Anti-aging additive for polypropylene and application of anti-aging additive

Abstract

The invention provides an anti-aging additive for polypropylene and application of the anti-aging additive. The anti-aging additive comprises the following components in parts by weight: 0.05-1.0 part of hindered phenol antioxidant, 0.1-1.0 part of phosphite antioxidant and 0.1-1.0 part of hindered amine light stabilizer, and the anti-aging additive comprises the following components in parts by weight: 0.05-1.0 part of hindered phenol antioxidant, 0.1-1.0 part of phosphite antioxidant and 0.1-1.0 part of hindered amine light 0.05 to 1.0 part of a phosphite ester antioxidant; and 0.2-1.0 part of a hindered amine light stabilizer. The anti-aging additive is compounded by specific components, so that the high-temperature thermo-oxidative aging resistance of the polypropylene composite material is obviously improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material functional additives, and in particular to an anti-aging additive for polypropylene and application thereof. Background Art

[0002] The peripheral parts of automobile engines can be roughly divided into intake and exhaust system parts, cooling system parts, fuel system parts and transmission system parts. The engine is the "heart" of the car, so the requirements for the materials used for its peripheral parts are very stringent. Since the engine generates a lot of heat when it is working, the engine temperature rises. And this heat will be transferred to the parts around the engine through thermal radiation, conduction, convection and other means, and the temperature can often reach 150°C. Therefore, the parts used in the engine periphery must withstand a long-term thermal environment of about 150°C. At this temperature, the speed of thermal oxidation aging of PP materials is very fast, and it is easy to have problems such as powdering, which seriously affects the service life of the parts. Especially with the development of new energy vehicles and new home appliances, the demand for this long-term heat resistance is increasing, and the requirements are becoming more and more stringent. Now more and more applications require that the powdering time of PP materials at 150°C is not less than 2000h or even 3000h.

[0003] The conventional solution is to add a combination of thioester antioxidants to polypropylene materials to improve their resistance to thermal oxidative aging. However, this solution has two problems: first, since the antioxidant combination contains sulfur, the product will have a certain sulfur smell, which limits its application in some fields that have requirements for odor; second, the antioxidant combination has limited improvement on the thermal oxidative aging performance of the material, and often cannot meet the long-term thermal aging requirements of more than 1000 hours at a temperature of 150°C.

[0004] Therefore, there is an urgent need in this field to develop a material that has no odor problem and can effectively improve the high-temperature thermal oxidation aging resistance of polypropylene materials. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an anti-aging agent for polypropylene and its application. The anti-aging agent significantly improves the high temperature thermal oxidation aging resistance of polypropylene composite materials through compounding of specific components.

[0006] In a first aspect, the present invention provides an anti-aging aid for polypropylene, comprising a hindered phenol antioxidant, a phosphite antioxidant and a hindered amine light stabilizer.

[0007] Wherein, the anti-aging additive comprises, by weight:

[0008] Hindered phenol antioxidant 0.05-1.0 part;

[0009] Phosphite antioxidant 0.05-1.0 part;

[0010] Hindered amine light stabilizer 0.2-1.0 part;

[0011] In some embodiments, the hindered phenol antioxidant can be 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part or any value therebetween.

[0012] In some embodiments, the hindered phenol antioxidant is 0.3-0.5 parts.

[0013] In some embodiments, the phosphite antioxidant can be 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part or any value therebetween.

[0014] In some embodiments, the hindered amine light stabilizer may be 0.2 parts, 0.25 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, or any value therebetween.

[0015] In some embodiments, the hindered amine light stabilizer is 0.3-0.6 parts.

[0016] Studies have found that hindered amine light stabilizer is a key factor affecting high-temperature thermal aging of polypropylene materials. The higher the hindered amine content, the better the long-term thermal aging effect. In order to balance demand and cost, in some embodiments, the mass ratio of the hindered amine light stabilizer to the hindered phenol antioxidant is (0.8-3):1, for example, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1 or any value therebetween.

[0017] In some embodiments, the mass ratio of the hindered amine light stabilizer to the hindered phenol antioxidant is (1-2):1, more preferably (1.15-1.72):1.

[0018] In some embodiments, based on the total weight of the polypropylene material, in the anti-aging additive, the weight percentage of the hindered phenol antioxidant is 0.15-0.5%; the weight percentage of the phosphite antioxidant is 0.1-1.5%; and the weight percentage of the hindered amine light stabilizer is 0.25-0.8%.

[0019] In some embodiments, based on the total weight of the polypropylene material, the mass proportion of the hindered phenol antioxidant in the anti-aging additive is 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% or any value therebetween.

[0020] In some embodiments, based on the total weight of the polypropylene material, the mass ratio of the phosphite antioxidant in the anti-aging aid is 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1.0% or any value therebetween.

[0021] In some embodiments, based on the total weight of the polypropylene material, the mass ratio of the hindered amine light stabilizer in the anti-aging additive is 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.9%, 1.0% or any value therebetween.

[0022] In order to achieve better technical effects and balance costs, preferably, the mass ratio of the hindered amine light stabilizer, the hindered phenol antioxidant and the phosphite antioxidant in the polypropylene material is 0.5% to 2%; more preferably 0.8 to 1.5%.

[0023] In some embodiments, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (1-3.5):1, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or any value therebetween.

[0024] In some embodiments, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (1.2-2.5):1.

[0025] In some embodiments, the mass ratio of the hindered amine light stabilizer to the phosphite is (1-6):1, for example, 1:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 5:1, 6:1 or any value therebetween.

[0026] In some embodiments, the mass ratio of the hindered amine light stabilizer to the phosphite is (2-4):1.

[0027] In some embodiments, the hindered amine light stabilizer is selected from piperidine series hindered amine light stabilizers and / or triazine series hindered amine light stabilizers.

[0028] In some embodiments, the weight average molecular weight of the hindered amine light stabilizer is greater than 1000, more preferably greater than 2000;

[0029] In some embodiments, the hindered amine light stabilizer is selected from N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine (i.e., UV-119), polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl-1- piperidine ethanol) ester (i.e., UV-622), poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexamethylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]} (i.e., UV944), copolymers of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-n-hexanediamine and 2,4,6-trichloro-1,3,5-triazine with N-butyl- 1-Butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction products (i.e. UV-2020), 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-pyridinyl)-, methylated polymerization products with morpholine-2,4,6-trichloro-1,3,5-triazine (i.e. UV-3529, CAS: 193098-40-7), N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl) )-1,3,5-triazine polymerization product (i.e., UV3346), α-olefin C20-24 polymer and maleic anhydride reaction product and 2,2,6,6-tetramethyl-4-piperidinamine (i.e., UV-5050H, CAS: 152261-33-1), 1,2,3,4-butanetetracarboxylic acid and 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl-4-piperidinyl ester polymer (i.e., LA-63P) One or more.

[0030] In some embodiments, the hindered amine light stabilizer is selected from N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine (i.e., UV-119S).

[0031] In some embodiments, the hindered phenol antioxidant is selected from tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol (i.e. antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester (i.e. antioxidant 1076), triethylene glycol bis(3-(3-tert-butyl-5 methyl-4-hydroxyphenyl) propionate) (i.e. antioxidant 245), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene (i.e. antioxidant 330), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxypropionamide) (i.e. antioxidant 1098), bis(3,5-di-tert-butyl-4-hydroxybenzoyl)hydrazine (i.e. antioxidant MD 1024), 2,2'-oxalylamino-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate (MD697), 4,6-bis(neothiomethyl)-o-cresol (antioxidant 1520), 4,6-di(dodecylthiomethyl)-o-cresol (antioxidant 1726), 2,2'-thioethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1035), 3,5-di-tert-butyl -4-Hydroxyphenylpropionic acid C7-C9 mixed esters (i.e. antioxidant 1135), 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid isooctyl ester (i.e. antioxidant 1135R), 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C13-15 branched and straight chain alkyl esters (i.e. antioxidant 1315), 2,6-di-tert-butyl-4-methylphenol (i.e. antioxidant BHT), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,2H,5H)-trione (i.e. antioxidant 1790), 1,1-di-tert-butyl-4-hydroxyphenyl)methyl)ethylphosphonate (i.e. antioxidant 1425), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (i.e. antioxidant 2246), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (i.e. antioxidant 425), 4,4'-thiobis(2-tert-butyl-5-methylphenyl) Phenol) (i.e. antioxidant 300), 6-(4-hydroxy-3,5-di-tert-butylphenylamino)-2,4-di-n-octylthio-1,3,5-triazine (i.e. antioxidant 565) or 4,4'-di(phenylisopropyl)diphenylamine (i.e. antioxidant 445), 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester (i.e. antioxidant O3).

[0032] In some embodiments, the hindered phenol antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0033] In some embodiments, the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite (i.e., antioxidant 168), bis(2,4-di-tert-butylphenyl) pentaerythritol bis diphosphite (i.e., antioxidant 626), pentaerythritol diphosphite distearyl (i.e., antioxidant 618), bis(2,4-dicumylphenyl) pentaerythritol-diphosphite (i.e., antioxidant 686), bis(2,4-dicumylphenyl) pentaerythritol-diphosphite (i.e., antioxidant P-EP Q), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphate (i.e. antioxidant 126), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (i.e. antioxidant 636), 2,2'-methylenebis(4,6-di-tert-butyl-1-diphenoxy)(2-ethylhexyloxy)phosphite (i.e. antioxidant HP-10), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (i.e. antioxidant PEP-36).

[0034] In some embodiments, the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite (ie, antioxidant 168) and / or bis(2,4-di-tert-butylphenyl) pentaerythritol bis diphosphite (ie, antioxidant 626).

[0035] In some embodiments, the anti-aging agent comprises:

[0036] N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

[0037] In some embodiments, the anti-aging agent comprises:

[0038] N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-di(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0039] In a second aspect, the present invention provides a polypropylene composite material composition, comprising polypropylene and the anti-aging additive described in the first aspect.

[0040] In some embodiments, the polypropylene is selected from homopolypropylene and / or copolymer polypropylene.

[0041] In some embodiments, the polypropylene composite composition comprises, by weight:

[0042] Polypropylene 70-80 parts;

[0043] Hindered phenol antioxidant 0.05-1.0 part;

[0044] Phosphite antioxidant 0.05-1.0 part;

[0045] Hindered amine light stabilizer 0.2-1.0 part

[0046] In some embodiments, the polypropylene may be 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, or any value therebetween.

[0047] In some embodiments, the hindered phenol antioxidant can be 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part or any value therebetween.

[0048] In some embodiments, the hindered phenol antioxidant is 0.3-0.5 parts.

[0049] In some embodiments, the phosphite antioxidant can be 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part or any value therebetween.

[0050] In some embodiments, the hindered amine light stabilizer may be 0.2 parts, 0.25 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, or any value therebetween.

[0051] In some embodiments, the hindered amine light stabilizer is 0.3-0.6 parts.

[0052] In some embodiments, the hindered amine light stabilizer is 0.35-0.6 parts.

[0053] In some embodiments, in the polypropylene composite material composition, the mass proportion of the anti-aging additive is 0.5-2%, for example, 0.5%, 1%, 1.5%, 2% or any value therebetween.

[0054] In some embodiments, in the polypropylene composite material composition, the weight proportion of the anti-aging additive is 0.8-1.5%.

[0055] In some embodiments, in the polypropylene composite material composition, the mass proportion of the anti-aging additive is 0.7-1.5%, for example, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% or any value therebetween.

[0056] In some embodiments, in the polypropylene composite material composition, the weight proportion of the anti-aging additive is 0.8-1.2%.

[0057] In some embodiments, the polypropylene composite material composition further includes one or more of a toughening agent, a reinforcing agent, a masterbatch or an acid absorbent.

[0058] In some embodiments, the polypropylene composite composition further comprises, by weight:

[0059] Toughener 5-20 parts, reinforcing agent 10-30 parts, masterbatch 1-3 parts, acid absorber 0.01-0.1 parts.

[0060] In some embodiments, the toughening agent may be 5 parts, 8 parts, 11 parts, 14 parts, 17 parts, 20 parts, or any value therebetween.

[0061] In some embodiments, the enhancer may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or any value therebetween.

[0062] In some embodiments, the color masterbatch may be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, or any value therebetween.

[0063] In some embodiments, the acid scavenger may be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part, or any value therebetween.

[0064] In some embodiments, the toughening agent is selected from one or more of ethylene copolymer elastomers, polybutadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, styrene butadiene rubber, styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene-styrene terpolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.

[0065] In some embodiments, the reinforcing agent is selected from one or more of talc, calcium carbonate, wollastonite, graphite, carbon black, carbon fiber, glass fiber or ceramic fiber.

[0066] In some embodiments, the color masterbatch is selected from one or more of a black masterbatch, a white masterbatch, a red masterbatch, and a blue masterbatch.

[0067] In some embodiments, the black masterbatch contains 50 wt % of carbon black.

[0068] In some embodiments, the acid absorber is selected from one or more of calcium stearate, zinc stearate, hydrotalcite, hydrocalumite or zinc oxide.

[0069] In some embodiments, the polypropylene composite composition comprises:

[0070] Polypropylene 70-80 parts, toughening agent 5-20 parts, reinforcing agent 10-30 parts, masterbatch 1-3 parts, acid absorber 0.01-0.1 parts, hindered phenol antioxidant 0.05-1.0 parts, phosphite antioxidant 0.05-1.0 parts, hindered amine light stabilizer 0.25-1.0 parts.

[0071] In some embodiments, the polypropylene composite composition comprises:

[0072] Polypropylene 70-80 parts, toughening agent 5-20 parts, reinforcing agent 10-30 parts, masterbatch 1-3 parts, acid absorber 0.01-0.1 parts, hindered phenol antioxidant 0.3-0.5 parts, phosphite auxiliary antioxidant 0.1-0.5 parts, hindered amine light stabilizer 0.35-0.6 parts.

[0073] The present invention provides a polypropylene composite material, comprising the polypropylene composite material composition described in the second aspect.

[0074] In a third aspect, the present invention provides a method for preparing a polypropylene composite material, comprising the following steps:

[0075] (1) mixing the polypropylene composite material composition described in the second aspect of the present invention uniformly;

[0076] (2) Extrusion granulation is performed to obtain a material.

[0077] In some embodiments, in step (1), the extrusion granulation is carried out in a twin-screw extruder.

[0078] In some embodiments, the screws of the twin-screw extruder are co-rotating twin screws.

[0079] In some embodiments, the aspect ratio of the twin-screw extruder is (32:1)-(48:1); for example, 32:1, 35:1, 38:1, 41:1, 44:1, 47:1 or any value therebetween.

[0080] In some embodiments, the rotation speed of the twin-screw extruder is 200-250 r / min; for example, 200 r / min, 210 r / min, 220 r / min, 230 r / min, 240 r / min, 250 r / min or any value therebetween.

[0081] In some embodiments, the processing temperature of the twin-screw extruder is 210-260°C, for example, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C or any value therebetween.

[0082] In a fourth aspect, the present invention provides a use of the polypropylene composite material composition described in the second aspect or the polypropylene composite material prepared by the preparation method described in the third aspect in engine peripheral parts.

[0083] In some embodiments, the engine peripheral components are selected from one or more of intake and exhaust system components, cooling system components, fuel system components, and transmission system components.

[0084] Compared with the prior art, the present invention has the following beneficial effects:

[0085] The anti-aging aid of the present invention significantly improves the high-temperature thermal oxidation aging resistance of the polypropylene composite material through the compounding of specific components, especially the thermal oxidation aging resistance at 150°C can reach more than one thousand hours, and under preferred conditions can reach more than two thousand to six thousand hours, which can meet the thermal oxidation aging requirements of polypropylene materials of automobile engine peripheral parts. DETAILED DESCRIPTION

[0086] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation to the present invention.

[0087] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0088] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples, etc., can all be purchased on the market or can be obtained by existing methods; the reagent amounts, unless otherwise specified, are the reagent amounts used in conventional experimental operations; the experimental methods, unless otherwise specified, are all conventional methods.

[0089] The raw materials used in the embodiments and comparative examples are the following, but are not limited to the following:

[0090] Polypropylene: PP EP548R, Wanhua Chemical.

[0091] Ethylene copolymer elastomer: POE 875, Korea SK.

[0092] Reinforcement agent: talcum powder 3092, Yingkou Jintong New Material Technology Co., Ltd.

[0093] Masterbatch: Black masterbatch PE2772, Cabot.

[0094] Acid absorbent: calcium stearate, FACI.

[0095] Hindered phenol antioxidant: 1010, Tianjin Lianlong New Materials Co., Ltd.

[0096] Phosphite antioxidant: 168, DSTP, 412, Tianjin Lianlong New Materials Co., Ltd.

[0097] Hindered amine light stabilizer: UV-119, CAS: 106990-43-6; UV-770 (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate), Tianjin Lianlong New Materials Co., Ltd.

[0098] Examples 1-16 and Comparative Examples 1-7

[0099] After all the raw materials were dried, 70 parts of polypropylene (PP EP548R), 8 parts of ethylene copolymer elastomer (POE875), 20 parts of reinforcing agent (talc 3092), 2 parts of black masterbatch PE2772, 0.5 parts of acid absorber (calcium stearate, cast) and the formula (weight parts) of the anti-aging agent in Table 1 were pre-mixed to make the raw materials preliminarily mixed and uniform to obtain a premix. The premix was added to a twin-screw extruder for extrusion granulation.

[0100] The anti-aging compositions of high temperature resistant polyamide of this embodiment and comparative example were prepared according to the above preparation method, injection molded and subjected to performance tests. The test results are shown in Table 1.

[0101]

[0102] Performance Test:

[0103] The polypropylene composite materials prepared in the examples and comparative examples were tested for performance according to the following method:

[0104] Thermal aging: Place the sample in a 150°C oven for thermal aging. Observe the powdering time of the sample.

[0105] The test results are shown in Table 1.

[0106] The technical solution of the present application significantly improves the powdering time of polypropylene materials under heat-oxidative aging at high temperatures. Comparative Examples 3 and 4 are currently conventional solutions for improving the long-term heat aging of PP materials. It can be seen from the powdering time that when the same amount is added, the powdering time of the new formula of the present invention is much higher than that of the traditional formula. Comparative Examples 5 and 6 are when the amount of UV-119 added is not within the specified range, and its powdering time is obviously too low, unable to meet the long-term heat resistance requirements of 150°C and more than 1000h. It can be seen from Comparative Examples 1 and 5 that when the amount of UV-119 added is too little, not only will it fail to improve the high-temperature heat-oxidative aging performance of the material, but it will slightly reduce it.

[0107] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An anti-aging aid for polypropylene, comprising a hindered phenol antioxidant, a phosphite antioxidant and a hindered amine light stabilizer, wherein: The anti-aging additives include, by weight: 0.05-1.0 part of hindered phenol antioxidant, preferably 0.3-0.5 part; Phosphite antioxidant 0.05-1.0 part; The hindered amine light stabilizer is 0.2-1.0 part, preferably 0.3-0.6 part.

2. The anti-aging aid according to claim 1, characterized in that The weight average molecular weight of the hindered amine light stabilizer is greater than 1,000.

3. The anti-aging aid according to claim 2, characterized in that The hindered amine light stabilizer is selected from N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, polysuccinic acid (4-hydroxy-2,2 ,6,6-tetramethyl-1-piperidinylethanol) ester, poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]}, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4, Copolymers of 6-trichloro-1,3,5-triazine, reaction products with N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-pyridinyl)-, methylated polymerization products with morpholine-2,4,6-trichloro-1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and one or more of the polymers of 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine, the reaction products of alpha-olefin C20-24 polymers with maleic anhydride and 2,2,6,6-tetramethyl-4-piperidinamine, 1,2,3,4-butanetetracarboxylic acid and 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanal, 1,2,2,6,6-pentamethyl-4-piperidinyl ester; Preferably, the hindered amine light stabilizer is selected from N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine.

4. The anti-aging aid according to any one of claims 1 to 3, characterized in that The hindered phenol antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis(3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzyl) propionamide), bis( 3,5-di-tert-butyl-4-hydroxybenzoyl)hydrazine, 2,2'-oxalyl-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, 4,6-bis(neothiomethyl)-o-cresol, 4,6-di(dodecylthiomethyl)-o-cresol, 2,2'-thioethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid C7-C9 mixed ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid 2-Hydroxy-1,2-Di-(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C13-15 branched and straight chain alkyl esters, 2,6-di-tert-butyl-4-methylphenol, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,2H,5H)-trione, 1,1-di-tert-butyl-4-hydroxyphenyl)methyl)ethylphosphonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2 , 2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 6-(4-hydroxy-3,5-di-tert-butylphenylamino)-2,4-di-n-octylthio-1,3,5-triazine or 4,4'-bis(phenylisopropyl)diphenylamine, 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester or one or more thereof; Preferably, the hindered phenol antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; and / or The phosphite antioxidant is selected from one or more of tris(2,4-di-tert-butylbenzene) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol bis diphosphite, dioctadecyl pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol-diphosphate, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, 2,2'-methylenebis(4,6-di-tert-butyl-1-diphenyloxy)(2-ethylhexyloxy)phosphite, and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; Preferably, the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite and / or bis(2,4-di-tert-butylphenyl) pentaerythritol bisdiphosphite.

5. The anti-aging aid according to any one of claims 1 to 4, characterized in that: The anti-aging aids include: N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; or N,N"'-1,2-ethanediylbis[N-[3[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N"-dibutyl-N,N"-di(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

6. A polypropylene composite material composition, comprising polypropylene and the anti-aging aid according to any one of claims 1 to 5, Preferably, the polypropylene is selected from homopolypropylene and / or copolymer polypropylene; Preferably, the polypropylene composite material composition comprises, by weight: Polypropylene 70-80 parts; 0.05-1.0 part of hindered phenol antioxidant, preferably 0.3-0.5 part; Phosphite antioxidant 0.05-1.0 part; The hindered amine light stabilizer is 0.2-1.0 part, preferably 0.3-0.6 part.

7. The polypropylene composite material composition according to claim 6, characterized in that: In the polypropylene composite material composition, the weight proportion of the anti-aging additive is 0.5-2%, preferably 0.8-1.5%.

8. The polypropylene composite material composition according to claim 6 or 7, characterized in that: The polypropylene composite material composition further comprises one or more of a toughening agent, a reinforcing agent, a masterbatch or an acid absorbent; Preferably, the polypropylene composite material composition further comprises, by weight: Toughener 5-20 parts, reinforcing agent 10-30 parts, masterbatch 1-3 parts, acid absorbent 0.01-0.1 parts; Preferably, the toughening agent is selected from one or more of ethylene copolymer elastomers, polybutadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, styrene butadiene rubber, styrene-butadiene thermoplastic elastomer, methyl methacrylate-butadiene-styrene terpolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer; and / or The reinforcing agent is selected from one or more of talc, calcium carbonate, wollastonite, graphite, carbon black, carbon fiber, glass fiber or ceramic fiber; and / or The color masterbatch is selected from one or more of black masterbatch, white masterbatch, red masterbatch and blue masterbatch; The acid absorbent is selected from one or more of calcium stearate, zinc stearate, hydrotalcite, hydrocalumite or zinc oxide.

9. A method for preparing a polypropylene composite material, comprising the following steps: (1) uniformly mixing the polypropylene composite material composition according to any one of claims 6 to 8; (2) Perform extrusion granulation to obtain a material.

10. Use of the polypropylene composite material composition according to any one of claims 6 to 8 or the polypropylene composite material prepared by the preparation method according to claim 9 in engine peripheral parts, Preferably, the engine peripheral components are selected from one or more of intake and exhaust system components, cooling system components, fuel system components and transmission system components.

Images