CN106633267A - Synthesis method of reactive hindered phenol oxidation-resistant polyolefin additive and application thereof - Google Patents
Synthesis method of reactive hindered phenol oxidation-resistant polyolefin additive and application thereof Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention relates to a synthesis method of a reactive hindered phenol oxidation-resistant polyolefin additive and application thereof. The synthesis method comprises the following steps that a catalyst and 2,4 dyhydroxyl diphenylketone are dissolved in a solvent according to the molar ratio to 1-1.2 to 1, stirring reaction is performed at the temperature of 40-60 DEG C for 2-8 hours, then allyl halide is slowly and dropwise added, constant temperature reaction is performed at the temperature of 40-60 DEG C for 2-6 hours, standing and crystallization are performed, and a product is filtered to obtain the reactive hindered phenol oxidation-resistant polyolefin additive. The reactive hindered phenol oxidation-resistant polyolefin additive is applied to a polyolefin composite material, can improve the compatibility between the additive and polyolefin resin, has the advantages of extraction resistance, difficult migration, difficult volatilization and no environmental pollution, can keep a lasting oxidation-resistant effect, can capture peroxy radicals and can also capture alkyl free radicals, can play the oxidation-resistant effect simultaneously in the surface and interior of a polymer and is high in oxidation-resistant efficiency.
Description
Technical field
The present invention relates to technical field of polymer materials, the anti-oxidant polyolefin of more particularly to a kind of response type hindered phenol is helped
The synthetic method of agent and its application.
Background technology
Polyolefin polymer, particularly polypropylene and polyvinyl chloride have intensity high because of it, and hardness is big, wear-resisting, chemically-resistant
Corrosion, easy processing, it is cheap the advantages of, be widely used as the primary raw material of medical supplies.But medical plastic phase
It is higher than common plasticses requirement, radiation treatment of sterilizing is typically passed through, now the easily oxidized generation performance of common polyolefin is bad
Become, and cause its colour changed into yellow.With the increase of storage time, aging phenomenon increases, and these defects obviously can be subject to certain answering
With restriction.
Polyolefinic oxidation, it is considered that be the automatic oxidation reaction process of free radical, and the oxygen in air, environment temperature increases
Plus will accelerate this kinds of oxidation reaction with some impurity metal ions.In order to suppress or delaying the process of above-mentioned change. extend them
Service life, improve its use value and combination property, antioxidant is as a conventional auxiliary agent in high molecular polymer
Preparation process in used.Wherein, hindered phenol and fragrant phenol are the maximally effective primary antioxidants of two classes, but the toxicity due to fragrant phenol,
Color stain and the compatibility poor to polyolefin, in terms of druggist rubber sundrier, plastics and fiber, it is gradually more effective
, the nontoxic, hindered phenol antioxidant without color stain replaced.The mechanism of hindered phenol antioxidant is to contain an OH in structure
Functional group, is easier to provide hydrogen atom, by with peroxylradicals (ROO.), alkoxy free group (RO.), hydroxy radical
(.OH) etc. combine and be allowed to lose activity, so that the chain reaction of thermo-oxidative ageing terminates；Simultaneously can also hydroperoxide decomposition
RO0H so as to generate stable nonactive product.
At present the developing direction of hindered phenol antioxidant is broadly divided into three classes：High relative molecular mass, compound antioxygen
Agent and response type antioxidant.Wherein, although the hindered phenol antioxygen that macromolecular quantifies has, volatility is low, resistant to extraction, it is resistance to compared with
High temperature, be difficult to pollute, good heat endurance the advantages of, but the drawbacks of there is also certain, one side preparation process technique
More complicated, final is relatively costly, it is difficult to promote the use of on a large scale.On the other hand, it is anti-when what is played a role in product surface
When oxygen agent is depleted, it is that it plays asking for efficiency that internal macromolecule antioxidant even presence can not in time move to surface
Topic.Although another kind of compound antioxidant effect is good, while there is also, conjunction bad with polyolefin high molecular polymer compatibility
It is complex, relatively costly into structure, the shortcomings of complex process, it is unfavorable for industrial extensive application.
The content of the invention
Based on this, it is an object of the invention to provide a kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol.
Specific technical scheme is as follows：
A kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol, comprises the steps：
It is 1-1.2 by mol ratio：1 catalyst and 2,4 dihydroxy benaophenonels are dissolved in solvent, are stirred in 40-60 DEG C
Reaction 2-8h is mixed, allyl halide is then slowly dropped into, 40-60 DEG C of isothermal reaction 2-6h, vacuum fractionation, products therefrom is
The anti-oxidant polyolefin auxiliary agent of the response type hindered phenol.
Wherein in one embodiment, the allyl halide is selected from allyl chloride, allyl bromide, bromoallylene or allyl iodide.
Wherein in one embodiment, described 2,4 dihydroxy benaophenonels are with the mol ratio of the allyl halide
1:1-2。
Wherein in one embodiment, the catalyst is selected from potassium hydroxide, NaOH, sodium methoxide or caustic alcohol.
Wherein in one embodiment, the solvent be acetone, butanone, cyclohexanone, DMF, N, N- bis-
One or more in methylacetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
Wherein in one embodiment, the time for adding of the allyl halide is 30-60min.
It is a further object of the present invention to provide the anti-oxidant polyolefin auxiliary agent of above-mentioned hindered phenol is in composite polyolefine material
Using
Application of the anti-oxidant polyolefin auxiliary agent of above-mentioned response type hindered phenol in composite polyolefine material.
Wherein in some embodiments, the preparation method of the composite polyolefine material comprises the steps：
By response type hindered amine radioresistance polyolefin auxiliary agent 0.05-0.5wt%, response type hindered phenol antioxygen described above
Change the vistanex of polyolefin auxiliary agent 0.05-0.5wt%, per-compound initiator 0.5-1.0wt% and surplus, be placed in
In screw rod blender, extruding pelletization or direct injection mo(u)lding obtain final product the composite polyolefine material.
Wherein in one embodiment, the vistanex is selected from polypropylene, polyethylene or polyvinyl chloride；The initiation
Agent is selected from benzoyl peroxide, dicumyl peroxide or tert-butyl peroxide.
Wherein in one embodiment, each zone temperatures are distributed as 180～230 DEG C in the screw rod blender, and screw rod turns
Speed is：40～100 revs/min.
The anti-oxidant polyolefin auxiliary agent of above-mentioned response type hindered phenol carries allyl reaction using a step low temperature process Fast back-projection algorithm
The small molecule hindered phenol compound of group, the synthetic reaction condition is simple, and yield is high.Using the pi-allyl hindered phenol auxiliary agent of synthesis
Fusion-grafting blending is carried out with polyolefin, reactive group is and poly- by hindered phenol antioxygen molecular linkage to main polymer chain
Compound compatibility is good, and process is simple is with low cost.
Additionally, not only improve the compatibility between auxiliary agent and vistanex, and with resistance to extraction, be difficult to migrate, be difficult
Volatilization and advantage free from environmental pollution, can keep lasting antioxidant effect.Another aspect ortho position pi-allyl Hinered phenols antioxygen
Agent can capture peroxy radical and can capture alkyl diradical again, and oxidation resistant work is played simultaneously on the surface of polymer and inside
With antioxygen efficiency comparison is high.
Specific embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But, the present invention can be with perhaps
More different forms is realizing, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
Understanding to the disclosure is more thorough comprehensive.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field for belonging to the present invention
The implication that technical staff is generally understood that is identical.The term for being used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that of the invention in limiting.Term as used herein "and/or" includes one or more phases
The arbitrary and all of combination of the Listed Items of pass.
Embodiment 1
A kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol of the present embodiment, comprises the steps：
1st, the analytically pure acetone of 100ml is taken, the dihydroxy benaophenonels of 5mol 2,4 of the anhydrous potassium hydroxide sums of 5mol are added,
4h is kept stirring at room temperature, is reacted, then keep the temperature at 40 DEG C.
2nd, the acetone soln of the allyl bromide, bromoallylene of 5mol is slowly dropped in (time for adding 30min) above-mentioned solution, after dripping off
Continue to react 2h at 40 DEG C.
3rd, reactant liquor is cooled to into room temperature, is filtered to remove impurity, vacuum distillation, obtain crude product.Finally use 50% ethanol
Solid (2- hydroxyls -4- allyloxys-benzophenone) is obtained after aqueous solution recrystallization.
4th, detect that solid purity is 94% by GC, yield is 86%.Solvent in filtrate is reused after can distilling.
Embodiment 2
A kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol of the present embodiment, comprises the steps：
1st, the analytically pure acetone of 100ml is taken, the dihydroxy benaophenonels of 5mol 2,4 of the anhydrous potassium hydroxide sums of 5mol are added,
4h is kept stirring at room temperature, is reacted, then keep the temperature at 40 DEG C.
2nd, the acetone soln of the allyl bromide, bromoallylene of 5mol is slowly dropped in above-mentioned solution, reaction is continued at 40 DEG C after dripping off
6h。
3rd, reactant liquor is cooled to into room temperature, is filtered to remove impurity, vacuum distillation, obtain crude product.Finally use 50% ethanol
Solid (2- hydroxyls -4- allyloxys-benzophenone) is obtained after aqueous solution recrystallization.
4th, detect that solid purity is 97% by GC, yield is 97%.Solvent in filtrate is reused after can distilling.
Embodiment 3
A kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol of the present embodiment, comprises the steps：
1st, the analytically pure acetone of 100ml is taken, the dihydroxy benaophenonels of 5mol 2,4 of the anhydrous potassium hydroxide sums of 5mol are added,
4h is kept stirring at room temperature, is reacted, then keep the temperature at 50 DEG C.
2nd, the acetone soln of the allyl bromide, bromoallylene of 5mol is slowly dropped in above-mentioned solution, reaction is continued at 50 DEG C after dripping off
6h。
3rd, reactant liquor is cooled to into room temperature, is filtered to remove impurity, vacuum distillation, obtain crude product.Finally use 50% ethanol
Solid (2- hydroxyls -4- allyloxys-benzophenone) is obtained after aqueous solution recrystallization.
4th, detect that solid purity is 97% by GC, yield is 93%.Solvent in filtrate is reused after can distilling.
The reaction equation of above-mentioned preparation method is as follows：
Embodiment 4
A kind of synthetic method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol of the present embodiment, comprises the steps：
1st, the analytically pure acetone of 100ml is taken, the dihydroxy benaophenonels of 5mol 2,4 of the anhydrous potassium hydroxide sums of 5mol are added,
4h is kept stirring at room temperature, is reacted, then keep the temperature at 40 DEG C.
2nd, the acetone soln of the allyl chloride of 5mol is slowly dropped in above-mentioned solution, reaction is continued at 40 DEG C after dripping off
6h,
3rd, reactant liquor is cooled to into room temperature, is filtered to remove impurity, vacuum distillation, obtain crude product.Finally use 50% ethanol
Solid (2- hydroxyls -4- allyloxys-benzophenone) is obtained after aqueous solution recrystallization.
4th, detect that solid purity is 94% by GC, yield is 93%.Solvent in filtrate is reused after can distilling.
The using method of the anti-oxidant polyolefin auxiliary agent of response type hindered phenol of the synthesis of 1～embodiment of embodiment 4 is：By allyl
[this pi-allyl hindered amine A will be another for base hindered phenol, 4- allyloxy -1,2,2,6,6- tetramethyl piperidines referred to as (hindered amine A)
Apply for a patent of invention in individual case], pi-allyl hindered phenol and peroxide initiator be 0.05% according to pi-allyl hindered amine
～0.5%, hindered phenol A are 0.05%～0.5%, and per-compound initiator is 0.5%～1%, and remaining mass ratio is poly-
Olefin resin.Polyolefin and various additives first carry out pre-dispersed in room temperature, then carry out at certain temperature in screw rod
Melt blending is grafted, and extruding pelletization is stand-by, or directly injection mo(u)lding.
The preparation method of the pi-allyl hindered amine (4- allyloxy -1,2,2,6,6- tetramethyl piperidines), including it is as follows
Step：
It is 1-1.2 by mol ratio：1 catalyst (potassium hydroxide, NaOH, sodium methoxide or caustic alcohol) and 1,2,2,6,
6- pentamethvl alcohol be dissolved in solvent (acetone, butanone, cyclohexanone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide,
One or more in dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE) in, then stir-activating 4-6h is slowly dropped into (time for adding
For 30～60min) equimolar allyl halide (allyl chloride, allyl bromide, bromoallylene or allyl iodide), 40-60 DEG C of isothermal reaction
4-8h, or vacuum fractionation, products therefrom be the response type hindered amine radioresistance polyolefin auxiliary agent (4- allyloxy -1,2,
2,6,6- tetramethyl piperidines).
PP is modified and its performance test is illustrated：By the pi-allyl hindered amine of 0.1% mass fraction (4- allyloxy -1,2,
2,6,6- tetramethyl piperidines), the hindered phenol A (2- hydroxyls -4- allyloxys-benzophenone) of 0.1% mass fraction, 0.5% matter
Amount number dicumyl peroxide and Maoming Petrochemical polypropylene PP9025NX first carry out it is pre-dispersed, then in 200 DEG C, 50rmp
Blending injection punching is carried out under screw speed, sheet thickness is 2mm.Finally carry out 25KGy gamma radiations, mechanics and optical property
And test is analyzed to soak after acetone soak 24h, test result is as follows：
Sample is after 25KGy gamma radiations without xanthochromia, 5 average tensile yield strengths 23MPa, average hazes 8%, acetone
Soak carries out GC analysis tests, if GC peaks only one of which solvent peak proves to be moved out without auxiliary agent.Simultaneously unmodified PP is increased,
Addition antioxidant 1330,2,4 dihydroxy benaophenonels (DB) small molecule hindered phenol auxiliary agent, and addition 4- allyloxy -2- hydroxyls
The contrast experiment of the same step operation of base benzophenone (ADB).All of sample tests such as following table：
The performance comparison test of table 1.PP-9025NX and its modified materials after 25KGy gamma radiations
Contrasted from upper table, the PP modified materials radiation resistances of 2,4 dihydroxy benaophenonel auxiliary agents of addition are better than and add
Plus the PP of the auxiliary agent of antioxidant 1330 expects, and the hindered phenol modified materials containing pi-allyl grafting are moved in test process without auxiliary molecules
Go out, the modified materials of hindered phenol containing small molecule of contrast there are a small amount of auxiliary molecules to move out in test process.Therefore, 4- allyloxys-
The modified PP of 2- dihydroxy benaophenonels expects that various combination properties are more stable.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. the synthetic method of the anti-oxidant polyolefin auxiliary agent of a kind of response type hindered phenol, it is characterised in that comprise the steps：
It is 1-1.2 by mol ratio：1 catalyst and 2,4 dihydroxy benaophenonels are dissolved in solvent, anti-in 40-60 DEG C of stirring
2-8h is answered, allyl halide is then slowly dropped into, 40-60 DEG C of isothermal reaction 2-6h stands still for crystals or vacuum fractionation, gained is produced
Thing is the anti-oxidant polyolefin auxiliary agent of the response type hindered phenol.
2. synthetic method according to claim 1, it is characterised in that the allyl halide is selected from allyl chloride, alkene
Propyl bromide or allyl iodide.
3. synthetic method according to claim 1, it is characterised in that described 2,4 dihydroxy benaophenonels and the allyl
The mol ratio of base halide is 1:1-2.
4. the synthetic method according to any one of claim 1-3, it is characterised in that the catalyst selected from potassium hydroxide,
NaOH, sodium methoxide or caustic alcohol.
5. the synthetic method according to any one of claim 1-3, it is characterised in that the solvent is acetone, butanone, hexamethylene
One or more in ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
6. the synthetic method according to any one of claim 1-3, it is characterised in that during the dropwise addition of the allyl halide
Between be 30-60min.
7. the anti-oxidant polyolefin auxiliary agent of response type hindered phenol described in any one of claim 1-6 is in composite polyolefine material
Using.
8. application according to claim 7, it is characterised in that the preparation method of the composite polyolefine material includes as follows
Step：
By the response type described in response type hindered amine radioresistance polyolefin auxiliary agent 0.05-0.5wt%, any one of claim 1-6
The vistanex of the anti-oxidant polyolefin auxiliary agent 0.05-0.5wt% of hindered phenol, initiator 0.5-1.0wt% and surplus, is placed in
Melt blending grafting, extruding pelletization or direct injection mo(u)lding are carried out in screw rod blender, the composite polyolefine material is obtained final product.
9. application according to claim 8, it is characterised in that the vistanex is selected from polypropylene, polyethylene or poly-
Vinyl chloride；The initiator is selected from benzoyl peroxide, dicumyl peroxide or tert-butyl peroxide.
10. application according to claim 8, it is characterised in that each zone temperatures are distributed as 180 in the screw rod blender
～230 DEG C, screw speed is：40～100 revs/min.
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| CN107382710A (en) * | 2017-08-19 | 2017-11-24 | 中国铁道科学研究院铁道建筑研究所 | A kind of polyalcohol for being grafted antioxygen agent molecule |
| CN112048030A (en) * | 2019-06-05 | 2020-12-08 | 中国科学院化学研究所 | Polyethylene grafted hindered phenol antioxidant and preparation method and application thereof |
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Application publication date: 20170510 |