WO2019137197A1 - Coloured polypropylene fibre and preparation method therefor - Google Patents

Coloured polypropylene fibre and preparation method therefor Download PDF

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Publication number
WO2019137197A1
WO2019137197A1 PCT/CN2018/123330 CN2018123330W WO2019137197A1 WO 2019137197 A1 WO2019137197 A1 WO 2019137197A1 CN 2018123330 W CN2018123330 W CN 2018123330W WO 2019137197 A1 WO2019137197 A1 WO 2019137197A1
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WO
WIPO (PCT)
Prior art keywords
component
tert
bis
antioxidant
butyl
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PCT/CN2018/123330
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French (fr)
Chinese (zh)
Inventor
范志恒
陈彬彬
吉宫隆之
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东丽纤维研究所（中国）有限公司
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Application filed by 东丽纤维研究所（中国）有限公司 filed Critical 东丽纤维研究所（中国）有限公司
Priority to JP2020538668A priority Critical patent/JP7180675B2/en
Priority to CN201880083309.8A priority patent/CN111479958A/en
Publication of WO2019137197A1 publication Critical patent/WO2019137197A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the invention relates to a colored polypropylene fiber with good oxidation resistance and a preparation method thereof.
  • Polypropylene fibers are widely used due to their advantages of light weight and fast drying.
  • polypropylene undergoes oxidative decomposition to produce alkyl radicals, and this reaction proceeds continuously.
  • auto-oxidation cycle polypropylene itself oxidatively cleaves, and at the same time, the cleavage reaction is an exothermic reaction, and the polypropylene will melt, smoke or even burn under the action of self-heating.
  • patent CN02112743.3 discloses a transparent polyester composition in which phenolic and phosphonite or sulfuric acid antioxidants are added in order to improve the oxidation resistance of polypropylene.
  • colored polypropylene has poorer oxidation resistance, and colorants such as carbon black in colored polypropylene have an adsorption effect on the antioxidant, which affects the distribution of the antioxidant in the polypropylene and weakens the resistance.
  • the role of oxygen agents is important to add an antioxidant.
  • a colored polypropylene fiber comprising a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, wherein component a 800 to 15000 ppm of the colored polypropylene fiber, preferably 1000 to 8000 ppm of the colored polypropylene fiber; and when the component b is contained, the weight ratio of the component b to the component a is less than 0.80, preferably 0.20 or less and 0.80 or less; In the case of c, the component c accounts for 4,000 to 50,000 ppm, preferably 4,000 to 20,000 ppm of the colored polypropylene fiber.
  • the colored polypropylene fibers contain both component a, component b and component c.
  • the component a hindered phenol antioxidant-type antioxidant is preferably tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; ⁇ -(3,5-di Tert-butyl-4-hydroxyphenyl)propanoic acid stearyl alcohol; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl Benzene or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, At least one of 3H, 5H)-trione.
  • the component b phosphite antioxidant is preferably poly(dipropylene glycol) phenyl phosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate; three (2 , 4-di-tert-butylphenyl)phenylphosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenol)- 4,4'-biphenyldiphosphite or 3,9-bisoctadecyloxy-2,4,8,10-tetraoxa-3,9-diphosphorylcyclo[5.5]undecane At least one.
  • the component c hindered amine antioxidant-type antioxidant is preferably poly ⁇ [6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine- 2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene [[2,2,6,6-tetramethyl-4-piperidin] Pyridyl)imino] ⁇ ; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); N I , N II , N III , N IV -tetrakis(2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-triazine-6 -yl)-4,7-diazanonane-1,10-diamine; bis(1-undecethane-2,2,6,6-tetramethylpiperid
  • the invention also discloses a preparation method of colored polypropylene fiber, which comprises a polypropylene and a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidation
  • the mixture is uniformly mixed and extruded into granules to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added.
  • the weight ratio of the fraction b to the component a is less than 0.80; when the component c is added, the component c accounts for 4000 to 50000 ppm of the polypropylene mixture.
  • the colored polypropylene fiber of the invention has excellent oxidation resistance, low cracking heat generation and wide application.
  • polypropylene itself is unstable, easily oxidized, and the oxidation process is accompanied by heat generation, thus affecting the safety of articles using polypropylene fibers.
  • an antioxidant can improve the oxidation resistance of the polypropylene, for a colored polypropylene containing a colorant which is less resistant to oxidation, the effect of the antioxidant is affected by the adsorption of the colorant against the oxygen. Adding too much antioxidant will reduce the physical properties of the polypropylene product and cause the colored polypropylene product to be susceptible to yellowing.
  • the colored polypropylene fiber provided by the invention not only has excellent oxidation resistance, but also has physical properties such as strength, and is not prone to yellowing.
  • the colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, and component a occupies colored polypropylene fiber. 800 to 15000 ppm.
  • the weight ratio of component b to component a is less than 0.80; when the polypropylene fiber contains component c, component c accounts for 4000 to 50000 ppm of the colored polypropylene fiber.
  • alkyl radicals and peroxy radicals are formed, wherein the alkyl radicals are further oxidized to peroxy radicals.
  • the peroxidic free radicals are unstable, and a part of the peroxidic free radicals will further form hydroperoxides, which accelerate the oxidative decomposition of the polypropylene.
  • the above component a hindered phenolic antioxidant can capture peroxidic free radicals
  • component b phosphite antioxidant can capture hydroperoxide
  • component c hindered amine antioxidant can simultaneously capture peroxidic free radicals And alkyl radicals.
  • the content of the hindered phenolic antioxidant in the fiber must be above 800 ppm, otherwise the component a hindered phenolic antioxidant is mostly adsorbed by the colorant in the fiber. After that, it will be difficult to improve the oxidation resistance of the colored polypropylene fiber, and the colorant itself has poor oxidation resistance, which may cause further deterioration of the oxidation resistance of the colored polypropylene fiber.
  • the content of the hindered phenolic antioxidant in the colored polypropylene fiber is higher than 15000 ppm, not only the preparation cost of the colored polypropylene fiber is increased, but also the excess component a hindered phenolic antioxidant is in the air. Oxidation to form terpenoids results in yellowing of colored polypropylene fibers.
  • the component a hindered phenolic antioxidant in the colored polypropylene fiber of the present invention preferably has a content of from 1,000 to 8,000 ppm.
  • the component b phosphite antioxidant can effectively inhibit the oxidation of the component a hindered phenolic antioxidant in the air, thereby suppressing the yellowing of the polypropylene.
  • the weight ratio of component b to component a in the colored polypropylene fiber is less than 0.80.
  • the weight ratio of component b to component a is greater than or equal to 0.80, there is more component b phosphite antioxidant remaining in the colored polypropylene fiber relative to component a hindered phenolic antioxidant, Since there is no hydroperoxide available for capture, this component b phosphite antioxidant does not have an antioxidant effect, but will increase the preparation cost of the colored polypropylene fiber, while a large amount of component b Phosphite antioxidants reduce the strength of polypropylene fibers.
  • the weight ratio of component b to component a in the colored polypropylene fiber of the present invention is preferably 0.20 or less and 0.80 or less.
  • Component c is a hindered amine antioxidant that acts to capture alkyl radicals and peroxy radicals.
  • the content of the component c hindered amine antioxidant in the colored polypropylene fiber is less than 4000 ppm, the alkyl radical and the peroxy radical are not effectively captured, and the excess alkyl radical is further oxidized to the peroxidation free
  • the peroxide radical generates a large amount of hydroperoxide, which further accelerates the oxidation of the polypropylene and does not improve the oxidation resistance of the colored polypropylene fiber.
  • the content of the component c hindered amine antioxidant is more than 50,000 ppm, the strength of the colored polypropylene fiber is lowered, and the cost is also increased.
  • the content of the component c in the colored polypropylene fiber of the present invention is preferably from 4,000 to 20,000 ppm.
  • the colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, that is, there are three cases: One contains component a and component b, the second contains component a and component c, and the third contains component a, component b and component c. Among them, the third case is preferred, that is, the colored polypropylene fiber contains both a component a hindered phenol antioxidant, a component b phosphite antioxidant, and a component c hindered amine antioxidant.
  • the hindered phenolic antioxidant of the component a is not particularly limited and may be methyl ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; N,N'-1,6 - hexylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]; 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl Isocyanurate; N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]indole; 3-(3,5-di-tert-butyl-4 -hydroxy) octadecyl propionate; 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,6-di-tert-butyl-4-methylphenol; 4,4 '-Methylene bis(2,6-di-tert-butyl
  • the component b phosphite antioxidant is not particularly limited and may be dimethyl phosphite, bis(2,4-di-tert-butylphenyl)phenyl phosphite; three (1, 2,2,6,6-pentamethylpiperidinol phosphite; tris(nonylphenol) phosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol di Phosphate; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl bisphosphite; Nonylphenyl phosphite; diphenyl isooctyl phosphite; poly(dipropylene glycol) phenyl phosphite
  • the component c hindered amine antioxidant is not particularly limited and may be bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; 3-(2 , 2,6,6-tetramethylpiperidin-4-amino)propionic acid dodecyl ester; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzo Triazole; 2,4,6-trichloro-1,3,5-triazine; N-butyl-1-butylamine; N-butyl-2,2,6,6-tetramethyl-4- Piperidine; poly ⁇ [6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6, 6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene [(2,2,6,6-tetramethyl-4-piperidinyl)imino] ⁇ ;
  • poly ⁇ [6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-) is preferred.
  • the antioxidant of the present invention may also be used in combination with a hydroxylamine, and among them, a octadecylhydroxylamine may be mentioned.
  • the invention also discloses a preparation method of colored polypropylene fiber, which comprises a polypropylene and a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidation
  • the mixture is uniformly mixed and extruded into granules to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added.
  • the weight ratio of the fraction b to the component a is less than 0.80; when the component c is added, the component c accounts for 4000 to 50000 ppm of the polypropylene mixture.
  • the colored polypropylene fiber of the present invention may be a fiber obtained by blending a colorant masterbatch in a polypropylene chip and then spinning, or a fiber obtained by blending a polypropylene chip and a polyester, followed by spinning and dyeing.
  • the coloring agent may be a pigment or a dye.
  • the type of the pigment and the dye in the present invention is not particularly limited, and may be various pigments and dyes for the polymer, such as carbon black, titanium white powder, cadmium red, and ultrafine crystals. , phthalocyanine green, phthalocyanine blue, water solid red, zinc yellow, Hansa yellow, TERATOP BLUE NFB GR, TERATOP RED NFR, TERATOP YELLOW NFG, TERASIL BLACK WW-KSN, etc.
  • the content of the colorant in the polypropylene fiber is also not particularly limited, and can be adjusted according to the application or market demand within the known range of the prior art.
  • the manner and timing of introduction of the coloring agent are not particularly limited.
  • the coloring agent may be directly added, or the mother particle containing the coloring agent may be added; the timing of introduction may be when the polypropylene is blended with the antioxidant. Addition may also be carried out by mixing and remelting the spun after the polypropylene and the antioxidant are blended and extruded.
  • the colored polypropylene fiber of the invention has excellent anti-oxidation property, good physical property and not easy to yellowing due to mutual synergy between the different components of the antioxidant.
  • test methods involved in the present invention are as follows:
  • the colored polypropylene fibers were first prepared into a cylinder and pretreated in accordance with JIS L 0217 103. Then, it was tested and evaluated in accordance with the "Test method for acidification and heating of polypropylene fibers (acceleration method)" (Japan Chemical Fiber Association Law). When the test time reached 100 hours, it did not generate heat itself, that is, it was judged that the polypropylene fiber was qualified for oxidation resistance. Otherwise, it is judged as unqualified.
  • test speed is 200 mm/min and the distance between the two clamps is 200 mm.
  • the L value of the cartridge was measured by a Datacolor 650 spectrophotometer.
  • the sample was dissolved in a solvent and centrifuged to obtain a mixture containing an antioxidant.
  • the mixture was further measured by HPLC, and the type and content of the antioxidant were obtained by pattern analysis.
  • antioxidant 1010 tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester
  • antioxidant 330 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene
  • antioxidant 1024 N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
  • antioxidant 2246 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (abbreviation: antioxidant 2246);
  • antioxidant BHT 2,6-Di-tert-butyl-4-methylphenol
  • antioxidant PDP poly(dipropylene glycol) phenyl phosphite
  • Tris(1,2,2,6,6-pentamethylpiperidinol) phosphite (abbreviation: component b1);
  • antioxidant 633 bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite
  • Slicing polypropylene, component a (methyl ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), component c (polysuccinic acid (4-hydroxyethyl-2, 2,6,6-tetramethyl-1-piperidineethanol) and colorant masterbatch (black) were added to a mixer for kneading and extrusion granulation, wherein component a accounted for 6000 ppm of the polypropylene mixture.
  • Component c represents 10,000 ppm of the polypropylene mixture; finally, the pellets are melt spun to form colored polypropylene fibers.
  • component a N, N'-1,6-hexylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]
  • component b Bis(2,4-di-tert-butylphenyl)phenylphosphite
  • component a accounts for 10,000 ppm of the polypropylene mixture, component b and component a
  • the weight ratio was 0.10; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
  • the polypropylene was sliced, the component a(N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine) and the component b (three (1, 2, 2,6,6-pentamethylpiperidinol phosphite) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 6000 ppm of the polypropylene mixture, and the weight of component b and component a The ratio was 0.80; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
  • Polypropylene section component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]B Base]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c(bis(1,2,2,6,6-pentamethyl-4-piperidinyl)anthracene
  • component a accounts for 1100 ppm of the polypropylene mixture
  • component c accounts for 5000 ppm of the polypropylene mixture
  • the pellet and the colorant masterbatch black
  • Polypropylene section component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]B Base]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c(3-(2,2,6,6-tetramethylpiperidin-4-amino)propionic acid
  • the dodecyl ester) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 15000 ppm of the polypropylene mixture, component c accounts for 13,000 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (black) After mixing, melt-spun to form colored polypropylene fibers.
  • Slicing polypropylene, component a (2,2'-methylenebis(4-methyl-6-tert-butylphenol)), component b (bis(2,4,6-tri-tert-butylbenzene) Base) pentaerythritol diphosphite) and component c (2,4,6-trichloro-1,3,5-triazine) are added to a mixer for kneading and extrusion granulation, wherein component a occupies 7000ppm of the propylene mixture, the weight ratio of component b to component a is 0.50, component c is 5000ppm of the polypropylene mixture; finally, the pellet is mixed with the colorant masterbatch (black) and melt-spun to form colored poly Acrylic fiber.
  • component a (2,6-di-tert-butyl-4-methylphenol), component b (bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite) And component c (N-butyl-2,2,6,6-tetramethyl-4-piperidinamine) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for the polypropylene mixture 1300 ppm, the weight ratio of component b to component a was 0.75, and component c was 15000 ppm of the polypropylene mixture; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
  • component a (2,6-di-tert-butyl-4-methylphenol)
  • component b bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite
  • Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (double (2,2,6,6) -tetramethylpiperidinyl) sebacate) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 1200 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.60.
  • Component c constitutes 50,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
  • Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component c (bis(2,2,6,6-tetramethylpiperidinyl) sebacate) is added to the mixer for mixing and extrusion Granulation was carried out in which component a was 1200 ppm of the polypropylene mixture and component c was 50,000 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (red) and melt-spun to form colored polypropylene fibers.
  • Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (double (2,2,6,6) - Tetramethylpiperidinyl) sebacate) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 850 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.70.
  • Component c constitutes 50,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the colorant masterbatch (white) and melt-spun to form colored polypropylene fibers.
  • Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (bis(1-undecane-2) , 2,6,6-tetramethylpiperidin-4-yl)carbonate) is added to a mixer for mixing and extrusion granulation, wherein component a accounts for 4500 ppm of the polypropylene mixture, component b and components The weight ratio of a was 0.65, and the component c was 5200 ppm of the polypropylene mixture; finally, the pellets were mixed with the colorant master batch (black) and melt-spun to obtain colored polypropylene fibers.
  • component a (1,3,5-tris(4-tert-but
  • component a accounts for 100 ppm of the polypropylene mixture
  • component b was 0.10
  • component c was 80,000 ppm of the polypropylene mixture
  • the pellet was mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fiber.
  • the content of component c is too large, resulting in low strength of the polypropylene fiber.

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Abstract

A coloured polypropylene fibre, the fibre containing component a hindered phenolic antioxidant and component b phosphite ester antioxidant and/or component c hindered amine antioxidant, component a accounting for 800-15000 ppm of the coloured polypropylene fibre; the weight ratio of component b to component a is less than 0.80, and component c accounts for 4000-50000 ppm of the coloured polypropylene fibre. The coloured polypropylene fibre has excellent antioxidant properties, low pyrolysis and heat generation, and a wide range of application.

Description

一种有色聚丙烯纤维及其制备方法Colored polypropylene fiber and preparation method thereof 技术领域Technical field
本发明涉及一种抗氧化性好的有色聚丙烯纤维及其制备方法。The invention relates to a colored polypropylene fiber with good oxidation resistance and a preparation method thereof.
背景技术Background technique
聚丙烯纤维由于具有轻量、快干等优点受到广泛的利用。然而聚丙烯在光和热的作用下会进行氧化分解，产生烷基自由基，而且这种反应会连续不断的进行下去。通过这种被称作自动氧化循环的连锁反应，聚丙烯自身氧化裂解，同时该裂解反应为发热反应，在自身发热的作用下聚丙烯会发生熔融、发烟甚至烧毁。Polypropylene fibers are widely used due to their advantages of light weight and fast drying. However, under the action of light and heat, polypropylene undergoes oxidative decomposition to produce alkyl radicals, and this reaction proceeds continuously. Through this chain reaction called auto-oxidation cycle, polypropylene itself oxidatively cleaves, and at the same time, the cleavage reaction is an exothermic reaction, and the polypropylene will melt, smoke or even burn under the action of self-heating.
为了降低聚丙烯的氧化发热问题，现有技术中的主要措施是添加抗氧化剂。如专利CN02112743.3公开了一种可透明化聚丙烯组合物，为了提高聚丙烯的抗氧化性能在其中加入了酚类及亚膦酸酯类或硫酸类抗氧化剂。然而不同于透明聚丙烯，有色聚丙烯的抗氧化性更差，同时有色聚丙烯中的着色剂如炭黑等对抗氧剂有吸附作用，会影响抗氧剂在聚丙烯中的分布，削弱抗氧剂的作用。In order to reduce the problem of oxidative heating of polypropylene, the main measure in the prior art is to add an antioxidant. For example, patent CN02112743.3 discloses a transparent polyester composition in which phenolic and phosphonite or sulfuric acid antioxidants are added in order to improve the oxidation resistance of polypropylene. However, unlike transparent polypropylene, colored polypropylene has poorer oxidation resistance, and colorants such as carbon black in colored polypropylene have an adsorption effect on the antioxidant, which affects the distribution of the antioxidant in the polypropylene and weakens the resistance. The role of oxygen agents.
发明内容Summary of the invention
本发明的目的在于提供一种抗氧化性好的有色聚丙烯纤维。It is an object of the present invention to provide a colored polypropylene fiber which is excellent in oxidation resistance.
本发明的技术解决方法：Technical solution of the invention:
一种有色聚丙烯纤维，该聚丙烯纤维中含有组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂，其中组分a占有色聚丙烯纤维的800～15000ppm，优选占有色聚丙烯纤维的1000～8000ppm；含有组分b时，组分b与组分a的重量比小于0.80，优选大于等于0.20小于0.80；含有组分c时，组分c占有色聚丙烯纤维的4000～50000ppm，优选4000～20000ppm。A colored polypropylene fiber comprising a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, wherein component a 800 to 15000 ppm of the colored polypropylene fiber, preferably 1000 to 8000 ppm of the colored polypropylene fiber; and when the component b is contained, the weight ratio of the component b to the component a is less than 0.80, preferably 0.20 or less and 0.80 or less; In the case of c, the component c accounts for 4,000 to 50,000 ppm, preferably 4,000 to 20,000 ppm of the colored polypropylene fiber.
该有色聚丙烯纤维中优选同时含有组分a、组分b和组分c。It is preferred that the colored polypropylene fibers contain both component a, component b and component c.
所述组分a受阻酚类抗氧剂类抗氧剂优选四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯；β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯；1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯或1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮中的至少一种。The component a hindered phenol antioxidant-type antioxidant is preferably tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; β-(3,5-di Tert-butyl-4-hydroxyphenyl)propanoic acid stearyl alcohol; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl Benzene or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, At least one of 3H, 5H)-trione.
所述组分b亚磷酸酯类抗氧剂优选聚(二丙二醇)苯基亚磷酸酯；双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯；三(2,4-二叔丁基苯基)苯基亚磷酸酯；双(2,4,6-三叔丁基苯基)季戊 四醇二亚磷酸酯；四(2,4-二叔丁基酚)-4,4'-联苯二亚磷酸酯或3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷中的至少一种。The component b phosphite antioxidant is preferably poly(dipropylene glycol) phenyl phosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate; three (2 , 4-di-tert-butylphenyl)phenylphosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenol)- 4,4'-biphenyldiphosphite or 3,9-bisoctadecyloxy-2,4,8,10-tetraoxa-3,9-diphosphorylcyclo[5.5]undecane At least one.
所述组分c受阻胺类抗氧剂类抗氧剂优选聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}；聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯；N Ⅰ，N Ⅱ，N Ⅲ，N Ⅳ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺；双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯或1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3，1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]中的至少一种。 The component c hindered amine antioxidant-type antioxidant is preferably poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine- 2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene [[2,2,6,6-tetramethyl-4-piperidin] Pyridyl)imino]}; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); N I , N II , N III , N IV -tetrakis(2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino)-1,3,5-triazine-6 -yl)-4,7-diazanonane-1,10-diamine; bis(1-undecethane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate or 1 ,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2,2,6) ,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-double [N'-N" At least one of dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl).
本发明还公开了一种有色聚丙烯纤维的制备方法，将聚丙烯与组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂混合均匀并挤出造粒得到有色聚丙烯混合物，然后将有色聚丙烯混合物进行熔融纺丝得到有色聚丙烯纤维，其中组分a占聚丙烯混合物的800～15000ppm，添加组分b时，组分b与组分a的重量比小于0.80；添加组分c时，组分c占聚丙烯混合物的4000～50000ppm。The invention also discloses a preparation method of colored polypropylene fiber, which comprises a polypropylene and a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidation The mixture is uniformly mixed and extruded into granules to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added. The weight ratio of the fraction b to the component a is less than 0.80; when the component c is added, the component c accounts for 4000 to 50000 ppm of the polypropylene mixture.
本发明所述的有色聚丙烯纤维具有优异的抗氧化性能，裂解发热少，应用广泛。The colored polypropylene fiber of the invention has excellent oxidation resistance, low cracking heat generation and wide application.
具体实施方式Detailed ways
聚丙烯本身的结构不稳定，容易被氧化，并且氧化过程伴随有发热现象，因此会影响使用聚丙烯纤维的制品的安全性。虽然添加抗氧剂可以提高聚丙烯的抗氧化性能，但是对于抗氧化性更差的含有着色剂的有色聚丙烯而言，由于着色剂对抗氧剂的吸附，会影响抗氧化剂的效果。而添加过多的抗氧剂又会降低聚丙烯制品的物理性能，且会导致有色聚丙烯制品容易黄变。The structure of polypropylene itself is unstable, easily oxidized, and the oxidation process is accompanied by heat generation, thus affecting the safety of articles using polypropylene fibers. Although the addition of an antioxidant can improve the oxidation resistance of the polypropylene, for a colored polypropylene containing a colorant which is less resistant to oxidation, the effect of the antioxidant is affected by the adsorption of the colorant against the oxygen. Adding too much antioxidant will reduce the physical properties of the polypropylene product and cause the colored polypropylene product to be susceptible to yellowing.
本发明提供的有色聚丙烯纤维不仅具有优良的抗氧化性能，纤维的物理性能如强度也较好，且不容易发生黄变。The colored polypropylene fiber provided by the invention not only has excellent oxidation resistance, but also has physical properties such as strength, and is not prone to yellowing.
本发明的有色聚丙烯纤维中含有组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂，组分a占有色聚丙烯纤维的800～15000ppm。当聚丙烯纤维含有组分b时，组分b与组分a的重量比小于0.80；当聚丙烯纤维含有组分c时，组分c占有色聚丙烯纤维的4000～50000ppm。The colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, and component a occupies colored polypropylene fiber. 800 to 15000 ppm. When the polypropylene fiber contains component b, the weight ratio of component b to component a is less than 0.80; when the polypropylene fiber contains component c, component c accounts for 4000 to 50000 ppm of the colored polypropylene fiber.
在聚丙烯氧化分解的过程中会生成烷基自由基和过氧化自由基，其中烷基自由基会进一步氧化成过氧化自由基。而过氧化自由基不稳定，一部分过氧化自由基又会进一步生成氢过氧化物，加速聚丙烯的氧化分解。上述组分a受阻酚类抗氧剂可以捕捉过氧化自由基，组分b亚磷 酸酯类抗氧剂可以捕捉氢过氧化物，组分c受阻胺类抗氧剂可以同时捕捉过氧化自由基和烷基自由基。During the oxidative decomposition of polypropylene, alkyl radicals and peroxy radicals are formed, wherein the alkyl radicals are further oxidized to peroxy radicals. The peroxidic free radicals are unstable, and a part of the peroxidic free radicals will further form hydroperoxides, which accelerate the oxidative decomposition of the polypropylene. The above component a hindered phenolic antioxidant can capture peroxidic free radicals, component b phosphite antioxidant can capture hydroperoxide, and component c hindered amine antioxidant can simultaneously capture peroxidic free radicals And alkyl radicals.
为了获得具有一定抗氧化性的有色聚丙烯纤维，纤维中组分a受阻酚类抗氧剂的含量必须在800ppm以上，否则组分a受阻酚类抗氧剂大部分被纤维中的着色剂吸附后将难以提高有色聚丙烯纤维的抗氧化性能，同时着色剂本身的抗氧化性能也较差，会导致有色聚丙烯纤维抗氧化性能的进一步恶化。而当有色聚丙烯纤维中组分a受阻酚类抗氧剂含量高于15000ppm时，不仅会增加有色聚丙烯纤维的制备成本，同时过量的组分a受阻酚类抗氧剂在空气中会被氧化生成醌类化合物，导致有色聚丙烯纤维发生黄变。In order to obtain a colored polypropylene fiber with certain oxidation resistance, the content of the hindered phenolic antioxidant in the fiber must be above 800 ppm, otherwise the component a hindered phenolic antioxidant is mostly adsorbed by the colorant in the fiber. After that, it will be difficult to improve the oxidation resistance of the colored polypropylene fiber, and the colorant itself has poor oxidation resistance, which may cause further deterioration of the oxidation resistance of the colored polypropylene fiber. When the content of the hindered phenolic antioxidant in the colored polypropylene fiber is higher than 15000 ppm, not only the preparation cost of the colored polypropylene fiber is increased, but also the excess component a hindered phenolic antioxidant is in the air. Oxidation to form terpenoids results in yellowing of colored polypropylene fibers.
本发明的有色聚丙烯纤维中组分a受阻酚类抗氧剂含量优选为1000～8000ppm。The component a hindered phenolic antioxidant in the colored polypropylene fiber of the present invention preferably has a content of from 1,000 to 8,000 ppm.
组分b亚磷酸酯类抗氧剂除了具有上述捕捉氢过氧化物的作用外，还可以有效地抑制组分a受阻酚类抗氧剂在空气中的氧化，从而抑制聚丙烯的黄变。为了同时达到上述效果，有色聚丙烯纤维中组分b与组分a的重量比小于0.80。当组分b与组分a的重量比大于等于0.80时，相对于组分a受阻酚类抗氧剂会有较多的组分b亚磷酸酯类抗氧剂残留在有色聚丙烯纤维中，而由于已经没有可供捕捉的氢过氧化物，这部分组分b亚磷酸酯类抗氧剂起不到抗氧化的作用，反而会增加有色聚丙烯纤维的制备成本，同时大量的组分b亚磷酸酯类抗氧剂会使聚丙烯纤维的强度下降。在含有组分b亚磷酸酯类抗氧剂时，本发明的有色聚丙烯纤维中组分b与组分a的重量比优选大于等于0.20小于0.80。In addition to the above-mentioned function of capturing a hydroperoxide, the component b phosphite antioxidant can effectively inhibit the oxidation of the component a hindered phenolic antioxidant in the air, thereby suppressing the yellowing of the polypropylene. In order to achieve the above effects at the same time, the weight ratio of component b to component a in the colored polypropylene fiber is less than 0.80. When the weight ratio of component b to component a is greater than or equal to 0.80, there is more component b phosphite antioxidant remaining in the colored polypropylene fiber relative to component a hindered phenolic antioxidant, Since there is no hydroperoxide available for capture, this component b phosphite antioxidant does not have an antioxidant effect, but will increase the preparation cost of the colored polypropylene fiber, while a large amount of component b Phosphite antioxidants reduce the strength of polypropylene fibers. In the case of containing the component b phosphite antioxidant, the weight ratio of component b to component a in the colored polypropylene fiber of the present invention is preferably 0.20 or less and 0.80 or less.
组分c受阻胺类抗氧剂的作用为捕捉烷基自由基及过氧化自由基。当有色聚丙烯纤维中组分c受阻胺类抗氧剂的含量低于4000ppm时，不能有效地捕捉烷基自由基及过氧化自由基，过多的烷基自由基会进一步氧化成过氧化自由基，而过氧化自由基又会生成大量的氢过氧化物，进一步加速聚丙烯的氧化，无法提高有色聚丙烯纤维的抗氧化性能。而当组分c受阻胺类抗氧剂的含量高于50000ppm时，有色聚丙烯纤维的强度下降，同时成本也会增加。在含有组分c受阻胺类抗氧剂时，本发明的有色聚丙烯纤维中组分c的含量优选4000～20000ppm。Component c is a hindered amine antioxidant that acts to capture alkyl radicals and peroxy radicals. When the content of the component c hindered amine antioxidant in the colored polypropylene fiber is less than 4000 ppm, the alkyl radical and the peroxy radical are not effectively captured, and the excess alkyl radical is further oxidized to the peroxidation free The peroxide radical generates a large amount of hydroperoxide, which further accelerates the oxidation of the polypropylene and does not improve the oxidation resistance of the colored polypropylene fiber. When the content of the component c hindered amine antioxidant is more than 50,000 ppm, the strength of the colored polypropylene fiber is lowered, and the cost is also increased. In the case of containing the component c hindered amine type antioxidant, the content of the component c in the colored polypropylene fiber of the present invention is preferably from 4,000 to 20,000 ppm.
本发明所述有色聚丙烯纤维中含有组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂，也即存在三种情况：一是含有组分a和组分b，二是含有组分a和组分c，三是含有组分a、组分b和组分c。其中优选第三种情况，即有色聚丙烯纤维中同时含有组分a受阻酚类抗氧剂、组分b亚磷酸酯类抗氧剂和组分c受阻胺类抗氧剂。The colored polypropylene fiber of the present invention contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, that is, there are three cases: One contains component a and component b, the second contains component a and component c, and the third contains component a, component b and component c. Among them, the third case is preferred, that is, the colored polypropylene fiber contains both a component a hindered phenol antioxidant, a component b phosphite antioxidant, and a component c hindered amine antioxidant.
对所述组分a受阻酚类抗氧剂没有特别的限定，可以是β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯；N,N'-1,6-亚己基-双[3-(3,5-二叔丁基-4–羟基苯基)丙酰胺]；1,3,5-三-(3,5-二环己基-4-羟基苄基)异氰尿酸酯；N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼；3-(3,5-二叔 丁基-4-羟基)丙酸十八酯；2,2'-亚甲基双(4-甲基-6-叔丁基酚)；2,6-二叔丁基-4-甲基苯酚；4,4'-甲撑双(2,6-二叔丁基苯酚)；2,2-硫代双[3-(3,5-二叔丁基-4-羟基苯基)丙酸乙酯]；四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯；β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯；1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯或1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮；3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷中的至少一种，其中优选四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯；β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯；1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯或1,3,5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮中的至少一种。The hindered phenolic antioxidant of the component a is not particularly limited and may be methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; N,N'-1,6 - hexylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]; 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl Isocyanurate; N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]indole; 3-(3,5-di-tert-butyl-4 -hydroxy) octadecyl propionate; 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,6-di-tert-butyl-4-methylphenol; 4,4 '-Methylene bis(2,6-di-tert-butylphenol); 2,2-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid ethyl ester]; [β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester; β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl alcohol ester ; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or 1,3,5-tris(4-tert-butyl- 3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 3,9-bis[1,1 - dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5] At least one of undecane, wherein four [β-(3,5-di-tert-butyl) is preferred -4-hydroxyphenyl)propionic acid] pentaerythritol ester; octadecyl alcohol β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate; 1,3,5-trimethyl-2 ,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl At least one of -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
对所述组分b亚磷酸酯类抗氧剂没有特别的限定，可以是二甲基亚磷酸酯、双(2,4-二叔丁基苯基)苯基亚磷酸酯；三(1,2,2,6,6-五甲基哌啶醇)亚磷酸酯；三(壬基酚)亚磷酸酯；双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯；双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯；四(2,4-二叔丁基酚)-4,4'-联苯二亚磷酸酯；二癸基苯基亚磷酸酯；二苯基异辛基亚磷酸酯；聚(二丙二醇)苯基亚磷酸酯；三(2,4-二叔丁基苯基)亚磷酸酯；3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷；三苄基亚磷酸酯或亚磷酸三(2-乙基己基)酯中的至少一种，其中优选聚(二丙二醇)苯基亚磷酸酯；双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯；三(2,4-二叔丁基苯基)亚磷酸酯；双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯；四(2,4-二叔丁基酚)-4,4'-联苯二亚磷酸酯或3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷中的至少一种。The component b phosphite antioxidant is not particularly limited and may be dimethyl phosphite, bis(2,4-di-tert-butylphenyl)phenyl phosphite; three (1, 2,2,6,6-pentamethylpiperidinol phosphite; tris(nonylphenol) phosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol di Phosphate; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl bisphosphite; Nonylphenyl phosphite; diphenyl isooctyl phosphite; poly(dipropylene glycol) phenyl phosphite; tris(2,4-di-tert-butylphenyl) phosphite; 3,9- Dioctadecanoyloxy-2,4,8,10-tetraoxy-3,9-diphosphorylcyclo[5.5]undecane; tribenzylphosphite or tris(2-ethylhexyl)phosphite At least one of esters, preferably poly(dipropylene glycol) phenyl phosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate; three (2,4-di) Tert-butylphenyl)phosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenol)-4,4'-linked Benzoyl phosphite or 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3 At least one of 9-diphosphorylcyclo[5.5]undecane.
对所述组分c受阻胺类抗氧剂没有特别的限定，可以是双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯；3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸十二酯；2-(3',5'-二叔丁基-2'-羟基苯基)-5-氯苯并三唑；2,4,6-三氯-1,3,5-三嗪；N-丁基-1-丁胺；N-丁基-2,2,6,6-四甲基-4-哌啶胺；聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}；聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯；N Ⅰ，N Ⅱ，N Ⅲ，N Ⅳ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺；双(2,2,6,6-四甲基哌啶基)癸二酸酯或1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]；双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯或1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌 啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]中的至少一种。其中优选聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}；聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯；NⅠ，NⅡ，NⅢ，NⅣ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺；1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]或双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯中的至少一种。其中，组分c更优选1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]，与组分a、组分b并用的情况下，纺丝温度在260℃以下。 The component c hindered amine antioxidant is not particularly limited and may be bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; 3-(2 , 2,6,6-tetramethylpiperidin-4-amino)propionic acid dodecyl ester; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzo Triazole; 2,4,6-trichloro-1,3,5-triazine; N-butyl-1-butylamine; N-butyl-2,2,6,6-tetramethyl-4- Piperidine; poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6, 6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene [(2,2,6,6-tetramethyl-4-piperidinyl)imino]}; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol) ester; N I , N II , N III , N IV - tetra (2,4-di((N- 1,2,2,6,6-pentamethyl-4-piperidinyl)-n-butylamino)-1,3,5-triazin-6-yl)-4,7-diazonium -1,10-diamine; bis(2,2,6,6-tetramethylpiperidinyl) sebacate or 1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-1,3,5-trimazine-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]; double (1-ten Monoal-2,2,6,6-tetramethylpiperidin-4-yl)carbonate or 1,3,5-triazine-2,4,6-triamine-NN"'-[1,2 - ethanediyl bis[[[,4-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-1,3,5-trimazine -2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-penta At least one of keto-4-piperidinyl)]. Among them, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-) is preferred. Tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}; polysuccinic acid (4 -hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol); NI, NII, NIII, NIV-tetra (2, 4-di((N-1, 2, 2, 6,6-pentamethyl-4-piperidinyl)-n-butylamino)-1,3,5-triazin-6-yl)-4,7-diazonium-1,10-di Amine; 1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2, 2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-double [N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)] or bis(1-undecane-2,2, At least one of 6,6-tetramethylpiperidin-4-yl)carbonate, wherein component c is more preferably 1,3,5-triazine-2,4,6-triamine-NN"' -[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-1,3, 5-trimoxazin-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis (1,2,2,6 ,6-pentamethyl-4-piperidinyl)], in combination with component a, component b, The spinning temperature is below 260 °C.
本发明所述的抗氧化剂，也可以与羟基胺类并用，其中可列举的有二十八烷基羟胺。The antioxidant of the present invention may also be used in combination with a hydroxylamine, and among them, a octadecylhydroxylamine may be mentioned.
本发明还公开了一种有色聚丙烯纤维的制备方法，将聚丙烯与组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂混合均匀并挤出造粒得到有色聚丙烯混合物，然后将有色聚丙烯混合物进行熔融纺丝得到有色聚丙烯纤维，其中组分a占聚丙烯混合物的800～15000ppm，添加组分b时，组分b与组分a的重量比小于0.80；添加组分c时，组分c占聚丙烯混合物的4000～50000ppm。The invention also discloses a preparation method of colored polypropylene fiber, which comprises a polypropylene and a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidation The mixture is uniformly mixed and extruded into granules to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain colored polypropylene fibers, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and component b is added. The weight ratio of the fraction b to the component a is less than 0.80; when the component c is added, the component c accounts for 4000 to 50000 ppm of the polypropylene mixture.
本发明的有色聚丙烯纤维可以是在聚丙烯切片中共混着色剂母粒然后进行纺丝得到的纤维，也可以是聚丙烯切片和聚酯共混后再进行纺丝、染色得到的纤维。The colored polypropylene fiber of the present invention may be a fiber obtained by blending a colorant masterbatch in a polypropylene chip and then spinning, or a fiber obtained by blending a polypropylene chip and a polyester, followed by spinning and dyeing.
所述着色剂可以是颜料，也可以是染料，本发明对颜料和染料的种类不做特别的限定，可以是聚合物用各种颜料和染料，如炭黑、钛白粉、镉红、群菁、酞菁绿、酞菁蓝、水固红、锌黄、汉沙黄、TERATOP BLUE NFB GR、TERATOP RED NFR、TERATOP YELLOW NFG、TERASIL BLACK WW-KSN等。对聚丙烯纤维中着色剂的含量也不做特别的限定，在现有技术的公知范围内，根据应用场合或市场需求可以做出相应的调整。另外，对着色剂的引入方式和时机也不作特别的限定，如引入方式可以是直接添加着色剂，也可以添加含有着色剂的母粒；引入时机可以是在聚丙烯与抗氧化剂共混时一起加入，也可以在聚丙烯与抗氧化剂共混挤出之后加入混合再熔融纺丝。The coloring agent may be a pigment or a dye. The type of the pigment and the dye in the present invention is not particularly limited, and may be various pigments and dyes for the polymer, such as carbon black, titanium white powder, cadmium red, and ultrafine crystals. , phthalocyanine green, phthalocyanine blue, water solid red, zinc yellow, Hansa yellow, TERATOP BLUE NFB GR, TERATOP RED NFR, TERATOP YELLOW NFG, TERASIL BLACK WW-KSN, etc. The content of the colorant in the polypropylene fiber is also not particularly limited, and can be adjusted according to the application or market demand within the known range of the prior art. In addition, the manner and timing of introduction of the coloring agent are not particularly limited. For example, the coloring agent may be directly added, or the mother particle containing the coloring agent may be added; the timing of introduction may be when the polypropylene is blended with the antioxidant. Addition may also be carried out by mixing and remelting the spun after the polypropylene and the antioxidant are blended and extruded.
本发明所述的有色聚丙烯纤维，由于其中不同组分抗氧剂之间的相互协同作用，使其具有优异的抗氧化性能，物性好，不易黄变。The colored polypropylene fiber of the invention has excellent anti-oxidation property, good physical property and not easy to yellowing due to mutual synergy between the different components of the antioxidant.
本发明所涉及的测试方法如下：The test methods involved in the present invention are as follows:
(1)耐氧化发热测试(1) oxidation resistance test
首先将有色聚丙烯纤维制备成筒编物，并按照JIS L 0217 103法进行前处理。然后依据《聚丙烯纤维的酸化发热试验方法(加速法)》(日本化学纤维协会法)进行测试并评价。当试验时间到达100小时时，自身并未发热，即判断该聚丙烯纤维的耐氧化发热性合格。否则，判定为不合格。The colored polypropylene fibers were first prepared into a cylinder and pretreated in accordance with JIS L 0217 103. Then, it was tested and evaluated in accordance with the "Test method for acidification and heating of polypropylene fibers (acceleration method)" (Japan Chemical Fiber Association Law). When the test time reached 100 hours, it did not generate heat itself, that is, it was judged that the polypropylene fiber was qualified for oxidation resistance. Otherwise, it is judged as unqualified.
(2)纤维的黄变值测试(2) Yellowing value test of fiber
在密闭容器中放入NOx气体发生剂(85％磷酸及2％的亚硝酸水溶液)，然后将试样及蓝色标准染色布置于容器内，当蓝色标准染色布颜色褪为标准灰度板3号时，更换蓝色标准染色布，当颜色再次达到标准灰度板3号时，将试样取出，并清洗2次，晾干。通过Datacolor 650分光光度仪对黄变值进行测定。Put a NOx gas generating agent (85% phosphoric acid and 2% aqueous nitrous acid solution) in a closed container, and then arrange the sample and blue standard dyeing in the container. When the color of the blue standard dyeing cloth fades to the standard gray plate On the 3rd, replace the blue standard dyeing cloth. When the color reaches the standard gray board No. 3 again, take out the sample, wash it twice, and dry it. The yellowing value was measured by a Datacolor 650 spectrophotometer.
(3)纤维的强度测试(3) Fiber strength test
通过强伸度测试仪进行测试。测试速度为200mm/min，两夹具之间的距离是200mm。Tested by a tensile tester. The test speed is 200 mm/min and the distance between the two clamps is 200 mm.
(4)纤维的抗氧化发热性(简易法/wt％)(4) Antioxidant and heat-generating properties of fibers (simple method / wt%)
取纤维样品，称取重量为W1，用差示扫描量热仪，在气体氛围为压空、气体流量为60±0.05ml条件下，从25℃开始以30℃/min的速度升温至160℃，保持22小时，通过分析得出重量减少率，重量减少率在10wt％以下的话，科肯法判断为合格。重量减少率越低，表明抗氧化性越好。Take the fiber sample, weigh the weight W1, and use a differential scanning calorimeter to raise the temperature to 30 °C/min from 30 °C to 160 °C under the condition of gas atmosphere pressure and gas flow rate of 60±0.05ml. After maintaining for 22 hours, the weight reduction rate was obtained by analysis, and if the weight reduction rate was 10% by weight or less, the Cocken method was judged to be acceptable. The lower the weight reduction rate, the better the oxidation resistance.
(5)筒编物L值(5) barrel braided L value
通过Datacolor 650分光光度仪对筒编物进行L值测定。The L value of the cartridge was measured by a Datacolor 650 spectrophotometer.
(6)抗氧化剂种类及含量的测试(6) Testing of the types and contents of antioxidants
将样品通过溶媒进行溶解后进行离心分离，得到含有抗氧化剂的混合物。再将该混合物通过HPLC进行测定，通过图谱分析得出抗氧化剂种类以及含量。The sample was dissolved in a solvent and centrifuged to obtain a mixture containing an antioxidant. The mixture was further measured by HPLC, and the type and content of the antioxidant were obtained by pattern analysis.
本发明实施例中涉及的抗氧剂的的简写如下。Abbreviations of the antioxidants involved in the embodiments of the present invention are as follows.
组分a：Component a:
(1)1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮(简写：抗氧剂1790)；(1) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione (abbreviation: antioxidant 1790);
(2)四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)(简写：抗氧剂1010)；(2) tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester) (abbreviation: antioxidant 1010);
(3)1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯(简写：抗氧剂330)；(3) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (abbreviation: antioxidant 330);
(4)β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯(简写：组分a1)；(4) Methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (abbreviation: component a1);
(5)N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼(简写：抗氧剂1024)；(5) N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (abbreviation: antioxidant 1024);
(6)3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷(简写：AO80)；(6) 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl]-2,4 , 8,10-tetraoxaspiro[5.5]undecane (abbreviation: AO80);
(7)2,2'-亚甲基双(4-甲基-6-叔丁基酚)(简写：抗氧剂2246)；(7) 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (abbreviation: antioxidant 2246);
(8)2,6-二叔丁基-4-甲基苯酚(简写：抗氧剂BHT)。(8) 2,6-Di-tert-butyl-4-methylphenol (abbreviation: antioxidant BHT).
(9)N,N'-1,6-亚己基-双[3-(3,5-二叔丁基-4–羟基苯基)丙酰胺](简写：抗氧剂1098)。(9) N,N'-1,6-hexylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (abbreviation: antioxidant 1098).
组分b：Component b:
(1)聚(二丙二醇)苯基亚磷酸酯(简写：抗氧剂PDP)；(1) poly(dipropylene glycol) phenyl phosphite (abbreviation: antioxidant PDP);
(2)3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷(简写：抗氧剂619)；(2) 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3,9-diphosphorylcyclo[5.5]undecane (abbreviation: antioxidant 619);
(3)三(2,4-二叔丁基苯基)亚磷酸酯(简写：抗氧剂168)；(3) Tris(2,4-di-tert-butylphenyl) phosphite (abbreviation: antioxidant 168);
(4)三(1,2,2,6,6-五甲基哌啶醇)亚磷酸酯(简写：组分b1)；(4) Tris(1,2,2,6,6-pentamethylpiperidinol) phosphite (abbreviation: component b1);
(5)双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯(简写：抗氧剂633)；(5) bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite (abbreviation: antioxidant 633);
(6)双(2,4-二叔丁基苯基)苯基亚磷酸酯(简写：组分b2)。(6) Bis(2,4-di-tert-butylphenyl)phenylphosphite (abbreviation: component b2).
组分c：Component c:
(1)聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}(简写：HS944)；(1) Poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6 -tetramethyl-piperidinyl)imino]-1,6-hexamethylene [(2,2,6,6-tetramethyl-4-piperidinyl)imino]} (abbreviation: HS944);
(2)N Ⅰ，N Ⅱ，N Ⅲ，N Ⅳ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺(简写：组分c1)； (2) N I , N II , N III , N IV - tetra (2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidinyl)-n-butyl) -amino)-1,3,5-triazin-6-yl)-4,7-diazanonane-1,10-diamine (abbreviation: component c1);
(3)聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯(简写：UV622)；(3) polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidineethanol) ester (abbreviation: UV622);
(4)双(2,2,6,6-四甲基哌啶基)癸二酸酯(简写：TINUVIN770)；(4) bis(2,2,6,6-tetramethylpiperidinyl) sebacate (abbreviation: TINUVIN770);
(5)3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸十二酯(简写：组分c2)；(5) 3-(2,2,6,6-tetramethylpiperidin-4-amino)propionic acid lauryl ester (abbreviation: component c2);
(6)2,4,6-三氯-1,3,5-三嗪(简写：组分c3)；(6) 2,4,6-trichloro-1,3,5-triazine (abbreviation: component c3);
(7)N-丁基-2,2,6,6-四甲基-4-哌啶胺(简写：组分c4)；(7) N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (abbreviation: component c4);
(8)1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N'，N”-双(1,2,2,6,6-五甲基-4-哌啶基)](简写：HALS119)；(8) 1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl bis[[[4,6-bis[butyl(1,2) ,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-double [N '-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)] (abbreviation: HALS119);
(9)双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(简写：UV-292)；(9) bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (abbreviation: UV-292);
(10)双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯(简写：LA-81)。(10) Bis(1-undecethane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (abbreviation: LA-81).
实施例1Example 1
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪 -2,4,6-(1H,3H,5H)-三酮)、组分b(聚(二丙二醇)苯基亚磷酸酯)、组分c(聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6,-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]})和着色剂母粒(黑色)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的3000ppm，组分b与组分a的重量比为0.60，组分c占聚丙烯混合物的13000ppm；最后将粒料经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite), component c (poly{[6-[(1,1,3,3-) Tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6- Hexamethylene [(2,2,6,6-tetramethyl-4-piperidinyl)imino]}) and colorant masterbatch (black) are added to a mixer for kneading and extrusion granulation, wherein Component a was 3000 ppm of the polypropylene mixture, the weight ratio of component b to component a was 0.60, and component c was 13,000 ppm of the polypropylene mixture; finally, the pellets were melt spun into colored polypropylene fibers.
实施例2Example 2
将聚丙烯切片、组分a(四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)、组分b(3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷)和组分c(N Ⅰ，N Ⅱ，N Ⅲ，N Ⅳ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺)和着色剂母粒(黑色)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的15000ppm，组分b与组分a的重量比为0.20，组分c占聚丙烯混合物的8000ppm；最后将粒料经熔融纺丝制成有色聚丙烯纤维。 Section of polypropylene, component a (tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate]pentaerythritol ester), component b (3,9-bisoctadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphorylcyclo[5.5]undecane) and component c(N I , N II , N III , N IV -tetra (2,4- Bis((N-1,2,2,6,6-pentamethyl-4-piperidinyl)-n-butylamino)-1,3,5-triazin-6-yl)-4,7 - Diazononane-1,10-diamine) and colorant masterbatch (black) are added to the mixer for mixing and extrusion granulation, wherein component a accounts for 15000 ppm of the polypropylene mixture, component b and group The weight ratio of the fraction a was 0.20, and the component c was 8000 ppm of the polypropylene mixture; finally, the pellets were melt spun into a colored polypropylene fiber.
实施例3Example 3
将聚丙烯切片、组分a(1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和着色剂母粒(黑色)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1100ppm，组分b与组分a的重量比为0.75；最后将粒料经熔融纺丝制成有色聚丙烯纤维。Slice polypropylene, component a (1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), component b (three (2,4-di-tert-butylphenyl)phosphite) and colorant masterbatch (black) were added to a mixer for kneading and extrusion granulation, wherein component a accounted for 1100 ppm of the polypropylene mixture, component The weight ratio of b to component a was 0.75; finally, the pellets were melt spun into colored polypropylene fibers.
实施例4Example 4
将聚丙烯切片、组分a(β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯)、组分c(聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯)和着色剂母粒(黑色)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的6000ppm，组分c占聚丙烯混合物的10000ppm；最后将粒料经熔融纺丝制成有色聚丙烯纤维。Slicing polypropylene, component a (methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), component c (polysuccinic acid (4-hydroxyethyl-2, 2,6,6-tetramethyl-1-piperidineethanol) and colorant masterbatch (black) were added to a mixer for kneading and extrusion granulation, wherein component a accounted for 6000 ppm of the polypropylene mixture. Component c represents 10,000 ppm of the polypropylene mixture; finally, the pellets are melt spun to form colored polypropylene fibers.
实施例5Example 5
将聚丙烯切片、组分a(N,N'-1,6-亚己基-双[3-(3,5-二叔丁基-4–羟基苯基)丙酰胺])和组分b(双(2,4-二叔丁基苯基)苯基亚磷酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的10000ppm，组分b与组分a的重量比为0.10；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Polypropylene section, component a (N, N'-1,6-hexylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]) and component b ( Bis(2,4-di-tert-butylphenyl)phenylphosphite) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 10,000 ppm of the polypropylene mixture, component b and component a The weight ratio was 0.10; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
实施例6Example 6
将聚丙烯切片、组分a(N，N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼)和组分b(三(1,2,2,6,6-五甲基哌啶醇)亚磷酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯 混合物的6000ppm，组分b与组分a的重量比为0.80；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。The polypropylene was sliced, the component a(N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine) and the component b (three (1, 2, 2,6,6-pentamethylpiperidinol phosphite) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 6000 ppm of the polypropylene mixture, and the weight of component b and component a The ratio was 0.80; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
实施例7Example 7
将聚丙烯切片、组分a(3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷)和组分c(双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1100ppm，组分c占聚丙烯混合物的5000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Polypropylene section, component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]B Base]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c(bis(1,2,2,6,6-pentamethyl-4-piperidinyl)anthracene The diester) is added to the mixer for mixing and extrusion granulation, wherein component a accounts for 1100 ppm of the polypropylene mixture, component c accounts for 5000 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (black) After mixing, melt-spun to form colored polypropylene fibers.
实施例8Example 8
将聚丙烯切片、组分a(3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷)和组分c(3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸十二酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的15000ppm，组分c占聚丙烯混合物的13000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Polypropylene section, component a (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]B Base]-2,4,8,10-tetraoxaspiro[5.5]undecane) and component c(3-(2,2,6,6-tetramethylpiperidin-4-amino)propionic acid The dodecyl ester) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 15000 ppm of the polypropylene mixture, component c accounts for 13,000 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (black) After mixing, melt-spun to form colored polypropylene fibers.
实施例9Example 9
将聚丙烯切片、组分a(2,2'-亚甲基双(4-甲基-6-叔丁基酚))、组分b(双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯)和组分c(2,4,6-三氯-1,3,5-三嗪)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的7000ppm，组分b与组分a的重量比为0.50，组分c占聚丙烯混合物的5000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Slicing polypropylene, component a (2,2'-methylenebis(4-methyl-6-tert-butylphenol)), component b (bis(2,4,6-tri-tert-butylbenzene) Base) pentaerythritol diphosphite) and component c (2,4,6-trichloro-1,3,5-triazine) are added to a mixer for kneading and extrusion granulation, wherein component a occupies 7000ppm of the propylene mixture, the weight ratio of component b to component a is 0.50, component c is 5000ppm of the polypropylene mixture; finally, the pellet is mixed with the colorant masterbatch (black) and melt-spun to form colored poly Acrylic fiber.
实施例10Example 10
将聚丙烯切片、组分a(2,6-二叔丁基-4-甲基苯酚)、组分b(双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯)和组分c(N-丁基-2,2,6,6-四甲基-4-哌啶胺)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1300ppm，组分b与组分a的重量比为0.75，组分c占聚丙烯混合物的15000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Slicing polypropylene, component a (2,6-di-tert-butyl-4-methylphenol), component b (bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite) And component c (N-butyl-2,2,6,6-tetramethyl-4-piperidinamine) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for the polypropylene mixture 1300 ppm, the weight ratio of component b to component a was 0.75, and component c was 15000 ppm of the polypropylene mixture; finally, the pellets were mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
实施例11Example 11
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(双(2,2,6,6-四甲基哌啶基)癸二酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的 1200ppm，组分b与组分a的重量比为0.60，组分c占聚丙烯混合物的50000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (double (2,2,6,6) -tetramethylpiperidinyl) sebacate) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 1200 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.60. Component c constitutes 50,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fibers.
实施例12Example 12
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1200ppm，组分b与组分a的重量比为0.75，组分c占聚丙烯混合物的8000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (1,3,5-triazine- 2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4) -piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N', N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 1200 ppm of the polypropylene mixture. The weight ratio of component b to component a was 0.75, and component c was 8000 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fiber.
实施例13Example 13
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3，1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的4000ppm，组分b与组分a的重量比为0.60，组分c占聚丙烯混合物的5200ppm；最后将粒料与着色剂母粒(蓝色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (1,3,5-triazine- 2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4) -piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N', N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 4000 ppm of the polypropylene mixture The weight ratio of component b to component a was 0.60, and component c was 5200 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (blue) and melt-spun to form colored polypropylene fiber.
实施例14Example 14
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的4500ppm，组分b与组分a的重量比为0.50，组分c占聚丙烯混合物的5200ppm；最后将粒料与着色剂母粒(蓝色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (1,3,5-triazine- 2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4) -piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N', N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]) was added to a mixer for kneading and extrusion granulation, wherein component a accounted for 4500 ppm of the polypropylene mixture The weight ratio of component b to component a was 0.50, and component c was 5200 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (blue) and melt-spun to form colored polypropylene fiber.
实施例15Example 15
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双 [N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的7000ppm，组分c占聚丙烯混合物的5200ppm；最后将粒料与着色剂母粒(红色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione), component c(1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl Bis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl] Imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl)]) is added to the mixer for mixing and extrusion granulation, wherein component a accounts for 7000 ppm of the polypropylene mixture, component c accounts for 5200 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (red) After mixing, melt-spun to form colored polypropylene fibers.
实施例16Example 16
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的10000ppm，组分b与组分a的重量比为0.10；最后将粒料与着色剂母粒(红色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) is added to a mixer for kneading and extrusion granulation, wherein Component a represents 10,000 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.10. Finally, the pellets are mixed with the colorant masterbatch (red) and melt-spun to form colored polypropylene fibers.
实施例17Example 17
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的4000ppm，组分c占聚丙烯混合物的4000ppm；最后将粒料与着色剂母粒(黄色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione), component c(1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl Bis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl] Imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl)]) is added to the mixer for mixing and extrusion granulation, wherein component a accounts for 4000 ppm of the polypropylene mixture, component c accounts for 4000 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (yellow) After mixing, melt-spun to form colored polypropylene fibers.
实施例18Example 18
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1000ppm，组分c占聚丙烯混合物的50000ppm；最后将粒料与着色剂母粒(蓝色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione), component c(1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl Bis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl] Imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl)]) is added to the mixer for mixing and extrusion granulation, wherein component a accounts for 1000 ppm of the polypropylene mixture, component c accounts for 50,000 ppm of the polypropylene mixture; finally, the pellet and the colorant masterbatch (blue) Color) After mixing, melt-spun to form colored polypropylene fibers.
实施例19Example 19
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分c(双(2,2,6,6-四甲基哌啶基)癸二酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1200ppm，组分c占聚丙烯混合物的50000ppm；最后将粒料与着色剂母粒(红色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component c (bis(2,2,6,6-tetramethylpiperidinyl) sebacate) is added to the mixer for mixing and extrusion Granulation was carried out in which component a was 1200 ppm of the polypropylene mixture and component c was 50,000 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (red) and melt-spun to form colored polypropylene fibers.
实施例20Example 20
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(双(2,2,6,6- 四甲基哌啶基)癸二酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的850ppm，组分b与组分a的重量比为0.70，组分c占聚丙烯混合物的50000ppm；最后将粒料与着色剂母粒(白色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (double (2,2,6,6) - Tetramethylpiperidinyl) sebacate) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 850 ppm of the polypropylene mixture, and the weight ratio of component b to component a is 0.70. Component c constitutes 50,000 ppm of the polypropylene mixture; finally, the pellets are mixed with the colorant masterbatch (white) and melt-spun to form colored polypropylene fibers.
实施例21Example 21
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的4500ppm，组分b与组分a的重量比为0.65，组分c占聚丙烯混合物的5200ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (bis(1-undecane-2) , 2,6,6-tetramethylpiperidin-4-yl)carbonate) is added to a mixer for mixing and extrusion granulation, wherein component a accounts for 4500 ppm of the polypropylene mixture, component b and components The weight ratio of a was 0.65, and the component c was 5200 ppm of the polypropylene mixture; finally, the pellets were mixed with the colorant master batch (black) and melt-spun to obtain colored polypropylene fibers.
比较例1Comparative example 1
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(聚(二丙二醇)苯基亚磷酸酯)、组分c(聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]})和着色剂母粒(黑色)加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的3000ppm，组分b与组分a的重量比为2.00，组分c占聚丙烯混合物的50000ppm；最后将粒料经熔融纺丝制成有色聚丙烯纤维。组分b与组分a的重量比过大，过量的组分b导致聚丙烯纤维的强度低。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite), component c (poly{[6-[(1,1,3,3-) Tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexyl Bis[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}) and colorant masterbatch (black) are added to the mixer for mixing and extrusion granulation, wherein the group The fraction a is 3000 ppm of the polypropylene mixture, the weight ratio of component b to component a is 2.00, and the component c is 50,000 ppm of the polypropylene mixture; finally, the pellets are melt-spun to form colored polypropylene fibers. The weight ratio of component b to component a is too large, and excess component b results in a low strength of the polypropylene fiber.
比较例2Comparative example 2
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(聚(二丙二醇)苯基亚磷酸酯)和组分c(聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]})加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的100ppm，组分b与组分a的重量比为0.70，组分c占聚丙烯混合物的5000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。组分a的含量太少，导致聚丙烯纤维的抗氧化性能差。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite) and component c (poly{[6-[(1,1,3,3-) Tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexyl Bis[[2,2,6,6-tetramethyl-4-piperidinyl)imino]}) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 100 ppm of the polypropylene mixture The weight ratio of component b to component a was 0.70, and component c was 5000 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fiber. The content of component a is too small, resulting in poor oxidation resistance of the polypropylene fibers.
比较例3Comparative example 3
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(聚(二丙二醇)苯基亚磷酸酯)和组分c(聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]})加入混炼机进行混炼并挤出造粒，其中组分a占聚丙 烯混合物的25000ppm，组分b与组分a的重量比为0.10，组分c占聚丙烯混合物的80000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。组分c的含量太多，导致聚丙烯纤维的强度低。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (poly(dipropylene glycol)phenylphosphite) and component c (poly{[6-[(1,1,3,3-) Tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexyl Bis[[2,2,6,6-tetramethyl-4-piperidinyl)imino]}) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 25,000 ppm of the polypropylene mixture. The weight ratio of component b to component a was 0.10, and component c was 80,000 ppm of the polypropylene mixture; finally, the pellet was mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fiber. The content of component c is too large, resulting in low strength of the polypropylene fiber.
比较例4Comparative example 4
将聚丙烯切片、组分a(1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮)、组分b(三(2,4-二叔丁基苯基)亚磷酸酯)和组分c(1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)])加入混炼机进行混炼并挤出造粒，其中组分a占聚丙烯混合物的1000ppm，组分b与组分a的重量比为0.75，组分c占聚丙烯混合物的3000ppm；最后将粒料与着色剂母粒(黑色)混合后经熔融纺丝制成有色聚丙烯纤维。组分c的含量太少，导致聚丙烯纤维的抗氧化性能差。Section of polypropylene, component a (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione), component b (tris(2,4-di-tert-butylphenyl)phosphite) and component c (1,3,5-triazine- 2,4,6-triamine-NN"'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4) -piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3,1-propanediyl]]-bis[N'-N"-dibutyl-N', N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]) is added to a mixer for kneading and extrusion granulation, wherein component a accounts for 1000 ppm of the polypropylene mixture The weight ratio of component b to component a is 0.75, and component c is 3000 ppm of the polypropylene mixture; finally, the pellet is mixed with the colorant masterbatch (black) and melt-spun to form colored polypropylene fiber. The content of the fraction c is too small, resulting in poor oxidation resistance of the polypropylene fiber.
Figure PCTCN2018123330-appb-000001
Figure PCTCN2018123330-appb-000001
Figure PCTCN2018123330-appb-000002
Figure PCTCN2018123330-appb-000002

Claims (9)

  1. 一种有色聚丙烯纤维，其特征是：该聚丙烯纤维中含有组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂，其中组分a占有色聚丙烯纤维的800～15000ppm；含有组分b时，组分b与组分a的重量比小于0.80；含有组分c时，组分c占有色聚丙烯纤维的4000～50000ppm。A colored polypropylene fiber characterized in that the polypropylene fiber contains a component a hindered phenolic antioxidant and a component b phosphite antioxidant and/or component c hindered amine antioxidant, Wherein component a accounts for 800-15000 ppm of colored polypropylene fiber; component b contains component ratio of component b to component a of less than 0.80; and component c contains component 4000 of colored polypropylene fiber. 50000ppm.
  2. 根据权利要求1所述的有色聚丙烯纤维，其特征是：所述的组分a占有色聚丙烯纤维的1000～8000ppm。The colored polypropylene fiber according to claim 1, wherein said component a accounts for 1000 to 8000 ppm of the colored polypropylene fiber.
  3. 根据权利要求1或2所述的有色聚丙烯纤维，其特征是：所述的组分b与组分a的重量比大于等于0.20，小于0.80。The colored polypropylene fiber according to claim 1 or 2, wherein the weight ratio of the component b to the component a is 0.20 or more and less than 0.80.
  4. 根据权利要求1或2所述的有色聚丙烯纤维，其特征是：所述的组分c占有色聚丙烯纤维的4000～20000ppm。The colored polypropylene fiber according to claim 1 or 2, wherein the component c accounts for 4,000 to 20,000 ppm of the colored polypropylene fiber.
  5. 根据权利要求1所述的有色聚丙烯纤维，其特征是：该有色聚丙烯纤维中含有组分a、组分b和组分c。The colored polypropylene fiber according to claim 1, wherein the colored polypropylene fiber contains component a, component b and component c.
  6. 根据权利要求1所述的有色聚丙烯纤维，其特征是：所述组分a受阻酚类抗氧剂类抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯；β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯；1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯或1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮中的至少一种。The colored polypropylene fiber according to claim 1, wherein said component a hindered phenolic antioxidant-based antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxybenzene) Propionate] pentaerythritol ester; β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl alcohol ester; 1,3,5-trimethyl-2,4,6- Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1, At least one of 3,5-triazine-2,4,6-(1H,3H,5H)-trione.
  7. 根据权利要求1所述的有色聚丙烯纤维，其特征是：所述组分b亚磷酸酯类抗氧剂为聚(二丙二醇)苯基亚磷酸酯；双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯；三(2,4-二叔丁基苯基)亚磷酸酯；双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯；四(2,4-二叔丁基酚)-4,4'-联苯二亚磷酸酯或3,9-双十八烷氧基-2,4,8,10-四氧-3,9-二磷螺环[5.5]十一烷中的至少一种。The colored polypropylene fiber according to claim 1, wherein said component b phosphite antioxidant is poly(dipropylene glycol) phenyl phosphite; bis (2,6-di-tert-butyl) -4-methylphenyl)pentaerythritol diphosphate; tris(2,4-di-tert-butylphenyl)phosphite; bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite Tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyldiphosphite or 3,9-bisoctadecyloxy-2,4,8,10-tetraoxy-3, At least one of 9-diphosphorylcyclo[5.5]undecane.
  8. 根据权利要求1所述的有色聚丙烯纤维，其特征是：所述组分c受阻胺类抗氧剂类抗氧剂为聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-[(2,2,6,6-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}；聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯；N Ⅰ，N Ⅱ，N Ⅲ，N Ⅳ-四(2，4-二((N-1，2，2，6，6-五甲基-4-哌啶基)-n-丁基氨基)-1，3，5-三嗪-6-基)-4，7-重氮癸烷-1，10-二胺；双(1-十一烷-2,2,6,6-四甲基哌啶-4-基)碳酸酯或1,3,5-三嗪-2,4,6-三胺-N-N”'-[1,2-乙烷二基双[[[4，6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三哑嗪-2-基]亚氨基]3,1-丙烷二基]]-双[N'-N”-二丁基-N',N”-双(1,2,2,6,6-五甲基-4-哌啶基)]中的至少一种。 The colored polypropylene fiber according to claim 1, wherein said component c hindered amine antioxidant-type antioxidant is poly{[6-[(1,1,3,3-tetramethyl). Butyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexanediene [ (2,2,6,6-tetramethyl-4-piperidinyl)imino]}; polysuccinic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidin Pyridinyl alcohol ester; N I , N II , N III , N IV - tetra (2,4-di((N-1,2,2,6,6-pentamethyl-4-piperidinyl)-n -butylamino)-1,3,5-triazin-6-yl)-4,7-diazonium-1,10-diamine; bis(1-undecane-2,2,6, 6-Tetramethylpiperidin-4-yl)carbonate or 1,3,5-triazine-2,4,6-triamine-NN"'-[1,2-ethanediyl bis[[[ 4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-trimoxazin-2-yl]imino]3 , 1-propanediyl]]-bis[N'-N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)] At least one of them.
  9. 一种权利要求1所述有色聚丙烯纤维的制备方法，其特征是：将聚丙烯与组分a受阻酚类抗氧剂以及组分b亚磷酸酯类抗氧剂和/或组分c受阻胺类抗氧剂混合均匀并挤出造粒得到有色聚丙烯混合物，然后将有色聚丙烯混合物进行熔融纺丝得到有色聚丙烯纤维，其中组分a占聚丙烯混合物的800～15000ppm，添加组分b时，组分b与组分a的重量比小于0.80；添加组分c时，组分c占聚丙烯混合物的4000～50000ppm。A method for preparing a colored polypropylene fiber according to claim 1, characterized in that the polypropylene and the component a hindered phenolic antioxidant and the component b phosphite antioxidant and/or component c are blocked The amine antioxidant is uniformly mixed and extruded and granulated to obtain a colored polypropylene mixture, and then the colored polypropylene mixture is melt-spun to obtain a colored polypropylene fiber, wherein component a accounts for 800 to 15000 ppm of the polypropylene mixture, and the added component When b is, the weight ratio of component b to component a is less than 0.80; when component c is added, component c is 4000 to 50000 ppm of the polypropylene mixture.
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WO2002031237A1 (en) * 2000-10-11 2002-04-18 Sunoco, Inc. (R&M) High strength spunbond fabric
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CN106319665A (en) * 2015-06-15 2017-01-11 东丽纤维研究所（中国）有限公司 Colored polypropylene fiber and preparation method thereof

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