CN105622931A - Nylon copolymer mixture, preparation method thereof, and nylon fiber containing same - Google Patents
Nylon copolymer mixture, preparation method thereof, and nylon fiber containing same Download PDFInfo
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- CN105622931A CN105622931A CN201410606040.0A CN201410606040A CN105622931A CN 105622931 A CN105622931 A CN 105622931A CN 201410606040 A CN201410606040 A CN 201410606040A CN 105622931 A CN105622931 A CN 105622931A
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Abstract
The invention provides a nylon copolymer mixture, comprising multiple nylon copolymers and having a general formula (I) as shown in the description, wherein the definition of each parameter is recorded in details in the description. In respect to the total weight of the nylon copolymer mixture, the total content of terminal amino groups of the nylon copolymers is 10-40mEq/kg. The nylon copolymer mixture provided by the invention has a low content of the terminal amino groups, and low reactivity with a general stain, so that an understain effect can be achieved. In addition, the ether group of a polyether diamine oligomer provides good moisture absorbing and releasing properties, so that a fabric prepared from the nylon copolymer mixture has a significant cool sense effect. A preparation method of the nylon copolymer mixture and a nylon fiber containing the same are also disclosed by the invention.
Description
Technical field
The present invention is about a kind of nylon copolymer mixture, especially with regard to the nylon copolymer mixture of a kind of low-end amine groups content.
Background technology
General nylon material is broadly divided into nylon66 fiber and nylon 6. Nylon66 fiber is the alternate copolymer (alternatingcopolymer) formed by hexamethylene diamine and adipic acid combined polymerization, and wherein the mole ratio of hexamethylene diamine and adipic acid is 1:1. Nylon 6 is the homopolymer formed by caprolactam hydrolysis post polymerization, and wherein an end of the ring-opened monomer that the hydrolysis of several lactams is formed is amido, and another end is carboxylic acid group.
By the structure of nylon66 fiber and nylon 6 and synthetic method it can be seen that the total content of the terminal amido of nylon66 fiber and nylon 6 is all about 50%. Additionally, in the dyeing course of general nylon material, owing to dyestuff is mostly acid, it is easy to react with general nylon material so that nylon66 fiber and nylon 6 not easily reach the purpose of understain under the kind not changing dyestuff and concentration. Therefore, a kind of new nylon copolymer mixture is needed at present badly to improve problem produced by conventional nylon material.
Summary of the invention
For improve conventional nylon material because of the characteristic of chemical constitution own under the kind not changing dyestuff and concentration the problem of not easily understain, a kind of nylon copolymer mixture provided by the present invention, its manufacture method and the nylon fiber comprising it may be used to improve problem encountered on dyeing nylon for a long time.
One aspect of the present invention is in that to provide a kind of nylon copolymer mixture. This nylon copolymer mixture comprises multiple nylon copolymer and has general structure shown below (I):
Wherein, monomer A is the lactam monomers of open loop, and the content (a) that monomer A is in nylon copolymer mixture is 100-(b+c+d) wt%; Monomer B is polyether diamine oligomer, and the content (b) that monomer B is in nylon copolymer mixture is 6��12wt%; Monomer C is the first diacid monomer, and the content (c) that monomer C is in nylon copolymer mixture is 0.3��4.0wt%; Monomer D is the second diacid monomer, and the content (d) that monomer D is in nylon copolymer mixture is 0.2��0.6wt%; And T1And T2It is each independently carboxylic acid group (-COOH) or amido (-NH2), and relative to the gross weight of nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 10��40 milliequivalents/kilogram.
According to embodiments of the invention, relative to the gross weight of above-mentioned nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 15��30 milliequivalents/kilogram.
According to embodiments of the invention, the chemical formula of above-mentioned monomer A isM is the integer of 5��11, and * is monomer A binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned monomer B isIts molecular weight is 500��2500g/mol, * is monomer B binding site in formula (I).
According to embodiments of the invention, above-mentioned monomer C comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isP is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
According to embodiments of the invention, in above-mentioned nylon copolymer mixture, the molal quantity of monomer B is identical with the molal quantity of monomer C.
According to embodiments of the invention, above-mentioned monomer D comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isP is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
It is another aspect of the invention to provide a kind of nylon fiber. This nylon fiber comprises above-mentioned nylon copolymer mixture, and has fiber shape.
According to embodiments of the invention, above-mentioned fiber shape comprises circle, yi word pattern, cross, Y-shaped or its combination.
Another aspect of the invention is in that to provide the manufacture method of a kind of nylon copolymer mixture. The manufacture method of this nylon copolymer mixture comprises and carries out copolymerization, makes lactam monomers (A), the first diacid monomer (B), polyether diamine oligomer (C) and the second diacid monomer (D) combined polymerization form nylon copolymer mixture. Nylon copolymer mixture comprises multiple nylon copolymer, and it has general structure shown below (I):
Wherein, in nylon copolymer mixture, the content (a) of lactam monomers (A) is 100-(b+c+d) wt%; The content (b) of polyether diamine oligomer (B) is 6��12wt%; The content (c) of the first diacid monomer (C) is 0.3��4.0wt%; The content (d) of the second diacid monomer (D) is 0.2��0.6wt%; And T1And T2It is each independently carboxylic acid group (-COOH) or amido (-NH2), and relative to the gross weight of nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 10��40 milliequivalents/kilogram.
According to embodiments of the invention, relative to the gross weight of above-mentioned nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 15��30 milliequivalents/kilogram.
According to embodiments of the invention, above-mentioned copolymerization is to carry out at temperature 200��270 DEG C and absolute pressure 0.2��3bar.
According to embodiments of the invention, the chemical formula of above-mentioned lactam monomers (A) isWherein m is the integer of 5��11, and * is this lactam monomers (A) binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned polyether diamine oligomer (B) isIts molecular weight is 900��2000g/mol, * is polyether diamine oligomer (B) binding site in formula (I).
According to embodiments of the invention, above-mentioned first diacid monomer (C) comprises an aliphatic diacid monomer, an aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isWherein p is the integer of 2��10, and * is this aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is this aromatic diacid monomer binding site in formula (I).
According to embodiments of the invention, in above-mentioned nylon copolymer mixture, the molal quantity of monomer B is identical with the molal quantity of monomer C.
According to embodiments of the invention, above-mentioned second diacid monomer (D) comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isWherein p is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
Nylon copolymer mixture provided by the present invention has low-end amine groups content, low with general stain reactivity, therefore can reach understain effect. Additionally, provide good absorb-discharge humid via the ether of polyether diamine oligomer, the fabric that thus nylon copolymer mixture is made is made to have significant cool feeling effect.
Detailed description of the invention
Then the present invention is described in detail with embodiment.
For improve conventional nylon material because of the characteristic of chemical constitution own under the kind not changing dyestuff and concentration the problem of not easily understain, a kind of nylon copolymer mixture provided by the present invention, its manufacture method and comprise its nylon fiber, wherein nylon copolymer mixture provided by the present invention has low-end amine groups content, relatively low with stain reactivity, therefore understain effect can be reached.
In an embodiment of the present invention, a kind of nylon copolymer mixture comprises multiple nylon copolymer and has a formula (I) as follows:
Monomer A is the lactam monomers of open loop, and the content (a) that monomer A is in nylon copolymer mixture is 100-(b+c+d) wt%. According to embodiments of the invention, the chemical formula of monomer A isM is the integer of 5��11, and * is monomer A binding site in formula (I).
Monomer B is polyether diamine oligomer, and the content (b) that monomer B is in nylon copolymer mixture is 6��12wt%. According to embodiments of the invention, the chemical formula of monomer B isIts molecular weight is 500��2500g/mol, * is monomer B binding site in formula (I).
Monomer C is the first diacid monomer, and the content (c) that monomer C is in nylon copolymer mixture is 0.3��4.0wt%. According to embodiments of the invention, in above-mentioned nylon copolymer mixture, the molal quantity of monomer B is identical with the molal quantity of monomer C. According to embodiments of the invention, monomer C comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isP is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
Monomer D is the second diacid monomer, and the content (d) that monomer D is in nylon copolymer mixture is 0.2��0.6wt%. According to embodiments of the invention, monomer D comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isP is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
T1And T2It is each independently carboxylic acid group (-COOH) or amido (-NH2), and relative to the gross weight of nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 10��40 milliequivalents/kilogram. According to embodiments of the invention, relative to the gross weight of nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 15��30 milliequivalents/kilogram.
In an embodiment of the present invention, the manufacture method of a kind of nylon copolymer mixture comprises and carries out copolymerization, makes lactam monomers (A), the first diacid monomer (B), polyether diamine oligomer (C) and the second diacid monomer (D) combined polymerization form nylon copolymer mixture. Nylon copolymer mixture comprises multiple nylon copolymer, and it has general structure shown below (I):
In nylon copolymer mixture, the content (a) of lactam monomers (A) is 100-(b+c+d) wt%. According to embodiments of the invention, the chemical formula of lactam monomers (A) isWherein m is the integer of 5��11, and * is this lactam monomers (A) binding site in formula (I).
In nylon copolymer mixture, the content (b) of polyether diamine oligomer (B) is 6��12wt%. According to embodiments of the invention, the chemical formula of polyether diamine oligomer (B) isIts molecular weight is 900��2000g/mol, * is polyether diamine oligomer (B) binding site in formula (I).
In nylon copolymer mixture, the content (c) of the first diacid monomer (C) is 0.3��4.0wt%. According to embodiments of the invention, in nylon copolymer mixture, the molal quantity of monomer B is identical with the molal quantity of monomer C. According to embodiments of the invention, the first diacid monomer (C) comprises an aliphatic diacid monomer, an aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isWherein p is the integer of 2��10, and * is this aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is this aromatic diacid monomer binding site in formula (I).
In nylon copolymer mixture, the content (d) of the second diacid monomer (D) is 0.2��0.6wt%. According to embodiments of the invention, the second diacid monomer (D) comprises aliphatic diacid monomer, aromatic diacid monomer or its combination.
According to embodiments of the invention, the chemical formula of above-mentioned aliphatic diacid monomer isWherein p is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
According to embodiments of the invention, the chemical formula of above-mentioned aromatic diacid monomer is* it is aromatic diacid monomer binding site in formula (I).
According to embodiments of the invention, by content (a) be 100-(b+c+d) wt% lactam monomers (A), content (b) is the polyether diamine oligomer (B) of 6��12wt%, content (c) be first diacid monomer (C) of 0.3��4.0wt% and the second diacid monomer (D) mix homogeneously that content (d) is 0.2��0.6wt% after, copolymerization is carried out, with the nylon copolymer mixture that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar.
The T of above-mentioned all nylon copolymers1And T2It is each independently carboxylic acid group (-COOH) or amido (-NH2). According to one embodiment of the invention, relative to the gross weight of nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 10��40 milliequivalents/kilogram. According to another embodiment of the present invention, relative to the gross weight of above-mentioned nylon copolymer mixture, the total content of the terminal amido of all nylon copolymers be 15��30 milliequivalents/kilogram.
In an embodiment of the present invention, a kind of nylon fiber comprises above-mentioned nylon copolymer mixture, and has fiber shape. According to embodiments of the invention, fiber shape comprises circle, yi word pattern, cross, Y-shaped or its combination.
Comparative example one: prepare nylon copolymer mixture C 1
After the caprolactam monomer of the open loop of 90.7wt%, the adipic acid of 1.3wt% and the polyether diamine oligomer mix homogeneously of 8wt%, copolymerization is carried out, with the nylon copolymer mixture C 1 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In comparative example one, the molecular weight of polyether diamine oligomer is 900g/mol. The terminal amido content of the nylon copolymer mixture C 1 that comparative example one provides be 56 milliequivalents/kilogram.
Comparative example two: prepare nylon copolymer mixture C 2
After the caprolactam monomer of the open loop of 91.42wt%, the adipic acid of 0.58wt% and the polyether diamine oligomer mix homogeneously of 8wt%, copolymerization is carried out, with the nylon copolymer mixture C 2 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In comparative example two, the molecular weight of polyether diamine oligomer is 2,000g/mol. The terminal amido content of the nylon copolymer mixture C 2 that comparative example two provides be 52 milliequivalents/kilogram.
Embodiment one: prepare nylon copolymer mixture E 1
After the caprolactam monomer of the open loop of 90.4wt%, the adipic acid of 1.3wt%, the polyether diamine oligomer of 8wt% and the adipic acid mix homogeneously of 0.3wt%, copolymerization is carried out, with the nylon copolymer mixture E 1 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment one, the molecular weight of polyether diamine oligomer is 900g/mol. The terminal amido content of the nylon copolymer mixture E 1 that embodiment one provides be 25 milliequivalents/kilogram.
Embodiment two: prepare nylon copolymer mixture E 2
After the caprolactam monomer of the open loop of 90.2wt%, the adipic acid of 1.3wt%, the polyether diamine oligomer of 8wt% and the adipic acid mix homogeneously of 0.5wt%, copolymerization is carried out, with the nylon copolymer mixture E 2 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment two, the molecular weight of polyether diamine oligomer is 900g/mol. The terminal amido content of the nylon copolymer mixture E 2 that embodiment two provides be 19 milliequivalents/kilogram.
Embodiment three: prepare nylon copolymer mixture E 3
After the caprolactam monomer of the open loop of 91.12wt%, the adipic acid of 0.58wt%, the polyether diamine oligomer of 8wt% and the adipic acid mix homogeneously of 0.3wt%, copolymerization is carried out, with the nylon copolymer mixture E 3 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment three, the molecular weight of polyether diamine oligomer is 2,000g/mol. The terminal amido content of the nylon copolymer mixture E 3 that embodiment three provides be 31 milliequivalents/kilogram.
Embodiment four: prepare nylon copolymer mixture E 4
After the caprolactam monomer of the open loop of 90.92wt%, the adipic acid of 0.58wt%, the polyether diamine oligomer of 8wt% and the adipic acid mix homogeneously of 0.5wt%, copolymerization is carried out, with the nylon copolymer mixture E 4 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment four, the molecular weight of polyether diamine oligomer is 2,000g/mol. The terminal amido content of the nylon copolymer mixture E 4 that embodiment four provides be 16 milliequivalents/kilogram.
Embodiment five: prepare nylon copolymer mixture E 5
After the caprolactam monomer of the open loop of 90.4wt%, the adipic acid of 1.3wt%, the polyether diamine oligomer of 8wt% and the p-phthalic acid mix homogeneously of 0.3wt%, copolymerization is carried out, with the nylon copolymer mixture E 5 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment five, the molecular weight of polyether diamine oligomer is 900g/mol. The terminal amido content of the nylon copolymer mixture E 5 that embodiment five provides be 28 milliequivalents/kilogram.
Embodiment six: prepare nylon copolymer mixture E 6
After the caprolactam monomer of the open loop of 91.12wt%, the adipic acid of 0.58wt%, the polyether diamine oligomer of 8wt% and the p-phthalic acid mix homogeneously of 0.3wt%, copolymerization is carried out, with the nylon copolymer mixture E 6 that formation is made up of multiple nylon copolymers at temperature 200��270 DEG C and absolute pressure 0.2��3bar. In embodiment six, the molecular weight of polyether diamine oligomer is 2,000g/mol. The terminal amido content of the nylon copolymer mixture E 6 that embodiment six provides be 33 milliequivalents/kilogram.
Table one: the composition and ratio transitivity comparison sheet of comparative example 1��2 and embodiment 1��6
By the result of table one it can be seen that the nylon copolymer mixture E 1��E6 that provides of the embodiment of the present invention one��six viscosity in 25 DEG C time and fusing point are all similar to nylon copolymer mixture C 1��C2 that comparative example one��bis-provides. But, compared to nylon copolymer mixture C 1��C2 that comparative example one��bis-provides, the embodiment of the present invention one��six is provided the nylon copolymer mixture E 1��E6 containing excessive adipic acid or p-phthalic acid to have obvious less terminal amido content (16��33 milliequivalents/kilogram), and wherein nylon copolymer mixture E 4 has relatively minimal terminal amido content (16 milliequivalents/kilogram).
Relatively terminal amido content and the excessive adipic acid content of nylon copolymer mixture E 1 and E2 are known, owing to the adipic acid content (0.5wt%) of nylon copolymer mixture E 2 is higher than the adipic acid content (0.3wt%) of nylon copolymer mixture E 1, therefore the terminal amido content (19 milliequivalents/kilogram) of nylon copolymer mixture E 2 is considerably less than the terminal amido content (25 milliequivalents/kilogram) of nylon copolymer mixture E 1. Relatively terminal amido content and the excessive adipic acid content of nylon copolymer mixture E 3 and E4 also can obtain identical result. If it follows that when in nylon copolymer mixture, excessive two acid contents are more, then the terminal amido content of nylon copolymer mixture is less.
In addition, relatively terminal amido content and the excessive diacid kind of nylon copolymer mixture E 1 and E5 are known, in nylon copolymer mixture E 1, adipic acid content is identical with terephthaldehyde's acid content in nylon copolymer mixture E 5, and the terminal amido content of nylon copolymer mixture E 1 and E5 is close. Yet with nylon copolymer mixture E 5 has adipic acid and p-phthalic acid simultaneously, these two kinds of diacid monomer can produce competitive effect, therefore compared to the copolymerization time of nylon copolymer mixture E 1, the copolymerization time of nylon copolymer mixture E 5 is longer.
In an embodiment of the present invention, nylon copolymer mixture E 1��E4 all spinning can become nylon fiber, and has fiber shape. According to embodiments of the invention, fiber shape comprises circle, yi word pattern, cross, Y-shaped or its combination.
Table two: the fibrous physical property comparison sheet of the nylon fiber made by nylon copolymer mixture E 1��E4
| Red Buddhist nun (g) | Intensity (g/d) | Degree of stretching (%) | |
| E1 | 73.7 | 3.51 | 44.8 |
| E2 | 75.5 | 3.56 | 45.0 |
| E3 | 75.3 | 3.79 | 41.7 |
| E4 | 74.8 | 3.55 | 40.3 |
Result from table one, the intensity of the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and degree of stretching all reach the application level of nylon fiber material, and the nylon fiber made by nylon copolymer mixture E 1��E4 that therefore embodiment of the present invention provides can be used for the related application field of generally commercially available nylon fiber material.
In an embodiment of the present invention, hydroscopicity (�� MRa) and the moisture releasing rate (�� MRd) of the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and generally commercially available nylon fiber material (comparative example C3��C5) are compared.
Following with the nylon fiber made by the nylon copolymer mixture E 1 that the embodiment of the present invention provides moisture adsorption and releasing condition determination is described, and the nylon fiber made by nylon copolymer mixture E 2��E4 that provides of other embodiment of the present invention and generally commercially available nylon fiber material (comparative example C3��C5) also moisture adsorption and releasing condition determination measures its hydroscopicity and moisture releasing rate according to this.
Demonstration example: utilize the nylon fiber made by nylon copolymer mixture E 1 that the embodiment of the present invention provides that moisture adsorption and releasing condition determination is described. Nylon fiber made by nylon copolymer mixture E 1 is placed in the environment of 105 DEG C after lower 2 hours, obtains the first weight W1. Then, above-mentioned nylon fiber is placed in 20 DEG C and lower 24 hours of environment that humidity is 65%, obtains the second weight W2. Then, above-mentioned nylon fiber is placed in 30 DEG C and lower 24 hours of environment that humidity is 90%, obtains the 3rd weight W3. Finally, above-mentioned nylon fiber is placed in 20 DEG C and lower 24 hours of environment that humidity is 65%, obtains the 4th weight W4.
Regain 1 (%)=(second weight W2-the first weight W1)/first weight W1 �� 100%; Regain 2 (%)=(the 3rd weight W3-the first weight W1)/first weight W1 �� 100%; And regain 3 (%)=(the 4th weight W4-the first weight W1)/first weight W1 �� 100%.
Hydroscopicity (�� MRa, the %)=regain 2-regain 1 of the nylon fiber made by nylon copolymer mixture E 1 that the embodiment of the present invention provides; And moisture releasing rate (�� MRd, %)=regain 2-regain 3.
The nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and listed by the moisture adsorption and releasing measurement result such as table three of generally commercially available nylon fiber material (comparative example C3��C5).
Table three: the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and the moisture adsorption and releasing comparison sheet of generally commercially available nylon fiber material (comparative example C3��C5)
Result from table three, compared to generally commercially available nylon fiber material (comparative example C3��C5, the hydroscopicity (�� MRa) of the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and moisture releasing rate (�� MRd) are all significantly greater than generally commercially available nylon fiber material (comparative example C3��C5), and wherein nylon fiber made by nylon copolymer mixture E 1 and E3 has relatively the highest hydroscopicity (�� MRa=4.05) and moisture releasing rate (�� MRd=3.80) respectively.
In an embodiment of the present invention, the value of chromatism (�� E) of the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and generally commercially available nylon fiber material (comparative example C3��C5) is compared.
Following with the nylon fiber made by the nylon copolymer mixture E 1 that the embodiment of the present invention provides dyeing condition is described, and the nylon fiber made by nylon copolymer mixture E 2��E4 that provides of other embodiment of the present invention and generally commercially available nylon fiber material (comparative example C3��C5) also according to this dyeing condition measure its value of chromatism (�� E).
Demonstration example: utilize the nylon fiber made by nylon copolymer mixture E 1 that the embodiment of the present invention provides that dyeing condition is described. Under the environment of bath raio 1:20, nylon fiber made by nylon copolymer mixture E 1 is put and dyestuff (TalonblueAFN, 1wt%), dye leveller (Albegalset, 1wt%) and pH (sodium acetate of 0.8g/l and the acetic acid of 1.0g/l) mix homogeneously. Then, heat to 100 DEG C with the speed of 2 DEG C per minute, Temperature fall after continuing 60 minutes. It is eventually adding color fixing agent (the N-bromo-succinimide of 4g/l and the acetic acid of 0.3g/l), at 75 DEG C, carries out fixation react 15 minutes.
The nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and listed by the coloration result such as table four of generally commercially available nylon fiber material (comparative example C3��C5).
Table four: the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and aberration comparison sheet before and after the washing of generally commercially available nylon fiber material (comparative example C3��C5).
Result from table four, compared to generally commercially available nylon fiber material (comparative example C3��C5), after the washing of the nylon fiber made by nylon copolymer mixture E 2��E4 that the embodiment of the present invention provides, value of chromatism (�� E) is respectively less than generally commercially available nylon fiber material (comparative example C3��C5), and wherein the nylon fiber made by nylon copolymer mixture E 4 has value of chromatism (�� E=1.42) after relatively minimal washing. This result represents, after the washing of the nylon fiber made by nylon copolymer mixture E 2��E4 that the embodiment of the present invention provides, value of chromatism is less, therefore is not easy to fade when washing.
In addition, after the washing of the nylon fiber made by comparison nylon copolymer mixture E 1 and E3, value of chromatism (�� E) and the molecular weight of polyether diamine are known, compared to the nylon fiber made by the nylon copolymer mixture E 1 containing the polyether diamine that molecular weight is 900g/mol, after washing containing the nylon fiber made by the nylon copolymer mixture E 3 of the polyether diamine that molecular weight is 2,000g/mol, value of chromatism is less. After comparing the washing of the nylon fiber made by nylon copolymer mixture E 2 and E4, the molecular weight of value of chromatism (�� E) and polyether diamine also can obtain identical result. If it follows that when being the polyether diamine of 2,000g/mol containing molecular weight in nylon copolymer mixture, then after the washing of thus nylon fiber made by nylon copolymer mixture, value of chromatism is less, and not fugitive color.
Table five: the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides and the dyeing comparison sheet of generally commercially available nylon fiber material (comparative example C4��C5)
Result from table five, with the value of chromatism of generally commercially available nylon fiber material (comparative example C5) for benchmark, the value of chromatism to comparative example C5 (�� E) of the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides is significantly greater than generally commercially available nylon fiber material (comparative example C4), and wherein the nylon fiber made by nylon copolymer mixture E 2 has the value of chromatism to comparative example C5 (�� E=12.83) of relative maximum. Generally commercially available nylon fiber material (comparative example C5) easily reaches deeply to contaminate effect, review, the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides has low-end amine groups content, can as the nylon fiber material of understain, therefore with the value of chromatism of generally commercially available nylon fiber material (comparative example C5) for benchmark, the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides is significantly greater to the value of chromatism (�� E) of comparative example C5.
In one embodiment of this invention, the nylon fiber made by nylon copolymer mixture E 1��E4 that the embodiment of the present invention provides can with generally commercially available nylon fiber material blend dyeing, to reach two tone dyeing (twotone) or the effect of melange yarn (melange).
Table six: the nylon fiber made by nylon copolymer mixture E 3 that the embodiment of the present invention provides has the dyeing comparison sheet of different fiber shape
Result from table six, compared to circular yarn, yi word pattern yarn and Y-shaped yarn, the value of chromatism (�� E) that the nylon fiber made by nylon copolymer mixture E 3 that the embodiment of the present invention provides is during cross yarn is minimum, therefore is not easy to fade when washing.
For improve conventional nylon material because of the characteristic of chemical constitution own under the kind not changing dyestuff and concentration the problem of not easily understain, a kind of nylon copolymer mixture provided by the present invention, its manufacture method and comprise its nylon fiber, wherein nylon copolymer mixture provided by the present invention has low-end amine groups content, relatively low with the reactivity of general stain, therefore understain effect can be reached. Therefore, compared to generally commercially available nylon fiber material, the value of chromatism of the nylon fiber made by nylon copolymer mixture that the embodiment of the present invention provides is significantly greater, more can further with generally commercially available nylon fiber material blending and dyeing, to reach two tone dyeing (twotone) or the effect of melange yarn (melange).
On the other hand, the nylon copolymer mixture that embodiment of the present invention provides is to form by having the polyether diamine oligomer of secondary amine and ether, diacid monomer and caprolactam combined polymerization. This nylon copolymer mixture not only has low-end amido number, more can reach understain effect. Additionally, provide good absorb-discharge humid via the ether of polyether diamine oligomer, the fabric that thus nylon copolymer mixture is made is made to have significant cool feeling effect.
Although embodiments of the invention are disclosed above; so it is not limited to the present invention, any has the knack of this those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little change and retouching, therefore protection scope of the present invention ought be as the criterion with the scope that appended claims defines.
Claims (25)
1. a nylon copolymer mixture, comprises multiple nylon copolymer and has general structure shown below (I):
Wherein, monomer A is the lactam monomers of an open loop, and the content (a) that monomer A is in described nylon copolymer mixture is 100-(b+c+d) wt%;
Monomer B is a polyether diamine oligomer, and the content (b) that monomer B is in described nylon copolymer mixture is 6��12wt%;
Monomer C is one first diacid monomer, and the content (c) that monomer C is in described nylon copolymer mixture is 0.3��4.0wt%;
Monomer D is one second diacid monomer, and the content (d) that monomer D is in described nylon copolymer mixture is 0.2��0.6wt%; And
T1And T2Be each independently carboxylic acid group or amido, and relative to the gross weight of described nylon copolymer mixture, the total content of the terminal amido of described nylon copolymer be 10��40 milliequivalents/kilogram.
2. nylon copolymer mixture as claimed in claim 1, wherein relative to the gross weight of described nylon copolymer mixture, the total content of the terminal amido of described nylon copolymer be 15��30 milliequivalents/kilogram.
3. nylon copolymer mixture as claimed in claim 1, the chemical formula of wherein said monomer A isM is the integer of 5��11, and * is monomer A binding site in formula (I).
4. nylon copolymer mixture as claimed in claim 1, the chemical formula of wherein said monomer B isIts molecular weight is 500��2500g/mol, * is monomer B binding site in formula (I).
5. nylon copolymer mixture as claimed in claim 1, wherein said monomer C is aliphatic diacid monomer, aromatic diacid monomer or its combination.
6. nylon copolymer mixture as claimed in claim 5, the chemical formula of wherein said aliphatic diacid monomer isP is the integer of 2��10, and * is aliphatic diacid monomer binding site in formula (I).
7. nylon copolymer mixture as claimed in claim 5, the chemical formula of wherein said aromatic diacid monomer is* it is described aromatic diacid monomer binding site in formula (I).
8. nylon copolymer mixture as claimed in claim 1, wherein in described nylon copolymer mixture, the molal quantity of described monomer B is identical with the molal quantity of described monomer C.
9. nylon copolymer mixture as claimed in claim 1, wherein said monomer D is aliphatic diacid monomer, aromatic diacid monomer or its combination.
10. nylon copolymer mixture as claimed in claim 9, the chemical formula of wherein said aliphatic diacid monomer isP is the integer of 2��10, and * is described aliphatic diacid monomer binding site in formula (I).
11. nylon copolymer mixture as claimed in claim 9, the chemical formula of wherein said aromatic diacid monomer is* it is described aromatic diacid monomer binding site in formula (I).
12. a nylon fiber, comprise:
Nylon copolymer mixture as described in any one of claim 1��11, has fiber shape.
13. nylon fiber as claimed in claim 12, wherein said fiber shape is circle, yi word pattern, cross, Y-shaped or its combination.
14. a manufacture method for nylon copolymer mixture, comprise:
Carry out copolymerization, lactam monomers (A), the first diacid monomer (B), polyether diamine oligomer (C) and the second diacid monomer (D) combined polymerization is made to form nylon copolymer mixture, wherein said nylon copolymer mixture comprises multiple nylon copolymer, and it has general structure shown below (I):
Wherein, in described nylon copolymer mixture, the content (a) of described lactam monomers (A) is 100-(b+c+d) wt%; The content (b) of described polyether diamine oligomer (B) is 6��12wt%; The content (c) of described first diacid monomer (C) is 0.3��4.0wt%; The content (d) of described second diacid monomer (D) is 0.2��0.6wt%; And T1And T2Be each independently carboxylic acid group or amido, and relative to the gross weight of described nylon copolymer mixture, the total content of the terminal amido of described nylon copolymer be 10��40 milliequivalents/kilogram.
15. manufacture method as claimed in claim 14, wherein relative to the gross weight of described nylon copolymer mixture, the total content of the terminal amido of described nylon copolymer be 15��30 milliequivalents/kilogram.
16. manufacture method as claimed in claim 14, wherein said copolymerization is to carry out at temperature 200��270 DEG C and absolute pressure 0.2��3bar.
17. manufacture method as claimed in claim 14, wherein the chemical formula of lactam monomers (A) isWherein m is the integer of 5��11, and * is described lactam monomers (A) binding site in formula (I).
18. manufacture method as claimed in claim 14, wherein the chemical formula of polyether diamine oligomer (B) isIts molecular weight is 900��2000g/mol, * is described polyether diamine oligomer (B) binding site in formula (I).
19. manufacture method as claimed in claim 14, wherein said first diacid monomer (C) is aliphatic diacid monomer, aromatic diacid monomer or its combination.
20. manufacture method as claimed in claim 19, the chemical formula of wherein said aliphatic diacid monomer isWherein p is the integer of 2��10, and * is described aliphatic diacid monomer binding site in formula (I).
21. manufacture method as claimed in claim 19, the chemical formula of wherein said aromatic diacid monomer is* it is described aromatic diacid monomer binding site in formula (I).
22. manufacture method as claimed in claim 14, wherein in described nylon copolymer mixture, the molal quantity of described monomer B is identical with the molal quantity of described monomer C.
23. manufacture method as claimed in claim 14, wherein said second diacid monomer (D) is aliphatic diacid monomer, aromatic diacid monomer or its combination.
24. manufacture method as claimed in claim 23, the chemical formula of wherein said aliphatic diacid monomer isWherein p is the integer of 2��10, and * is described aliphatic diacid monomer binding site in formula (I).
25. manufacture method as claimed in claim 23, the chemical formula of wherein said aromatic diacid monomer is* it is described aromatic diacid monomer binding site in formula (I).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018068705A1 (en) * | 2016-10-11 | 2018-04-19 | 东丽先端材料研究开发（中国）有限公司 | Polyamide, preparation method therefor, and metal adaptor |
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| EP0373873A2 (en) * | 1988-12-12 | 1990-06-20 | Du Pont Canada Inc. | Process and apparatus for modifying polyamide dyeability or amine end content |
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| EP0373873A2 (en) * | 1988-12-12 | 1990-06-20 | Du Pont Canada Inc. | Process and apparatus for modifying polyamide dyeability or amine end content |
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| SYANG-PENG RWEI ET AL: ""Synthesis and Characterization of PolyethyleneOxide and Nylon-6 Copolymer in a Fiber Form"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018068705A1 (en) * | 2016-10-11 | 2018-04-19 | 东丽先端材料研究开发（中国）有限公司 | Polyamide, preparation method therefor, and metal adaptor |
| CN109715705A (en) * | 2016-10-11 | 2019-05-03 | 东丽先端材料研究开发（中国）有限公司 | A kind of polyamide, preparation method and a kind of metal bonded body |
| CN109715705B (en) * | 2016-10-11 | 2021-05-14 | 东丽先端材料研究开发（中国）有限公司 | Polyamide, preparation method thereof and metal conjugant |
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