CN116284742A - High molecular weight liquid hindered phenol antioxidant and preparation method thereof - Google Patents
High molecular weight liquid hindered phenol antioxidant and preparation method thereof Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 75
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 65
- 239000007788 liquid Substances 0.000 title claims abstract description 61
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011496 polyurethane foam Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 18
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 description 2
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate Chemical compound 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of antioxidants, in particular to a high-molecular-weight liquid hindered phenol antioxidant and a preparation method thereof. The liquid hindered phenol antioxidant prepared by the method has a simple process, greatly reduces the reaction difficulty in the preparation process of the antioxidant, and effectively reduces the raw materials and the production cost; the polypropylene glycol has moderate hydrophilicity and larger molecular weight, so the liquid hindered phenol antioxidant obtained by the invention has large molecular weight, better compatibility with polyurethane materials, difficult precipitation and more migration resistance.
Description
Technical Field
The invention relates to the technical field of antioxidants, in particular to a high-molecular-weight liquid hindered phenol antioxidant and a preparation method thereof.
Background
The polyurethane material and the raw materials polyether polyol and polyester polyol thereof can cause problems of odor, VOC or influencing the performance of raw materials or products and the like due to aging degradation during storage and use, so that an antioxidant is usually added into the polyurethane material, the polyether polyol or the polyester polyol to inhibit degradation and keep the stability of the polyurethane material, the polyether polyol or the polyester polyol.
The types of antioxidants are many, wherein the hindered phenol antioxidant is a common main antioxidant, and is divided into a solid hindered phenol antioxidant and a liquid hindered phenol antioxidant. The hindered phenol antioxidants commonly used in the market are mainly solid, such as antioxidants 1010, 1076, 3114 and 330 are all solid, and liquid antioxidants are few in types, but the solid hindered phenol antioxidants have the problems of difficult mixing and dissolving, high difficulty in mixing operation and the like in the use process. At present, the liquid hindered phenol antioxidant mainly used in the market has 1135 (isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), which has higher cost performance and wide application, but has smaller molecular weight, low compatibility with polyurethane materials, polyether polyols and polyester polyols, and is easy to separate out when being applied to the products. In the prior art, the liquid hindered phenol antioxidant is also researched, but the molecular weight of the obtained antioxidant is smaller, the maximum molecular weight is not more than 700, the compatibility with polyurethane materials, polyether polyol and polyester polyol is low, and the antioxidant is easy to separate out. In addition, the existing liquid antioxidant needs to be subjected to severe processes such as high temperature, high vacuum and the like to remove excessive raw materials after the production reaction is finished, or needs to strictly control the reaction process in order to control the raw material consumption and prevent the raw materials from being excessive, and the prior art generally has the problems of complex process, difficult reaction, high production cost and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the liquid hindered phenol antioxidant with high molecular weight and the preparation method thereof, which can obtain the liquid hindered phenol antioxidant with high molecular weight, good compatibility with polyurethane materials, polyester polyol and polyether polyol and more migration resistance, and the preparation process is simple and convenient, is easy to operate, and effectively reduces the raw materials and the production cost.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing a high molecular weight liquid hindered phenol antioxidant, comprising the steps of:
(1) Transesterification: adding 3, 5-methyl ester and polypropylene glycol in a certain proportion into a reaction container, adding a catalyst, stirring, heating, vacuumizing, performing transesterification reaction at a certain temperature and under a certain vacuum degree, extracting methanol generated by the reaction in the reaction process, and after the 3, 5-methyl ester is completely reacted, breaking vacuum and cooling to obtain a liquid hindered phenol antioxidant crude product;
(2) Removing the catalyst: removing the catalyst in the liquid hindered phenol antioxidant crude product to obtain the liquid hindered phenol antioxidant.
Concretely, the transesterification is carried out under the conditions that the temperature is 130-160 ℃ and the vacuum degree is 4-5.5 kPa.
Specifically, the catalyst removal comprises the steps of adding water into a liquid hindered phenol antioxidant crude product, dissolving the catalyst, standing for layering, and removing a water layer; and then heating the material, removing residual moisture in the material under a certain vacuum degree, breaking vacuum by using nitrogen, and cooling to obtain the liquid hindered phenol antioxidant.
Specifically, the molecular weight of the polypropylene glycol is 400-8000; preferably, the polypropylene glycol has a molecular weight of 400-2000.
Specifically, the molar ratio of the 3, 5-methyl ester to the polypropylene glycol is 1: (0.5-1).
Specifically, the catalyst is one or more of aluminum chloride, magnesium chloride, ferric chloride, zinc chloride, boron fluoride, potassium fluoride, magnesium acetate, lithium amide, sodium acetate, potassium acetate, zinc acetate, aluminum isopropoxide and triethanolamine.
Specifically, the catalyst is used in an amount of 0.1% -5% of the mass of the 3, 5-methyl ester; preferably, the catalyst is used in an amount of 0.5% -2% by mass of the 3, 5-methyl ester.
In another aspect, the present invention provides a high molecular weight liquid hindered phenol antioxidant comprising a compound of formula I and a compound of formula II
Specifically, the kinematic viscosity of the liquid hindered phenol antioxidant is 100-400mm at 40 DEG C 2 /s。
In particular, the liquid hindered phenol antioxidant is used in polyether polyols, polyester polyols, and polyurethane foams.
The beneficial effects of the invention are as follows:
1. according to the invention, 3, 5-methyl ester and polypropylene glycol are used as raw materials, and a liquid hindered phenol antioxidant can be prepared through transesterification, and the liquid hindered phenol antioxidant has a larger molecular weight, has better compatibility with polyurethane raw materials, polyester polyol and polyether polyol and is more migration-resistant;
2. the invention takes polypropylene glycol as raw material, and controls the dosage of 3, 5-methyl ester and polypropylene glycol to lead the ester group of 3, 5-methyl ester to completely react, thus directly carrying out the next treatment after the transesterification is finished, and removing the catalyst in the crude product of the liquid hindered phenol antioxidant, thus obtaining the liquid hindered phenol antioxidant. The polypropylene glycol is a raw material of polyurethane, so that whether the liquid hindered phenol antioxidant contains or remains the polypropylene glycol has no influence on the application of the liquid hindered phenol antioxidant in polyurethane, and compared with the prior art, the method does not need to carry out a severe high-temperature/high-vacuum process, has simple reaction process and reaction condition and is easy to operate, the preparation process of the liquid hindered phenol antioxidant is greatly simplified, the reaction difficulty of the production of the liquid hindered phenol antioxidant is reduced, the raw material and production cost are effectively reduced, and the product yield is improved;
3. compared with other alcohols, the polypropylene glycol (PPG) used in the invention has large molecular weight, is favorable for obtaining the liquid hindered phenol antioxidant with high molecular weight, has moderate hydrophilicity, and does not influence the compatibility of antioxidant products with polyurethane raw materials, polyether polyol and polyester polyol due to over-strong hydrophilicity.
Drawings
FIG. 1 is an infrared spectrum of a liquid hindered phenol antioxidant obtained in example 3 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to the drawings and the specific embodiments, without limiting the scope of the invention.
3, 5-methyl ester, chinese academic name: beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester; CAS NO:6386-38-5; molecular weight: 292.4; the chemical structural formula:
polypropylene glycol: PPG; the chemical structural formula:
example 1.
To a 500ml three-necked flask, 58.4 g of 3, 5-methyl ester and 150 g of PPG (1000 molecular weight) were successively added, and 1 g of zinc chloride catalyst was added to start the stirring and heating reaction.
Heating to 130-140 deg.c, and reaction at vacuum degree of 4kPa for 3 hr to eliminate methanol as by-product until no obvious distillate is produced. 6.2 g of methanol as a by-product was collected together by a cold trap.
Cooling to room temperature, and confirming that the 3, 5-methyl ester is completely reacted by gas chromatography.
Adding deionized water 20g, standing, layering, and removing a water layer.
The batch was warmed to 120℃and evacuated to 1kPa for 1 hour to remove residual water. Vacuum breaking with nitrogen and cooling gave 199.5 g of colorless transparent liquid. The kinematic viscosity (40 ℃) thereof is 250mm 2 /s。
Example 2.
To a 500ml three-necked flask, 48.7 g of 3, 5-methyl ester and 150 g of PPG (1000 molecular weight) were successively added, and 0.9 g of zinc chloride catalyst was added to start the stirring and heating reaction.
Heating to 140-150 deg.c, and reaction under vacuum of 5kPa for 3 hr to eliminate methanol as by-product until no obvious distillate is produced. 5.2 g of methanol as a by-product was collected together by a cold trap.
Cooling to room temperature, and confirming that the 3, 5-methyl ester is completely reacted by gas chromatography.
Adding deionized water 20g, standing, layering, and removing a water layer.
The batch was warmed to 120℃and evacuated to 1kPa for 1 hour to remove residual water. The vacuum was broken with nitrogen and the temperature was lowered to give 190.7 g of a colorless transparent liquid. Its kinematic viscosity (40 ℃ C.) is 200mm 2 /s。
Example 3.
To a 500ml three-necked flask, 116.8 g of 3, 5-methyl ester and 120 g of PPG (400 molecular weight) were successively added, and 2 g of an aluminum isopropoxide catalyst was added to start the stirring and heating reaction.
Heating to 150-160 deg.c, and vacuum reaction at 5.5kPa for 3 hr to eliminate methanol as by-product until no obvious distillate is produced. 12.5 g of methanol as a by-product was collected in total by a cold trap.
Cooling to room temperature, and confirming that the 3, 5-methyl ester is completely reacted by gas chromatography.
Adding deionized water 20g, standing, layering, and removing a water layer.
The batch was warmed to 120℃and evacuated to 1kPa for 1 hour to remove residual water. Vacuum was broken with nitrogen and the temperature was lowered to give 221.6 g of a colorless transparent liquid. The kinematic viscosity (40 ℃) thereof is 350mm 2 /s。
The liquid hindered phenol antioxidants obtained in examples 1, 2, 3 were used to stabilize conventional polyether polyols (molecular weight 3000), which were well compatible with polyether polyols, and Oxidation Induction Temperature (OIT) was measured by DSC. For comparison, after mixing the common antioxidants 1076, 1135 with the common polyether polyol (molecular weight 3000) uniformly, the Oxidation Induction Temperature (OIT) was measured by DSC, and the measurement results are shown in table 1 below:
table 1:
| stabilizing agent | Concentration of | OIT (oxidation induction temperature) | |
| Example 1 | Example 1 | 1000ppm | 176.4℃ |
| Example 2 | Example 2 | 1000ppm | 175.7℃ |
| Example 3 | Example 3 | 1000ppm | 176.7℃ |
| Comparative example 1 | Antioxidant 1076 | 1000ppm | 174.3℃ |
| Comparative example 2 | Antioxidant 1135 | 1000ppm | 174.9℃ |
| Blank examples | --- | --- | 156.3℃ |
FIG. 1 is an infrared spectrum of example 3 of the present invention, which can be seen at 1732cm -1 The absorption peak appears, which indicates that the 3, 5-methyl ester and the polypropylene glycol are subjected to transesterification reaction in the invention.
In the present invention, when the molecular weight of polypropylene glycol (PPG) used is 400, the molecular weight of the obtained liquid hindered phenol antioxidant is in the range of 674-949; when the molecular weight of polypropylene glycol (PPG) used is 1000, the molecular weight of the obtained liquid hindered phenol antioxidant is in the range of 1274-1549; when the molecular weight of polypropylene glycol (PPG) used is 2000, the molecular weight of the resulting liquid hindered phenol antioxidant is in the range of 2274-2549; similarly, when the polypropylene glycol used is higher in molecular weight, the liquid hindered phenol antioxidant obtained will also be higher in molecular weight. Therefore, the liquid hindered phenol antioxidant with higher molecular weight can be obtained, has better compatibility with polyurethane raw materials, polyester polyol and polyether polyol, is more migration-resistant, and is easier to mix and dissolve.
From the test results in table 1, it can be seen that the liquid hindered phenol antioxidant obtained by the invention can improve the oxidation resistance temperature of the raw materials, so that the raw materials have better stability; examples 1, 2, and 3 of the present invention are compared with comparative examples 1 and 2 (common solid antioxidant 1076 and liquid antioxidant 1135), and it can be seen that the Oxidation Induction Temperature (OIT) of the present invention is slightly better than that of the common antioxidants 1076 and 1135. The invention is a liquid hindered phenol antioxidant with a kinematic viscosity of 100-400mm at 40 DEG C 2 And/s, the product is convenient to pump and use, and compared with the existing antioxidant, the antioxidant has good compatibility with polyurethane raw materials, polyester polyol and polyether polyol, and is easier to mix and dissolve with the raw materials.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a high molecular weight liquid hindered phenol antioxidant is characterized by comprising the following steps: the method comprises the following steps:
(1) Transesterification: adding 3, 5-methyl ester and polypropylene glycol in a certain proportion into a reaction container, adding a catalyst, stirring, heating, vacuumizing, performing transesterification reaction at a certain temperature and under a certain vacuum degree, and extracting methanol generated in the reaction process; after the 3, 5-methyl ester is completely reacted, breaking vacuum and cooling to obtain a liquid hindered phenol antioxidant crude product;
(2) Removing the catalyst: removing the catalyst in the liquid hindered phenol antioxidant crude product to obtain the liquid hindered phenol antioxidant.
2. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: the transesterification is carried out at a temperature of 130-160 ℃ and a vacuum of 4-5.5 kPa.
3. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: removing the catalyst comprises adding water into the liquid hindered phenol antioxidant crude product to dissolve the catalyst, standing for layering, and removing a water layer; and then heating the material, removing residual moisture in the material under a certain vacuum degree, breaking vacuum by using nitrogen, and cooling to obtain the liquid hindered phenol antioxidant.
4. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: the molecular weight of the polypropylene glycol is 400-8000.
5. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: the molar ratio of the 3, 5-methyl ester to the polypropylene glycol is 1: (0.5-1).
6. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: the catalyst is one or more of aluminum chloride, magnesium chloride, ferric chloride, zinc chloride, boron fluoride, potassium fluoride, magnesium acetate, lithium amide, sodium acetate, potassium acetate, zinc acetate, aluminum isopropoxide and triethanolamine.
7. The method for preparing a high molecular weight liquid hindered phenol antioxidant according to claim 1, wherein: the dosage of the catalyst is 0.1% -5% of the mass of the 3, 5-methyl ester.
8. A high molecular weight liquid hindered phenol antioxidant according to the preparation process of claims 1 to 7, characterized in that: comprising a compound of the structural formula I and a compound of the structural formula II,
9. the high molecular weight liquid hindered phenol antioxidant of claim 8, wherein: the liquid hindered phenol antioxidant is used in polyether polyol, polyester polyol and polyurethane foam.
10. A high score according to claim 8The liquid hindered phenol antioxidant with the molecular weight is characterized in that: the kinematic viscosity of the liquid hindered phenol antioxidant is 100-400mm at 40 DEG C 2 /s。
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| US4032562A (en) * | 1974-11-05 | 1977-06-28 | Ciba-Geigy Corporation | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters of polyalkylene glycols |
| WO2001083605A2 (en) * | 2000-05-04 | 2001-11-08 | Dow Global Technologies Inc. | Molecular melt and methods for making and using the molecular melt |
| US6569927B1 (en) * | 2000-10-06 | 2003-05-27 | Uniroyal Chemical Company, Inc. | Thermoplastic resins stabilized by blends of sterically hindered phenols, secondary amines, and lactones |
| CN1806002A (en) * | 2003-06-12 | 2006-07-19 | 巴斯福股份公司 | Mixtures containing isocyanate stabilisers of the hindered phenol type with a high molecular weight |
| CN106588663A (en) * | 2016-10-28 | 2017-04-26 | 南雄志精细化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN110452518A (en) * | 2018-04-27 | 2019-11-15 | 上海凯赛生物技术股份有限公司 | A kind of starlike molecular structure hindered phenol compound and its application in polyesteramide synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032562A (en) * | 1974-11-05 | 1977-06-28 | Ciba-Geigy Corporation | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters of polyalkylene glycols |
| WO2001083605A2 (en) * | 2000-05-04 | 2001-11-08 | Dow Global Technologies Inc. | Molecular melt and methods for making and using the molecular melt |
| US6569927B1 (en) * | 2000-10-06 | 2003-05-27 | Uniroyal Chemical Company, Inc. | Thermoplastic resins stabilized by blends of sterically hindered phenols, secondary amines, and lactones |
| CN1806002A (en) * | 2003-06-12 | 2006-07-19 | 巴斯福股份公司 | Mixtures containing isocyanate stabilisers of the hindered phenol type with a high molecular weight |
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