CN115385961A

CN115385961A - Cardanol derived phosphite antioxidant and synthetic resin composition using same

Info

Publication number: CN115385961A
Application number: CN202210810894.5A
Authority: CN
Inventors: 李旭锋; 倪阳
Original assignee: Zhejiang Wansheng Co ltd
Current assignee: Zhejiang Wansheng Co ltd
Priority date: 2022-07-11
Filing date: 2022-07-11
Publication date: 2022-11-25

Abstract

The invention discloses a cardanol derived phosphite ester antioxidant and a synthetic resin composition using the same, wherein the main component of the cardanol derived phosphite ester antioxidant is represented by the following general formula (1):

r in the general formula (1) represents the structure of a monoene component, a diene component or a triene component of a cardanol group, and two substituent groups R in the general formula (1) are the same or different; wherein, the structure of the monoene component, the diene component or the triene component is as follows:

the invention discloses cardanol derived phosphite estersThe antioxidant is liquid at normal temperature, has high antioxidant activity and high heat resistance, and has good antioxidant effect when applied to a formula of synthetic resin.

Description

Cardanol-derived phosphite antioxidant and synthetic resin composition using same

Technical Field

The present invention relates to a novel compound useful as a phosphite antioxidant having high antioxidant activity and excellent compatibility with resin components, and more particularly, to a cardanol-derived phosphite antioxidant and a synthetic resin composition using the same.

Background

Substances which retard or prevent oxidation or autoxidation processes are known as antioxidants and are chemical substances which, when present in only small amounts in polymer systems, retard or inhibit the progress of the oxidation process of the polymer and retard the deterioration of materials, articles and supplies during storage and use and are therefore also known as "anti-aging agents". Generally, the dosage is small, and most of the dosage is substances with reducing property. The general requirements of antioxidants are small amounts, high efficiency, low price and no adverse consequences.

Phosphite antioxidants decompose polymer peroxides and prevent the decomposition thereof from inducing polymer thermo-oxidative degradation, also known as peroxide decomposers, are usually used in combination with primary antioxidants and have a good synergistic effect. Therefore, the high-temperature processing stability of the polymer can be obviously improved, the color and melt index change during the processing of the polymer is inhibited, and the color and melt index stability of a plastic product are improved. At present, in the markets at home and abroad, a representative variety of general phosphite antioxidants with large use amount is antioxidant 168.

The antioxidant 626, the antioxidant 9228 and the antioxidant PEP36 are representative high-performance phosphite antioxidants containing spiro rings, and compared with the general phosphite antioxidants, the antioxidant can be widely applied to medium-high-end formulas of general plastics and engineering plastics with harsh processing conditions due to the fact that the antioxidants have spiro unique structures and higher antioxidant activity, but the three high-efficiency spiro phosphite antioxidants 626, the antioxidant 9228 and the antioxidant PEP36 are all in normal-temperature solid states and cannot meet the requirements of using high-efficiency liquid antioxidants (for example, the antioxidants can be applied to liquid products and cannot cause the requirements of curing and the like).

Three typical high-efficiency phosphite antioxidants with spiro unique structures

TNPP is the most widely used phosphite antioxidant which is common in liquid state at normal temperature, has a triester structure similar to that of the antioxidant 168, is excellent in heat resistance and volatility resistance, has good compatibility with various polymers or matrixes, has a wide application range, and can be particularly applied to liquid products without causing solidification. Can be applied to elastomers, adhesives, general-purpose plastics, engineering plastics (SBS, TPR, IPS, PS, SBR, BR, PVC, PE, PP, ABS and the like) with lower processing temperature, plasticizers, industrial fat, mineral oil and other organic matrixes. Thereby protecting the polymer from changes in molecular weight (e.g., chain scission and cross-linking) and discoloration of the matrix during processing (mixing, pelletizing, molding, recycling applications) that are exposed to the oxidizing environment.

Antioxidant 168 and TNPP Structure (triester)

The cardanol is extracted from cashew nut oil (also called cashew nut shell liquid) to obtain a pure natural product, and the cashew nut oil is subjected to vacuum stuffing steaming to obtain relatively pure cardanol. The natural cashew nut oil is brown viscous liquid obtained by squeezing shell of fruit of cashew tree of tropical Lacqueraceae. The cashew nut fruits are 2-4cm long, the shell is of a honeycomb structure, and oily liquid is contained in the cashew nut fruits, and the cashew nut fruits are called cashew nut oil. With the intensive research on the composition of the cashew oil, the cashew oil is determined to contain about 90% of cardanol and 10% of cardol, and further, the composition and the structure of the cardanol are clearly known. The structure of cardanol is shown below:

cardanol is a compound having a saturated or unsaturated long-chain hydrocarbon group C ₁₅ H _25-31 Similar to urushiol. The cardanol has no environmental hormone effect, and is safe and environment-friendly. And analyzing the structure of cardanol, which has the characteristics of both aromatic compounds and aliphatic compounds, and meanwhile, phenolic hydroxyl groups on benzene rings enable cardanol to have phenolic properties. The saturated monoene, diene and triene of cardanol are light yellow oily liquid with the content of cardanol in sequenceIs soluble in water and soluble in organic solvents such as ethanol, ethylene glycol, butyl acetate, xylene, acetone, cyclohexane and chloroform.

Disclosure of Invention

In view of the above problems in the prior art, an object of the present invention is to provide a phosphite antioxidant which is liquid at room temperature and has high efficiency and a wide application range, and a synthetic resin composition using the phosphite antioxidant, thereby gradually and comprehensively replacing TNPP in various applications.

The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that a mixture of specific novel phosphite compounds having a cardanol structure and a spiro structure demonstrates the usefulness as a novel phosphite antioxidant for synthetic resins, and since the structure of the phosphite compounds is characterized by containing an alkenyl phenol and an olefin also has a reducing activity, that is, the structure has a higher antioxidant activity than 9228 and the like containing an alkylphenol structure, and the components in the mixture of the novel phosphite compounds have similar structures, have high antioxidant activity and high heat resistance, and can exert an effect directly as an antioxidant in the form of a mixture without separation, thereby completing the present invention.

That is, the present invention provides a simple synthesis method for synthesizing a mixture of highly efficient novel phosphite compounds having a spiro structure using cardanol as a raw material.

Due to the characteristics of the cardanol itself, the above synthesis is a mixture of novel phosphite compounds, the main component of which is represented by the following general formula (1):

the structure of the general formula (1) can be exemplified by 2 to 1,2 to 2,2 to 3 compounds typical in the following formula (2), and 3 to 1,3 to 2,3 to 3 compounds typical in the following formula (3).

The present invention also provides a liquid or solid antioxidant composition (also referred to as a stabilizer composition) containing 10 to 100 parts by mass of the novel phosphite compound represented by the above general formula (1) per 100 parts by mass of the antioxidant composition.

The present invention also provides a synthetic resin composition comprising 100 parts by mass of a synthetic resin and 0.001 to 20 parts by mass of a novel phosphite compound represented by the above general formula (1).

The present invention also provides a synthetic resin composition comprising 100 parts by mass of a synthetic resin and 0.001 to 10 parts by mass of a novel phosphite compound represented by the above general formula (1).

The present invention provides the synthetic resin composition, wherein the synthetic resin is a polyurethane resin, a polyester resin, a polyolefin resin, or a block polymer containing a polybutadiene block or a polypentadiene block (for example, SBS, TPR, IPS, SBR, BR, ABS, etc.).

The antioxidant composition of the present invention containing 10 to 100 mass% of the novel phosphite compound represented by the above general formula (1) is blended with a synthetic resin to prepare a synthetic resin composition described below for various applications.

Next, the synthetic resin composition of the present invention will be explained.

The synthetic resin composition of the present invention is obtained by blending a synthetic resin with a mixture containing 10 to 100 mass% of the novel phosphite compound represented by the general formula (1) as an antioxidant, wherein the synthetic resin contains 10 to 100 parts by mass of the novel phosphite compound represented by the general formula (1) per 100 parts by mass of the antioxidant.

In the synthetic resin composition of the present invention, the amount of the antioxidant mixture containing 10% to 100% by mass of the novel phosphite compound represented by the general formula (1) is 0.01 to 20 parts by mass per 100 parts by mass of the resin, and is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.005 to 3 parts by mass, from the viewpoint of compatibility with the resin, heat resistance, weather resistance, and volatility resistance. If the amount of the antioxidant mixture is less than 0.01 part by mass, the heat resistance and weather resistance are poor, and if it exceeds 20 parts by mass, the compatibility with the resin is poor.

Examples of the synthetic resin used in the present invention include: polyolefins such as an α -olefin polymer, e.g., polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-4-methylpentene, etc., an ethylene-vinyl acetate copolymer, an ethylene-propylene copolymer, etc., and copolymers thereof; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated rubbers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, and vinyl chloride-cyclohexylmaleimide copolymers; petroleum resin; coumarone resin; polystyrene; polyvinyl acetate; acrylic resin; copolymers (e.g., AS resins, ABS resins, MBS resins, heat-resistant ABS resins, etc.) of styrene and/or α -methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.); linear polyesters such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, polybutylene terephthalate, and polybutylene terephthalate; thermoplastic resins such as polyamides including polyphenylene ether, polycaprolactam and polyhexamethylene adipamide, polycarbonates, branched polycarbonates, polyacetals, polyphenylene sulfide, polyurethanes, and cellulose resins, and mixtures thereof; or thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Further, an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, or styrene-butadiene copolymer rubber may be included in the resin.

These synthetic resins can be used regardless of the molecular weight, polymerization degree, density, softening point, ratio of insoluble components in a solvent, degree of stereoregularity, presence or absence of catalyst residue, kind and blending ratio of monomers as raw materials, kind of polymerization catalyst (e.g., ziegler-natta catalyst, metallocene catalyst, etc.), and the like.

In the synthetic resin composition of the present invention, a polyurethane resin is preferred as the synthetic resin from the viewpoint of the compatibility with the resin and the high resistance to yellowing. The polyurethane resin may be those generally commercially available, for example, a polyurethane obtained by reacting 1 or more kinds of polyols with an isocyanate.

When a polyurethane resin is used as the synthetic resin, the content of the phosphite compound represented by the above general formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyurethane resin, and is preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass, from the viewpoint of heat resistance, weather resistance and compatibility.

In the synthetic resin composition of the present invention, a phenol-based antioxidant, a thioether-based antioxidant, a hindered amine-based light stabilizer, a triazine ring-containing compound, a metal hydroxide, a phosphate-based flame retardant, a condensed phosphate-based flame retardant, a phosphate-based flame retardant, an inorganic phosphorus-based flame retardant, (poly) phosphate-based flame retardant, a halogen-based flame retardant, a silicon-based flame retardant, antimony oxide, an inorganic flame retardant aid, an organic flame retardant aid, an antistatic agent, a lubricant, a nucleating agent, a plasticizer, a mold release agent, a compatibilizer, a foaming agent, a light absorbing pigment, a dye, a processing aid, a metal inactivating agent, inorganic fine particles, an antibacterial agent, a mildewproof agent, a filler and the like may be used as necessary within a range not to impair the effects of the present invention. Further, phosphite antioxidants other than the phosphite compound represented by the above general formula (1) may be used within a range not impairing the effects of the present invention.

The amount of the additive is preferably 10 parts by mass or less in total per 100 parts by mass of the synthetic resin.

As the above-mentioned phenol-based antioxidant, examples thereof include 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propanoic acid amide ], 4 '-thiobis (6-t-butyl-m-cresol), 2' -methylenebis (4-methyl-6-t-butylphenol), 2 '-methylenebis (4-ethyl-6-t-butylphenol) 4,4' -butylidenebis (6-tert-butyl-m-cresol), 2 '-ethylidenebis (4, 6-di-tert-butylphenol), 2' -ethylidenebis (4-tert-butyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl ] butane, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearoyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, methyl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, thiodiethylene glycol bis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexamethylenebis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis [3, 3-bis (4-hydroxy-3-t-butylphenyl) butanoic acid ] diol ester, bis [ 2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, 3, 9-bis [1, 1-dimethyl-2- { (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [ (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], and the like. The amount of the above-mentioned phenol antioxidant added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the synthetic resin.

Examples of the thioether-based antioxidant include dialkyl thiodipropionate esters such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetrakis (. Beta. -alkylthiopropionic acid) esters. The amount of the thioether antioxidant added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the synthetic resin.

<xnotran> , 2,2,6,6- -4- ,1,2,2,6,6- -4- ,2,2,6,6- -4- , (2,2,6,6- -4- ) , (1,2,2,6,6- -4- ) , (1- -2,2,6,6- -4- ) , (2,2,6,6- -4- ) -1,2,3,4- , (1,2,2,6,6- -4- ) -1,2,3,4- , (2,2,6,6- -4- ) · () -1,2,3,4- , (1,2,2,6,6- -4- ) · () -1,2,3,4- , (1,2,2,4,4- -4- ) -2- -2- (3,5- -4- ) , </xnotran> <xnotran> 1- (2- ) -2,2,6,6- -4- / ,1,6- (2,2,6,6- -4- ) /2,4- -6- - ,1,6- (2,2,6,6- -4- ) /2,4- -6- - ,1,5,8, 12- [2,4- (N- -N- (2,2,6,6- -4- ) ) - -6- ] -1,5,8, 12- ,1,5,8, 12- [2,4- (N- -N- (1,2,2,6,6- -4- ) ) - -6- ] -1,5,8, 12- ,1,6, 11- [2,4- (N- -N- (2,2,6,6- -4- ) ) - -6- ] ,1,6, 11- [2,4- (N- -N- (1, </xnotran> 2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane and the like. The amount of the hindered amine light stabilizer added is preferably 0.01 to 35 parts by mass, more preferably 0.1 to 8 parts by mass, based on 100 parts by mass of the synthetic resin.

Examples of the triazine ring-containing compound include melamine, ammeline, benzoguanamine, acetoguanamine, orthophthalguanamine (phthalandiguanamine), melamine isocyanurate, melamine pyrophosphate, butylidenediguanamine, norbornenediguanamine, methylenebiguanide, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1, 3-hexylenedimelamine, and the like.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and KISUMA5A (magnesium hydroxide, manufactured by Kyowa chemical Co., ltd.).

Examples of the phosphate-based flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, xylyldiphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis (tert-butylphenyl) phenyl phosphate, tris (tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis (isopropylphenyl) diphenyl phosphate, and tris (isopropylphenyl) phosphate.

Examples of the condensed phosphate-based flame retardant include 1, 3-phenylene bis (diphenyl phosphate), 1, 3-phenylene bis (dixylyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.

Examples of the (poly) phosphate flame retardants include ammonium salts and amine salts of (poly) phosphoric acids such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Examples of the inorganic flame retardant aid include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite.

Examples of the organic flame-retardant auxiliary include pentaerythritol.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary ammonium salts; anionic antistatic agents such as higher alcohol phosphate ester salts, higher alcohol ethylene oxide adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate ester salts, higher alcohol ethylene oxide adduct sulfate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts; nonionic antistatic agents such as polyol fatty acid esters, polyalkylene glycol phosphate esters and polyoxyethylene alkyl allyl ethers; amphoteric antistatic agents such as amphoteric alkylbetaines (e.g., alkyldimethylaminoacetic acid betaine) and imidazoline amphoteric activators.

Examples of the lubricant include hydrocarbon-based lubricants such as fluid paraffin, solid wax, and polyethylene wax; aliphatic lubricants such as stearyl alcohol, stearic acid, and 12-hydroxystearic acid; amide lubricants such as stearic acid amide, oleic acid amide, erucic acid amide, methylene bis stearic acid amide, and ethylene stearic acid amide; metal soap lubricants such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate/zinc stearate complex, and zinc stearate/calcium stearate complex; ester lubricants such as hardened fats and oils, glycerin monostearate, butyl stearate, pentaerythritol stearate, and stearyl stearate.

Examples of the nucleating agent include dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, hydroxy-bis (t-butyl benzoic acid) aluminum, bis (4-t-butylphenyl) sodium phosphate, and 2, 2-methylenebis (4, 6-di-t-butylphenyl) sodium phosphate.

Examples of the plasticizer include plasticizers such as phthalic acid esters, dibasic acid esters, chlorinated paraffins, polyesters, epoxidized esters, phosphoric acid esters, and trimellitic acid esters.

Examples of the filler include calcium silicate powder, silica powder, talc powder, mica powder, alumina powder, titanium oxide powder, and glass flakes.

Examples of the filler include glass fibers and carbon fibers.

Examples of the ultraviolet absorber (also referred to as another ultraviolet absorber) include 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5' -methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 '-hydroxyphenyl) benzotriazoles such as 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -dicumylphenyl) benzotriazole, 2 '-methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2' -hydroxy-3 '-tert-butyl-5' -carboxyphenyl) benzotriazole and the like; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2, 4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, 2, 4-di-t-amylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3, 5-di-t-butyl-4-hydroxybenzoate; substituted oxalanilides such as 2-ethyl-2 '-ethoxyoxalanilide and 2-ethoxy-4' -dodecyloxalanilide; cyanoacrylates such as ethyl- α -cyano- β, β -diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate), and the like; triaryltriazines such as 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-di-t-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-s-triazine, and 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4, 6-bis (2, 4-di-t-butylphenyl) -s-triazine.

The amount of the ultraviolet absorber is preferably 3 parts by mass or less based on 100 parts by mass of the synthetic resin.

Examples of the phosphite antioxidant other than the phosphite of the general formula (1) include tris (nonylphenyl) phosphite, tris [ 2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl ] phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, ditridecyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 4, 6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexatridecyl) -1, 3-tris (2-methyl-4-hydroxy-5-triphenylene) phosphite, tetra (2-tert-butyl-5-biphenylene) diphosphite, 9-10-dihydrophenanthrene-phosphite, 9-diphenyl-10-phosphine oxide, 2,2' -methylenebis (4, 6-tert-butylphenyl) -2-ethylhexyl phosphite, 2' -methylenebis (4, 6-tert-butylphenyl) -octadecyl phosphite, 2' -ethylidenebis (4, 6-di-tert-butylphenyl) fluorophosphite, tris (2- [ (2, 4,8, 10-tetra-tert-butylbenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl) oxy ] ethyl) amine, 2-ethyl-2-butylpropanediol phosphite with 2,4, 6-tri-tert-butylphenol, and the like.

When another phosphite antioxidant is used, the amount of the phosphite antioxidant is preferably 3 parts by mass or less based on 100 parts by mass of the synthetic resin.

The method for producing the synthetic resin composition of the present invention is not particularly limited, and any conventionally known method for producing a resin composition can be used.

Specifically, the following methods can be mentioned: the synthetic resin is mixed with the antioxidant of the general formula (1) and, if necessary, other synthetic resin additive components in advance using various mixers such as a roll mixer and a henschel mixer, and then melt-kneaded using an internal mixer, a roll mill, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, or the like. Alternatively, the resin composition may be produced by mixing only a part of the components in advance without premixing the components, feeding the mixture to an extruder using a feeder, and melt-kneading the mixture. Alternatively, a resin composition may be prepared by mixing a part of the components in advance, supplying the mixture to an extruder, and melt-kneading the mixture to prepare a master batch, and then mixing the master batch with the other components and melt-kneading the mixture.

That is, the synthetic resin composition and the molded article thereof of the present invention can be used in a wide range of industrial fields such as electric/electronic/communication, agriculture, forestry, marine industry, mining industry, construction, food, fiber, clothing, medical treatment, coal, petroleum, rubber, leather, automobile, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, and the like. More specifically, it can be used to: office supplies such as printers, computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, racks, stationery, and OA equipment; household appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game machines, irons, and furnaces; AV equipment such as TVs, VTRs, video cameras, radio cassette recorders, audio recorders, compact discs, CD players, loudspeakers, liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, bobbins, and semiconductor sealing materials; LED sealing materials, electric/electronic components such as wires, cables, transformers, deflection yokes, dials, and clocks, and housings (frames, housings, casings, and exterior cases) and components of communication devices, OA devices, and the like; use of automotive interior and exterior materials; and automotive, hybrid power vehicles, electric vehicles, ships, airplanes, buildings, houses, and building materials such as seats (fillers, fabrics, etc.), transmission belts, suspended ceilings, car roofs, armrests, door trim, rear window sill discs, carpets, cushions, sun shades, foil covers, mat covers, airbags, insulating materials, suspension ropes, harnesses, wire covers, electrically insulating materials, paints, coating materials, surface covers, flooring materials, corner walls, carpets, wallpaper, wall materials, exterior materials, interior materials, roofing materials, armor materials, wall materials, pillars, floors, wall materials, frameworks, and trim strips, window and door profile materials, veneers, sidings, balconies, decks, soundproofing boards, insulation panels, window materials; a civil engineering material; clothing, curtains, bed sheets, plywood, composite fiber boards, carpets, hallway mats, sheets, tubs, hoses, containers, glasses, bags, cases, goggles, snowboards, rackets, tents, musical instruments and other living goods, sporting goods and other various uses.

Drawings

FIG. 1 is P of a mixture of novel phosphite compounds of Synthesis example 1 ³¹ (CDCl ₃ ) A spectrogram;

FIG. 2 shows C of a mixture of the novel phosphite compounds of Synthesis example 1 ¹³ (CDCl ₃ ) A spectrogram;

FIG. 3 is a FT-IR spectrum of a mixture of the novel phosphite compounds of Synthesis example 1.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

Synthesis example 1:

a stirrer, a nitrogen inlet, a thermometer, a rectifying tube, and a cock (for sampling) were attached to a five-necked 1000ml flask, and a quantitative water receiver and a cooling tube were attached to the tip of the rectifying tube. Into the flask were charged pentaerythritol (13.6 g, approximately 0.1 mol) as a raw material, xylene (200.0 g) as a solvent, and triethylamine (0.2 g, 2 mmol) as a catalyst, and phosphorus trichloride (27.4 g,0.2 mol, purified by Wako K.K.) as a raw material was added dropwise at normal pressure and 70 ℃. After the completion of the dropwise addition, the system was kept at a temperature, and the esterification-reaction was carried out while removing the generated hydrogen chloride out of the system. The esterification reaction was terminated when less than 1% of the starting material was analyzed by HPLC. Subsequently, cardanol (57.3 g, about 0.2 mol, refined by watson corporation, 1 g/min, zhejiang) was added to the system at a constant rate. After the completion of the addition, the system was heated to reflux (> 110 ℃ C.), and the esterification reaction was carried out while removing the produced hydrogen chloride from the system. The esterification reaction was terminated when the amount of the starting material was less than 1% by HPLC analysis. Then, the temperature was reduced, and the solvent was distilled under reduced pressure to remove the solvent, followed by filtration, thereby producing a desired mixture of the novel phosphite compound represented by the above general formula (1) with a yield of 96%.

The identification of the mixture of the novel phosphite compounds represented by the above general formula (1) was carried out using nuclear magnetism and infrared, and the results are shown below.

P of a mixture of novel phosphite compounds represented by the above general formula (1) ³¹ (CDCl ₃ ) The spectrum is shown in FIG. 1, and the chemical shifts of the mixture of the novel phosphite compounds represented by the general formula (1) as the main component were 127.3ppm and 127.8ppm, showing two single peaks. C ¹³ (CDCl ₃ ) The spectrogram is shown in figure 2, the chemical shifts of the mixture of the novel phosphite compounds represented by the general formula (1) as the main component are 8.72ppm, 13.91ppm, 14.22ppm, 27.30ppm, 27.32ppm, 29.07ppm, 29.30ppm, 29.35ppm, 29.37ppm, 29.46ppm, 29.83ppm, 31.39ppm, 31.88ppm, 35.90ppm, 45.79ppm, 62.08ppm, 62.27ppm, 62.39ppm, 62.40ppm, 68.62ppm, 68.86ppm76.86ppm, 77.18ppm, 77.38ppm, 77.50ppm, 114.80ppm, 115.58ppm, 116.91ppm, 116.99ppm, 119.79ppm, 119.86ppm, 120.14ppm, 123.92ppm, 125.38ppm, 126.88ppm, 127.69ppm, 128.29ppm, 129.10ppm, 129.24ppm, 129.38ppm, 129.57ppm, 129.88ppm, 129.97ppm, 130.04ppm, 130.43ppm, 136.86ppm, 137.87ppm, 144.67ppm, 145.19ppm, 145.21ppm, 152.32ppm, 152.39ppm, 156.56ppm.

The infrared spectrum of the mixture of the novel phosphite compounds represented by the above general formula (1) is shown in FIG. 3.

Example 1-1 and comparative example 1-1

< evaluation of Hot workability resistance >

The mixture of the novel phosphite compounds represented by the general formula (1) obtained in synthesis example 1 or TNPP as a comparative compound was evaluated for heat-resistant processability by differential thermal analysis. The evaluation was checked with 1% and 3% thermogravimetric loss temperatures. The TGA test was conducted with room temperature as the starting temperature and temperature was raised at a rate of 5 ℃/min, recording the temperature at which 1% and 3% weight loss, and the results are shown in table 1, with higher thermogravimetric loss temperatures indicating better thermal processability of the phosphite. The results show that the heat-resistant processability of the mixture of the novel phosphite compounds represented by the above general formula (1) is significantly superior to that of TNPP.

TABLE 1 comparison of Heat resistance of phosphite Compounds (TGA)

Example 2-1 and comparative example 2-1

< TVOC evaluation >

The TVOC was evaluated by differential thermal analysis on the mixture of the novel phosphite compound represented by the general formula (1) obtained in synthesis example 1 or TNPP as a comparative compound. The evaluation was checked with TVOC test values. The results are shown in table 2, while lower TVOC indicates better volatile resistance of the phosphite, which is more advantageous for use as an antioxidant. The results show that TVOC of the mixture of the novel phosphite compounds represented by the above formula (1) is significantly superior to TNPP.

TABLE 2 comparison of the volatility of phosphite Compounds (TVOC)

Example 3-1 and comparative example 3-1

[ preparation of test piece ]

The mixture of the novel phosphite compounds represented by the general formula (1) obtained in synthesis example 1 or TNPP as a comparative compound was mixed in the amount shown in table 3 at a ratio shown in table 3 with respect to 100 parts by mass of the polyether polyol shown in table 3, and polyurethane foam was produced at room temperature using an ultra high speed mixer (35 machines, manufactured by nanjing sheng rubber and plastic machinery ltd.), wherein polyurethane foam obtained in formulation No. 1 was foam a and polyurethane foam obtained in formulation No. 2 was foam B.

TABLE 3

	Formulation No. 1	Formulation No. 2
			Polyether polyols	100	100
TDI	50	50
			Water (W)	3.8	3.8
Catalyst A33	0.2	0.2
			Silicone oil	1.2	1.2
Catalyst T9	0.2	0.2
			Mixtures of novel phosphite compounds	0.3
TNPP		0.3

The polyurethane cottons A and B obtained above were tested for yellowness index, tensile strength test (GB 6344-1996), ball rebound test (GB 6670-2008), fatigue test (GB 18941-2003).

TABLE 4 Effect of antioxidant type on foam Performance

	Foam A	Foam B
			Yellowness index
	4	10
			High tensile strengthDegree (KPa)	100	60
Falling ball rebound test (%)	40	30
			Fatigue test (%)	3	5

The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims

1. A cardanol-derived phosphite antioxidant is characterized in that the main component of the cardanol-derived phosphite antioxidant is represented by the following general formula (1):

r in the general formula (1) represents the structure of a monoene component, a diene component or a triene component of a cardanol group, and two substituent groups R in the general formula (1) are the same or different; wherein, the structures of the monoene component, the diene component or the triene component are as follows:

2. a synthetic resin composition characterized by compounding the cardanol-derived phosphite antioxidant according to claim 1 in a synthetic resin.

3. A synthetic resin composition according to claim 2, wherein the antioxidant composition is blended with the synthetic resin, and the antioxidant composition contains 10 to 100 parts by mass of the cardanol-derived phosphite antioxidant represented by the general formula (1) per 100 parts by mass of the antioxidant composition, and the cardanol-derived phosphite antioxidant represented by the general formula (1) in an amount of 10 to 100% by mass of the antioxidant composition is blended with the synthetic resin.

4. A synthetic resin composition according to claim 3, wherein the amount of the antioxidant composition containing the cardanol-derived phosphite based antioxidant represented by the general formula (1) in an amount of 10 to 100% by mass is 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the synthetic resin.

5. A synthetic resin composition according to claim 4, wherein the amount of the antioxidant composition containing the cardanol-derived phosphite antioxidant represented by the general formula (1) in an amount of 10 to 100% by mass is 0.03 to 5 parts by mass, preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the synthetic resin.

6. A synthetic resin composition according to claim 3 wherein the synthetic resin is at least one of a polyurethane resin, a polyester resin, a polyolefin resin, a block polymer containing polybutadiene blocks or polypentadiene blocks.