CN103450379A - Efficient and transfer-resistant hindered phenol antioxidant and preparation method thereof - Google Patents
Efficient and transfer-resistant hindered phenol antioxidant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of efficient, anti-migration hindered phenol antioxygens and preparation method thereof. Shown in the following formula (I) of its structure,
Wherein, PE is Polyethylene Chain; B1 and B2 can be identical or different, is each independently selected from C(R5) 2, NR6, O, S atom, wherein R5 is identical or different, is separately selected from H or C1-C6 alkyl; R6 is selected from H or C1-C6 alkyl; R1 and R2 can be identical or different, is each independently selected from hydrogen or the alkyl of C1-C5; M, n, x, y are the integer of 0-3; A is structure shown in formula (II),
Wherein, R3 and R4 are identical or different, are each independently selected from H or C1-C6 alkyl. By introducing chain alkyl in Hinered phenols antioxidant structure, it can take into account while keeping hindered phenol antioxygen itself antioxidant effect and improve molecular weight and improve and requirement of both polymer matrix compatability.
Description
Technical field
The present invention relates to efficient, anti-migration hindered phenol antioxygen of a class and preparation method thereof and application thereof.
Background technology
Hindered phenol antioxygen is widely used in polymkeric substance, and for reducing the thermo-oxidative ageing of polymer processing, the performance slowed down in the polymkeric substance use reduces, and extends the life cycle of polymkeric substance.The actual antioxidant effect of oxidation inhibitor in polymeric matrix depends on the factor aspect two: self antioxidant capacity 1. determined by the oxidation inhibitor chemical structure; 2. oxidation inhibitor is resisted the in use ability of Physical Loss or Damage.The Physical Loss or Damage of oxidation inhibitor, be included in the course of processing and use procedure, the volatilization of oxidation inhibitor, migration, gone out (the J. such as polymeric matrix by solvent extraction
et al., Macromol.Symp., 2001,164,389).It is comparatively serious that lower molecular weight and stronger self polarity (poor with polyolefine/alkyl body consistency) often cause traditional commodities oxidation inhibitor to move in the polyolefine/alkyl body, is unfavorable for the maintenance of long-term antioxidant capacity.In addition, when polyolefine material is used for food product pack, during the fields such as health care, lower molecular weight, the oxidation inhibitor with poor anti-transfer ability in use can be gone out by water or oil extraction, to human body threaten in health (M.S.Dopico-Garc í a, et al., J.Agr.Food Chem., 2007,55,3225).
By in the Hinered phenols antioxidant structure, introducing chain alkyl, can improve the oxidation inhibitor molecular weight on the one hand, can strengthen the consistency of oxidation inhibitor and polyolefine/alkyl body on the one hand, effectively reduce the Physical Loss or Damage of oxidation inhibitor in the course of processing and use procedure, strengthen long-term antioxidant capacity; The health threat that elimination simultaneously or minimizing cause human body because use oxidation inhibitor.
Summary of the invention
Based on above-mentioned purpose, the invention provides a kind of efficient, anti-migration hindered phenol antioxygen, its preparation method and application thereof.
The present invention is achieved through the following technical solutions:
1. a hindered phenol antioxygen, its structure is as shown in the formula shown in (I),
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3; A is structure shown in formula (II),
Wherein, R3 and R4 are identical or different, are selected from independently of one another H or C
1-C
6alkyl.
2. according to the hindered phenol antioxygen of the 1st, it is characterized in that, described formula (I) has following structure:
Wherein, each is substituent described as defined above.
3. according to the 1st or the hindered phenol antioxygen of 2, its Chinese style (I) oxidation inhibitor is selected from following structure:
Wherein, PE is Polyethylene Chain, and R1 is H or C
1-C
6alkyl, R2 is H or C
1-C
6alkyl, A is structure shown in formula II,
Wherein, R3 and R4 are identical or different, are H or C independently of one another
1-C
6alkyl.
4. according to the hindered phenol antioxygen of 1-3 any one, it is characterized in that, described oxidation inhibitor is selected from following structure:
5. the polymkeric substance shown in a formula (III),
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3.
6. according to the polymkeric substance of the 5th, it is characterized in that, described polymkeric substance is selected from following structure:
6. the preparation method of the hindered phenol antioxygen of above-mentioned 1-3 any one, is characterized in that, described method comprises the steps:
By the polyethylene of the terminal hydroxy group functionalization shown in formula (III),
, carry out transesterification reaction and be prepared under catalyst action with the propionic ester of the R7A structure shown in formula (IV),
Wherein, R3 and R4 are identical or different, are H or C independently of one another
1-C
6alkyl, R7 is selected from C
1-C
6alkyl, preferable methyl or ethyl;
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3.
According to the present invention, in the polyethylene of the terminal hydroxy group functionalization shown in the propionic ester shown in formula (IV) and formula (III), the molar ratio of hydroxy radical content is 1.0-50.0, preferably 5-20; In the polyethylene of catalyzer and formula (III), the molar ratio of hydroxy radical content is 0.001-0.01.
According to the present invention, described reaction is carried out under molten state or in organic solvent, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, heptane etc., and the poly mol ratio of organic solvent and formula (III) is 20-500, is preferably 40-200.The temperature of described reaction is 60-350 ℃, is preferably 100-200 ℃.Reaction times 5-50h, be preferably 8-30h.
According to the present invention, described reaction process is by keeping low pressure or utilizing water trap to remove the alcohol of generation.
According to the present invention, described catalyzer is selected following compound, three (2 ethyl hexanoic acid) butyl tin, two (2 ethyl hexanoic acid) dibutyl tin, dibutyltin diacetate, dibutyltin oxide, dibutyl tin laurate, toxilic acid dibutyl tin, tetraethyl titanate, tetrabutyl titanate, the different monooctyl ester of metatitanic acid four, lithium hydroxide, lithium hydride, Lithamide, one or several in aluminum isopropylate.
7. according to the preparation method of the 6th, it is characterized in that, the polyethylene of the terminal hydroxy group functionalization shown in formula (III) can be divided into Types Below according to molecular mass and distribution:
(1) number-average molecular weight Mn=500～1500g/mol, polydispersity index PDI=5～10;
（2）Mn=400～1000g/mol，PDI=1.1～2.0；
（3）Mn=1000～2000g/mol，PDI=1.1～2.0；
（4）Mn=2000～6000g/mol,PDI=3.0～6.0；
(5) by (2), the product that (3) and (4) component mixes by arbitrary proportion.
8. according to the 6th or the preparation method of 7, it is characterized in that, prepared by the polyethylene of the terminal hydroxy group functionalization shown in described formula (III) by the following method:
By terminal double bond polyethylene (V), set out, through the certain polyethylene of end group with functional hydroxyl that be converted to.
Wherein, PE is Polyethylene Chain.
9. the preparation method of the hindered phenol antioxygen of above-mentioned 6-8 any one, is characterized in that, prepared by the following method by the polyethylene of the terminal hydroxy group functionalization shown in formula (III):
Route one:
(1) obtained the polyethylene of the epoxy-terminated functionalization shown in formula (VI) by the terminal double bond polyethylene oxidation under certain condition shown in formula V,
Wherein PE is polyethylene;
(2) obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the functional poly ethene open loop under certain condition shown in formula (VI) again.
Route two:
Obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the terminal double bond polyethylene shown in formula V through hydroboration-oxidizing reaction or the reaction of aluminium hydro-oxidation.
According to the present invention, the polyethylene of described terminal hydroxy group functionalization, the end group selectivity is higher than 92%.
According to the present invention, concrete preparation method comprises the steps:
Terminal double bond polyethylene shown in formula V adds aluminium hydroborating reagent or hydroborating agents to carry out addition reaction after fully dissolving in organic solvent; Subsequently, pass into or do not pass into dry oxygen after for some time, add inorganic base aqueous solution and aqueous hydrogen peroxide solution to make it carry out oxidizing reaction, obtain corresponding construction terminal hydroxy group functional poly ethene.
According to the present invention, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, hexane, heptane, tetrahydrofuran (THF), acetonitrile, ethylene urea, dimethyl formamide, dimethyl sulfoxide (DMSO), HMPA; Described aluminium hydroborating reagent or hydroborating agents are one or more in di-isopropyl aluminum hydride, diisobutyl aluminium hydride, three aluminum hydride, ADEH, borine tetrahydrofuran complex, borine etherate.Described mineral alkali is one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide.Addition reaction single step reaction time 2-20 hour, temperature of reaction 50-150 ℃; Passing into oxygen (normal bubbling) time is 0.5-5 hour, temperature of reaction 20-80 ℃; Oxidation time is 1-10 hour, temperature of reaction 50-125 ℃.Terminal double bond polyethylene and hydroborating agents or aluminium hydroborating reagent mol ratio are 1:1-1:50, are preferably 1:3-1:10; The terminal double bond polyethylene with the mineral alkali mol ratio be 1:2-1:200, the terminal double bond polyethylene with the hydrogen peroxide mol ratio be 1:2-1:500.
Path three:
Obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the terminal double bond polyethylene shown in formula V and corresponding sulfo-alcohol addition under certain condition.
According to the present invention, the polyethylene of described terminal hydroxy group functionalization, the end group selectivity is higher than 90%.
According to the present invention, concrete preparation method comprises the steps:
The terminal double bond polyethylene adds sulfydryl to replace polyvalent alcohol and radical initiator after fully dissolving in organic solvent, obtains the functional poly of the terminal hydroxy group with the thioether bond ethene of corresponding construction.
According to the present invention, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, hexane, heptane.Described radical initiator is one or more in azo-bis-isobutyl cyanide, dibenzoyl peroxide, azo two cyclohexanenitriles.Described terminal double bond polyethylene and sulfydryl end-blocking siloxanes mol ratio are 1:1-1:100, are preferably 1:5-1:20.Described terminal double bond polyethylene and radical initiator mol ratio are 1:0.1-1:20, are preferably 1:0.5-1:5.Described terminal double bond polyethylene and organic solvent mol ratio are 1:10-1:500, are preferably 1:20-1:100.Temperature of reaction is 50-150 ℃, and the reaction times is 0.5-10 hour
10. according to the preparation method of the 9th, it is characterized in that, prepared by the polyethylene of the epoxy-terminated functionalization shown in formula (VI) by the following method:
Terminal double bond polyethylene shown in formula V, after fully dissolving in organic solvent, add peracid, adds or do not add phase-transfer catalyst, catalyzer etc. to obtain the polyethylene of epoxy-terminated functionalization shown in formula (VI).
According to the present invention, described organic solvent is selected from one or more in the organic solvents such as toluene, ethylbenzene, benzene, chlorobenzene, dimethylbenzene, heptane.Described peracid is one or more in the peracid such as metachloroperbenzoic acid, cumyl hydroperoxide, hydrogen peroxide.Described catalyzer is one or more in the catalyzer such as phosphoric acid, phosphato-molybdic heteropolyacid, phosphorus heteropoly tungstic acid, sodium wolframate, diethyl tartrate, isopropyl titanate.Described phase-transfer catalyst is a kind of or two or more in the phase-transfer catalysts such as Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, methyl tricapryl ammonium chloride, methyl trioctylphosphine monoammonium sulfate.Described terminal double bond polyethylene and peracid mol ratio are 1:0.5-1:50, are preferably 1:1-1:5.The mol ratio of described terminal double bond polyethylene and catalyzer is 1:0.001-1:0.05, is preferably 1:0.005-1:0.02.The mol ratio of described terminal double bond polyethylene and phase-transfer catalyst is 1:0.001-1:0.05, is preferably 1:0.01-1:0.02.Described terminal double bond polyethylene and organic solvent mol ratio are 1:10-1:500, are preferably 1:20-1:100.Temperature of reaction is 30-150 ℃, and the reaction times is 0.1-10 hour.
11. the preparation method of the hindered phenol antioxygen of above-mentioned 6-9 any one, is characterized in that, prepared by the terminal double bond polyethylene shown in formula V by the following method:
Make the terminal double bond polyethylene at the Fe-series catalyst suc as formula shown in (VII) and aluminum alkyl catalyst (preferable methyl aikyiaiurnirsoxan beta) catalyzed ethylene polymerization.
Wherein, the alkyl that R is C1-C4, phenyl, C1-C4 alkyl one, two or trisubstd phenyl and contain halogen one, two or tri-substituted phenyl or the C1-C4 alkyl corresponding, two or the tri-substituted phenyl that contain halogen.
According to the present invention, preferably, above-mentioned steps is at room temperature carried out, more preferably, the number-average molecular weight Mn=500 of the solid product made～1500g/mol, polydispersity index PDI=5～10, the two key selectivity of the end group of described solid product are higher than 95%.
According to the present invention, solid product is carried out to extracting, preferably carry out repeatedly extracting, more preferably, first by the normal hexane extracting, obtain the normal hexane extract; Again to normal hexane extracting residuum through hexanaphthene extracting solute.
According to the present invention, the number-average molecular weight Mn=400-1000g/mol of described normal hexane extract, PDI=1.1-2.0, its content is 30-45wt%.
According to the present invention, after normal hexane extracting residuum again through the number-average molecular weight Mn=1000-2000g/mol of hexanaphthene extracting solute, PDI=1.1-2.0, its content is 20-35wt%.
According to the present invention, the number-average molecular weight Mn=2000-6000g/mol of described hexanaphthene insolubles, PDI=3.0-6.0, its content is 30-45wt%.
According to the present invention, the terminal double bond polyethylene that described method prepares can be divided into a plurality of components after adopting separated from solvent, and wherein each independent component may be used to the end group functional polyethylene, and its structure is identical, the molecular size range difference.
12. the preparation method of the hindered phenol antioxygen of above-mentioned any one, wherein, prepared by the polyethylene of the terminal hydroxy group functionalization shown in formula (III) by the following method:
Route
Polyethylene by the epoxy-terminated functionalization shown in formula (VI) sets out, and after fully dissolving in organic solvent or under molten state, under certain catalyst action or do not add any catalyzer, through reaction reagent open loop or reduction, obtains.
According to the present invention, the polyethylene of the epoxy-terminated functionalization shown in described formula (VI) preferably obtains by the approach of aforementioned route one.
According to the present invention, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, hexane, heptane, tetrahydrofuran (THF), acetonitrile, ethylene urea, dimethyl formamide, dimethyl sulfoxide (DMSO), HMPA.
According to the present invention, described catalyzer is one or more in trifluoromethanesulfonic acid, hydrochloric acid, potassium hydroxide, triethylamine, pyridine.Described reaction reagent is one or more of water, diethanolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine, diisopropanolamine (DIPA), red aluminium, Lithium Aluminium Hydride, borine, sodium borohydride.
According to the present invention, shown in described formula (VI), epoxy-terminated functional poly ethene and reaction reagent mol ratio are 1:1-1:100, are preferably 1:5-1:20; Shown in described formula (VI), epoxy-terminated functional poly ethene and catalyst molar ratio are 1:0.01-1:20, are preferably 1:0.1-1:5; (VI) shown in described formula (VI) epoxy-terminated functional poly ethene and organic solvent mol ratio are 1:10-1:500, are preferably 1:20-1:100; Temperature of reaction is 50-200 ℃, and the reaction times is 1-20 hour.
13. the application of the hindered phenol antioxygen of aforementioned any one in plastics, rubber etc.Be particularly useful for the anti-oxidant of polyolefin resin.Preferably, described oxidation inhibitor and phosphite ester kind antioxidant are used in conjunction with.The oxidation inhibitor that this class is used in combination can reach better effect.
The present invention has following technique effect:
With the adjustable for height chain alkyl of molecular weight, can improve anti-solvent extraction ability and the anti-transfer ability of oxidation inhibitor; Chain alkyl can improve the consistency of Hinered phenols antioxidant and polymeric matrix simultaneously, it is able in polymeric matrix dispersed, this to non-polar polymer as particularly important based on polyolefinic polymkeric substance, blend; In part Hinered phenols antioxidant structure, include the thioesters structure simultaneously, can be used as auxiliary anti-oxidant and coordinate well synergy of Hinered phenols antioxidant performance.
The accompanying drawing explanation
Fig. 1. through the poly nuclear-magnetism carbon spectrum of the terminal double bond that embodiment 1 obtains, embodiment 2 is related.
Fig. 2. the poly nucleus magnetic hydrogen spectrum of the embodiment epoxy-terminated functionalization of 3 gained.
Fig. 3. the poly nuclear-magnetism carbon spectrum of embodiment 4 gained end trihydroxy-functionalization.
Fig. 4. the poly infrared spectrum of embodiment 6 gained 1,2 o-dihydroxy.
Fig. 5. embodiment 9 gained are with the poly nucleus magnetic hydrogen spectrum of sulfenyl o-dihydroxy.
The nucleus magnetic hydrogen spectrum of Fig. 6 embodiment 11 gained Hinered phenols antioxidants.
The infrared spectrum of Fig. 7 embodiment 13 gained Hinered phenols antioxidants.
The nuclear-magnetism carbon spectrum of Fig. 8 embodiment 15 gained Hinered phenols antioxidants.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.It should be noted that, following embodiment can not be as limiting the scope of the invention, and any improvement of making on basis of the present invention is all without prejudice to spirit of the present invention.
The dry there-necked flask of 500ml, successively with after nitrogen and polymer grade ethylene gas pump drainage three times, with ethylene gas, be full of and inject a certain amount of toluene, described Fe-series catalyst (toluene solution) and methylaluminoxane (toluene solution), after in 30 ℃ of reaction 30min, filter and collect white solid, 50 ℃ of vacuum-dryings after alcohol and deionized water wash, obtain initial terminal double bond polyethylene.Initial terminal double bond polyethylene, through independent or continuous extractings of organic solvent such as hexane, tetrahydrofuran (THF), hexanaphthenes, obtains the terminal double bond polyethylene of different molecular weight and polydispersity coefficient.
1h NMR reaches
13c NMR characterizes and determines, above-mentioned terminal double bond polyethylene is linear structure, and the terminal double bond selectivity is higher than 95%.
Embodiment 2
In the 250ml two-mouth bottle, add the described terminal double bond polyethylene of 5g embodiment 1 (molecular weight Mn=1200g/mol, polydispersity coefficient PDI=1.6), 40 ℃ of vacuum-dryings were filled with nitrogen after 1 hour, added the 70ml chlorobenzene, were warming up to 95 ℃, stir it is fully dissolved.Add the 0.15g sodium wolframate under nitrogen atmosphere, 0.12g methyl tricapryl ammonium chloride and 0.03g phosphoric acid.After stirring, slowly drip the hydrogen peroxide of 4ml30wt%.Continue stirring reaction 4h, with a large amount of methyl alcohol, separate out polymkeric substance, filter, 50 ℃ of vacuum-drying 12h of formic acid repetitive scrubbing, obtain epoxy-terminated functional poly ethene.
1h NMR reaches
13c NMR characterizes and determines, polyethylene end group unsaturated double-bond is converted into epoxide group fully.The GPC test shows, the epoxy-terminated functionalization molecular weight of polyethylene of gained Mn=1300g/mol, polydispersity coefficient PDI=1.5.
Embodiment 3
In the 250ml two-mouth bottle, add 1 described pair of key polyethylene of 4g embodiment (molecular weight Mn=600g/mol, polydispersity coefficient PDI=1.3), 40 ℃ of vacuum-dryings were filled with nitrogen after 1 hour, added the 30ml heptane, were warming up to 65 ℃, stir it is fully dissolved.Add the 2g metachloroperbenzoic acid under nitrogen atmosphere, after reaction 2h, with a large amount of methyl alcohol, separate out polymkeric substance, filter, 50 ℃ of vacuum-drying 12h of formic acid repetitive scrubbing, obtain epoxy-terminated functional poly ethene.
1h NMR reaches
13c NMR characterizes and determines, polyethylene end group unsaturated double-bond is converted into epoxide group fully.The GPC test shows, the epoxy-terminated functionalization molecular weight of polyethylene of gained Mn=620g/mol, polydispersity coefficient PDI=1.4.
Embodiment 4
In the 50ml two-mouth bottle, add the epoxy-terminated functional poly ethene of 4g embodiment 3 gained, 40 ℃ of vacuum-drying 1 hour.Add the 5g diethanolamine under nitrogen atmosphere, be warming up to 100 ℃, after frit reaction 6h, with a large amount of methanol wash polymkeric substance, filter, 40 ℃ of vacuum-drying 12h, obtain holding trihydroxy-polyethylene (as the formula (8)).
1h NMR reaches
13c NMR characterizes and determines, in epoxy-terminated functional poly ethene, epoxide group is fully by the diethanolamine open loop.The GPC test shows, gained end trihydroxy-molecular weight of polyethylene Mn=580g/mol, polydispersity coefficient PDI=1.3.
Embodiment 5
In the 250ml two-mouth bottle, add the epoxy-terminated functional poly ethene of 4g embodiment 3 gained, 40 ℃ of vacuum-drying 1 hour.Be filled with nitrogen, inject 50ml toluene, after stirring fully dissolving, add 2ml borine tetrahydrofuran complex under nitrogen atmosphere, reaction 5h, with a large amount of methyl alcohol and deionized water wash polymkeric substance, filter, 40 ℃ of vacuum-drying 12h, obtain 2-hydroxyl polyethylene (as the formula (9)).
1h NMR reaches
13c NMR characterizes and determines, in epoxy-terminated functional poly ethene, epoxide group is fully by borane reduction, and terminal hydroxy group functionalization efficiency approaches 100%.The GPC test shows, gained 2-hydroxyl molecular weight of polyethylene Mn=590g/mol, polydispersity coefficient PDI=1.3.
Embodiment 6
In the 25ml two-mouth bottle, add the epoxy-terminated functional poly ethene of 3g embodiment 2 gained, 40 ℃ of vacuum-drying 1 hour.Be filled with nitrogen, inject the 20ml tetrahydrofuran (THF), after being warming up to 80 ℃, add the 1.2ml trifluoromethanesulfonic acid aqueous solution (v/v=1/20), fully stir, reaction 3h, pour a large amount of methyl alcohol into and separate out polymkeric substance, with a large amount of deionized waters and methanol wash several, collect white solid, 40 ℃ of vacuum-drying 12h, obtain the two hydroxyl polyethylene (shown in formula (10)) of 1,2-.
1h NMR reaches
13c NMR characterizes and determines, in e-PE, the epoxide group Quantitative yield is the two hydroxyls in ortho position.The GPC test shows, gained 1, the two hydroxyl molecular weight of polyethylene Mn=1250g/mol of 2-, polydispersity coefficient PDI=1.5.
Embodiment 7
3g terminal double bond polyethylene (molecular weight Mn=1200g/mol, polydispersity coefficient PDI=1.5) adds the 250ml flask with magnetic stir bar, and pump drainage injects 100ml toluene and 10ml diisobutyl aluminium hydride (hexane solution of 1M); 95 ℃ of reactions 2 hours, be cooled to 50 ℃ after logical O
21 hour; Stop logical oxygen, inject 20ml aqueous hydrogen peroxide solution (30%), 5g sodium hydroxide (being dissolved in 10ml water), continue the vigorous stirring reaction and separate out polymkeric substance with a large amount of acid alcohols after 2 hours, filter, with acid alcohol/water mixed solution washed twice, finally use deionized water wash, filter, drying obtains terminal hydroxy group functional poly ethene shown in formula (11).
1h NMR reaches
13c NMR characterizes and determines, the terminal double bond polyethylene is converted into the terminal hydroxy group polyethylene fully.The GPC test shows, the Mn=1150g/mol of terminal hydroxy group functionalization molecular weight of polyethylene shown in gained formula (11), polydispersity coefficient PDI=1.4.
Embodiment 8
In the 25ml two-mouth bottle, add the described terminal double bond polyethylene of 5g embodiment 1 (molecular weight Mn=500g/mol, polydispersity coefficient PDI=1.5), 40 ℃ of vacuum-drying 1 hour.Be filled with nitrogen, inject 60ml toluene, after stirring fully dissolving, add 3ml2-mercaptoethanol and 1g Diisopropyl azodicarboxylate under nitrogen atmosphere, 90 ℃ of reaction 4h, with a large amount of anhydrous methanol washing copolymers, filter, 40 ℃ of vacuum-drying 12h, obtain the terminal hydroxy group functional poly ethene (shown in formula (12)) with thioether bond.
1h NMR reaches
13c NMR characterizes and determines, the unsaturated end group of terminal double bond polyethylene is fully by the sulfydryl addition.The GPC test shows, the Mn=450g/mol of terminal hydroxy group functionalization molecular weight of polyethylene shown in gained formula (12), polydispersity coefficient PDI=1.4.
Embodiment 9
In the 25ml two-mouth bottle, add the described terminal double bond polyethylene of 5g embodiment 1 (molecular weight Mn=1300g/mol, polydispersity coefficient PDI=1.3), 40 ℃ of vacuum-drying 1 hour.Be filled with nitrogen, inject 100ml toluene, after stirring fully dissolving, add 2.5ml3-mercapto glycerol and 1g azo two cyclohexanenitriles under nitrogen atmosphere, 110 ℃ of reaction 8h, with a large amount of anhydrous methanol washing copolymers, filter, 40 ℃ of vacuum-drying 12h, obtain the ortho position terminal dihydroxy functional poly ethene (formula (13)) with thioether bond.
1h NMR reaches
13c NMR characterizes and determines, the unsaturated end group of terminal double bond polyethylene is fully by the sulfydryl addition.The GPC test shows, the Mn=1200g/mol of terminal hydroxy group functionalization molecular weight of polyethylene shown in gained formula (13), polydispersity coefficient PDI=1.4.
Embodiment 10
In the 50ml two-mouth bottle, add the epoxy-terminated functional poly ethene of 5g embodiment 3,40 ℃ of vacuum-drying 1 hour.Add 10ml N-Mono Methyl Ethanol Amine under nitrogen atmosphere, be warming up to 100 ℃, after frit reaction 6h, with a large amount of methanol wash polymkeric substance, filter, 40 ℃ of vacuum-drying 12h, obtain non-ortho position end dihydroxyl polyethylene (shown in formula (14)).
1h NMR reaches
13c NMR characterizes and determines, in epoxy-terminated functional poly ethene, epoxide group is fully by the open loop of N-Mono Methyl Ethanol Amine.The GPC test shows, the non-ortho position of gained end dihydroxyl molecular weight of polyethylene Mn=600g/mol, polydispersity coefficient PDI=1.4.
Embodiment 11
To the 50ml bottle with two necks of agitator be housed, add 5g2-hydroxyl polyethylene (terminal hydroxyl content 8mmol), 7.3g(25mmol) 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, 0.05mmol dibutyltin diacetate.The control temperature of reaction is 100-120 ℃, make the reactant melting, controlling the reaction flask internal pressure is that 5KPa is to 10KPa, react 8 hours, after being cooled to 70 ℃, add 10ml toluene to make polymer dissolution, pour subsequently a large amount of methyl alcohol into and separate out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtain the Hinered phenols antioxidant shown in formula (15) (A is structure shown in formula (2)).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 95%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 12
By the 50ml bottle with two necks of agitator is housed, add 4g1, the two hydroxyl polyethylene (terminal hydroxyl content 10mmol) of 2-, 13g(45mmol) 3-(the 3-tertiary butyl-5-sec.-propyl-4-hydroxy phenyl) ethyl propionate, 0.05mmol tetraethyl titanate.The control temperature of reaction is 130-150 ℃, make the reactant melting, controlling the reaction flask internal pressure is that 2KPa is to 5KPa, react 12 hours, after being cooled to 70 ℃, add 10ml toluene to make polymer dissolution, pour subsequently a large amount of methyl alcohol into and separate out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtain Hinered phenols antioxidant (A is structure shown in formula (2)) as the formula (16).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 92%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 13
To the 50ml bottle with two necks of agitator be housed, add 4g end trihydroxy-polyethylene (terminal hydroxyl content 10mmol), 13g(45mmol) 3-(the 3-tertiary butyl-5-sec.-propyl-4-hydroxy phenyl) methyl propionate, 0.05mmol tetraethyl titanate.The control temperature of reaction is 130-150 ℃, make the reactant melting, controlling the reaction flask internal pressure is that 2KPa is to 5KPa, react 12 hours, after being cooled to 70 ℃, add 10ml toluene to make polymer dissolution, pour subsequently a large amount of methyl alcohol into and separate out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtain the Hinered phenols antioxidant shown in formula (17) (A is structure shown in formula (2)).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 92%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 14
Magneton will be housed, and the 25ml bottle with two necks of prolong and water trap, add terminal hydroxy group polyethylene shown in 4g formula (11) (terminal hydroxyl content 10mmol), 12g(40mmol) 3-(3,5-di-isopropyl-4-hydroxy phenyl) ethyl propionate, 0.05mmol aluminum isopropylate, 15ml toluene.The control temperature of reaction is 115-125 ℃, reacts 20 hours, pours a large amount of methyl alcohol into and separates out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtains the Hinered phenols antioxidant shown in formula (18) (A is structure shown in formula (2)).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 90%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
To the 50ml bottle with two necks of agitator be housed, add shown in 5g formula (12) the terminal hydroxy group polyethylene (terminal hydroxyl content 6mmol) with thioether bond, 7.3g(25mmol) 3-(3,5-di-tert-butyl-hydroxy phenyl) methyl propionate, the 0.05mmol dibutyltin diacetate.The control temperature of reaction is 12-14 ℃, make the reactant melting, controlling the reaction flask internal pressure is that 2KPa is to 5KPa, react 12 hours, after being cooled to 70 ℃, add 10ml toluene to make polymer dissolution, pour subsequently a large amount of methyl alcohol into and separate out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtain the Hinered phenols antioxidant with thioester bond (A is structure shown in formula (2)) as the formula (19).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 95%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 16
Magneton will be housed, the 50ml bottle with two necks of prolong and water trap, add shown in 4g formula (13) the ortho position end dihydroxyl functional poly ethene (terminal hydroxyl content 10mmol) with ehter bond, 12g(40mmol) 3-(3,5-diethyl-4-hydroxy phenyl) propyl propionate, 0.03mmol the toxilic acid dibutyl tin, 25ml toluene.The control temperature of reaction is 120-130 ℃, reacts 25 hours, pours a large amount of methyl alcohol into and separates out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtains the Hinered phenols antioxidant of thioester bond as the formula (20).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 93%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 17
To the 50ml bottle with two necks of agitator be housed, add the non-ortho position of 5g end dihydroxyl polyethylene (shown in formula (14), terminal hydroxyl content 8mmol), 13g(45mmol) 3-(the 3-tertiary butyl-5-sec.-propyl-4-hydroxy phenyl) propyl propionate, 0.05mmol tetraethyl titanate.The control temperature of reaction is 130-150 ℃, make the reactant melting, controlling the reaction flask internal pressure is that 2KPa is to 5KPa, react 12 hours, after being cooled to 70 ℃, add 10ml toluene to make polymer dissolution, pour subsequently a large amount of methyl alcohol into and separate out polymkeric substance, with first alcohol and water repetitive scrubbing final vacuum drying, obtain the Hinered phenols antioxidant shown in formula (21) (A is structure shown in formula (2)).
1h NMR shows, polyethylene terminal hydroxy group transformation efficiency surpasses 92%; The GPC curve display, the products therefrom molecular weight is significantly improved with respect to initiator.
Embodiment 18
By embodiment 14 gained hindered phenol antioxygens, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearate, 1:2:1.5 mixes in mass ratio, and mixes with powder.This mixture is joined in polypropylene, and total add-on is the 3000ppm(weight ratio), in screw rod, extrude continuously three times, be labeled as blend sample A.In the same manner, by commercially available hindered phenol antioxygen 1076, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester and calcium stearate, 1:2:1.5 mixes in mass ratio, and mixes with powder.This mixture is joined in polypropylene, and total add-on is the 3000ppm(weight ratio), in screw rod, extrude continuously three times, be labeled as blend sample B.
Blend sample A melting index is 3.5g/10min, and yellowness index is 4.2; Blend sample B melting index is 3.2g/10min, and yellowness index is 3.9.Show when adding the identical weight hindered phenol antioxygen, embodiment 14 gained hindered phenol antioxygens (having lower hindered phenol molar content) have suitable antioxidant effect with commercially available antioxidant 1076, illustrate that the antioxidant effect of embodiment 14 its hindered phenol unit of gained hindered phenol antioxygen is more fully played.Simultaneously, embodiment 14 gained hindered phenol antioxygens have long chain alkane, with polyolefinic polymeric matrix, have better consistency, can effectively avoid oxidation inhibitor to separate out from polymeric matrix because of reasons such as solvent extractions.
Claims (10)
1. a hindered phenol antioxygen, its structure is as shown in the formula shown in (I),
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3; A is structure shown in formula (II),
Wherein, R3 and R4 are identical or different, are selected from independently of one another H or C
1-C
6alkyl.
2. according to the hindered phenol antioxygen of claim 1, it is characterized in that, described formula (I) has following structure:
Wherein, each is substituent described as defined above.
3. according to the hindered phenol antioxygen of claim 1 or 2, its Chinese style (I) oxidation inhibitor is selected from following structure:
Wherein, PE is Polyethylene Chain, and R1 is H or C
1-C
6alkyl, R2 is H or C
1-C
6alkyl, A is structure shown in formula 8,
Wherein, R3 and R4 are identical or different, are H or C independently of one another
1-C
6alkyl.
4. the polymkeric substance shown in a formula (III),
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3.
Preferably, described polymkeric substance is selected from following structure:
5. the preparation method of the hindered phenol antioxygen of claim 1-3 any one, is characterized in that, described method comprises the steps:
By the polyethylene of the terminal hydroxy group functionalization shown in formula (III),
Wherein, PE is Polyethylene Chain; B
1and B
2can be identical or different, be selected from independently of one another C(R
5)
2, NR
6, O, S atom, wherein R
5identical or different, respectively independently selected from H or C
1-C
6alkyl; R
6be selected from H or C
1-C
6alkyl; R
1and R
2can be identical or different, be selected from independently of one another hydrogen or C
1-C
5alkyl; M, n, x, the integer that y is 0-3,
, carry out transesterification reaction and be prepared under catalyst action with the propionic ester shown in formula (IV),
Wherein, R3 and R4 are identical or different, are H or C independently of one another
1-C
6alkyl, R7 is selected from C
1-C
6alkyl, preferable methyl or ethyl.
Preferably, in the polyethylene of the terminal hydroxy group functionalization shown in the propionic ester shown in formula (IV) and formula (III), the molar ratio of hydroxy radical content is 1.0-50.0, preferably 5-20; In the polyethylene of catalyzer and formula (III), the molar ratio of hydroxy radical content is 0.001-0.01.
Preferably, described reaction is carried out under molten state or in organic solvent, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, heptane etc., and the poly mol ratio of organic solvent and formula (III) is 20-500, is preferably 40-200.The temperature of described reaction is 60-350 ℃, is preferably 100-200 ℃.Reaction times 5-50h, be preferably 8-30h.
Preferably, described reaction process is by keeping low pressure or utilizing water trap to remove the alcohol of generation.
Preferably, described catalyzer is selected following compound, three (2 ethyl hexanoic acid) butyl tin, two (2 ethyl hexanoic acid) dibutyl tin, dibutyltin diacetate, dibutyltin oxide, dibutyl tin laurate, toxilic acid dibutyl tin, tetraethyl titanate, tetrabutyl titanate, the different monooctyl ester of metatitanic acid four, lithium hydroxide, lithium hydride, Lithamide, one or several in aluminum isopropylate.
6. according to the preparation method of claim 5, it is characterized in that, the polyethylene of the terminal hydroxy group functionalization shown in formula (III) can be divided into Types Below according to molecular mass and distribution:
(1) number-average molecular weight Mn=500～1500g/mol, polydispersity index PDI=5～10;
（2）Mn=400～1000g/mol，PDI=1.1～2.0；
（3）Mn=1000～2000g/mol，PDI=1.1～2.0；
（4）Mn=2000～6000g/mol,PDI=3.0～6.0；
(5) by (2), the product that (3) and (4) component mixes by arbitrary proportion.
7. according to the preparation method of claim 5 or 6, it is characterized in that, prepared by the polyethylene of the terminal hydroxy group functionalization shown in described formula (III) by the following method:
By terminal double bond polyethylene (V), set out, through the certain polyethylene of end group with functional hydroxyl that be converted to.
Wherein, PE is Polyethylene Chain.
8. according to the preparation method of the hindered phenol antioxygen of claim 5-7 any one, it is characterized in that, prepared by the polyethylene of the terminal hydroxy group functionalization shown in formula (III) by the following method:
Route one:
(1) obtained the polyethylene of the epoxy-terminated functionalization shown in formula (VI) by the terminal double bond polyethylene oxidation under certain condition shown in formula V,
Wherein PE is polyethylene;
(2) obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the functional poly ethene open loop under certain condition shown in formula (VI) again.
Route two:
Obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the terminal double bond polyethylene shown in formula V through hydroboration-oxidizing reaction or the reaction of aluminium hydro-oxidation.
Preferably, the polyethylene of described terminal hydroxy group functionalization, the end group selectivity is higher than 92%.
Preferably, concrete preparation method comprises the steps:
Terminal double bond polyethylene shown in formula V adds aluminium hydroborating reagent or hydroborating agents to carry out addition reaction after fully dissolving in organic solvent; Subsequently, pass into or do not pass into dry oxygen after for some time, add inorganic base aqueous solution and aqueous hydrogen peroxide solution to make it carry out oxidizing reaction, obtain corresponding construction terminal hydroxy group functional poly ethene.
Preferably, described organic solvent is one or more in toluene, benzene, chlorobenzene, dimethylbenzene, hexane, heptane, tetrahydrofuran (THF), acetonitrile, ethylene urea, dimethyl formamide, dimethyl sulfoxide (DMSO), HMPA; Described aluminium hydroborating reagent or hydroborating agents are one or more in di-isopropyl aluminum hydride, diisobutyl aluminium hydride, three aluminum hydride, ADEH, borine tetrahydrofuran complex, borine etherate.Described mineral alkali is one or more in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide.Addition reaction single step reaction time 2-20 hour, temperature of reaction 50-150 ℃; Passing into oxygen (normal bubbling) time is 0.5-5 hour, temperature of reaction 20-80 ℃; Oxidation time is 1-10 hour, temperature of reaction 50-125 ℃.Terminal double bond polyethylene and hydroborating agents or aluminium hydroborating reagent mol ratio are 1:1-1:50, are preferably 1:3-1:10; The terminal double bond polyethylene with the mineral alkali mol ratio be 1:2-1:200, the terminal double bond polyethylene with the hydrogen peroxide mol ratio be 1:2-1:500;
Path three:
Obtain the terminal hydroxy group functional poly ethene shown in formula (III) by the terminal double bond polyethylene shown in formula V and corresponding sulfo-alcohol addition under certain condition.
Preferably, the polyethylene of described terminal hydroxy group functionalization, the end group selectivity is higher than 90%.
Preferably, concrete preparation method comprises the steps:
The terminal double bond polyethylene adds sulfydryl to replace polyvalent alcohol and radical initiator after fully dissolving in organic solvent, obtains the functional poly of the terminal hydroxy group with the thioether bond ethene of corresponding construction.
Preferably, prepared by the following method by the polyethylene of the epoxy-terminated functionalization shown in formula (VI):
Terminal double bond polyethylene shown in formula V, after fully dissolving in organic solvent, add peracid, adds or do not add phase-transfer catalyst, catalyzer etc. to obtain the polyethylene of epoxy-terminated functionalization shown in formula (VI).
More preferably, prepared by the following method by the terminal double bond polyethylene shown in formula V:
Make the terminal double bond polyethylene at the Fe-series catalyst suc as formula shown in (VII) and aluminum alkyl catalyst (preferable methyl aikyiaiurnirsoxan beta) catalyzed ethylene polymerization.
Wherein, the alkyl that R is C1-C4, phenyl, C1-C4 alkyl one, two or trisubstd phenyl and contain halogen one, two or tri-substituted phenyl or the C1-C4 alkyl corresponding, two or the tri-substituted phenyl that contain halogen.
Preferably, above-mentioned steps is at room temperature carried out, more preferably, the number-average molecular weight Mn=500 of the solid product made～1500g/mol, polydispersity index PDI=5～10, the two key selectivity of the end group of described solid product are higher than 95%.
Preferably, solid product is carried out to extracting, preferably carry out repeatedly extracting, more preferably, first by the normal hexane extracting, obtain the normal hexane extract; Again to normal hexane extracting residuum through hexanaphthene extracting solute.
Preferably, the number-average molecular weight Mn=400-1000g/mol of described normal hexane extract, PDI=1.1-2.0, its content is 30-45wt%.
Preferably, after normal hexane extracting residuum again through the number-average molecular weight Mn=1000-2000g/mol of hexanaphthene extracting solute, PDI=1.1-2.0, its content is 20-35wt%.
Preferably, the number-average molecular weight Mn=2000-6000g/mol of described hexanaphthene insolubles, PDI=3.0-6.0, its content is 30-45wt%.
Preferably, the terminal double bond polyethylene that described method prepares can be divided into a plurality of components after adopting separated from solvent, and wherein each independent component may be used to the end group functional polyethylene, and its structure is identical, the molecular size range difference.
9. the preparation method of the hindered phenol antioxygen of claim 4-8 any one, wherein, prepared by the polyethylene of the terminal hydroxy group functionalization shown in formula (III) by the following method:
Polyethylene by the epoxy-terminated functionalization shown in formula (VI) sets out, and after fully dissolving in organic solvent or under molten state, under certain catalyst action or do not add any catalyzer, through reaction reagent open loop or reduction, obtains.
Claim 1 ?the application of hindered phenol antioxygen in plastics, rubber etc. of 3 any one.Be particularly useful for the anti-oxidant of polyolefin resin.Preferably, described oxidation inhibitor and phosphite ester kind antioxidant are used in conjunction with.
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| 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 |
| CN112745410A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of in-situ crosslinked polyethylene with high thermal stability |
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| CN103130978B (en) * | 2012-12-17 | 2014-09-10 | 华南理工大学 | Macromolecule hindered phenol antioxidant, preparation method of macromolecule hindered phenol antioxidant, and application of macromolecule hindered phenol antioxidant |
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| 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 |
| CN112745410A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of in-situ crosslinked polyethylene with high thermal stability |
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