WO2023098473A1 - Hindered phenolic compound, preparation method therefor and use thereof - Google Patents

Abstract

The present invention relates to a hindered phenolic compound, a preparation method therefor and the use thereof. The hindered phenolic compound is β-(3,5-di-tert-butyl-4-hydroxyphenyl) docosyl propanoate. The hindered phenolic compound provided in the present invention has good thermal stability, good compatibility, and excellent resistance to thermo-oxidative aging. The compound can be used as an antioxidant and added into resin materials such as a talc powder modified polypropylene material to obtain a polypropylene material. The obtained polypropylene material has excellent resistance to thermo-oxidative aging.

Description

A kind of hindered phenol compound and its preparation method and application technical field

The invention belongs to the technical field of polymer materials, and in particular relates to a hindered phenolic compound and its preparation method and application.

Background technique

Polypropylene (PP) is a semi-crystalline thermoplastic with high impact resistance, strong mechanical properties, and resistance to various organic solvents and acid and alkali corrosion. It is widely used in industry and is the most common high One of the molecular materials, it is widely used in automotive interior parts or home appliance shell products.

But polypropylene contains unstable tertiary carbon groups, which form tertiary carbon free radicals in the presence of heat, light or oxygen. Tertiary carbon free radicals are very active, causing chain scission and degradation of polypropylene molecular chains, leading to the aging of PP materials. For this reason, antioxidants must be added to delay or inhibit the aging process, thereby prolonging the storage period and service life of polypropylene and its products. The heat-resistant aging additive of polypropylene is mainly hindered phenol, and there are many varieties on the market at present. Antioxidant 1076 is a phenolic ester compound with excellent performance, and it is one of the most representative varieties of monophenolic antioxidants. Because of its low melting point, it is widely used. Antioxidant 1076 has the advantages of small amount of use, no odor, good compatibility with polymer resins, good extraction resistance, high antioxidant efficiency, low volatility, no pollution, and washing resistance. Polystyrene, PP, PE and other polymers are widely used in some food packaging materials. However, its thermal stability is poor, and its thermal and oxidative aging resistance in inorganically filled (such as talcum powder) polypropylene materials is not good, so it is limited in the application field with long-term aging performance.

At present, the heat and oxygen aging resistance of polypropylene materials is generally improved by compounding various antioxidants, adding heat and oxygen aging additives and modified resins. For example, an existing patent discloses a polypropylene material with low density, high light transmittance and long-term thermal-oxidative aging resistance. Syndiotactic polypropylene and isotactic polypropylene resin are used as matrix, and high molecular weight hindered phenolic antioxidant and low molecular weight are used. The compound of hindered phenolic antioxidant (such as antioxidant 1010 and antioxidant 1076) is used as the main antioxidant, and metal ion deactivator, non-polar adsorption resin and high-melting index and homopolymeric Poly-4-methyl-1-pentene resin effectively improves the thermal and oxidative aging resistance of polypropylene materials, and the non-powdering and non-cracking time is over 900h. However, the composition of this scheme is complex and the cost is high. If a new type of antioxidant can be developed to endow polypropylene with excellent heat and oxygen aging resistance, it will have important research significance and application value.

Contents of the invention

The purpose of the present invention is to overcome the defects or deficiencies of the prior art and provide a hindered phenolic compound. The hindered phenolic compound provided by the present invention has better thermal stability and better compatibility, and is resistant to thermal and oxidative aging The effect is excellent, and it can be added as an antioxidant to resin materials such as talcum powder-modified polypropylene materials, and the obtained polypropylene materials have excellent heat-oxidative aging resistance.

Another object of the present invention is to provide a preparation method for the aforementioned hindered phenolic compound.

Another object of the present invention is to provide the above-mentioned hindered phenolic compound as an antioxidant in the preparation of resin materials.

Another object of the present invention is to provide a polypropylene material.

Another object of the present invention is to provide a preparation method of the above-mentioned polypropylene material.

Another object of the present invention is to provide the application of the above-mentioned polypropylene material in the preparation of interior parts for automobiles or housings for home appliances.

A hindered phenolic compound, the hindered phenolic compound is behenyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

The inventors of the present invention found that compared with the antioxidant 1076 (β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate), β-(3,5- Di-tert-butyl-4-hydroxyphenyl) docosanyl propionate introduces a longer carbon chain, reduces the polarity of the antioxidant molecule, improves compatibility with the matrix resin, and resists thermal oxygen The aging effect is excellent, and it can be added to the talcum powder modified polypropylene material as an antioxidant, and the obtained polypropylene material has excellent heat and oxygen aging resistance.

Preferably, the preparation method of the above-mentioned hindered phenolic compound comprises the following steps:

Methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and carbon behenyl alcohol undergo transesterification under the action of a catalyst to obtain the hindered phenolic compound.

The hindered phenolic compound can be prepared by conventional transesterification in the field, wherein the selection of catalyst, the control of the amount of reaction raw materials and the regulation of reaction conditions are all conventional control conditions in the field.

Preferably, the catalyst is an alkali metal (such as potassium acetate, lithium acetate, sodium methylate, potassium tert-butoxide, zinc octoate, dibutyltin dilaurate, dibutyltin oxide, etc.), organic zinc or organic tin catalysts one or more of.

Preferably, the molar ratio of methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate to carbon behenyl alcohol is (1.01˜1.05):1.

Preferably, the temperature of the transesterification reaction is 150-170° C., and the time is 4-6 hours.

The application of the above-mentioned hindered phenolic compounds as antioxidants in the preparation of resin materials, especially polypropylene materials is also within the protection scope of the present invention.

The present invention also claims a polypropylene material, comprising the following components in parts by weight:

Talc powder is a commonly used inorganic filler, adding it to polypropylene resin can effectively improve the rigidity and dimensional stability of polypropylene materials. However, affected by the surface of talc powder, the introduction of talc powder will greatly reduce the thermo-oxidative aging performance of the system. There are several reasons: first, impurity elements on the surface of talc powder catalyze the decomposition of hydroperoxide and accelerate aging; The second is that the surface of talc powder has a certain adsorption effect on antioxidants. The main component of talc powder is hydrous magnesium silicate, which is polar and alkaline. When the content of ester groups in the molecular structure of antioxidants is high, the polarity increases, the interaction with talcum powder is enhanced, and the adsorption increases. The hindered phenolic compound β-(3,5-di-tert-butyl-4-hydroxyphenyl) behenyl propionate of the present invention contains only one ester group in the molecular structure, and the introduction of a longer carbon chain The polarity of the molecule is further reduced, and the compatibility with the PP resin system is also improved. Therefore, the polypropylene material is endowed with excellent heat and oxygen aging resistance.

The introduction of elastomer can enhance the toughness of polypropylene material.

Common polypropylene resins, elastomers and antioxidants in the field can be used in the present invention.

Preferably, the polypropylene resin is a copolymerized polypropylene resin and/or a homopolymerized polypropylene resin. Further preferred is a homopolymerized polypropylene resin.

Preferably, the density of the elastomer is 0.850-0.900 g/cm ³ , which is obtained by testing according to ASTM D1505-2018.

Preferably, the elastomer is ethylene-propylene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, styrene-butadiene-styrene copolymer or hydrogenated styrene - One or more of butadiene-styrene copolymers.

The preparation method of the above-mentioned polypropylene material comprises the following steps: uniformly mixing polypropylene, elastomer, talcum powder, and hindered phenolic compounds to obtain a premix, then melting the premix, extruding, and granulating to obtain the described Polypropylene material.

Preferably, the preparation method of the polypropylene material comprises the following steps: adding polypropylene, elastomer, talcum powder, and hindered phenolic compounds into a high-mixer and mixing for 1 to 3 minutes at a speed of 1000 to 2000 rpm to obtain The premixed material is then melted in a twin-screw extruder, extruded, and vacuum granulated to obtain the polypropylene material. The temperature of each zone of the twin-screw extruder is 190-230°C.

The application of the above-mentioned polypropylene material in the preparation of automotive interior parts, such as instrument panels, sub-dashboards, pillars, glove boxes, door panels, thresholds, car light brackets, etc., or home appliance shell products is also within the protection scope of the present invention.

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

The hindered phenolic compound provided by the present invention has good thermal stability and good compatibility, and has an excellent anti-thermal and oxidative aging effect, and can be added to resin materials such as polypropylene materials as an antioxidant to obtain polypropylene The material has excellent heat and oxygen aging resistance.

Description of drawings

Fig. 1 is the liquid chromatogram of beta-(3,5-di-tert-butyl-4-hydroxyl phenyl) behenyl propionate (Fig. 1 (1)) and antioxidant 1076 (Fig. 1 (Fig. 1) 2)).

Fig. 2 is the mass spectrogram of behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate with an eluting time of 18.834min.

Fig. 3 is the mass spectrogram of the antioxidant 1076 whose elution time is 16.033min.

Figure 4 is a graph showing the melting point test results of behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (a) and antioxidant 1076 (b).

Detailed ways

The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.

The partial reagents that each embodiment of the present invention and comparative examples select are described as follows:

Polypropylene 1#: Homopolypropylene, PP N-Z30S, Maoming Petrochemical;

Polypropylene 2#: Copolymerized polypropylene, PP EP548R, China Sea Shell;

Elastomer 1#: POE Engage 8137, ethylene-octene copolymer, tested according to ASTM D1505-2018, density 0.864g/cm ³ ; Dow Chemical;

Elastomer 2#: POE DF610, ethylene-butylene copolymer, tested according to ASTM D1505-2018, density 0.862g/cm3; Mitsui Chemicals;

Talc powder: TYT-777A, Beihai Tianyuan;

Antioxidant 1#: hindered phenolic antioxidant, model: Irganox 1010, BASF;

Antioxidant 2#: hindered phenolic antioxidant, model: Irganox 1076, BASF.

The preparation method of the polypropylene material of each embodiment of the present invention and the comparative example is: take polypropylene, elastomer (if any), talcum powder, hindered phenolic compound and join in the high mixer and mix for 2 minutes, the rotating speed is 1500 rpm /min to obtain the premix; the premix is added at the main feeding port of the twin-screw extruder, and the temperature of each zone of the screw is 190°C, 200°C, 210°C, 210°C, 220°C, 220°C, 230°C, 230°C °C, 220 °C, 190 °C, vacuum granulation to obtain the polypropylene composition (referred to as polypropylene composition particles).

Each embodiment of the present invention and the polypropylene material of comparative example carry out following test:

2mm square plate pulverization time d (days): The thermal aging test chamber is selected according to GB/T 7141-2008 method B, the oven temperature is set at 150°C, and the oven ventilation rate is controlled at 5-20 times/h. The polypropylene composition particles are injected into a 50cm*50cm*2mm square plate in an injection molding machine, and the injection molding temperature is 200°C. Record the date t ₀ of putting the sample in, follow up and observe the date t ₁ of the pulverization point on the surface of the sample during the aging process, and the pulverization time is t ₁ -t ₀ . The thermal aging pulverization time is not less than 40d (days), indicating that it has good thermal and oxygen aging resistance.

Example 1

This example provides a hindered phenolic compound named β-(3,5-di-tert-butyl-4-hydroxyphenyl) behenyl propionate, which is prepared through the following process:

Add to the three-neck flask according to the material molar ratio n(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methyl ester):n(carbon behenyl alcohol)=1.02:1, and pass After the nitrogen gas is removed and the air is completely removed, vacuumize to control the vacuum degree below -80KPa. The temperature was raised, and the reduced pressure was stopped when the temperature reached 90°C. Under the protection of nitrogen, a catalyst (2wt% β-(3,5-di-tert-butyl-4-hydroxyphenyl)) was added, and the temperature was raised to 160°C for 5 hours. After the reaction, cool down to 50°C, add 95% ethanol solution, dissolve in a water bath at a constant temperature of 50°C, slowly stir in an ice-water bath and cool down to 0-4°C, crystallize out, filter and dry to obtain the reaction product β-(3,5 - behenyl di-tert-butyl-4-hydroxyphenyl)propionate.

Figure 1 is a liquid chromatogram of β-(3,5-di-tert-butyl-4-hydroxyphenyl) behenyl propionate and antioxidant 1076. It can be seen from Figure 1 that the outflow time of behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is 18.843min, and the outflow time of antioxidant 1076 is 16.033min.

Figure 2 is the mass spectrum of β-(3,5-di-tert-butyl-4-hydroxyphenyl) docosanyl propionate with an eluting time of 18.843 minutes. After searching and comparing with the spectral library, it was not found This substance is a new substance.

Figure 3 is the mass spectrum of the antioxidant 1076 with an eluting time of 16.033 minutes. After searching the spectrum, the substance is octadecyl alcohol β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate . At the same time, compare behenyl alcohol ester of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid The mass spectrum of octadecyl alcohol ester found that the charge-mass ratio of 586.6 is 56 higher than that of 530.6, which is exactly 4 CH ₂ . At the same time, because the two structures are very similar, it is determined that the synthesized substance is β-(3,5-di tert-Butyl-4-hydroxyphenyl)propionate behenyl ester.

Figure 4 is a graph showing the melting point test results of behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and antioxidant 1076 (determined by differential scanning calorimeter). It can be seen from Figure 4 that the melting point of behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is 69.9°C, which is higher than the melting point of antioxidant 1076 (52°C).

The hindered phenolic compounds in each example are all prepared in this example.

Embodiment 2-9

This embodiment provides a series of polypropylene materials, and the parts by weight and performance test results of each component in the formula are shown in Table 2.

The formula (part) and performance test result of the polypropylene material that table 2 embodiment 2～9 provides

Comparative example 1～3

This comparative example provides a series of polypropylene materials, and the parts by weight and performance test results of each component in the formula are shown in Table 2.

The formula (part) and performance test result of the polypropylene material that table 2 comparative example provides

From the above test results, it can be seen that the polypropylene materials provided by each example have excellent thermal oxidation resistance; from Examples 3 to 4, Example 2 and Example 5, it can be seen that with the increase of the amount of hindered phenolic compound added, The heat-resistant oxygen stability is also continuously improved, but when a large amount of hindered phenolic compounds are added, the cost will increase, and the risk of appearance defects due to enrichment and precipitation on the surface of polypropylene is prone to occur. Therefore, comprehensive consideration, the comprehensive performance of Example 2 is the best . In Comparative Example 1, no hindered phenolic compound was added, pulverization occurred within 2 days, and the heat-oxidative aging resistance was not good. Adding antioxidant 1010 and antioxidant 1076 in comparative examples 2 and 3, respectively, the performance of thermal oxygen aging resistance was limited.

Those skilled in the art will appreciate that the embodiments herein are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.

Claims (10)

1. A hindered phenolic compound, characterized in that the hindered phenolic compound is behenyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
2. The preparation method of hindered phenolic compound described in claim 1, is characterized in that, comprises the steps:

   Methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and carbon behenyl alcohol undergo transesterification under the action of a catalyst to obtain the hindered phenolic compound.
3. The method for preparing hindered phenolic compounds according to claim 1, wherein the catalyst is one or more of alkali metal, organozinc or organotin catalysts.
4. According to the preparation method of the said hindered phenolic compound of claim 1, it is characterized in that, the mole of methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and carbon behenyl alcohol The ratio is (1.01～1.05):1; the temperature of the transesterification reaction is 150～170°C, and the time is 4～6 h.
5. The hindered phenol compound described in claim 1 is used as an antioxidant in the preparation of resin materials.
6. A polypropylene material, characterized in that it comprises the following components in parts by weight:

   
7. The polypropylene material according to claim 1, wherein the polypropylene resin is a copolymerized polypropylene resin and/or a homopolymerized polypropylene resin.
8. The polypropylene material according to claim 1, wherein the density of the elastomer is 0.850-0.900g/cm ³ ; the elastomer is an ethylene-propylene copolymer, an ethylene-hexene copolymer, an ethylene-butylene copolymer, One or more of ethylene copolymer, ethylene-octene copolymer, styrene-butadiene-styrene copolymer or hydrogenated styrene-butadiene-styrene copolymer.
9. The preparation method of the polypropylene material according to any one of claims 6 to 8, characterized in that it comprises the following steps: uniformly mixing polypropylene, elastomer, talcum powder, and hindered phenolic compounds to obtain a premix, and then mixing the premix Melt, extrude and granulate to obtain the polypropylene material.
10. The application of the polypropylene material according to any one of claims 6 to 8 in the preparation of automotive interior parts or home appliance shell products.

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