CN108330559A - One kind can contaminate polyolefine fiber - Google Patents
One kind can contaminate polyolefine fiber Download PDFInfo
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- CN108330559A CN108330559A CN201710042187.5A CN201710042187A CN108330559A CN 108330559 A CN108330559 A CN 108330559A CN 201710042187 A CN201710042187 A CN 201710042187A CN 108330559 A CN108330559 A CN 108330559A
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- polyolefine fiber
- polyolefin
- copolyesters
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- 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
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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Abstract
The invention discloses one kind can contaminating polyolefine fiber, this can contaminate polyolefine fiber mainly by polyolefin, 1,4 cyclohexane cyclohexanedimethanodibasics or 1, copolyesters, compatilizer, component A non-symmetrical hindered phenols kind antioxidant and the component B phosphite ester kind antioxidants composition that 4 dimethyl hexahydrophthalates are modified, wherein dispersion diameter ranging from 30nm~1000nm of the modified copolyester in it can contaminate polyolefine fiber, the molar content of component A, which accounts for, can contaminate polyolefine fiber weight ratio for 0.2~45.0mmol/kg, and the molar content of component B is 0.01 with the molar content ratio of component A:1~10.00:1.The polyolefine fiber of the present invention that contaminates has disperse dye dyeable, and tone is good, while having excellent antioxygenic property, and cracking fever is few, is widely used.
Description
Technical field
The present invention relates to a kind of disperse dye dyeable, tone well has the polyolefin of good oxidation resistance energy fine simultaneously
Dimension.
Background technology
Polyolefine fiber has the excellent properties such as light weight, heat preservation, rapid-curing cutback, environmental-friendly.But since polyolefin does not have pole
Property functional group, can not be combined with dye molecule, cause the dyeing of polyolefine fiber extremely difficult, cannot be widely used in dress material
Field.Currently, other than not requiring the dress material of color that can use polyolefine fiber on a small quantity, polyolefine fiber is mostly used for preparing
Non-woven fabrics, filter material, carpet etc..
The method for assigning polyolefin color has very much, and the most commonly used is obtained by the way that pigment is added into polyolefin at present
Coloured polyolefine fiber.In addition to this color method also has some other colouring method.Such as reached by chemical surface treatment
It is stainable to require, assign color, method of composite spinning etc. by CO 2 supercritical dyeing.
Japanese Laid-Open Patent Unexamined Patent 4-209824 is disclosed obtains dyeable polypropylene by adding nylon into polypropylene
The method of fiber, but this method cannot obtain hyperchromatic polypropylene fibre.Chinese patent CN102719009A is disclosed
A method of dyeable polypropylene fibre being obtained by the way that modified poly ester is added into polypropylene, but it is modified disclosed in the patent
The preparation method of polyester is complicated, and the polypropylene fibre for adding this polyester cannot contaminate dark color, using being restricted.It is Chinese special
Sharp CN101365834A and Japanese Patent Laid 2001-522947 disclose by into polypropylene be added amorphism can contaminate it is poly-
It closes object and makes it have stainability energy.Although polypropylene fibre also obtains stainability, can only obtain light color contaminates poly- third
Alkene fiber, can not obtain can hyperchromatic polypropylene fibre, and the intensity of fiber is also low, in practical applications by the very day of one's doom
System.
Polyolefin is easy to carry out oxygenolysis under the action of light and heat simultaneously, generates alkyl diradical, and this anti-
It can should continuously go on.The problem of this is by the exothermic oxidation for leading to polyolefine fiber.In order to improve the anti-of polyolefin
Oxidation susceptibility, major measure in the prior art are addition antioxidants.As patent TWI428382B discloses one kind can be transparent
Change polypropene composition, polyacrylic antioxygenic property adds phenols and phosphorous acid esters wherein or amine is anti-in order to improve
Oxidant.
Polyolefine fiber can be contaminated due to containing polyolefin component, it may have oxidation resistant problem as described above.Therefore have
Necessity prepares a kind of disperse dye dyeable, and tone is good and what antioxygenic property was excellent contaminates polyolefine fiber.
Invention content
The purpose of the present invention is to provide a kind of disperse dye dyeable, tone well has good oxidation resistance energy simultaneously
Polyolefine fiber.
Technical solution of the invention is：
One kind can contaminate polyolefine fiber, this can contaminate polyolefine fiber mainly by polyolefin, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-ring
The ester modified copolyesters of hexane dicarboxylic acid diformazan, compatilizer, the component A non-symmetrical hindered phenol classes containing structure as shown in Equation 1 are anti-
Oxygen agent and component B phosphite ester kind antioxidants composition, wherein dispersion diameter model of the modified copolyester in it can contaminate polyolefine fiber
It encloses for 30nm~1000nm, the molar content of component A accounts for that can to contaminate polyolefine fiber weight ratio be 0.2~45.0mmol/kg,
The molar content of component B is 0.01 with the molar content ratio of component A:1~10.00:1,
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
In the modified copolyester, preferably Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-dimethyl hexahydrophthalate accounts for copolyesters
10~the 60mol%, more preferably 15~50mol% of acid and ester total amount.
Preferred polyolefm is straight chain type polypropylene.
It is preferred that modified copolyester accounts for the 4.00~20.00wt% that can contaminate polyolefine fiber weight.
It is preferred that compatilizer is maleic anhydride modified polypropylene.
It is preferred that compatilizer accounts for the 0.05~5.00wt% that can contaminate polyolefine fiber weight.
Preferred ingredient A non-symmetrical hindered phenol antioxidant is：Bis- [1,1- dimethyl -2- [(the 3- tertiary butyl-4-hydroxies-of 3,9-
5- aminomethyl phenyls) propionyloxy] ethyl] -2,4,8,10- four oxaspiro [5.5] hendecane.
Preferred ingredient B phosphite ester kind antioxidants are poly- (dipropylene glycol) phenyl phosphites, bis- (2,6- di-t-butyls-
4- aminomethyl phenyls) pentaerythritol diphosphate, three (2,4- di-tert-butyl-phenyls) phenyl phosphites, four (2,4- di-t-butyls
Phenol) 4,4'- biphenyl diphosphites or four oxygen -3,9- hosphospiros [5.5] of the bis- octadecane epoxide -2,4,8,10- of 3,9- 11
At least one of alkane.
The invention also discloses a kind of preparation methods contaminating polyolefine fiber：First by polyolefin, containing as shown in Equation 1
Component A non-symmetrical hindered phenols kind antioxidant, component B phosphite ester kind antioxidants and the compatilizer of structure are uniformly mixed and squeeze
Go out granulation and obtain anti-oxidant polyolefin master batch, then by above-mentioned anti-oxidant polyolefin master batch, polyolefin and Isosorbide-5-Nitrae-hexamethylene two
Formic acid or the ester modified copolyesters of 1,4 cyclohexanedicarboxylic acid diformazan, which are uniformly mixed, and extruding pelletization obtains can contaminate polyolefin mixing
Object can contaminate polyolefin blend progress melt spinning and obtain that polyolefine fiber can be contaminated；The molar content of wherein component A, which accounts for, to be contaminated
Polyolefine fiber weight ratio is 0.2~45.0mmol/kg, and the molar content of component B is with the molar content ratio of component A
0.01:1~10.00:1,
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
The polyolefine fiber of the present invention that contaminates has disperse dye dyeable, and tone is good, while having excellent resist
Oxidation susceptibility, cracking fever is few, is widely used.
Specific implementation mode
The present invention is added copolymerization esters and can dye point to assign polyolefine fiber stainability by being blended in polyolefin
Energy.Non-symmetrical hindered phenol and phosphite ester kind antioxidant are added simultaneously, imparting can contaminate the excellent antioxygenic property of polyolefine fiber.
Dispersion diameter of the modified copolyester in polyolefine fiber is 30~1000nm.Due to copolyesters and polyolefin
Compatibility is bad, and copolyesters is not easy to disperse in polyolefin.The present invention controls modified copolyester by the addition of compatilizer and exists
Dispersion diameter in polyolefine fiber is between 30nm~1000nm.When disperseing diameter less than 30nm, it is unfavorable for the entrance of dyestuff, dyes
Hue difference afterwards；Disperse diameter more than if 1000nm, the strength and elongation product of gained polyolefine fiber can reduce, and fibrous physical property is deteriorated.
Under normal circumstances, dye molecule is primarily present in the amorphous area of polyester.Therefore, in order to improve the tone of polyester, this
Copolymer composition is added in invention into polyester, reduces the crystallinity of polyester, improves the non-crystalline areas in polyester, it is more convenient for accommodating
Dye molecule.
In addition, the refractive index of polyester can influence the tone of polyester after dyeing.It can occur when light is irradiated on fiber anti-
It penetrates, transmit and scatters.Reflected light is white light, in the case of more than the reflected light, can drop low-fiber tone.As polyester reflects
The reflected light of the reduction of rate, fiber surface is reduced, and can improve the tone of fiber.Thus by adding in the polyester in the present invention
Copolymer composition plays the effect for reducing polyester refractive index to a certain extent.
In conclusion being modified to polyester by adding copolymer composition to reduce the crystallinity and refractive index of polyester, carry
The tone of high final polyolefin of the present invention.Selectable copolymer composition can be glycols or two acids copolymer compositions.The present invention
In preferred copolymer composition be Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-dimethyl hexahydrophthalate.
The copolymerization resultant of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-dimethyl hexahydrophthalate accounts in the modified copolyester
5~100mol% of copolyesters acid and ester total amount.In modified copolyester the content of copolymer composition can influence the crystallinity of copolyesters with
And refractive index.
From the point of view of crystallinity, when modified copolymer ingredient is added into polyester, due to modified copolymer component damage
The regularity of polyester molecule, makes the crystallinity deterioration of polyester.Therefore, the modified copolymer ingredient in modified copolyester is more, changes
Property copolyesters crystallinity it is poorer, for dye molecule accommodate place it is more, dyeability is better.
From the point of view of refractive index, refractive index is lower, and the tone that copolyesters is shown is better.And the refraction of copolyesters
Rate is related with the content of phenyl ring in copolyesters, and phenyl ring content is lower, and the refractive index of copolyesters is also lower.Isosorbide-5-Nitrae-hexamethylene is added
Dioctyl phthalate or Isosorbide-5-Nitrae-dimethyl hexahydrophthalate can reduce aromatic acid or the amount of its carboxylate as copolymer composition,
Namely the content of phenyl ring in copolyesters is reduced, and then reduce the refractive index of copolyesters.Therefore, the modified copolymer in modified copolyester
Ingredient is more, and the refractive index of modified copolyester is lower, and tone is better.
But if modified copolymer ingredient is excessive in modified copolyester, the glass transition temperature of modified copolyester can drop
Low, slice has caking phenomenon when preserving, and influences the follow-up use of modified copolyester.So in copolyesters of the present invention
Modified copolymer ingredient accounts for acid and ester total amount preferably 10~60mol%, more preferable 15~50mol% in modified copolyester.
Polyolefin of the present invention is by ethylene, propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4-methyl-1-pentene
It waits alpha-olefins and certain cycloolefin are polymerized alone or combined polymerization forms.Wherein preferred polyethylene or its copolymer, polypropylene or
Its copolymer, more preferable straight chain type polypropylene.
The present invention contaminate modified copolyester described in polyolefine fiber account for can contaminate polyolefine fiber 3.00~
20.00wt%.Modified copolyester in fiber is more, and the tone of fiber is better.But consider from spinning angle, modified copolyester
More, the spinnability of mixture is deteriorated after blending, and fibrous physical property is also deteriorated.The additive amount of modified copolyester is very few, although to fibre
The material properties affect of dimension is smaller, but can drop low-fiber tone.The preferably described modified copolyester of the present invention, which accounts for, can contaminate polyolefin fibre
4.00~the 20.00wt%, more preferable 4.00~15.00wt% of dimension.
In order to improve the compatibility of modified copolyester and polyolefin substrate, need that compatilizer is added thereto.Compatilizer
Main function is the dispersibility for improving modified copolyester in polyolefin, improves the dyeability of fiber.Compatilizer can be selected from
The homopolymerization of maleic anhydride modified homopolymerization or copolymeric polyolefin, amino or imido grpup modification or copolymeric polyolefin, epoxy group
The modified versions polyolefin such as modified homopolymerization or copolymeric polyolefin.Specifically, what can be enumerated has maleic anhydride modified polypropylene, horse
Come anhydride modified lldpe, the styrene copolymerized alkene of amino modified styrene ethylene butadiene-, maleic anhydride modified benzene second
Alkene-ethylene-butadiene-styrene copolyalkenamer, epoxy group modified polypropene etc..The present invention is more preferably maleic anhydride modified poly-
Propylene.
The content of the compatilizer in the fibre is 0.01~10.00wt%.When the content of compatilizer is less than 0.01wt%, rise
Less than dispersion effect of the raising modified copolyester in polyolefin；When the content of compatilizer is higher than 10.00wt%, polyene can be influenced
The physical property of hydrocarbon fiber and production operation.Content of the preferred compatilizer of the present invention in it can contaminate polyolefine fiber be 0.05~
5.00wt%。
Polyolefin the problem of there is also oxygenolysis simultaneously.Alkyl can be generated during oxidation of polyolefins is decomposed certainly
By base and peroxylradicals, wherein alkyl diradical can be further oxidized to peroxylradicals.And peroxylradicals are not
Stablize, a part of peroxylradicals can further generate hydroperoxides, accelerate the oxygenolysis of polyolefin again.Polyene can be contaminated
Hydrocarbon fiber also has a problem that due to containing polyolefin component.Component A containing structure as shown in Equation 1 is asymmetric
Hinered phenols antioxidant can capture peroxylradicals, simultaneously because the neighboring group on hydroxyl one side is methyl, steric hindrance
It is smaller, the xanthochromia caused by oxynitrides can be inhibited.Component B phosphite ester kind antioxidants can capture hydroperoxidation
Object.
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
From the point of view of anti-oxidant, the additive amount of component A Hinered phenols antioxidants is more in fiber, captures free radical
Ability is stronger, and the antioxygenic property that can contaminate polyolefine fiber is more excellent.However when component A additive amounts are excessive, can not only it increase
The manufacturing cost of polyolefine fiber can be contaminated by adding, while the strength and elongation of fiber can also be made to accumulate reduction, and fibrous physical property is deteriorated.Therefore this hair
The amount of the bright component A accounts for 0.1~50.0mmol/kg of polyolefine fiber in terms of molal quantity, preferably 0.2~
45.0mmol/kg。
Component B phosphite ester kind antioxidants have the function of that capture hydroperoxides has when being used in combination with component A
Synergistic effect.However when component B amounts are more, more component B phosphorous is had relative to component A Hinered phenols antioxidants
Acid esters kind antioxidant, which remains in, to be contaminated in polyolefine fiber, and due to not for the hydroperoxides of capture, this part
Component B phosphite ester kind antioxidants do not have oxidation resistant effect, can increase the manufacturing cost that can contaminate polyolefine fiber instead, together
When a large amount of component B phosphite ester kind antioxidants the intensity that can contaminate polyolefine fiber can be made to decline.Therefore of the present invention group
The amount proportional region of the amount for dividing B and component A is calculated as 0.01 with molal quantity:1~10.00:1, preferably 0.05:1~
6.00:1, further preferably 0.20:1~4.00:1.
Component A is preferably triethylene-glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters], 1,3,
5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 2- (tertiary fourths
Base) -6- methyl -4- (3- ((2,4,8,10- tetra- (tertiary butyl) dibenzo [d, f] [1,3,2] dioxathion cycloheptane -6- bases) oxygen)
Propyl) phenol, 3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,
Tetra- oxaspiros of 4,8,10- [5.5] at least one of hendecane or 6 t butyl 2,4 dimethyl phenol.It finds in an experiment
Antioxidant 3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,4,
8,10- tetra- oxaspiro [5.5] hendecanes have good compatibility with polyolefin, are conducive to that the anti-oxidant of polyolefine fiber can be contaminated
The raising of performance.Therefore component A is more preferably bis- [1,1- dimethyl-the 2- [(3- tertiary butyl-4-hydroxy -5- methyl of 3,9-
Phenyl) propionyloxy] ethyl] -2,4,8,10- four oxaspiro [5.5] hendecane.
To the component B phosphite ester kind antioxidants, there is no particular limitation, can be poly- (dipropylene glycol) phenyl phosphorous
Acid esters, bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, three (2,4- di-tert-butyl-phenyls) phenyl phosphorous
Acid esters, four (2,4- di-tert-butylphenols) 4,4'- biphenyl diphosphites or bis- four oxygen -3 octadecane epoxide -2,4,8,10- 3,9-,
At least one of 9- hosphospiros [5.5] hendecane.
It can contaminate and contain modified poly ester ingredient in polyolefine fiber simultaneously, there is differences on constituting with simple polyolefin for this
Not.There is also difference for the distribution of antioxidant wherein.When antioxidant be distributed in polyolefin it is more, rather than in modified poly ester
In ingredient, it will help the raising of the oxidation resistance of polyolefine fiber can be contaminated.Particularly with the bis- [1,1- bis- of antioxidant 3,9-
Methyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyl] four oxaspiros [5.5] 11 of -2,4,8,10-
Alkane, due to that with ester group, ester exchange reaction can occur with modified copolyester, if directly by it with modified copolyester, it is compatible
Agent, polyolefin mixing granulation, since ester exchange reaction occurs with modified copolyester, it will reduce the amount of antioxidant, together
The parts Shi Huiyou antioxidant enters in modified copolyester, this will be unfavorable for contaminate the improvement of the antioxygenic property of polyolefine fiber.
Based on above-mentioned viewpoint, the present invention provides a kind of preparation methods contaminating polyolefine fiber, in order to promote antioxidant in polyolefin
In distribution, reduce and the effect of polyester, first by polyolefin, the component A non-symmetrical hindered phenol classes containing structure as shown in Equation 1
Antioxidant, component B phosphite ester kind antioxidants and compatilizer are uniformly mixed and extruding pelletization obtains anti-oxidant polyolefin mother
Grain, then by above-mentioned anti-oxidant polyolefin master batch, polyolefin and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two
The copolyesters that methyl esters is modified is uniformly mixed and extruding pelletization obtains that polyolefin blend can be contaminated, and can contaminate polyolefin blend progress
Melt spinning obtains that polyolefine fiber can be contaminated；The molar content of wherein component A account for can contaminate polyolefine fiber weight ratio be 0.2~
The molar content of 45.0mmol/kg, component B are 0.01 with the molar content ratio of component A:1~10.00:1,
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
Contaminating for the present invention has good tone after polyolefine fiber is dyed with disperse dyes, such as contaminated by blue
Material（1.0%o.w.f）When being dyed, L values can reach 50 hereinafter, the physical properties excellent of fiber, fiber strength and elongation are accumulated 24 simultaneously
More than, and antioxygenic property is good, is not susceptible to xanthochromia, xanthochromia value is 9 hereinafter, can be widely used for dress material field.
Test method according to the present invention is as follows：
（1）Antioxygenic property is tested
Polyolefine fiber can be contaminated first and is prepared into cylinder volume object, and carries out pre-treatment according to 0,217 103 methods of JIS L.Then according to
According to《The acidification heat run method of polypropylene fibre（Accelerated process）》（Japanese chemical fibre association method）It is tested and is evaluated.Examination
When testing the time and reaching 100 hours, itself does not generate heat, that is, judges that the resistance to oxidation heat generation of the polypropylene fibre is qualified.Otherwise, sentence
It is set to unqualified.
（2）The xanthochromia value of fiber is tested
NOx gas-forming agents are put into closed container（85% phosphoric acid and 2% nitrous acid aqueous solution）, then by sample and blue
Standard dyeing is arranged in container, when blue standard stained clot-h color take off for standard grayscale plate 3 when, replace blue standard dyeing
Cloth takes out sample when color reaches standard grayscale plate 3 again, and cleans 2 times, dries.Pass through Datacolor650 points
Light photometer is measured xanthochromia value.Xanthochromia value is bigger, indicates the easier xanthochromia of fiber.
（3）The additive amount of copolyesters in fiber
Polyolefine fiber can be contaminated to dissolve using hexafluoroisopropanol, insoluble polyolefine fiber is removed, then steams solvent
It is dry, by the additive amount for testing dissolved element content calculation copolyesters.
（4）The resultant of copolymer composition in copolyesters
Take method（3）Obtained dissolved element（That is copolyesters）, copolyesters is measured into its nuclear magnetic spectrum using trifluoroacetic acid dissolving.
The copolymer composition content in copolyesters is calculated by the peculiar peak of nuclear magnetic spectrum cyclohexane dicarboxylic acid dimethyl ester.
（5）The tone of polyolefine fiber can be contaminated
Polyolefine fiber can be contaminated first and is prepared into cylinder volume object, and passes through disperse dyes（Blue, 1.0%o.w.f）It is contaminated
Sample after dyeing is overlapped into after opaque shape with spectral photometric colour measuring meter (Datacolor Asia Pacific (H.K.) by color
Ltd. the Datacolor 650 manufactured is in CEI standard sources D65, and 10oColour examining is carried out under corner condition.The smaller expression dyeability of L values
It is better.
（6）The dispersion diameter of copolyesters
Pass through transmission electron microscope（TEM）It is measured.
（7）The strength and elongation of fiber is accumulated
Intensity and degree of stretching are measured with reference to JIS L1013：2010（Chemical fibre medium-length fibre experimental method）8.8.1 benchmark calculate
Go out.By ORIENTEC Co., RTC-1225A strength and elongation testing machines measure intensity and degree of stretching,
Strength and elongation product=intensity × (degree of stretching)0.5,
The physical property that strength and elongation accumulates smaller expression fiber is poorer.
（8）The content of antioxidant component A
Polyolefine fiber can be contaminated to be heated to reflux in toluene solution, take out solution, methanol dilution is added.Simultaneously in dilution
Internal standard is added（P-terphenyl）, then tested with the LC-10ADVP type high performance liquid chromatographs of Shimadzu Corporation's production.Pass through
The peculiar peak of antioxidant and the peak area at the peculiar peak of interior target are calculated.
（9）The content of antioxidant component B
Polyolefine fiber MTG YBCO bulk can be contaminated.Pass through the standby ZSX Primus III+type X-ray fluorescence spectras of corporation of science
Instrument is tested.By the amount of test P elements, the amount of component B contained is calculated,
,
P is the amount of P elements in formula, and n is the molal quantity of P element, and M is the molecular weight of component b.
Technical scheme of the present invention is explained in more detail below by specific implementation mode, but the present invention and unlimited
In these embodiments.
Embodiment 1
The preparation of copolyesters：By dimethyl terephthalate (DMT), ethylene glycol, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate（DMCD）, catalysis
Agent manganese acetate is put into transesterification reactor after mixing, and ester exchange reaction is carried out in 170 DEG C~230 DEG C.Transesterification is anti-
After answering, reaction product is moved into polycondensation vessel, adds the catalytic antimony trioxide and heat stabilizer trimethyl phosphate, in
260 DEG C~290 DEG C progress polycondensation reactions.Object to be polymerized reaches need viscosity after spue, pelletizing, obtain required copolyesters.
Isosorbide-5-Nitrae-the dimethyl hexahydrophthalate being copolymerized in copolyesters accounts for dimethyl terephthalate (DMT) and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic diformazan
The 5mol% of ester total amount（That is the combined polymerization rate of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate）.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatilizer：Maleic anhydride modified polypropylene (mPP), group
Divide A：Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] the ethyl] -2,4,8,10- of 3,9-
Four oxaspiros [5.5] hendecane（AO-80）, component B：Poly- (dipropylene glycol) phenyl phosphites（B2）Kneading machine is added in 230-
It carries out being kneaded under 260 degree and extruding pelletization, wherein compatilizer accounts for the 1wt% of anti-oxidant polyolefin master batch, component A accounts for anti-oxidant poly-
The molar ratio of the 100mmol/Kg of alkene master batch, component B and component A are 0.05：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 15 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：5：80.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 0.05wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 15.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 505nm, and the content of component A is accounted for the 5.0mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.05：1.
Embodiment 2
The preparation of copolyesters：By dimethyl terephthalate (DMT), ethylene glycol, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic（CHDA）After mixing by
It is gradually added in reaction kettle of the esterification, esterification and ester exchange reaction is carried out in 230 DEG C~260 DEG C.After reaction, by reaction product
Move into polycondensation vessel, addition the catalytic antimony trioxide, co-catalyst manganese acetate and heat stabilizer trimethyl phosphate, in 260 DEG C
~290 DEG C of progress polycondensation reactions.Object to be polymerized reaches need viscosity after spue, pelletizing, obtain required copolyesters.Copolyesters
Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic of middle copolymerization accounts for the 15mol% of dimethyl terephthalate (DMT) and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic total amount（I.e. 1,
The combined polymerization rate of 4- cyclohexane cyclohexanedimethanodibasics）.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatilizer：Maleic anhydride modified styrene-ethylene-fourth
Diene-styrene copolymer (mSEBS), component A：1,3,5- tri- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) -1,3,
5- triazines -2,4,6- (1H, 3H, 5H)-triketone（CN1790）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites
（B1）Addition kneading machine carries out being kneaded under 230-260 degree and extruding pelletization, wherein compatilizer account for anti-oxidant polyolefin master batch
The molar ratio that 0.10wt%, component A account for the 450mmol/Kg of anti-oxidant polyolefin master batch, component B and component A is 0.2：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 20 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：10：70.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 0.01wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 20.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 1000nm, and the content of component A is accounted for the 45mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.2：1.
Embodiment 3
The preparation of copolyesters：The combined polymerization rate for changing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate in copolyesters is 10mol%, other
In a kind of part and embodiment copolyesters prepare it is identical.
The preparation of anti-oxidant polyolefin master batch：By polyethylene（PE）, compatilizer：Imido grpup modified phenylethylene-ethylene-fourth two
Alkene-styrol copolymer (aSEBS), component A：Bis- [the β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) third of triethylene-glycol
Acid esters]（AO-245）, component B：Four (2,4- di-tert-butylphenols) 4,4'- biphenyl diphosphites（B4）Kneading machine is added in 230-
It carries out being kneaded under 260 degree and extruding pelletization, wherein compatilizer accounts for the 50wt% of anti-oxidant polyolefin master batch, component a accounts for anti-oxidant poly-
The molar ratio of the 0.5mmol/Kg of alkene master batch, component B and component A are 6：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- second
Alkene（PE）It is kneaded to obtain between 230 DEG C~260 DEG C using kneading machine and can contaminate polyethylene slice.The wherein addition of copolyesters
Amount is 4 with the weight ratio of the additive amount of anti-oxidant polyolefin master batch and the additive amount of polyethylene：20：76.
It above-mentioned slice at 230 DEG C is carried out melt spinning finally obtains that polyethylene fibre can be contaminated.Compatibilizer content in fiber
The 10.00wt% of polyethylene fibre can be contaminated by accounting for, and copolymerization ester content accounts for the 4.00wt% that can contaminate polyethylene fibre, dispersion in the fibre
Diameter is 30nm, and the content of component A is accounted for the 0.1mmol/Kg that can contaminate polyethylene fibre, mole of component B and component A by mole number scale
Than being 6.00：1.
Embodiment 4
The preparation of copolyesters：The combined polymerization rate for changing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate in copolyesters is 100mol%, other
In a kind of part and embodiment copolyesters prepare it is identical.
The preparation of anti-oxidant polyolefin master batch：By polyethylene-propylene copolymer（EMP）, compatilizer：It is maleic anhydride modified poly-
Propylene (mPP), component A：2- (tertiary butyl) -6- methyl -4- (3- ((2,4,8,10- tetra- (tertiary butyl) dibenzo [d, f] [1,3,
2] dioxathion cycloheptane -6- bases) oxygen) propyl) phenol（GP）, component B：Bis- (2,6- di-t-butyl -4- aminomethyl phenyls) Ji Wusi
Alcohol bisphosphate（B3）Kneading machine is added and carries out being kneaded simultaneously extruding pelletization under 230-260 degree, wherein compatilizer accounts for anti-oxidant poly-
The 25wt% of alkene master batch, component A account for the 225mmol/Kg of anti-oxidant polyolefin master batch, and component B and the molar ratio of component A are
0.01：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- second
Alkene-propylene copolymer is kneaded to obtain using kneading machine between 230 DEG C~260 DEG C can contaminate polyethylene-propylene copolymer and cut
Piece.The wherein additive amount of copolyesters and the additive amount of anti-oxidant polyolefin master batch and the additive amount of polyethylene-propylene copolymer
Weight ratio be 3：20：77.
It above-mentioned slice at 230 DEG C is carried out melt spinning finally obtains that polyethylene-propylene copolymer fibre can be contaminated.In fiber
Compatibilizer content accounts for the 5.00wt% that can contaminate polyethylene-propylene copolymer fibre, and copolymerization ester content accounts for that can to contaminate polyethylene-propylene total
The 3.00wt% of polymer fibre, dispersion diameter in the fibre is 560nm, and the content of component A accounts for dyeable polypropylene fibre by a mole number scale
The molar ratio of the 45.0mmol/Kg of dimension, component B and component A are 0.01：1.
Embodiment 5
The preparation of copolyesters：The combined polymerization rate for changing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate in copolyesters is 60mol%, other
In a kind of part and embodiment copolyesters prepare it is identical.
The preparation of anti-oxidant polyolefin master batch：By poly- 4- methyl -3- amylenes（PMP）, compatilizer：Maleic anhydride modified poly- third
Alkene (mPP), component A：Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] second of 3,9-
Base] -2,4,8,10- four oxaspiro [5.5] hendecane（AO-80）, component B：Bis- four oxygen of octadecane epoxide -2,4,8,10--of 3,9-
3,9- hosphospiros [5.5] hendecane（B5）Kneading machine is added and carries out being kneaded simultaneously extruding pelletization under 230-260 degree, wherein compatible
Agent accounts for the 4wt% of anti-oxidant polyolefin master batch, and component A accounts for the 100mmol/Kg of anti-oxidant polyolefin master batch, component B and component A
Molar ratio is 0.01：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- 4-
Methyl -3- amylenes are kneaded to obtain using kneading machine between 230 DEG C~260 DEG C can contaminate poly- 4- methyl -3- amylenes slice.Its
The weight ratio of the additive amount of middle copolyesters and the additive amount of anti-oxidant polyolefin master batch and the additive amount of poly- 4- methyl -3- amylenes
It is 4：50：46.
It above-mentioned slice at 230 DEG C is carried out melt spinning finally obtains that poly- 4- methyl -3- amylene fibers can be contaminated.Phase in fiber
Hold agent content and account for the 2.00wt% that can contaminate poly- 4- methyl -3- amylene fibers, copolymerization ester content, which accounts for, can contaminate poly- 4- methyl -3- amylenes fibre
The 4.00wt% of dimension, dispersion diameter in the fibre is 100nm, and the content of component A is accounted for by a mole number scale can contaminate poly- 4- methyl -3- penta
The molar ratio of the 50.0mmol/Kg of alkene fiber, component B and component A are 0.01：1.
Embodiment 6
The preparation of copolyesters：The combined polymerization rate for changing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate in copolyesters is 30mol%, other
In a kind of part and embodiment copolyesters prepare it is identical.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatilizer：Maleic anhydride modified polypropylene (mPP), group
Divide A：Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] the ethyl] -2,4,8,10- of 3,9-
Four oxaspiros [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites（B1）It is added and is kneaded
Machine carries out being kneaded under 230-260 degree and extruding pelletization, and wherein compatilizer accounts for the 50wt% of anti-oxidant polyolefin master batch, and component A is accounted for
The molar ratio of the 10mmol/Kg of anti-oxidant polyolefin master batch, component b and component A are 0.1：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 10 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：2：88.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 786nm, and the content of component A is accounted for the 0.2mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.10：1.
Embodiment 7
The preparation of copolyesters：The combined polymerization rate for changing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate in copolyesters is 30mol%, other
In a kind of part and embodiment copolyesters prepare it is identical.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatilizer：Maleic anhydride modified polypropylene (mPP), group
Divide A：Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] the ethyl] -2,4,8,10- of 3,9-
Four oxaspiros [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites（B1）It is added and is kneaded
Machine carries out being kneaded under 230-260 degree and extruding pelletization, and wherein compatilizer accounts for the 10wt% of anti-oxidant polyolefin master batch, and component A is accounted for
The molar ratio of the 10mmol/Kg of anti-oxidant polyolefin master batch, component B and component A are 0.1：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 10 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：10：80.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 600nm, and the content of component A is accounted for the 1mmol/Kg of dyeable polypropylene fibre, mole of component B and component A by mole number scale
Than being 0.1：1.
Comparative example 1
Virgin pp slice is subjected to spinning using the spinning condition of embodiment 1, obtains polypropylene fibre.
Due to not having an addition modified poly ester, and as the component A of antioxidant, component B, finally obtained dyeable polypropylene is fine
The dyeability of dimension is poor（L values：78）, oxidative resistance is also poor（Antioxygenic property test failure）.
Comparative example 2
The preparation of copolyesters：It is identical as the preparation method of the polyester in embodiment 7.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, the maleic anhydride modified polypropylene of compatilizer
(mPP) and polypropylene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.It will
Above-mentioned slice carries out melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content, which accounts for, in fiber can contaminate poly- third
The 1wt% of alkene fiber, copolymerization ester content account for the 10wt% of dyeable polypropylene fibre, and dispersion diameter in the fibre is 600nm.
Due to modified poly ester being only added without being added component A and component B as antioxidant, it is finally obtained contaminate it is poly-
The dyeability of tacryl is good（L values：34）, however oxidative resistance is poor（Antioxygenic property test failure）.
Comparative example 3
By component A：3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -
Tetra- oxaspiros of 2,4,8,10- [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites
（B1）And polypropylene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.It will be upper
Stating slice, progress melt spinning finally obtains dyeable polypropylene fibre at 230 DEG C.The content of component A is accounted for by a mole number scale in fiber
The molar ratio of the 1mmol/Kg of dyeable polypropylene fibre, component B and component A are 0.1：1.
Since the component A as antioxidant, component B is only added, without be added modified poly ester, it is finally obtained contaminate it is poly-
The oxidative resistance of tacryl is good（Antioxygenic property test passes）, however dyeability is poor（L values：78）.
Comparative example 4
The preparation of copolyesters：It is identical as the preparation method of the polyester in embodiment 7.
By component A：Bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] second of 3,9-
Base] -2,4,8,10- four oxaspiro [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenylphosphonous acids
Ester（B1）, copolyesters, compatibility agent and polypropylene（PP）It is kneaded to obtain between 230 DEG C~260 DEG C using kneading machine
Dyeable polypropylene is sliced.The additive amount of wherein compatibility agent accounts for the 1wt% of dyeable polypropylene slice, and copolyesters additive amount, which accounts for, to be contaminated
The additive amount of the 10wt% of polypropylene chip, component A are accounted for the 1mmol/Kg of dyeable polypropylene slice by mole number scale, component B's
Additive amount is 0.1 by the molar ratio of mole number scale and component A：1.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 600nm, and the content of component A is accounted for the 0.5mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.10：1.
Since polypropylene, component A antioxidant, component B antioxidant and compatilizer are not uniformly mixed to squeeze out and be made first
Grain obtains anti-oxidant polyolefin master batch, and anti-oxidant polyolefin master batch is then uniformly mixed extruding pelletization with modified poly ester again obtains
Dyeable polypropylene is sliced, but directly polypropylene, component A, component B, compatilizer and modified poly ester are mixed together and are uniformly squeezed
Go out granulation and obtains dyeable polypropylene slice.This will cause component A antioxidant part to be reacted with modified poly ester, while part is present in
It is poor so as to cause the oxidative resistance of dyeable polypropylene fibre in modified poly ester（Antioxygenic property test failure）.
Comparative example 5
The preparation of copolyesters：It is identical as the preparation method of the polyester in embodiment 7.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatibility agent：Maleic anhydride modified polypropylene (mPP),
Component A：3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,4,8,
Tetra- oxaspiros of 10- [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites（B1）It is added
Kneading machine carries out being kneaded under 230-260 degree and extruding pelletization, and wherein compatibility agent accounts for the 10wt% of anti-oxidant polyolefin master batch,
The molar ratio that component A accounts for the 10mmol/Kg of anti-oxidant polyolefin master batch, component B and component A is 0.1：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 10 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：10：80.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 1500nm, and the content of component A is accounted for the 1.0mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.10：1.
Since dispersion diameter of the modified poly ester in dyeable polypropylene fibre is big, lead to the strength and elongation product of gained polyolefine fiber
It reduces（Strength and elongation is accumulated：12）, fibrous physical property variation.
Comparative example 6
The preparation of copolyesters：It is identical as the preparation method of the polyester in embodiment 7.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatibility agent：Maleic anhydride modified polypropylene (mPP),
Component A：Four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester（IR1010）Kneading machine is added in 230-
It carries out being kneaded under 260 degree and extruding pelletization, wherein compatibility agent accounts for the 10wt% of anti-oxidant polyolefin master batch, component A accounts for anti-oxidant
The molar ratio of the 10mmol/Kg of polyolefin master batch, component B and component A are 0.1：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 10 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：10：80.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 1500nm, and the content of component A is accounted for the 1.0mmol/Kg of dyeable polypropylene fibre by mole number scale, and component B and component A's rubs
You are than being 0.10：1.
Due to the antioxidant IR1010 as component A, in structure the neighboring group on hydroxyl both sides be be tertiary butyl, it is empty
Between steric hindrance it is larger, oxynitrides effect under easily cause xanthochromia.Therefore the xanthochromia value for obtaining dyeable polypropylene fibre is larger（It is yellow
Variate：16.7）.
Comparative example 7
The preparation of copolyesters：It is identical as the preparation method of the polyester in embodiment 7.
The preparation of anti-oxidant polyolefin master batch：By polypropylene（PP）, compatibility agent：Maleic anhydride modified polypropylene (mPP),
Component A：3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,4,8,
Tetra- oxaspiros of 10- [5.5] hendecane（AO-80）, component B：Three (2,4- di-tert-butyl-phenyls) phenyl phosphites（B1）It is added
Kneading machine carries out being kneaded under 230-260 degree and extruding pelletization, and wherein compatibility agent accounts for the 10wt% of anti-oxidant polyolefin master batch,
The molar ratio that component A accounts for the 800mmol/Kg of anti-oxidant polyolefin master batch, component B and component A is 15：1.
The preparation of polyolefine fiber can be contaminated：By the above-mentioned copolyesters being prepared, anti-oxidant polyolefin master batch and poly- third
Alkene（PP）It is kneaded between 230 DEG C~260 DEG C to obtain dyeable polypropylene slice using kneading machine.The wherein addition of copolyesters
Amount is 10 with the additive amount of anti-oxidant polyolefin master batch and the weight ratio of polyacrylic additive amount：10：80.
Above-mentioned slice is subjected to melt spinning at 230 DEG C and finally obtains dyeable polypropylene fibre.Compatibilizer content in fiber
The 1.00wt% of dyeable polypropylene fibre is accounted for, copolymerization ester content accounts for the 10.00wt% of dyeable polypropylene fibre, dispersion in the fibre
Diameter is 1500nm, and the content of component A is accounted for the 80.0mmol/Kg of dyeable polypropylene fibre, component B and component A by mole number scale
Molar ratio is 15.00：1.
Since the additive amount of component A is excessive, so that the strength and elongation product of dyeable polypropylene fibre reduces（Strength and elongation is accumulated：
11）, fibrous physical property variation.
Each component content in the polyolefine fiber of preparation and evaluation results are shown in Table 1.
Claims (10)
1. one kind can contaminate polyolefine fiber, it is characterized in that：This can contaminate polyolefine fiber mainly by polyolefin, 1,4- hexamethylene diformazans
Acid or the ester modified copolyesters of 1,4 cyclohexanedicarboxylic acid diformazan, compatilizer, the component A containing structure as shown in Equation 1 are asymmetric
Hinered phenols antioxidant and component B phosphite ester kind antioxidants composition, wherein modified copolyester is in it can contaminate polyolefine fiber
Dispersion diameter ranging from 30nm~1000nm, component A molar content account for can contaminate polyolefine fiber weight ratio be 0.2~
The molar content of 45.0mmol/kg, component B are 0.01 with the molar content ratio of component A:1~10.00:1,
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
2. according to claim 1 contaminate polyolefine fiber, it is characterized in that：In the modified copolyester, Isosorbide-5-Nitrae-hexamethylene
Dioctyl phthalate or 1,4 cyclohexanedicarboxylic acid dimethyl ester account for 10~60mol% of copolyesters acid and ester total amount.
3. according to claim 2 contaminate polyolefine fiber, it is characterized in that：In the modified copolyester, Isosorbide-5-Nitrae-hexamethylene
Dioctyl phthalate or 1,4 cyclohexanedicarboxylic acid dimethyl ester account for 15~50mol% of copolyesters acid and ester total amount.
4. according to claim 1 or 2 contaminate polyolefine fiber, it is characterized in that：The polyolefin is straight chain type polypropylene.
5. according to claim 1 or claim 2 contaminate polyolefine fiber, it is characterized in that：The modified copolyester, which accounts for, can contaminate polyolefin
4.00~20.00wt% of fibre weight.
6. according to claim 1 or claim 2 contaminate polyolefine fiber, it is characterized in that：The compatilizer is maleic anhydride modified poly-
Propylene.
7. polyolefine fiber can be contaminated according to claim 6, it is characterized in that：The compatilizer, which accounts for, can contaminate polyolefine fiber weight
0.05~5.00wt%.
8. according to claim 1 or 2 contaminate polyolefine fiber, it is characterized in that：The component A non-symmetrical hindered phenol antioxygens
Agent is：3,9- bis- [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,4,8,
Tetra- oxaspiros of 10- [5.5] hendecane.
9. according to claim 1 or 2 contaminate polyolefine fiber, it is characterized in that：The component B phosphite ester kind antioxidants
For poly- (dipropylene glycol) phenyl phosphites, bis- (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, three (2,
4- di-tert-butyl-phenyls) phenyl phosphites, four (2,4- di-tert-butylphenols) 4,4'- biphenyl diphosphites or 3,9- bis- 18
At least one of alkoxy -2,4,8,10- four oxygen -3,9- hosphospiros [5.5] hendecane.
10. the preparation method described in claim 1 for contaminating polyolefine fiber, it is characterized in that：First by polyolefin, containing such as formula
Component A non-symmetrical hindered phenols kind antioxidant, component B phosphite ester kind antioxidants and the compatilizer of structure shown in 1 are uniformly mixed
And extruding pelletization obtains anti-oxidant polyolefin master batch, then by above-mentioned anti-oxidant polyolefin master batch, polyolefin and Isosorbide-5-Nitrae-hexamethylene
Alkane dioctyl phthalate or the ester modified copolyesters of 1,4 cyclohexanedicarboxylic acid diformazan are uniformly mixed and extruding pelletization obtains that polyolefin can be contaminated
Mixture can contaminate polyolefin blend progress melt spinning and obtain that polyolefine fiber can be contaminated；The molar content of wherein component A accounts for
It is 0.2~45.0mmol/kg that polyolefine fiber weight ratio, which can be contaminated, and the molar content of component B is with the molar content ratio of component A
0.01:1~10.00:1,
（Formula 1）,
Wherein, it is hydrogen, carbon that R1, which is that any type combines half hindered phenol anti-oxidants formed, R2 in hydrocarbon, oxygen, nitrogen,
Any type combines half hindered phenol anti-oxidants formed in hydrogen, oxygen, nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710042187.5A CN108330559A (en) | 2017-01-20 | 2017-01-20 | One kind can contaminate polyolefine fiber |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710042187.5A CN108330559A (en) | 2017-01-20 | 2017-01-20 | One kind can contaminate polyolefine fiber |
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| CN201710042187.5A Pending CN108330559A (en) | 2017-01-20 | 2017-01-20 | One kind can contaminate polyolefine fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111379046A (en) * | 2020-04-10 | 2020-07-07 | 广东彩艳股份有限公司 | High-color-fastness composite fiber for preventing dye sensitization and carcinogenesis and preparation method thereof |
| CN113638076A (en) * | 2021-08-19 | 2021-11-12 | 江苏尚科聚合新材料有限公司 | Preparation method of polyolefin core-sheath composite fiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009076990A1 (en) * | 2007-12-14 | 2009-06-25 | Balta Industries Nv | Process for the preparation of synthetic fibres for yarns with increased dyeability |
| CN103132174A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Normal temperature and pressure disperse dyeable modified polyester fiber |
| CN104711695A (en) * | 2013-12-13 | 2015-06-17 | 东丽纤维研究所（中国）有限公司 | Fiber, and preparation method and use thereof |
| 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 |
-
2017
- 2017-01-20 CN CN201710042187.5A patent/CN108330559A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009076990A1 (en) * | 2007-12-14 | 2009-06-25 | Balta Industries Nv | Process for the preparation of synthetic fibres for yarns with increased dyeability |
| CN103132174A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Normal temperature and pressure disperse dyeable modified polyester fiber |
| CN104711695A (en) * | 2013-12-13 | 2015-06-17 | 东丽纤维研究所（中国）有限公司 | Fiber, and preparation method and use thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 沈新元: "《化学纤维手册》", 30 September 2008, 中国纺织出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111379046A (en) * | 2020-04-10 | 2020-07-07 | 广东彩艳股份有限公司 | High-color-fastness composite fiber for preventing dye sensitization and carcinogenesis and preparation method thereof |
| CN113638076A (en) * | 2021-08-19 | 2021-11-12 | 江苏尚科聚合新材料有限公司 | Preparation method of polyolefin core-sheath composite fiber |
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