阅读说明：本技术 一种双（十八烷基）羟胺的制备方法 (Preparation method of bis (octadecyl) hydroxylamine ) 是由 刘恩静 陈超 胡新利 王光腾 张朋 李国华 韩炎 于 2021-08-20 设计创作，主要内容包括：本发明涉及一种双(十八烷基)羟胺的制备方法,包括以下步骤：在反应釜内加入原料溶剂、盐酸羟胺、缚酸剂和催化剂,搅拌预混合,预混合后,升温至滴加温度,滴加卤代十八烷,然后升温进行保温反应；反应结束后,对反应液进行水洗过滤,最终合成目标产物双(十八烷基)羟胺；本发明以卤代十八烷和盐酸羟胺进行反应生成产物,催化剂促进反应的进行,原料来源广泛且廉价,产品的最终收率高,是实现工业化生产的理想工艺。(The invention relates to a preparation method of bis (octadecyl) hydroxylamine, which comprises the following steps: adding a raw material solvent, hydroxylamine hydrochloride, an acid-binding agent and a catalyst into a reaction kettle, stirring and premixing, heating to a dripping temperature after premixing, dripping halogenated octadecane, and heating for carrying out heat preservation reaction; after the reaction is finished, washing and filtering the reaction solution to finally synthesize a target product, namely bis (octadecyl) hydroxylamine; the method uses the halogenated octadecane and the hydroxylamine hydrochloride to react to generate a product, the catalyst promotes the reaction, the raw material source is wide and cheap, the final yield of the product is high, and the method is an ideal process for realizing industrial production.)

1. A preparation method of bis (octadecyl) hydroxylamine is characterized by comprising the following steps: stirring and premixing a solvent, hydroxylamine hydrochloride and an acid-binding agent, heating to a dripping temperature after premixing, dripping halogenated octadecane, and heating for a heat preservation reaction; and after the heat preservation reaction is finished, filtering, washing and drying the reaction solution to obtain the bis (octadecyl) hydroxylamine.

2. The method of claim 1, wherein the molar ratio of said halogenated octadecane to hydroxylamine hydrochloride is 1: 0.3 to 0.6.

3. The method of claim 1, wherein the molar ratio of said halogenated octadecane to said acid-binding agent is 1: 2.5 to 5.

4. The method for preparing bis (octadecyl) hydroxylamine according to claim 1, wherein the mass ratio of the halogenated octadecane to the solvent is 1: 3 to 6.

5. A method of making a bis (octadecyl) hydroxylamine as in claims 1-4 wherein the halogenated octadecane is one or more of chlorooctadecane, bromooctadecane, iodooctadecane.

6. The method of claim 3, wherein the acid-binding agent is one or more selected from pyridine, triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, and N, N-dimethylaniline.

7. The method of claim 4, wherein the solvent is one or more of toluene, xylene, methylene chloride, petroleum ether, and tetrahydrofuran.

8. The method of claim 1, wherein the pre-mixing temperature is 25-30 ℃.

9. The method for preparing bis (octadecyl) hydroxylamine according to claim 1, wherein the dropping temperature is 60 to 65 ℃.

10. The method for preparing bis (octadecyl) hydroxylamine according to claim 1, wherein the reaction temperature is 85 to 88 ℃; the time of the heat preservation reaction is 6-20 h.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of bis (octadecyl) hydroxylamine.

Background

At present, the demand of the antioxidant is increased suddenly at home and abroad, and the Asia-Pacific region is the region with the largest antioxidant consumption in the world, accounts for more than 30 percent, and accounts for more than 20 percent in China. Antioxidants on the market are tending to discolor under the influence of nitrogen oxides, a phenomenon known as gas fading. Discoloration is exacerbated by various factors such as the presence of phenolic antioxidants, the use of phenolic-type additives, and the like. In the aspect of inhibiting gas fading and discoloration, the hydroxylamine antioxidant avoids the existence of phenolic substances, so that the product has good gas fumigation and yellowing resistance and good color stability, and is more effective than the traditional hindered phenol antioxidant.

The hydroxylamine antioxidant can capture various free radicals and decompose hydroperoxide, and has high hydroxylamine efficiency as a carbon free radical capture agent. The specific mechanism is as follows:

。

the hydroxylamine antioxidant firstly provides an active hydrogen atom to form a free radical with a stable structure in the process of resisting oxygen, then the free radical captures a carbon free radical and an alkoxy radical which cause the degradation of the polymer so as to stop the autoxidation process of the polymer, and the hydroxylamine simultaneously contains a nitrogen oxygen atom with an unshared electron so as to capture a plurality of free radicals.

The hydroxylamine antioxidant has good thermal stability and water extraction resistance, can effectively inhibit carbon free radicals, peroxy radicals, hydroperoxides and reduced quinone compounds generated in the thermal processing process of decomposed polymers, has good thermal processing stability and color protection property on resin materials under the conditions of high temperature and ultrahigh temperature (above 300 ℃), has good light stability, maintains and improves original color tone through the hydroxylamine antioxidant, improves processing performance, and enters polymer particle products to play subsequent effects while protecting the polymers from decomposition.

The current polypropylene fiber, automotive TPO industry is demanding ever higher color stability, and is demanding color protection and systems that are less prone to gas fading, such as polyolefin applications. The hydroxylamine antioxidant has good color protection, high compatibility, low volatility and stable high temperature storage property, and is particularly excellent as a stabilizer in the processing treatment such as melting, granulation, extrusion and the like. The phenomenon of 'phenol yellow/gas fading' caused by hindered phenol antioxidants is avoided, and the hydroxylamine antioxidants are better antioxidants for solving the aspect of gas fading.

Hydroxylamine antioxidants in the market are mainly represented by lrgastab FS042 produced by Pasteur, and the lrgastab FS042 is a novel high-temperature-resistant high-efficiency multifunctional phenol-free antioxidant with the CAS number of 143925-92-2, the chemical formula of C36H75NO and the molecular weight of 538.

At present, the use of the hydroxylamine antioxidant bis (octadecyl) hydroxylamine completely depends on import, relevant research reports at home and abroad are extremely deficient, the production process is almost monopolized at home and abroad, and a technical barrier is formed.

Disclosure of Invention

In order to solve the problems, the invention discloses a preparation method of bis (octadecyl) hydroxylamine with high yield and content, which is suitable for industrial production, and provides technical support for the domestic production of the bis (octadecyl) hydroxylamine.

In order to achieve the purpose, the invention provides the following technical scheme:

the invention provides a preparation method of bis (octadecyl) hydroxylamine, which comprises the following steps: stirring and premixing a solvent, hydroxylamine hydrochloride and an acid-binding agent, heating to a dripping temperature after premixing, dripping halogenated octadecane, and heating for a heat preservation reaction; and after the heat preservation reaction is finished, filtering, washing and drying the reaction solution to obtain the bis (octadecyl) hydroxylamine.

The synthetic process route of the bis (octadecyl) hydroxylamine compound is as follows:

。

further, the molar ratio of the halogenated octadecane to the hydroxylamine hydrochloride is 1: 0.3 to 0.6.

Further, the molar ratio of the halogenated octadecane to the acid-binding agent is 1: 2.5 to 5.

Further, the mass ratio of the halogenated octadecane to the solvent is 1: 3 to 6.

Further, the halogenated octadecane is one or more of chlorooctadecane, bromooctadecane and iodooctadecane.

Further, the acid binding agent is one or more of pyridine, triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine and N, N-dimethylaniline.

Further, the solvent is one or more of toluene, xylene, dichloromethane, petroleum ether and tetrahydrofuran.

Further, the temperature of the premixing is 25-30 ℃.

Further, the dropping temperature is 60-65 ℃.

Further, the temperature of the heat preservation reaction is 85-88 ℃; the time of the heat preservation reaction is 6-20 h

Compared with the prior art, the invention has the following advantages and beneficial effects:

1. the invention firstly provides the method which takes the halogenated octadecane and the hydroxylamine hydrochloride as raw materials, the raw materials are wide in source and low in cost, and the industrial production cost is low.

2. The preparation method adopts the steps of firstly carrying out premixing reaction to generate free hydroxylamine, and then carrying out reaction on the hydroxylamine and halogenated alkane to generate a product, wherein the purity of the final reaction product can reach more than 98%, the purity is high, and the market demand is met.

3. The invention has simple overall reaction operation, safety and reliability, and high final yield of the product, so that the product has higher economic value.

Drawings

FIG. 1 is an infrared spectrum of a target product prepared in example 1 of the present invention;

FIG. 2 is HNMR map of the target product prepared in example 2 of the present invention.

Detailed Description

The technical solutions provided by the present invention will be described in detail below with reference to specific examples, and it should be understood that the following specific embodiments are only illustrative of the present invention and are not intended to limit the scope of the present invention.

Example 1:

in a 1000mL four-necked flask equipped with a thermometer, 10.4g of hydroxylamine hydrochloride, 120g of triethylamine and 450g of tetrahydrofuran were charged, and the mixture was placed in a stirrer and a condenser and premixed at 30 ℃ for 30 minutes. Then raising the temperature to 60 ℃, dropwise adding 99.9g of bromooctadecane, raising the temperature to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 14 hours. And after the reaction is finished, cooling and filtering the reaction liquid, and washing and drying a filter cake obtained by filtering to obtain a white powdery product, namely the bis (octadecyl) hydroxylamine.

Detecting the target product prepared by the embodiment by using an infrared spectrometer, wherein an infrared spectrum is shown in figure 1, and can be seen from the infrared spectrum shown in figure 1, and the infrared spectrum ranges from 1400 cm to 1420cm^-1A strong absorption peak of carbon-hydrogen bond stretching vibration indicates that a v-C-N functional group exists; 2850 to 2960cm^-1There are two strong characteristic absorption peaks indicating the presence of saturated v-C-H functional groups on the alkyl group; 3000-3300 cm^-1Has a stretching vibration absorption peak of v-OH. The product molecule can thus be demonstrated to have the following structural formula:

；

the molecular formula is as follows: C36H75NO, relative molecular weight: 538.

example 2:

in a 500mL four-necked flask equipped with a thermometer, 6.94g of hydroxylamine hydrochloride, 84.8g of triethylamine and 300g of tetrahydrofuran were charged, and the mixture was premixed at 30 ℃ for 30 minutes by installing a stirrer and a condenser. Then raising the temperature to 65 ℃, dropwise adding 99.9g of bromooctadecane, raising the temperature to 87 ℃ after dropwise adding, and carrying out heat preservation reaction for 18 hours. And after the reaction is finished, cooling and filtering the reaction liquid, and washing and drying a filter cake obtained by filtering to obtain a white powdery product, namely the bis (octadecyl) hydroxylamine.

The target product prepared in this example was examined by nuclear magnetic resonance (1 HNMR (400MHz, D2O): 2.71(t, 2H),2.63 (t, 2H), 1.63 (m, 2H),1.33 (m, 2H),1.31 (s, 60H),0.93 (t, 6H). The HNMR map is shown in FIG. 2.

Example 3:

in a 500mL four-necked flask equipped with a thermometer, 8.34g of hydroxylamine hydrochloride, 141.6g of triethylamine, and 300g of tetrahydrofuran were charged, and the mixture was premixed with a stirrer and a condenser at 30 ℃ for 30 minutes. And then raising the temperature to 65 ℃, dropwise adding 66.6g of bromooctadecane and 32.8g of iodooctadecane, raising the temperature to 87 ℃ after dropwise adding, and carrying out heat preservation reaction for 16 hours. And after the reaction is finished, cooling and filtering the reaction liquid, and washing and drying a filter cake obtained by filtering to obtain a white powdery product, namely the bis (octadecyl) hydroxylamine.

Test example:

the polypropylene has good mechanical property and processing property, so that the polypropylene has wide application in various fields, and the antioxidant can improve the aging resistance of the polypropylene and delay the service life of the polypropylene, so that the performance of the product is greatly improved. Antioxidant 1076, antioxidant 1010, antioxidant lrgastab FS042, antioxidant prepared by the invention and polypropylene are prepared into master batches, and antioxidant properties of antioxidant 1076, antioxidant 1010, antioxidant lrgastab FS042 and antioxidant prepared by the invention are evaluated.

Sample 1: accurately weighing 1kg of polypropylene powder, 5g of calcium stearate and 3g of antioxidant 1076, adding into a high-speed mixer at normal temperature after the materials are weighed, and mixing for 30min in a high-speed mixing state to fully mix the materials. Then, the mixed powder was put on a ZJL-200 type torque rheometer and a single-screw extruder to extrude, draw and pelletize, using a ZJL-200 type torque rheometer (set conditions: 300Nm rated torque, 110rpm rotation, 210. + -.5 ℃ temperature, 14:1 reduction ratio) and a single-screw extruder (set conditions: L =25:1 screw length-diameter ratio, 20mm screw diameter, 2.5:1 screw compression ratio, 210. + -.5 ℃ screw extrusion temperature). And (3) injection molding the obtained master batch into a standard tensile and impact sample strip, wherein the injection molding temperature is 200 +/-5 ℃, the second-stage temperature is 185 +/-5 ℃, the injection pressure is 9 +/-1 MPa, the sol pressure is 8 +/-1 MPa, and the pressure maintaining pressure is 7 +/-1 MPa, and the master batch is naturally cooled for 24 hours for later use.

Sample 2: accurately weighing 1kg of polypropylene powder, 5g of calcium stearate and 3g of antioxidant 1010, adding into a high-speed mixer at normal temperature after weighing, and mixing for 30min in a high-speed mixing state to fully mix the materials. Then, the mixed powder was put on a ZJL-200 type torque rheometer and a single-screw extruder to extrude, draw and pelletize, using a ZJL-200 type torque rheometer (set conditions: 300Nm rated torque, 110rpm rotation, 210. + -.5 ℃ temperature, 14:1 reduction ratio) and a single-screw extruder (set conditions: L =25:1 screw length-diameter ratio, 20mm screw diameter, 2.5:1 screw compression ratio, 210. + -.5 ℃ screw extrusion temperature). And (3) injection molding the obtained master batch into a standard tensile and impact sample strip, wherein the injection molding temperature is 200 +/-5 ℃, the second-stage temperature is 185 +/-5 ℃, the injection pressure is 9 +/-1 MPa, the sol pressure is 8 +/-1 MPa, and the pressure maintaining pressure is 7 +/-1 MPa, and the master batch is naturally cooled for 24 hours for later use.

Sample 3: accurately weighing 1kg of polypropylene powder, 5g of calcium stearate and 3g of antioxidant lrgastab FS042, adding into a high-speed mixer at normal temperature after the materials are weighed, and mixing for 30min in a high-speed mixing state to fully mix the materials. Then, the mixed powder was put on a ZJL-200 type torque rheometer and a single-screw extruder to extrude, draw and pelletize, using a ZJL-200 type torque rheometer (set conditions: 300Nm rated torque, 110rpm rotation, 210. + -.5 ℃ temperature, 14:1 reduction ratio) and a single-screw extruder (set conditions: L =25:1 screw length-diameter ratio, 20mm screw diameter, 2.5:1 screw compression ratio, 210. + -.5 ℃ screw extrusion temperature). And (3) injection molding the obtained master batch into a standard tensile and impact sample strip, wherein the injection molding temperature is 200 +/-5 ℃, the second-stage temperature is 185 +/-5 ℃, the injection pressure is 9 +/-1 MPa, the sol pressure is 8 +/-1 MPa, and the pressure maintaining pressure is 7 +/-1 MPa, and the master batch is naturally cooled for 24 hours for later use.

Sample 4: 1kg of polypropylene powder, 5g of calcium stearate and 3g of the antioxidant bis (octadecyl) hydroxylamine prepared in the embodiment 1 of the invention are accurately weighed, and after the materials are weighed, the materials are added into a high-speed mixer at normal temperature and mixed for 30min in a high-speed mixing state, so that the materials are fully mixed. Then, the mixed powder was put on a ZJL-200 type torque rheometer and a single-screw extruder to extrude, draw and pelletize, using a ZJL-200 type torque rheometer (set conditions: 300Nm rated torque, 110rpm rotation, 210. + -.5 ℃ temperature, 14:1 reduction ratio) and a single-screw extruder (set conditions: L =25:1 screw length-diameter ratio, 20mm screw diameter, 2.5:1 screw compression ratio, 210. + -.5 ℃ screw extrusion temperature). And (3) injection molding the obtained master batch into a standard tensile and impact sample strip, wherein the injection molding temperature is 200 +/-5 ℃, the second-stage temperature is 185 +/-5 ℃, the injection pressure is 9 +/-1 MPa, the sol pressure is 8 +/-1 MPa, and the pressure maintaining pressure is 7 +/-1 MPa, and the master batch is naturally cooled for 24 hours for later use.

Carrying out a thermal oxidation light indoor aging test on the prepared sample 1 sample strip, the prepared sample 2 sample strip, the prepared sample 3 sample strip and the prepared sample 4 sample strip, wherein the aging test device and conditions are as follows: a Ci3000+ xenon lamp aging tester of ATLAS company in the United states is adopted. A. The light source 4500W water-cooled xenon lamp. B. Blackboard temperature: (70 +/-1) DEG C. C. Average temperature: at 45 ℃. D. Relative humidity: (50. + -. 5)%. E. The rainfall period: rainfall was continued for 20min every 105 min. F. The distance between the sample and the light source is 450 mm. Ultraviolet irradiance: 60W/square meter (300-400 nm wavelength range), and the irradiation time is 200 h.

The tensile strength of a bar is the ultimate ability of a polypropylene article to resist tensile failure, and is one of the important indicators for a polypropylene article, and the lifetime of a polypropylene article is directly related to the tensile strength. The tensile properties were determined according to GB/T528-2009, at a tensile rate of 100mm min^-1The temperature was 25 ℃. The impact strength is determined according to GB/T1043.1-2008, the impact capacity is 7.5J, and the sample bar has no notch. The oxidation induction time of the high polymer material can directly reflect the aging degree of the material, and a Differential Scanning Calorimeter (DSC) is generally used for testing, wherein the longer the oxidation induction time is, the higher the oxidation induction temperature is, and the better the oxidation resistance of the antioxidant is. The oxidation induction time was measured using a Differential Scanning Calorimeter (DSC). The test results are shown in table 1.

TABLE 1 test results of the Properties of the specimens

According to the test results, the elongation at break of the polypropylene blank sample after thermal-oxidative photo-aging for 200 hours is 167.2%, the oxidation induction time is 6min, and the elongation at break and the oxidation induction time of the polypropylene modified by adding the antioxidant are improved. The elongation at break after 200h of thermo-oxidative photo-aging is that from large to small, the elongation at break is sequentially that of sample 4 (381.1%) > sample 3 (380.5%) > sample 1 (228.6%) > sample 2 (223.4%) > blank (167.2%), which indicates that the antioxidant is added to play a certain anti-aging role, and the antioxidant prepared by the invention has the anti-aging capacity equivalent to that of commercial lrgastab FS 042. The oxidation induction time after the thermo-oxidative photo-aging for 200h is from large to small, namely that the oxidation induction time of the antioxidant prepared by the method is longest, the oxidation induction time is long, the oxidation resistance is good, the antioxidant capacity is equivalent to the antioxidant capacity of commercial lrgastab FS042, and even the antioxidant capacity is better than the antioxidant capacity of commercial lrgastab FS 042.

The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.