CN115368632A

CN115368632A - Phosphite antioxidant composition and synthetic resin composition using same

Info

Publication number: CN115368632A
Application number: CN202210810903.0A
Authority: CN
Inventors: 倪阳; 李旭锋; 褚昭宁; 关俊涛
Original assignee: Zhejiang Wansheng Co ltd
Current assignee: Zhejiang Wansheng Co ltd
Priority date: 2022-07-11
Filing date: 2022-07-11
Publication date: 2022-11-22

Abstract

The invention discloses a phosphite ester antioxidant composition and a synthetic resin composition using the same, the phosphite ester antioxidant composition is characterized by comprising a phosphite ester antioxidant compound with a cardanol structure and shown in a general formula (1),

in the general formula (1), R represents a hydrogen atom, a hydroxyl group, an alkyl group with 1-30 carbon atoms or an alkoxy group with 1-30 carbon atoms, and the alkyl group and the alkoxy group are optionally interrupted by one or more oxygen atoms or carbonyl groups; in the general formula (1), n, m and k respectively represent the number of cardanol groups containing monoene, diene and trieneN, m and k are integers which are more than or equal to 0 and less than or equal to 3, and the sum of n, m and k is 3. The invention provides a novel compound of normal temperature liquid phosphite ester which has better heat resistance and antioxidant effect than TNPP and is easy to synthesize, and a synthetic resin composition using the compound can gradually and comprehensively replace the existing conventional TNPP in terms of application, and has good application prospect.

Description

Phosphite antioxidant composition and synthetic resin composition using same

Technical Field

The present invention relates to a novel compound useful as an antioxidant which is excellent in heat resistance and volatility resistance and also excellent in compatibility with resin components, and more particularly to a phosphite antioxidant composition and a synthetic resin composition using the same.

Background

Polymeric material resins produced in the 20 th century have been expanded in the field of application in production and living, but as organic materials, they are easily oxidized to show apparent phenomena such as discoloration, yellowing, hardening, cracking, loss of gloss, and further, they have significantly reduced physical properties such as impact strength, flexural strength, tensile strength, and elongation, and thus have an influence on the normal use of the materials.

The antioxidant is an additive for inhibiting or delaying the degradation of a polymer caused by oxidation, is the most widely applied auxiliary agent in the production of polymer material resins (plastics, rubber, fibers and the like), and can be applied to various polymer material products such as polypropylene, polyethylene films, high-density polyethylene injection products, ABS, polycarbonate, polyester molded products and the like. Polymeric antioxidants can be generally classified into primary antioxidants and secondary antioxidants in terms of function and mechanism of action. The main antioxidant takes polymer oxidation free radicals or peroxy radicals as main functions, is also called as a free radical scavenger and comprises arylamine compounds, hindered phenol compounds and the like; the auxiliary antioxidant can decompose polymer peroxide to prevent the polymer from thermal-oxidative degradation induced by cracking, is also called peroxide decomposer, and is commonly used together with the main antioxidant in the current market, wherein the main variety of the auxiliary antioxidant comprises thioether and phosphite ester antioxidants and has good synergistic effect.

The phosphite antioxidant can obviously improve the high-temperature processing stability of the polymer, can inhibit the color and melt index change during the processing of the polymer to the maximum extent, and improves the color and melt index stability of plastic products. The currently used phosphite antioxidant varieties such as antioxidant 168 and antioxidant TNPP belong to general auxiliary antioxidants. The antioxidant TNPP is liquid at normal temperature, has excellent heat resistance and volatility resistance, good compatibility with various polymers or matrixes and wide application field, 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.

Although the antioxidant TNPP has excellent performance, the raw material of the antioxidant TNPP is nonylphenol, so that the antioxidant TNPP can be gradually hydrolyzed to generate the nonylphenol when meeting water, and the nonylphenol is the pollutant which is most toxic and difficult to biodegrade by environmental hormones, and shows toxicity to aquatic organisms, mammals and the like to different degrees by seriously influencing a biological endocrine system, so that the survival, development and growth of the organisms are deteriorated.

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. Cardanol 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, triene and other components of cardanol are light yellow oily liquids, and the cardanol content is sequentially that the cardanol is insoluble in water and soluble in organic solvents such as ethanol, ethylene chain, butyl acetate, xylene, acetone, cyclohexane, chloroform and the like.

Disclosure of Invention

In view of the above problems in the prior art, an object of the present invention is to provide a novel compound of room temperature liquid phosphite having superior heat resistance and antioxidant effect to TNPP and being easily synthesized, and a synthetic resin composition using the same, thereby gradually and comprehensively substituting TNPP for various uses.

The easy synthesis of the novel compound of the normal-temperature liquid phosphite ester refers to the synthesis of the novel compound of the normal-temperature liquid phosphite ester by using a one-step reaction method and using a nontoxic and harmless phenolic compound as a raw material.

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

That is, the present invention provides a simple synthesis method for synthesizing a mixture of novel phosphite compounds having high antioxidant activity in one step 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):

in the general formula (1), R represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and the alkyl group and the alkoxy group are optionally interrupted by one or more oxygen atoms or carbonyl groups. In the general formula (1), R is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a 2-propynyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, and tert-octyloxy.

In the general formula (1), n, m and k respectively represent the number of cardanol groups containing monoenes, dienes and trienes, n, m and k are integers which are more than or equal to 0 and less than or equal to 3, and the sum of n, m and k is 3. And 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 compounds typical in the following formula (3), and 4 to 1,4 to 2 compounds typical in the following formula (4), and 5 to 1,5 to 2 compounds typical in the following formula (5), and 6 to 1 compounds typical in the following formula (6):

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. That is, the antioxidant composition may contain 10 to 100 mass% of the phosphite antioxidant compound represented by the 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 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% by 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 and used in various applications.

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

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, that is, 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 0.004 to 3 parts by mass, from the viewpoint of compatibility with the resin, heat resistance, weather resistance, and volatility. 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 alpha-olefin polymers including polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, poly-4-methylpentene and the like, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and the like, 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, the synthetic resin is preferably a polycarbonate resin, a polyester resin, an acrylic resin, or an ABS resin, and more preferably an alloy resin of a polycarbonate resin and an ABS resin, from the viewpoint of the compatibility with the resin and the resistance to yellowing.

The polycarbonate resin may be those generally commercially available, for example, a polycarbonate resin obtained by reacting 1 or more bisphenols with phosgene or a carbonic acid diester; or a polycarbonate resin obtained by reacting 1 or more bisphenols with diphenyl carbonate by an ester exchange method. Examples of the bisphenols include hydroquinone, 4-dihydroxyphenyl, bis (4-hydroxyphenyl) -alkane, bis (4-hydroxyphenyl) -cycloalkane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, bisphenol fluorene, and alkyl-, aryl-, and halogen-substituted derivatives thereof, and 1 or more of these may be used in combination. Of the above-mentioned polycarbonates, bisphenol a polycarbonate using 2, 2-bis (4-hydroxyphenyl) propane, so-called bisphenol a, as a raw material is preferred from the viewpoint of being readily available on the market. The polycarbonate resin may be not only a resin in which the polycarbonate is 100% but also a so-called polymer alloy in which a polycarbonate and another resin are mixed. Examples of such polymer alloys include polycarbonate/ABS resin, polycarbonate/AS resin, polycarbonate/rubber-based polymer compound, polycarbonate/ABS resin/rubber-based polymer compound, polycarbonate/polyethylene terephthalate, polycarbonate/polybutylene terephthalate, polycarbonate/ASA resin, and polycarbonate/AES resin.

When an alloy resin of a polycarbonate resin and an ABS 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 impairing the effects of the present invention. In addition, within the scope of not damaging the effect of the invention, can also use by the general formula (1) representation of the phosphite ester compounds other than phosphite ester antioxidant. 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, distearoyl (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 antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetrakis (. Beta. -alkylthiopropionate) 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 KISUMA 5A (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.

The organic flame retardant auxiliary may be, for example, pentaerythritol.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium salt and polyamine quaternary salt; 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-butylbenzoic 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 phosphite antioxidants other than the phosphites represented by the above 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, bis (decyl) 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, tetrakis (tridecyl) isopropylidenediphenol diphosphite, tetrakis (tridecyl) -4,4' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1, 3-tris (2-methyl-4-hydroxy-5-triphenylene) butane, tetrakis (2-tert-butyl-5-methylphenylene) diphosphite, hexa-10-dihydrophenanthrylene phosphite, 9-10-dihydrophenanthrene phosphite, 9-10-bis (2-tert-butyl-4-phenyl) phosphite, 10-dihydrophenanthrene phosphite, 9, 10-dihydrophenanthrene phosphite, and the like, 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 thereof 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, the antioxidant of the general formula (1) and, if necessary, other synthetic resin additive components are mixed 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 premixing only a part of the components without premixing them, supplying the premixed component to an extruder using a feeder, and melt-kneading the kneaded component. 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 register), 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 ovens; 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; as well as automotive, hybrid vehicle, electric vehicle, ship, airplane, building, housing, and construction materials such as seats (fillers, fabrics, etc.), transmission belts, suspended ceilings, headliners, armrests, door trim strips, rear window tray, carpets, mats, sun shades, foil covers, mat covers, airbags, insulating materials, suspension ropes, suspension straps, 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, framework and trim strips, window and door profile materials, veneers, sidings, balconies, terraces, soundproofing boards, insulation panels, window materials, hybrid vehicles, electric vehicles, ships, airplanes, buildings, housing, and construction 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 Synthesis example 1, mixture No.1 of novel phosphite Compound ³¹ (CDCl ₃ ) A spectrogram;

FIG. 2 shows C of No.1 which is a mixture of the novel phosphite compounds of Synthesis example 1 ¹³ (CDCl ₃ ) A spectrogram;

FIG. 3 is an FT-IR spectrum of mixture No.1 of the novel phosphite compound 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. Cardanol (86.0 g, about 0.3 mol, purified by kikai gmbh) as a phenol component as a raw material, xylene (300.0 g) as a solvent, and triethylamine (0.2 g, 2 mmol) as a catalyst were added to the flask, and phosphorus trichloride (13.7 g,0.1 mol, purified by kiji gmbh) as a raw material was added dropwise at 70 ℃ and normal pressure. After the completion of the dropwise addition, the system was heated to reflux (> 135 ℃ C.), and the esterification reaction was carried out while removing the generated hydrogen chloride from the system. The esterification was terminated when less than 1% of the starting material was analyzed by HPLC. Thereafter, the temperature was reduced, the solvent was distilled under reduced pressure to remove the solvent, and then the filtrate was filtered to produce a target mixture No.1 of the novel phosphite compound represented by the above general formula (1) in a yield of 95%.

The identification of the mixture No.1 of the novel phosphite compounds represented by the above general formula (1) was carried out using nuclear magnetism and infrared, and the identification results are shown below.

P of the mixture No.1 of the novel phosphite compounds represented by the above formula (1) ³¹ (CDCl ₃ ) The spectrum is shown in FIG. 1, and the chemical shift of the mixture of the novel phosphite compounds represented by the general formula (1) as the main component was 128ppm, showing a single peak. C ¹³ (CDCl ₃ ) The spectrum of the novel phosphite compound mixture shown by the general formula (1) shown in FIG. 2 was found to have chemical shifts of 13.91ppm, 14.23ppm, 22.78ppm, 22.90ppm, 25.68ppm, 25.76ppm, 27.30ppm, 27.32ppm, 27.33ppm, 29.10ppm, 29.33ppm, 29.39ppm, 29.51ppm, 29.74ppm, 29.77ppm, 29.85ppm, 29.87ppm, 31.35ppm, 31.62ppm, 31.90ppm, 35.88ppm, 76.85ppm, 77.16ppm, 77.48ppm, 114.80ppm, 117.95ppm, 118.02ppm, 120.77ppm, 120.84ppm, 124.34ppm, 126.88ppm, 127.69ppm, 128.11ppm, 128.25ppm, 128.29ppm, 129.10ppm, 129.38ppm, 129.88ppm, 129.96ppm, 130.02ppm, 130.84 ppm, 130.151.144 ppm, 151.144 ppm and 144 ppm.

The IR spectrum of the mixture NO.1 of the novel phosphite compound represented by the above general formula (1) is shown in FIG. 3, in which 691cm ^-1 、806cm ^-1 、945cm ^-1 Is the bending vibration peak of benzene ring, 2853cm ^-1 、2924cm ^-1 、3009cm ^-1 Is C-H stretching vibration peak.

Synthesis example 2

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. Cardanol (86.0 g, about 0.3 mol, purified in ten thousand of entries in zhejiang) as a phenol component of the raw material, xylene (300.0 g) as a solvent, and triethylamine (30 g, 0.3 mol) as a catalyst were added to the flask, and phosphorus trichloride (13.7 g,0.1 mol, purified in ten thousand of entries in zhejiang) as a raw material was added dropwise at normal pressure and room temperature. After the dropwise addition, the temperature of the system was raised to 40 ℃ and maintained for 2 hours or more. The esterification was terminated when less than 1% of the starting material was analyzed by HPLC. After that, the temperature was reduced, filtration was performed, and then the solvent was distilled off under reduced pressure to produce the target product No.2 with a yield of 97%.

Comparison of nuclear magnetic properties and infrared rays confirmed that the target product NO.2 was a mixture of the novel phosphite compounds represented by the above general formula (1) in the same manner as the compound NO. 1.

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 using 1% and 3% thermogravimetric loss temperatures, with the TGA test being performed with room temperature as the starting temperature and temperature ramping at 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 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 volatility 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 compound represented by the above general formula (1) obtained in synthesis example 1 or TNPP as a comparative compound was blended in the blending amount shown in table 3 with respect to 100 parts by mass of the PC/ABS alloy resin shown in table 3, and pellets were produced at 230 ℃. Pellets were again produced from pellets A or B above at 230 ℃ using an extruder to give pellets C or D, respectively. By analogy, the pellets obtained were processed at 230 ℃ using an extruder repeatedly to give E or F, G or H, I or J.

TABLE 3

The pellets A, B, E, F, I, J obtained above were tested for melt index. The pellets A, B, E, F, I and J thus obtained were injection molded at 230 ℃ to prepare dumbbell pieces for tensile test (GB 1040.2-2006) and sample pieces for impact resistance test (GB 1043.1-2008), and the following evaluations were carried out. The results are shown in tables 4, 5 and 6. From the above results, it can be seen that the mixture of the novel phosphite compounds represented by the above general formula (1) is effective in reducing the degradation of the polymer by thermal processing, resulting in a small increase in the melt index and a small decrease in the tensile strength and impact strength, as compared to TNPP.

TABLE 4 influence of thermal processing on melt index

TABLE 5 Effect of Hot working on tensile Strength

TABLE 6 impact resistance Effect of Hot working

	Formulation No.1	Formulation No.2
			Impact Strength after Hot working Once (kJ/m) ² )	3.26	3.01
Impact Strength after three Heat working (kJ/m) ² )	2.73	2.34
			Impact Strength after Hot working five times (kJ/m) ² )	2.34	1.87

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 phosphite antioxidant composition characterized by comprising a phosphite antioxidant compound having a cardanol structure and represented by the following general formula (1),

in the general formula (1), R represents a hydrogen atom, a hydroxyl group, an alkyl group with 1-30 carbon atoms or an alkoxy group with 1-30 carbon atoms, and the alkyl group and the alkoxy group are optionally interrupted by one or more oxygen atoms or carbonyl groups;

in the general formula (1), n, m and k respectively represent the number of cardanol groups containing monoenes, dienes and trienes, n, m and k are integers which are more than or equal to 0 and less than or equal to 3, and the sum of n, m and k is 3.

2. The phosphite antioxidant composition according to claim 1, wherein R in the general formula (1) represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

3. An antioxidant synthetic resin composition characterized by compounding the phosphite antioxidant composition of claim 1 in a synthetic resin.

4. The antioxidant synthetic resin composition as claimed in claim 3, wherein the antioxidant composition is compounded in the synthetic resin by mixing 10 to 100 mass parts of the phosphite antioxidant compound represented by the general formula (1) with respect to 100 mass parts of the antioxidant composition, and the antioxidant composition containing 10 to 100 mass% of the phosphite antioxidant compound represented by the general formula (1) is compounded in the synthetic resin.

5. The antioxidant synthetic resin composition as claimed in claim 4, wherein the amount of the antioxidant composition containing the phosphite antioxidant compound 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.

6. The antioxidant synthetic resin composition as claimed in claim 5, wherein the amount of the antioxidant composition containing 10 to 100 mass% of the phosphite antioxidant compound represented by the general formula (1) is 0.03 to 5 parts by mass, preferably 0.04 to 3 parts by mass, based on 100 parts by mass of the synthetic resin.

7. The antioxidant synthetic resin composition as claimed in claim 3, wherein the synthetic resin is a polyurethane resin, a polyester resin, a polyolefin resin, a block polymer containing polybutadiene block or polypentadiene block.