CN110577640A - 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant and application thereof - Google Patents

3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant and application thereof Download PDF

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Publication number
CN110577640A
CN110577640A CN201910820006.6A CN201910820006A CN110577640A CN 110577640 A CN110577640 A CN 110577640A CN 201910820006 A CN201910820006 A CN 201910820006A CN 110577640 A CN110577640 A CN 110577640A
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CN
China
Prior art keywords
tert
butyl
antioxidant
hydroxybenzyl acrylate
macromolecular antioxidant
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Pending
Application number
CN201910820006.6A
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Chinese (zh)
Inventor
何敏
刘玉飞
于杰
秦舒浩
徐国敏
张凯
张道海
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Guizhou University
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Guizhou University
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Priority to CN201910820006.6A priority Critical patent/CN110577640A/en
Publication of CN110577640A publication Critical patent/CN110577640A/en
Pending legal-status Critical Current

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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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

Abstract

The invention discloses a macromolecular antioxidant, which is characterized in that: the antioxidant contains functional group 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate. The invention prepares 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant; the polymer has good thermal oxidative aging resistance, can be used as a thermal oxidative aging resistance modifier for common plastics such as PVC, ABS and the like, can also be used as a thermal oxidative aging resistance modifier for engineering plastics such as polylactic acid, PA6, PPO and the like, and has good effect.

Description

3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant and application thereof
Technical Field
The invention relates to preparation of a macromolecular antioxidant and modified nylon 6 thereof, and particularly belongs to the field of synthesis of resin raw materials and pharmaceutical and pesticide intermediates.
Background
The current literature reports that the antioxidant is compounded by two antioxidants of a chain termination type and a prevention type, such as: the complex formulation of AN alcohol ester antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and a phosphite ester antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite) [23], the complex formulation of a hindered phenol 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine) and the antioxidant 168 [24], the complex formulation of the hindered phenol antioxidant 245 and a phosphite ester auxiliary antioxidant 626, a copper salt heat stabilizer AN [19] and the like. However, the molecular weight of the above antioxidants is low, and the small molecular antioxidants have low boiling points, are volatile and are easy to separate out in the processing process.
Disclosure of Invention
the technical problem to be solved by the invention is as follows: provides a 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant, which aims to solve the limitations that the molecular weight of the antioxidant is low, the boiling point is low, and the antioxidant is easy to volatilize and separate out in the processing process in the prior art.
The technical scheme of the invention is as follows: a macromolecular antioxidant contains a functional group of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate.
The antioxidant is a binary copolymer, a ternary copolymer or a copolymer of more than two components containing 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate.
the reaction formula of the preparation method of the macromolecular antioxidant is as follows:
n＝10-100。
The preparation method of the macromolecular antioxidant comprises the following reaction steps: heating the oil bath kettle to 50-100 ℃, adding the brominated cyclohexanone solution of the 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and the ethylenediamine into the reactor, and stirring for 20-60min at the temperature; adding xylene and introducing N2Stirring, heating to 95-130 deg.C, reacting for 3-5 hr to obtain initial product, dissolving in acetone while it is hot, and precipitating with methanolPrecipitating, and vacuum drying the obtained product at 40-130 deg.C for 4-24h to obtain powdery binary copolymer resin sample, i.e. macromolecular antioxidant.
The molar ratio of the brominated 3,6 di-tert-butyl 4 hydroxybenzyl acrylate to the ethylenediamine is 1: 18-22.
The invention has the beneficial effects that: the invention prepares 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant; the polymer has good thermal oxidative aging resistance, can be used as a thermal oxidative aging resistance modifier for common plastics such as PVC, ABS and the like, can also be used as a thermal oxidative aging resistance modifier for engineering plastics such as polylactic acid, PA6, PPO and the like, and has good effect.
Detailed Description
The invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
Example 1
Bromination of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate: 3.24g of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate were dissolved in 50mL of CCl4And CH3In COOH; at 0 ℃ and below, 1.96g of Br was added dropwise2CCl of (2)4Adding the solution into the solution of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate, reacting for 1 hour, pouring the reaction system into distilled water, standing for 3-5 minutes, and filtering while the solution is cold. And drying the filter cake in an oven at 70 ℃.
The brominated 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine are subjected to polycondensation to obtain a binary copolymerization product, and the preparation method comprises the following steps:
Heating the oil bath to 76 deg.C, adding 0.7g of brominated 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and 1.86g of ethylenediamine in cyclohexanone solution into a beaker, and stirring at this temperature for 40 min; the solution was transferred to a 250ml four necked flask equipped with a stirrer, condenser, thermometer, gas-line, 70ml xylene was added and N was passed through2Stirring, heating to 125 deg.C, reacting for 4h to obtain the primary product. Dissolving the initial product in acetone while hot, precipitating with methanol as precipitant to remove residual monomer and small molecules, and vacuum drying at 60 deg.C for 24 hr to removeAnd removing small molecules. A powdery sample of the copolymer resin was obtained.
Example 2
Bromination of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate: 32.4g of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate were dissolved in 50mL of CCl4And CH3In COOH; at 0 ℃ and below, 19.6g of Br was added dropwise2CCl of (2)4Adding the solution into the solution of 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate, reacting for 1 hour, pouring the reaction system into distilled water, standing for 3-5 minutes, and filtering while the solution is cold. And drying the filter cake in an oven at 70 ℃.
The brominated 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine are subjected to polycondensation to obtain a binary copolymerization product, and the preparation method comprises the following steps:
Heating the oil bath to 76 deg.C, adding 7g of brominated 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and 18.6g of ethylenediamine in cyclohexanone solution into a beaker, and stirring at this temperature for 40 min; the solution was transferred to a 1000ml four necked flask equipped with a stirrer, condenser, thermometer, gas-guide tube, 700ml xylene was added and N was passed through2Stirring, heating to 125 deg.C, reacting for 4h to obtain the primary product. Dissolving the initial product in acetone while the solution is hot, re-precipitating with methanol as precipitant to remove residual monomer and small molecules, and vacuum drying the obtained product at 60 deg.C for 24 hr to remove small molecules. A powdery sample of the copolymer resin was obtained.
The product obtained in example 2 was added to polylactic acid (PLA) and the composites were subjected to thermo-oxidative ageing for 50 days at 60 ℃ with tensile strength results as shown in the following table:
Sample number 1 1 3 4
Before thermo-oxidative aging 56MPa 55MPa 57MPa 59MPa
After thermal oxygen aging 26MPa 35PMa 45MPa 52MPa
note: in the table, No. 1 shows that binary copolymerization was not added, No. 2 shows that 1 part of binary copolymerization was added, No. 3 shows that 2 parts of binary copolymerization was added, and No. 4 shows that 3 parts of binary copolymerization was added.
The skilled worker is able to associate with his general knowledge that copolymers of two, three and more members containing 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate are also within the scope of protection.

Claims (5)

1. A macromolecular antioxidant, characterized by: the antioxidant contains functional group 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate.
2. The macromolecular antioxidant according to claim 1, characterized in that: the antioxidant is a binary copolymer, a ternary copolymer or a copolymer of more than two components containing 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate.
3. The method for preparing a macromolecular antioxidant according to claim 1, wherein: the reaction formula is shown as follows:
n＝10-100。
4. The method for preparing a macromolecular antioxidant according to claim 2, characterized in that: the reaction steps are as follows: heating the oil bath kettle to 50-100 ℃, adding the brominated cyclohexanone solution of the 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and the ethylenediamine into the reactor, and stirring for 20-60min at the temperature; adding xylene and introducing N2Stirring, heating to 95-130 ℃ for reaction, reacting for 3-5h to obtain an initial product, dissolving the initial product in acetone while the initial product is hot, re-precipitating with methanol, and vacuum drying the obtained product at 40-130 ℃ for 4-24h to obtain a powdery binary copolymer resin sample, namely the macromolecular antioxidant.
5. the method for preparing a macromolecular antioxidant according to claim 4, characterized in that: the molar ratio of the brominated 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate to the ethylene diamine is 1: 18-22.
CN201910820006.6A 2019-08-31 2019-08-31 3, 6-di-tert-butyl-4-hydroxybenzyl acrylate and ethylenediamine copolymerized macromolecular antioxidant and application thereof Pending CN110577640A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039814A (en) * 1988-06-02 1990-02-21 宇部与产株式会社 The method of stabilized oxymethylene copolymer
CN1506035A (en) * 2002-12-13 2004-06-23 莱雅公司 Hair conditioning composition containing film forming gradient copolymer, airsol composition containing the same hair care composition and treatment method
US6770785B1 (en) * 2003-03-25 2004-08-03 Council Of Scientific And Industrial Research Antiozonant cum antioxidant, process for preparation
CN1846018A (en) * 2003-09-01 2006-10-11 株式会社晓星 Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance
CN101293957A (en) * 2008-06-19 2008-10-29 湖北华丽生物产业园有限公司 Appropriately crosslinked biodegradable polyester-amides random block copolymer and synthesizing method thereof
CN102167762A (en) * 2011-02-25 2011-08-31 山东润科化工股份有限公司 Method for producing poly(pentabromobenzyl acrylate)
CN104292141A (en) * 2014-08-18 2015-01-21 华南理工大学 Macromolecular hindered phenol antioxidant containing thioether and carbamate groups and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039814A (en) * 1988-06-02 1990-02-21 宇部与产株式会社 The method of stabilized oxymethylene copolymer
CN1506035A (en) * 2002-12-13 2004-06-23 莱雅公司 Hair conditioning composition containing film forming gradient copolymer, airsol composition containing the same hair care composition and treatment method
US6770785B1 (en) * 2003-03-25 2004-08-03 Council Of Scientific And Industrial Research Antiozonant cum antioxidant, process for preparation
CN1846018A (en) * 2003-09-01 2006-10-11 株式会社晓星 Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance
CN101293957A (en) * 2008-06-19 2008-10-29 湖北华丽生物产业园有限公司 Appropriately crosslinked biodegradable polyester-amides random block copolymer and synthesizing method thereof
CN102167762A (en) * 2011-02-25 2011-08-31 山东润科化工股份有限公司 Method for producing poly(pentabromobenzyl acrylate)
CN104292141A (en) * 2014-08-18 2015-01-21 华南理工大学 Macromolecular hindered phenol antioxidant containing thioether and carbamate groups and preparation method and application thereof

Non-Patent Citations (4)

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Title
（美）格罗金斯: "《化工有机合成单元过程》", 30 June 1972, 燃料化学工业出版社 *
B. W. EVANS等: "《MECHANISMS O F ANTIOXIDANT ACTION:POLYMER GRAFTED ANTIOXIDANTS》", 《EUROPEAN POLYMER JOURNAL》 *
S. AL-MALAIKA等: "《Reactive processing of polymers: mechanisms of grafting reactions of functional antioxidants of polyolefins in the presence of a coagent》", 《POLYMER DEGRADATION AND STABILITY》 *
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