CN110452377A - A kind of 2- allyl -6- methyl-6-tert-butylphenol and ethylenediamine copolymerization macromolecular antioxidant and its application - Google Patents
A kind of 2- allyl -6- methyl-6-tert-butylphenol and ethylenediamine copolymerization macromolecular antioxidant and its application Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 23
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 title 1
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006026 co-polymeric resin Polymers 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- ZPRWCDITPUGNOB-UHFFFAOYSA-N 6-tert-butyl-6-methylcyclohexa-2,4-dien-1-ol Chemical compound CC(C)(C)C1(C)C=CC=CC1O ZPRWCDITPUGNOB-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 10
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- JBSODNBBAKNHEU-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(CO)(CO)CO JBSODNBBAKNHEU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种大分子抗氧剂，其特征在于：所述的抗氧剂含有官能团2‑烯丙基‑6‑甲基‑6‑叔丁基苯酚。本发明制备了2‑烯丙基‑6‑甲基‑6‑叔丁基苯酚与乙二胺共聚大分子抗氧剂；该类聚合物具有良好的抗热氧老化性能，不仅可以作为PVC、ABS等普通塑料的耐热氧老化改性剂，也可以作为聚乙烯，PA6、PPO等工程塑料的抗热氧老化剂且效果良好。The invention discloses a macromolecular antioxidant, which is characterized in that the antioxidant contains a functional group 2-allyl-6-methyl-6-tert-butylphenol. The invention prepares 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine copolymerized macromolecular antioxidant; the polymer has good anti-thermal-oxidative aging performance, and can not only be used as PVC, It can also be used as an anti-oxidative aging modifier for common plastics such as ABS, and can also be used as an anti-oxidative aging agent for engineering plastics such as polyethylene, PA6, and PPO, with good results.
Description
技术领域technical field
本发明涉及一种大分子抗氧剂的制备及其改性尼龙6，具体属于树脂原料、医药农药中间体的合成领域。The invention relates to the preparation of a macromolecular antioxidant and its modified nylon 6, and specifically belongs to the field of synthesis of resin raw materials and pharmaceutical and pesticide intermediates.
背景技术Background technique
目前文献报道一般都是由链终止型和预防型两种抗氧剂复配，比如：醇酯抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)与亚磷酸酯抗氧剂168(三[2,4-二叔丁基苯基]亚磷酸酯)的复配[23]、受阻酚类1098(N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺)与抗氧剂168复配[24]、受阻酚类抗氧剂245与亚磷酸酯类辅助型抗氧剂626、铜盐类热稳定剂AN复配[19]等。但是，以上抗氧剂分子量皆较低，而小分子抗氧剂沸点低，在加工的过程中易挥发、易析出。The current literature reports are generally composed of chain-terminating and preventive antioxidants, such as: alcohol ester antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)] Compound of pentaerythritol propionate) and phosphite antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite)[23], hindered phenols 1098 (N,N'-bis -(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine) and antioxidant 168 [24], hindered phenolic antioxidant 245 and phosphite Auxiliary antioxidant 626, copper salt heat stabilizer AN compound [19] and so on. However, the molecular weights of the above antioxidants are all low, and the small molecule antioxidants have a low boiling point and are volatile and easy to separate out during processing.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是：提供2-烯丙基-6-甲基-6-叔丁基苯酚与乙二胺共聚大分子抗氧剂，以解决现有技术中抗氧剂分子量皆较低，沸点低，在加工的过程中易挥发、易析出的局限性。The technical problem to be solved by the present invention is: to provide 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine copolymerized macromolecular antioxidant, so as to solve the problem that the molecular weight of the antioxidant in the prior art is relatively high. Low, low boiling point, volatile and easy to precipitate during processing.
本发明的技术方案是：一种大分子抗氧剂，所述的抗氧剂含有官能团2-烯丙基-6-甲基-6-叔丁基苯酚。The technical scheme of the present invention is: a macromolecular antioxidant, the antioxidant contains a functional group 2-allyl-6-methyl-6-tert-butylphenol.
所述的抗氧剂为含2-烯丙基-6-甲基-6-叔丁基苯酚的二元、三元及以上的共聚物。The antioxidant is a binary, ternary or above copolymer containing 2-allyl-6-methyl-6-tert-butylphenol.
所述的一种大分子抗氧剂的制备方法，其反应式如下所示：Described a kind of preparation method of macromolecular antioxidant, its reaction formula is as follows:
n＝10-100。n=10-100.
所述的一种大分子抗氧剂的制备方法，其反应步骤如下：加热油浴锅至50-100℃，将溴化后的2-烯丙基-6-甲基-6-叔丁基苯酚和乙二胺的环己酮溶液加入反应器，并在此温度下搅拌20-60min；加入二甲苯，通入N2气，搅拌、加热至95-130℃反应，反应3-5h，得到初产物，趁热将初产物溶于丙酮，用甲醇重沉淀，将得到的产物于40-130℃真空干燥4-24h，得到粉状二元共聚物树脂样品，即大分子抗氧剂。The preparation method of the macromolecular antioxidant, the reaction steps are as follows: heating an oil bath to 50-100 DEG C, brominated 2-allyl-6-methyl-6-tert-butyl The cyclohexanone solution of phenol and ethylenediamine was added to the reactor, and stirred at this temperature for 20-60min; added xylene, passed N 2 gas, stirred and heated to 95-130°C for reaction, and reacted for 3-5h to obtain The initial product was dissolved in acetone while still hot, reprecipitated with methanol, and the obtained product was vacuum-dried at 40-130 °C for 4-24 h to obtain a powdery binary copolymer resin sample, namely a macromolecular antioxidant.
所述的溴化后的2-烯丙基-6-甲基-6-叔丁基苯酚和乙二胺的摩尔比为1:11～15。The molar ratio of the brominated 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine is 1:11-15.
本发明的有益效果：本发明制备了2-烯丙基-6-甲基-6-叔丁基苯酚与乙二胺共聚大分子抗氧剂；该类聚合物具有良好的抗热氧老化性能，不仅可以作为PVC、ABS等普通塑料的耐热氧老化改性剂，也可以作为聚乙烯，PA6、PPO等工程塑料的抗热氧老化剂且效果良好。Beneficial effects of the present invention: the present invention prepares 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine copolymerized macromolecular antioxidants; this type of polymer has good anti-thermal oxidation aging performance , not only can be used as a thermal oxygen aging modifier for common plastics such as PVC and ABS, but also as a thermal oxygen aging resistance agent for engineering plastics such as polyethylene, PA6 and PPO with good effect.
具体实施方式Detailed ways
下面通过具体实例进一步说明本发明，但实例并不限制本发明的保护范围。The present invention is further described below through specific examples, but the examples do not limit the protection scope of the present invention.
实施例1Example 1
2-烯丙基-6-甲基-6-叔丁基苯酚溴化：将5.26g2-烯丙基-6-甲基-6-叔丁基苯酚溶于50mL的CCl4和CH3COOH中；在0℃及以下，逐滴将3.84g Br2的CCl4溶液加到2-烯丙基-6-甲基-6-叔丁基苯酚的溶液中，反应1小时后将反应体系倒入到蒸馏水中，放置3-5分钟，趁冷抽滤。将滤饼放在70℃烘箱内烘干。2-Allyl-6-methyl-6-tert-butylphenol bromination: Dissolve 5.26 g of 2-allyl-6-methyl-6-tert-butylphenol in 50 mL of CCl4 and CH3COOH ; at 0°C and below, dropwise add 3.84g of Br 2 in CCl 4 solution to the solution of 2-allyl-6-methyl-6-tert-butylphenol, and pour the reaction system into the reaction system after 1 hour of reaction Place in distilled water for 3-5 minutes, and filter with suction while cold. The filter cake was dried in an oven at 70°C.
将溴化的2-烯丙基-6-甲基-6-叔丁基苯酚、乙二胺缩聚，得到二元共聚产物，制备方法如下：The brominated 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine are polycondensed to obtain a binary copolymer product, and the preparation method is as follows:
加热油浴锅至76℃，将1.5g溴化后的2-烯丙基-6-甲基-6-叔丁基苯酚和3.08g乙二胺的环己酮溶液加入烧杯，并在此温度下搅拌40min；把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的250ml四颈瓶中，加入70ml二甲苯，通入N2气，搅拌、加热至125℃反应，反应4h，得到初产物。趁热将初产物溶于丙酮，用甲醇作沉淀剂重沉淀去除残留的单体和小分子，将得到的产物与60℃真空干燥24h，以去除小分子。得到粉状二元共聚物树脂样品。Heat the oil bath to 76°C, add 1.5g of brominated 2-allyl-6-methyl-6-tert-butylphenol and 3.08g of ethylenediamine in cyclohexanone solution into the beaker, and at this temperature Stir for 40min; transfer the solution to a 250ml four - neck flask equipped with a stirrer, a condenser, a thermometer and an airway, add 70ml of xylene, introduce N gas, stir and heat to 125°C for reaction, react for 4h, and obtain primary product. The initial product was dissolved in acetone while hot, and the residual monomers and small molecules were removed by reprecipitation with methanol as a precipitant, and the obtained product was vacuum-dried at 60 °C for 24 h to remove small molecules. A powdery binary copolymer resin sample was obtained.
实施例2Example 2
2-烯丙基-6-甲基-6-叔丁基苯酚溴化：将52.6g 2-烯丙基-6-甲基-6-叔丁基苯酚溶于50mL的CCl4和CH3COOH中；在0℃及以下，逐滴将38.4g Br2的CCl4溶液加到2-烯丙基-6-甲基-6-叔丁基苯酚的溶液中，反应1小时后将反应体系倒入到蒸馏水中，放置3-5分钟，趁冷抽滤。将滤饼放在70℃烘箱内烘干。2-Allyl-6-methyl-6-tert-butylphenol bromination: Dissolve 52.6 g of 2-allyl-6-methyl-6-tert-butylphenol in 50 mL of CCl4 and CH3COOH at 0 °C and below, add 38.4 g of Br2 in CCl4 solution dropwise to the solution of 2 -allyl-6-methyl-6-tert-butylphenol, react for 1 hour and pour the reaction system into Pour into distilled water, let stand for 3-5 minutes, and filter with suction while cold. The filter cake was dried in an oven at 70°C.
将溴化的2-烯丙基-6-甲基-6-叔丁基苯酚、乙二胺缩聚，得到二元共聚产物，制备方法如下：The brominated 2-allyl-6-methyl-6-tert-butylphenol and ethylenediamine are polycondensed to obtain a binary copolymer product, and the preparation method is as follows:
加热油浴锅至76℃，将15g溴化后的2-烯丙基-6-甲基-6-叔丁基苯酚和30.8g乙二胺的环己酮溶液加入烧杯，并在此温度下搅拌40min；把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的1000ml四颈瓶中，加入700ml二甲苯，通入N2气，搅拌、加热至125℃反应，反应4h，得到初产物。趁热将初产物溶于丙酮，用甲醇作沉淀剂重沉淀去除残留的单体和小分子，将得到的产物与60℃真空干燥24h，以去除小分子。得到粉状二元共聚物树脂样品。Heat the oil bath to 76°C, add 15g of brominated 2-allyl-6-methyl-6-tert-butylphenol and 30.8g of ethylenediamine in cyclohexanone solution into the beaker, and at this temperature Stir for 40min; transfer the solution to a 1000ml four-neck flask equipped with a stirrer, a condenser, a thermometer and an airway, add 700ml of xylene, introduce N gas, stir and heat to 125°C for reaction, react for 4h, and obtain the initial product. The initial product was dissolved in acetone while hot, and the residual monomers and small molecules were removed by reprecipitation with methanol as a precipitant, and the obtained product was vacuum-dried at 60 °C for 24 h to remove small molecules. A powdery binary copolymer resin sample was obtained.
将实例2中得到的产物加入到聚乙烯(PE)，并对复合材料进行热氧老化性能研究，120℃下热氧老化50天，拉伸强度结果如下表所示：The product obtained in Example 2 was added to polyethylene (PE), and the thermal oxidative aging performance of the composite material was studied, and the thermal oxidative aging was performed at 120 ° C for 50 days. The tensile strength results are shown in the following table:
注：表中1号为未添加二元共聚，2号添加了1份二元共聚，3号添加了2份，4号添加了3份。Note: No. 1 in the table is without adding binary copolymer, No. 2 has added 1 part of binary copolymer, No. 3 has added 2 copies, and No. 4 has added 3 copies.
专业人员能够通过常识联想到的只要含有2-烯丙基-6-甲基-6-叔丁基苯酚的二元、三元及以上的共聚物也在保护的范围之内。As long as the divalent, tertiary and above copolymers containing 2-allyl-6-methyl-6-tert-butylphenol can be imagined by professionals through common sense, the protection scope is also within the scope of protection.
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