, the 1/3 of chain-transferring agent total amount, it is added molten in reactor
Dissolution is sufficiently stirred in dioxane in solution at normal temperature；The 2/3 of another container Chain transfer agent total amount, is dissolved in dioxy six
In ring；
B. under the protection of nitrogen, the first stage, starts initial reaction, time 0.5-2.0 hour by 50-60 DEG C of temperature；Second stage
60-70 DEG C of temperature, remaining 2/3 chain-transferring agent solution is added dropwise in reactor, the reaction was continued, time 1.0-4.0 hour；Third
Stage is added dropwise after the completion of chain-transferring agent, heats up 70-90 DEG C, reaction time 2.5-6.0 hour；
C. after the reaction was completed, product mixture is poured into methanol or methanol and water 1:1 volume ratio mixed liquor and is precipitated, and is filtered,
Drying obtains product, and a small amount of tetrahydrofuran of product is dissolved, then pour into methanol or methanol in water 1:1 volume ratio mixed liquor into
Row precipitating repeats above step and obtains final product for several times；
Wherein, the polymerizable type benzotriazole, the molar ratio of chain-transferring agent and azodiisobutyronitrile are as follows: 30-200:1:
0.1-0.5；
The polymerizable type benzotriazole and styrene molar ratio is 0.1~2.
2. according to the preparation method of benzotriazole styrol copolymer described in claim 1, which is characterized in that wherein, described
The benzotriazole of polymerizable type is 2- (2 '-propionyloxies -5 '-aminomethyl phenyl) benzotriazole.
3. according to the preparation method of benzotriazole styrol copolymer described in claim 1, which is characterized in that wherein, the chain
Transfer agent be dithiobenzoic acid isopropyl phenyl ester, dithio benzyl benzoate, dithiobenzoic acid -1- ethoxycarbonyl-n-propyl, S,
S '-two (α, α '-methyl-α "-acetic acid) trithiocarbonate, S, S '-two (α-acetophenone) trithiocarbonate, S, S '-dipropyl
Sour trithiocarbonate or S- propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate.
4. a kind of controllable molecular weight benzotriazole styrol copolymer that the preparation method according to claim 1,2 or 3 synthesizes,
It is characterized in that, molecular weight is 1 × 103-2×104Between, molecular weight distribution is between 1.05-1.3.
5. a kind of controllable molecular weight benzotriazole styrol copolymer according to claim 4 is used as light stabilizer anti-
The only application of high molecular material light aging.
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| US4260768A (en) * | 1980-01-17 | 1981-04-07 | Gaf Corporation | Copolymerizable, ultraviolet light absorber 2-(2H-benzotriazol-2-yl)-4-alkylphenol acrylic acid esters |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260768A (en) * | 1980-01-17 | 1981-04-07 | Gaf Corporation | Copolymerizable, ultraviolet light absorber 2-(2H-benzotriazol-2-yl)-4-alkylphenol acrylic acid esters |
| 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 |
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| Title |
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| 可控摩尔质量窄分布受阻胺光稳定剂的合成及应用;刘文亮等;《塑料工业》;20160331;第44卷(第3期);第131-134页 * |
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