CN110437838A - Novel chelate polymer antioxidative stabilizer and its preparation method and application - Google Patents
Novel chelate polymer antioxidative stabilizer and its preparation method and application Download PDFInfo
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- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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Abstract
The invention belongs to innovate the design of the structure of chelating type high molecular material antioxidant to play double protection and preparation method thereof with a kind of application of field more particularly to novel chelating antioxidative stabilizer in high molecular material is synthetically prepared.A kind of preparation method of chelating type antioxidative stabilizer includes: that compound 1 and epoxychloropropane is added in (1), it is slowly added to sodium hydroxide or potassium hydroxide in batches, insulation reaction is added 1L MTBE or DCM or DCE, obtains colorless oil compounds 2 to 1 fully reacting of compound；(2) mercaptan is added, solvent is added, stirs 30min, in 5-10 DEG C of addition compound 2 under nitrogen protection, ice bath half an hour is slowly added to sodium hydroxide or potassium hydroxide, obtains compound 3 or compound 4.The present invention not only has the function of thioether long-life, high-temperature antioxidant activity base, also has and forms sulphur and hydroxyl coordination five-membered cyclic complexation of metal ions function, this function plays complexing eradicant action to the metal ion of catalysis Degradation of Polymer Materials.
Description
Technical field
The invention belongs to the preparation field of high molecular material functional additive more particularly to a kind of novel chelating type are anti-oxidant
Stabilizer and preparation method thereof.
Background technique
High molecular material antioxidative stabilizer is also known as antioxidant, is that one kind can help rapidly when high molecular material is oxidized
The function additive of free radical is captured and neutralizes, so that dispelling free radical prevents the substance of high molecular material oxidative degradation.When its
In polymeric system it is only a small amount of in the presence of, so that it may the progress for delaying or inhibiting polymer oxidation process, to prevent polymer
Aging keeps its original various performance, and designs or prolong its service life as needed.The organic compounds category of sulfur-bearing assists
Antioxidant is because that can become a major class long-life, high-temperature antioxidant critically important in auxiliary antioxidant due to effective hydroperoxide decomposition.
High molecular material, can band in finished product often because of the reasons such as material source and its polymeric additive and processing method
Enter some metals or metal ion, such as Cr, Cu, Zn, Fe, the trace meter or metal ion of these variable valencies can be the most
Catalyst is catalyzed Degradation of Polymer Materials, to accelerate the Oxidative Degradation Process of high molecular material.This not only seriously affects height
The use function of molecular material and service life increase environmental pollution, while also constituting potential threat to our life security.If
The complex compound just lewis acidic catalytic action of attenuating metal or metal ion significantly is complexed into this metalloid or metal ion,
It is greatly passivated catalytic oxidation process, this plays the role of to despise to the protection of high molecular material.Furthermore some gold
Belong to complex compound in some high molecular materials have heat stabilizer effect, these complex compounds with it is conventional use of in high molecular material
Metallo-chelate resistant to thermal aging stabilizer function is consistent.
Summary of the invention
Foreign metal ion catalysis Degradation of Polymer Materials protection high molecular material must be taken into consideration in high molecular material
One of key factor, in order to solve deficiency in the prior art, it is anti-oxidant steady with chelating function that the present invention provides a kind of
Determine agent and preparation method thereof, concrete scheme is as follows:
A kind of chelating type antioxidative stabilizer, general structure are as follows:
Wherein R1For phenyl, xenyl, isocyanuric acid, diphenyl methane, diphenyldimethyhnethane, diphenyl sulfone, alkane
Base or substitutional crylic acid ester group；R and R2For C6~C20 straight chain or contain branched paraffin；M=0,1,2,3,4；N=01,2,3,4, and
M and n can be identical, can be different, but m and n are not 0 simultaneously.
It chemically reacts general formula are as follows:
Wherein R1For phenyl, xenyl, isocyanuric acid, diphenyl methane, diphenyldimethyhnethane, diphenyl sulfone, alkane
Base or substitutional crylic acid ester group；R and R2For C6~C20 straight chain or contain branched paraffin；M=0,1,2,3,4；N=01,2,3,4, and
M and n can be identical, can be different, but m and n are not 0 simultaneously.
A kind of preparation method of chelating type antioxidative stabilizer includes the following steps:
(1) compound 1 and epoxychloropropane, add-back flow tube is added, N2 is protected, heating stirring, when interior temperature reaches 65 DEG C,
Divide 4 batches and be slowly added to sodium hydroxide, insulation reaction to compound 1 has been reacted, and 1L MTBE is added after being cooled to 50 DEG C, filtering is not
Molten object, filtrate decompression recycle MTBE and epoxychloropropane, obtain colorless oil compounds 2, be not directly used in through being further purified
In next step.
(2) mercaptan is added, solvent is added, cools down 5-15 DEG C in the case where stirring nitrogen protection, compound 2, ice bath constant temperature is added
Half an hour is slowly added to sodium hydroxide or potassium hydroxide, obtains compound 3 or compound 4.
The solvent of the step (2) is anhydrous methylene chloride or dichloroethanes or acetone or alcohol or isopropanol or methanol.
It after the step (2) is slowly added to sodium hydroxide, warms naturally to after room temperature insulated and stirred 4-18 hours, detection is extremely
Thiol reaction is complete, through washing except solvent is removed under reduced pressure in alkali and impurity, obtains compound 3 or compound 4.
The molar ratio of compound 1 and epoxychloropropane is 1:2-15 in step (1).
The molar ratio of mercaptan and compound 2 is 1:1.5-7 in step (2).
Above-mentioned chelating type antioxidative stabilizer, which is applied to be used as in high molecular material, guarantees the quality, protects color, keeps the various reasons of material
Learn the anti-oxidant stabilization additives of function.
The synthesis of chelating type antioxidant of the present invention utilizes alcohol, and phenol or sour hydroxyl introduce epoxy-functional, epoxy-functional into
One step and mercaptan carry out opening under alkaline condition, thus obtain a kind of sulphur of the novel ortho position with hydroxy functional group
Ethers long-life, high-temperature antioxidative stabilizer, while there is certain metal-chelating functional ligand structure；The present invention is in some conditions
Under can be used as the unique antioxidative stabilizer of difunctional effect and give development innovation high molecular material under different applicable cases
Industrial development provides a new selection.
Antioxidant of the invention not only has the function of thioether long-life, high-temperature antioxidant activity base, also while having to form thioether
The function of five-membered cyclic complexation of metal ions, metal of this function to catalysis Degradation of Polymer Materials are coordinated with vicinal hydroxyl groups
Ion plays complexing eradicant action, to play significantly more efficient protective effect to high molecular material.In addition, if this chelating
Type long-life, high-temperature antioxidant is formed with thermal stability metal ion-chelant with thermal stability complexing of metal ion
Object, it is more preferable with high molecular compatible matching, to be promoted to high molecular material protective value.This patent also its to be related to chelating type long
The application of the preparation method as well as the anti-oxidant stabilization additives of new material of antioxidant in high molecular material is imitated,
It can be used in high molecular material as anti-oxidant, yellowing-resistant, keep its mechanical mechanics property high performance antioxidation stabilization add
Add agent.This kind of chelating type high performance antioxidants can be applied to plastics, rubber, fiber, coating, the series macromoleculars product such as paint
In.
Specific embodiment
Embodiment 1
The structural formula of target product 1
The synthesis of target product 1:
Step (1): the preparation of bisphenol A diglycidyl ether (compound 2)；
Addition 1mol (i.e. 228g) bisphenol-A into 2 liters of there-necked flasks, 2.8mol (i.e. 260g) epoxychloropropane, add-back flow tube,
N2 protection, 70 DEG C of heating stirrings divide 4 batches and are slowly added to 2.05mol (i.e. 82g) sodium hydroxide, finish when interior temperature reaches 65 DEG C
Insulation reaction is complete to bisphenol-a reaction, and 1L MTBE is added after being cooled to 50 DEG C, filters insoluble matter, and filtrate decompression recycles MTBE and ring
Oxygen chloropropane obtains colorless oil i.e. bisphenol A diglycidyl ether 306g, is not further purified and is directly used in next step.
The synthesis of step (2) target product 1；
When compound 2 is the double glycidyl ethers of bisphenol-A, mercaptan is n- dodecyl mereaptan.
N- dodecyl mereaptan 0.20mol (i.e. 38.2g) is added into 250ml reaction flask, 120ml anhydrous methylene chloride or dichloro
Ethane or acetone or alcohol stir 30min, in 5-10 DEG C of additions 0.1mol (34g) bisphenol-A pair dehydration glycerol under nitrogen protection
Ether, ice bath half an hour are slowly added to 2.5mmol (i.e. 0.1g) sodium hydroxide, warm naturally to after room temperature insulated and stirred 12 hours,
Detection is complete to thiol reaction, through washing except solvent is removed under reduced pressure in alkali and impurity, obtains transparent oil 69g, yield 95.6%.
ESI/MS+: 745.32,543.39；1H-NMR/400MHz,CDCl3:δ7.22–7.04(m,1H),6.95–6.76(m,1H),
4.20-3.96 (m, 1H), 2.99-2.43 (m, 1H), 1.60 (d, J=22.5Hz, 2H), 1.26 (s, 5H), 0.88 (t, J=
6.7Hz,1H))
Embodiment 2
2 example synthesis step of chemical synthesis target product:
2 structural formula of target product
2 synthesis step of target product:
When compound 2 is the double glycidyl ethers of Bisphenol F, mercaptan is n- dodecyl mereaptan, if m=2.0, n=0.Reaction step
Suddenly are as follows: be added into 2.5L reaction flask the double glycidyl ethers of 313 grams of Bisphenol Fs, 1200ml anhydrous methylene chloride or dichloroethanes or
Acetone or acetonitrile, stirring to dissolved clarification are added 405 grams of n- dodecyl mereaptan, and nitrogen protection, is slowly added to hydroxide at ice bath half an hour
It 5 grams of sodium, warms naturally to after room temperature insulated and stirred 20 hours, detection is complete to thiol reaction, and methylene chloride is recovered under reduced pressure, and freezes
715 grams of white solid are obtained, yield 99.6%.
(ESI/MS+:493.71,515,739.6,827.5,1029.48；1H-NMR/400MHZ,CDCl3:δ7.11–7.03
(m, 1H), 6.83 (ddd, J=8.6,4.3,2.2Hz, 1H), 4.05-3.89 (m, 2H), 2.75-2.55 (m, 1H), 2.58-
2.47 (m, 1H), 1.58 (q, J=7.4Hz, 1H), 1.35 (d, J=7.1Hz, 1H), 1.32-1.25 (m, 2H), 1.26 (s,
9H), 0.88 (t, J=6.8Hz, 2H))
Embodiment 3
3 example synthesis step of chemical synthesis target product:
3 structural formula of target product
3 synthesis step of target product:
When compound 2 is isocyanuric acid three-glycidyl ester (TGIC), mercaptan is n- dodecyl mereaptan, toward 250ml reaction flask
29.7 grams of TGIC of middle addition, 120ml anhydrous ethyl acetate or anhydrous methylene chloride or anhydrous dichloroethanes stir to dissolved clarification, add
Enter 60.7 grams of n- dodecyl mereaptan, nitrogen protection is slowly added to 0.5 gram of sodium hydroxide, is stirred at room temperature 16 hours, detects anti-to mercaptan
90 grams of white solid should be filtered to obtain, yield 99.6% completely.
ESI/MS+:904.52,701.98；1H-NMR/400MHZ,CDCl3:δ6.54(s,1H),4.18–3.80(m,1H),
2.79-2.37 (m, 1H), 1.98 (s, 1H), 1.51 (p, J=7.4Hz, 1H), 1.19 (s, 6H), 0.81 (t, J=6.7Hz,
1H).
Embodiment 4
4 structural formula of target product
4 synthesis step of target product
When compound 2 is glycidyl methacrylate, mercaptan is n- dodecyl mereaptan, m=2 or 1；It is reacted toward 250ml
20 grams of glycidyl methacrylate, 120ml methylene chloride are added in bottle, n- dodecyl mereaptan 56.8 is added in stirring to dissolved clarification
Gram, nitrogen protection, ice bath half an hour is slowly added to 1 gram of sodium hydroxide, warms naturally to after room temperature insulated and stirred 12 hours, examines
Survey is complete to thiol reaction, and methylene chloride is recovered under reduced pressure, obtains 75 grams of transparent oil, yield 97.7%.
1H-NMR (400MHz, Chloroform-d) δ 3.87-3.72 (m, 2H), 3.57 (dd, J=11.1,5.9Hz,
1H), 1.67-1.52 (m, 2H), 0.90 (t, J=6.8Hz, 3H).MS/ESI+:569.32 (M+Na+), 344.93.
Embodiment 5
5 structural formula of target product
5 synthesis step of target product
Bisphenol-s epoxy resin intermediate is reacted with lauryl mercaptan
When compound 2 is the double glycidyl ethers of bisphenol S, mercaptan is n- dodecyl mereaptan, m=1.3
The double glycidyl ethers of 50 grams of bisphenol Ss, 120ml dichloroethanes or acetonitrile or ethyl alcohol are added into 250ml reaction flask, stirs
It mixes to dissolved clarification, is added 36 grams of n- dodecyl mereaptan, nitrogen protection, ice bath half an hour is slowly added to 0.5 gram of sodium hydroxide, rises naturally
Warm to room temperature rear insulated and stirred 12 hours, detection is complete to thiol reaction, and methylene chloride is recovered under reduced pressure, obtains transparent oil 80
Gram, yield 93.1%.
1H-NMR(400MHz,Chloroform-d)δ7.90–7.83(m,1H),7.03–6.96(m,1H),2.79–2.66
(m,3H),2.63–2.51(m,1H),1.67–1.54(m,2H),0.98–0.82(m,3H)。ESI/MS+: 766.91；ESI/MS-:
764.91,507.24。
Claims (8)
1. a kind of antioxidative stabilizer structure feature with chelating function is that it can form chelate knot with metal ion
Structure, the passive metal ionic catalysis macromolecule degradation function in high molecular material, while excellent anti-oxidation function is kept, it ties
Structure formula are as follows:
Wherein X=O, N, NH；R1For phenyl, xenyl, isocyanuric acid base, diphenyl methane, diphenyldimethyhnethane, hexichol
Base sulfone, alkyl or substituted acrylate；R and R2For C6~C20 straight chain or alkyl containing branched alkane；M=0,1,2,3,4；N=01,
2,3,4, and m and n are not 0 simultaneously.
2. a kind of preparation method of antioxidative stabilizer as described in claim 1, which is characterized in that it chemically reacts general formula
Are as follows:
Wherein X=O, N, NH；R1For benzene, biphenyl, isocyanuric acid, diphenyl methane, diphenyldimethyhnethane, diphenyl sulfone, alkane
Base or substitutional crylic acid ester group；R and R2For C6~C20 straight chain or contain branched paraffin；M=0,1,2,3,4；N=01,2,3,4, m
It cannot simultaneously be 0 with n.
3. a kind of preparation method of antioxidative stabilizer as claimed in claim 2, which comprises the steps of:
(1) compound 1 and epoxychloropropane, add-back flow tube is added, N2 is protected, heating stirring, when interior temperature reaches 65 DEG C, in batches
It is slowly added to sodium hydroxide, insulation reaction to compound 1 has been reacted, 1L MTBE or ethyl acetate are added after being cooled to 50 DEG C,
Or methylene chloride or petroleum ether, insoluble matter, filtrate decompression recycling design and excessive epoxychloropropane are filtered, colorless oil is obtained
Compound 2 is not further purified and is directly used in next step.
(2) mercaptan is added, methylene chloride or acetone or ethyl acetate or ethyl alcohol or methanol solvate is added, is protected in stirring nitrogen
0-15 DEG C is cooled under shield, compound 2 is added, and ice bath is kept for temperature half an hour, sodium hydroxide is slowly added portionwise, obtains compound
3 or compound 4.
4. a kind of preparation method of antioxidative stabilizer as claimed in claim 3, which comprises the steps of: institute
The solvent for stating step (2) is anhydrous methylene chloride, dichloroethanes, acetone or alcohol or ethyl acetate or methanol or tetrahydrofuran.
5. a kind of preparation method of antioxidative stabilizer as claimed in claim 3, which comprises the steps of: institute
State step (2) slowly sodium hydroxide is added portionwise after, warm naturally to after room temperature insulated and stirred 3-24 hour, detection it is anti-to mercaptan
Through washing except solvent is removed under reduced pressure in alkali and impurity, compound 3 or compound 4 should be obtained completely.
6. a kind of preparation method of antioxidative stabilizer as claimed in claim 3, which comprises the steps of: institute
Stating the molar ratio of compound 1 and epoxychloropropane in step (1) is 1:2-15.
7. a kind of preparation method of antioxidative stabilizer as claimed in claim 3, which comprises the steps of: institute
Stating the molar ratio of mercaptan and compound 2 in step (2) is 1:1.5-7.
8. a kind of antioxidative stabilizer as described in claim 1 is applied in high molecular material, as long-life, high-temperature antioxidant
Function, the price reduction of passive metal ionic catalysis macromolecule form complexing heat stabilizer with certain metal ions, are that high molecular material rises
To the anti-oxidant stabilization additives for guaranteeing the quality, protecting color, keeping function.
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| CN201910743109.7A CN110437838A (en) | 2019-08-13 | 2019-08-13 | Novel chelate polymer antioxidative stabilizer and its preparation method and application |
| PCT/CN2019/124727 WO2021027202A1 (en) | 2019-08-13 | 2019-12-12 | Chelating macromolecular anti-oxidation stabilising agent, preparation method therefor, and application thereof |
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| WO2021027202A1 (en) * | 2019-08-13 | 2021-02-18 | 绍兴瑞康生物科技有限公司 | Chelating macromolecular anti-oxidation stabilising agent, preparation method therefor, and application thereof |
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| CN106674591B (en) * | 2016-12-07 | 2019-02-01 | 绍兴瑞康生物科技有限公司 | A kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered and its application |
| CN107311897A (en) * | 2017-06-14 | 2017-11-03 | 吉林省九新实业集团化工有限公司 | The n-octylthiomethylene phenol of 2,4 di-t-butyl 6 and its preparation technology |
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| US4125516A (en) * | 1976-03-22 | 1978-11-14 | Ciba-Geigy Corporation | Alkylthioalkanoyloxyalkyl and alkylthioalkyl substituted bis-hydantoin compounds |
| CN1200113A (en) * | 1995-10-19 | 1998-11-25 | 希巴特殊化学控股公司 | Antioxidants containing phenol groups and aromatic amine groups |
| CN105801456A (en) * | 2016-04-27 | 2016-07-27 | 双键化工（上海）有限公司 | Reaction type thioester antioxidant and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021027202A1 (en) * | 2019-08-13 | 2021-02-18 | 绍兴瑞康生物科技有限公司 | Chelating macromolecular anti-oxidation stabilising agent, preparation method therefor, and application thereof |
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| Publication number | Publication date |
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| WO2021027202A1 (en) | 2021-02-18 |
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