CN110343244B - Method for producing polyamide fiber-forming polymers and use thereof - Google Patents
Method for producing polyamide fiber-forming polymers and use thereof Download PDFInfo
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- CN110343244B CN110343244B CN201910733934.9A CN201910733934A CN110343244B CN 110343244 B CN110343244 B CN 110343244B CN 201910733934 A CN201910733934 A CN 201910733934A CN 110343244 B CN110343244 B CN 110343244B
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- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
Abstract
The invention relates to a method for producing polyamide fibre-forming polymers and to the use thereof. The process for the preparation of polyamide fiber-forming polymers comprises the preparation of a "soft-block" polyamide oligomer and a "hard-block" polyamide oligomer, and then the melt of the "soft-block" polyamide oligomer and the melt of the "hard-block" polyamide oligomer are mixed and reacted to give a polyamide fiber-forming polymer. The invention uses caprolactam as the base, introduces rigid group to synthesize 'hard-segment' polyamide oligomer, introduces flexible group to synthesize 'soft-segment' polyamide oligomer, and combines the 'soft-segment' polyamide oligomer and the 'hard-segment' polyamide oligomer to prepare the elastic polyamide fiber-forming polymer with 'soft and hard segments' similar to polyurethane. The elastic recovery rate of the polyamide fiber prepared by the polymer can still reach more than 50 percent after 300 cycles at 30 percent fixed elongation.
Description
Technical Field
The present invention belongs to the field of polymer synthesis and fiber forming technology. More particularly, the invention relates to a process for preparing polyamide fiber-forming polymers and the use thereof.
Background
The fabric made of the elastic fiber is comfortable to wear, has good shape retention and wrinkle resistance, and the application field is also expanded from the traditional clothing field to the new fields of leisure wear, high-elasticity fashion wear, high-grade ready-made clothes and the like, and is expanded to the fields of automobile decoration, medical use and the like. Currently, elastic fabrics have become a mainstream textile product.
The elastic fibers on the market are various and can be roughly divided into: spandex, polyether ester elastic fibers, polyolefin elastic fibers, PTT fibers, bi-component composite crimped fibers and the like. These elastic fibers have many advantages, but also have disadvantages, and further improvements are desired. For example, PTT fiber has a good elastic recovery property due to its own structural characteristics, and also has a problem of low strength. The strength and elasticity of the bicomponent composite fiber represented by T400 are moderate, but the cost of PBT is slightly higher. Spandex is the fiber with the best elasticity in the industry at present, the elastic recovery rate can reach 800%, but the strength is too low and is only about 1cN/dtex, and the cost is particularly high, so that the spandex is often combined with terylene or chinlon synthetic yarns when in use, and large elasticity residue exists.
There are a number of patents which disclose copolymers having polyamide blocks and polyether blocks.
U.S. Pat. No. 4,4820796 discloses copolymers having polyamide blocks made of caprolactam and polyether blocks having a number average molecular weight of between 680 and 4040.
Japanese patent JP63-182343 discloses a process for preparing nylon elastomers by melt polymerization of amides having amine groups as end groups and polyethers having carboxyl groups.
EP-A01163902 discloses polyetheramides which are synthesized from lactam-reactive aminocarboxylic acids, dicarboxylic acids and polyethers.
Chinese patent CN1708538A discloses a transparent polyamide block and polyether block copolymer whose polyamide blocks are composed of linear (acyclic, unbranched) aliphatic predominantly semi-crystalline monomers and a sufficient amount of at least one comonomer such that the block crystallinity is reduced while remaining immiscible with the amorphous polyether block. Thereby ensuring the transparency of the polymerized resin.
The polyamide elastomers disclosed in the above patent documents are easily decomposed during processing because of their non-miscibility between the hard segment and the soft segment, and the resulting products have low strength.
Accordingly, there remains a need in the art for polymeric materials that are capable of forming fibers that are resilient and strong.
Disclosure of Invention
It is an object of the present invention to provide a polymeric material capable of forming fibers having good elasticity and high strength.
Another object of the present invention is to provide a fiber having high elasticity and high strength.
To achieve the above and other objects, the present invention provides the following technical solutions.
According to a first aspect of the present invention, there is provided a process for preparing a polyamide fiber-forming polymer, comprising the steps of:
i) preparation of "soft block" polyamide oligomer: polymerizing caprolactam, adipic acid, and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to obtain a "soft-block" polyamide oligomer having a relative viscosity of 0.6 to 0.8;
ii) preparation of "hard-stage" polyamide oligomers: reacting caprolactam with NH2-R-COOH, wherein R is selected from phenylene and naphthylene, to obtain a "hard-block" polyamide oligomer with a relative viscosity of 0.8 to 1.0; and
iii) preparation of polyamide fiber-forming polymers: the melt of the polyamide oligomer of the "soft block" and the melt of the polyamide oligomer of the "hard block" are mixed and reacted to give a polyamide fiber-forming polymer with a relative viscosity of 2.5 to 3.0.
According to a second aspect of the present invention, there is provided a polyamide fiber obtained by melt-spinning the above polyamide fiber-forming polymer.
According to a third aspect of the present invention, there is provided a process for producing polyamide fibers, characterized in that it comprises melt-spinning the above polyamide fiber-forming polymer.
The invention uses caprolactam as the base, introduces rigid group to synthesize 'hard-segment' polyamide oligomer, introduces flexible group to synthesize 'soft-segment' polyamide oligomer, and combines the 'soft-segment' polyamide oligomer and the 'hard-segment' polyamide oligomer to prepare the elastic polyamide fiber-forming polymer with 'soft and hard segments' similar to polyurethane. The elastic recovery rate of the polyamide fiber prepared by the polymer can still reach more than 50 percent after 300 cycles at 30 percent fixed elongation.
Detailed description of the preferred embodiments
The invention will be further illustrated with reference to specific embodiments. It should be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention.
According to one aspect of the present invention, a process for preparing a polyamide fiber-forming polymer is provided, characterized in that it comprises the following steps:
i) preparation of "soft block" polyamide oligomer: polymerizing caprolactam, adipic acid, and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to obtain a "soft-block" polyamide oligomer having a relative viscosity of 0.6 to 0.8;
ii) preparation of "hard-stage" polyamide oligomers: reacting caprolactam with NH2-R-COOH, wherein R is selected from phenylene and naphthylene, to obtain a "hard-block" polyamide oligomer with a relative viscosity of 0.8 to 1.0; and
iii) preparation of polyamide fiber-forming polymers: the melt of the polyamide oligomer of the "soft block" and the melt of the polyamide oligomer of the "hard block" are mixed and reacted to give a polyamide fiber-forming polymer with a relative viscosity of 2.5 to 3.0.
The relative viscosity described herein can be measured by the Ubbelohde viscometer method.
After reading this specification, it will be understood by those skilled in the art that the present invention does not impose strict requirements on the order of preparation of the "soft-block" polyamide oligomer and the "hard-block" polyamide oligomer.
The polyamide fiber-forming polymer can be obtained by preparing a "soft-block" polyamide oligomer, then preparing a "hard-block" polyamide oligomer, and then mixing the melts of the two together to continue the polymerization.
It is also possible to prepare the polyamide oligomer "hard block" first and then the polyamide oligomer "soft block" and to mix the melts of the two together for further polymerization to give the polyamide fiber-forming polymer.
It is also possible to prepare both "hard-block" polyamide oligomers and "soft-block" polyamide oligomers and then to mix the melts of the two together to continue the polymerization to give the polyamide fiber-forming polymer.
In some embodiments, step i) is performed by:
adipic acid and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane are reacted in the presence of caprolactam, and then the caprolactam is hydrolyzed, followed by vacuum polymerization.
Alternatively, adipic acid and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane are reacted at a temperature in the range of 130 to 150 ℃, preferably 140 ℃, for 1 to 3 hours, preferably 2 hours.
Alternatively, the caprolactam may be melted prior to reacting the adipic acid and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane.
Alternatively, the caprolactam is melted at a temperature in the range of 80 to 100 ℃, preferably at 90 ℃.
Alternatively, the caprolactam is hydrolyzed at a temperature in the range of 245 ℃ to 255 ℃, preferably 250 ℃.
Alternatively, in the preparation of the "soft block" polyamide oligomer, the molar ratio of adipic acid to 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is 1: 1.
Alternatively, in the preparation of the "soft block" polyamide oligomer, the weight of adipic acid is from 5% to 20%, preferably from 10% to 15%, of the weight of caprolactam.
In some embodiments, step ii) is performed by:
at NH2In the presence of R-COOH, using water as a ring-opening agent to open and hydrolyze caprolactam, and then vacuumizing for polymerization.
Alternatively, the caprolactam is hydrolyzed at a temperature in the range of 245 ℃ to 255 ℃, preferably 250 ℃.
Alternatively, NH during the preparation of the "hard-block" polyamide oligomer2The weight of R-COOH is 5% -10%, preferably 8% -10% of the weight of caprolactam.
Alternatively, the weight ratio of "soft-stage" polyamide oligomer melt to "hard-stage" polyamide oligomer during the preparation of the polyamide fiber-forming polymer is 1:2 to 2:1, preferably 1: 1.
alternatively, the melt of the "soft-block" polyamide oligomer and the "hard-block" polyamide oligomer are reacted at a temperature of 260 ℃ and a pressure of-0.06 MPa for a period of 2 to 4 hours.
According to a second aspect of the present invention, there is provided a polyamide fiber obtained by melt-spinning the above polyamide fiber-forming polymer.
In some embodiments, the polyamide fibers have a cross-sectional shape selected from the group consisting of round, dumbbell, oval, and near-round.
In some embodiments, the polyamide fibers have a linear density of 1 to 2 dtex.
Optionally, the polyamide fiber has an elastic recovery of 50% or more after 300 cycles at 30% constant elongation.
Optionally, the tensile strength of the polyamide fiber is not lower than 7.0cN/dtex, and the elongation at break is not less than 40%.
According to a third aspect of the present invention, there is provided a process for producing polyamide fibers, characterized in that it comprises melt-spinning the above polyamide fiber-forming polymer.
In some embodiments, the polyamide fiber-forming polymer is dried and melt extruded through a screw extruder and extruded through a metering pump and a spin pack from a spinneret.
In some embodiments, the shape of the orifices on the spinneret are such that the resulting fibers are circular, dumbbell, elliptical, or near circular in cross-section.
Alternatively, the spinning temperature is 260 ℃ and 270 ℃, preferably 265 ℃.
One skilled in the art can adjust the spinneret temperature, metering pump pressure and spinning speed as desired.
In the present specification and claims, where a term is referred to, it is understood that the term has any definition set forth in the specification of the application for that term unless a definition clearly contradicts the context of the term.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, and so forth, in the specification and claims are to be understood as being modified in all instances by the term "about".
The terms "comprising" and "including" used in the specification of the present application encompass the case where other elements not explicitly mentioned are also contained or included and the case where they are composed of the elements mentioned.
Examples
The conception and the resulting technical effects of the present invention will be further described with reference to the following examples so that those skilled in the art can fully understand the objects, features and effects of the present invention. It will be understood by those skilled in the art that the embodiments herein are for illustrative purposes only and the scope of the present invention is not limited thereto.
Example 1
i) Preparation of "Soft Block" Polyamide oligomers
Mixing and stirring caprolactam, 10 wt% of adipic acid relative to the weight of the caprolactam and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane in an equimolar amount with the adipic acid, melting the caprolactam at 90 ℃, raising the temperature to 140 ℃ to react the adipic acid with the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane for 2 hours, then raising the temperature to 250 ℃ and carrying out ring-opening hydrolysis on the caprolactam, controlling the pressure to be about 0.2MPa, vacuumizing after the hydrolysis is finished (the hydrolysis stage is about 2 hours, and the system pressure is reduced after the hydrolysis is finished), and obtaining the 'soft-block' polyamide oligomer, wherein the relative viscosity is measured to be 0.75.
ii) preparation of "hard-stage" polyamide oligomers
Caprolactam is used as a basic raw material, p-aminobenzoic acid copolymerization components accounting for 8 wt% of the caprolactam are added, water is used as a ring-opening agent, ring opening hydrolysis is carried out at 250 ℃, after the hydrolysis is finished, vacuum pumping is carried out, and 'hard-segment' polyamide oligomer is obtained, and the relative viscosity is measured to be 0.83.
iii) preparation of Polyamide fiber-Forming Polymer
Pumping the soft-section polyamide oligomer melt into the hard-section polyamide oligomer melt, heating to 265 ℃, reacting for 2 hours under the vacuum degree of 0.06MPa to obtain polyamide fiber-forming polymer, measuring the relative viscosity of the polyamide fiber-forming polymer to be 2.86, cooling and dicing to obtain polyamide fiber-forming polymer chips.
iv) preparation of Polyamide fibers
The polyamide fiber-forming polymer slices are extracted in boiling water at 100 ℃, then are dried by hot air at 110 ℃, and finally are dried in a vacuum drum at 150 ℃ to ensure that the water content of the dry slices is less than 30 ppm.
And (3) carrying out melt extrusion on the dried polyamide fiber-forming polymer slices through a screw extruder, carrying out extrusion molding from a spinneret plate through a metering pump and a spinning assembly, wherein the temperature of a spinning box body is 265 ℃, the number of holes of the spinneret plate is 36, and carrying out stretching and shaping to obtain the FDY fiber. The obtained polyamide fiber had a high three-dimensional spiral crimp characteristic, and the performance index of the obtained polyamide fiber was as shown in table 1.
TABLE 1 Properties of the Polyamide fibers obtained
Example 2
Caprolactam, adipic acid in an amount of 15% by weight relative to the weight of caprolactam and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane in an equimolar amount to the weight of adipic acid are mixed and stirred, the caprolactam is melted at 90 ℃, the adipic acid is reacted with 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane for 2 hours at an elevated temperature of 140 ℃, the temperature is then raised to 250 ℃ and the caprolactam is subjected to ring-opening hydrolysis, the pressure is controlled so as not to exceed 0.2MPa, after the hydrolysis is complete, a vacuum is applied to obtain a "soft-block" polyamide oligomer, the relative viscosity of which is determined to be 0.65.
ii) preparation of "hard-stage" polyamide oligomers
Caprolactam is used as a basic raw material, a p-aminonaphthoic acid copolymerization component accounting for 10 wt% of caprolactam is added, water is used as a ring-opening agent, ring opening hydrolysis is carried out at 250 ℃, after the hydrolysis is finished (about 2 hours of hydrolysis, the system pressure is reduced after the hydrolysis is finished), vacuum pumping is carried out, and the polyamide oligomer with a hard segment is obtained, and the relative viscosity is measured to be 0.92.
iii) preparation of Polyamide fiber-Forming Polymer
Pumping the soft-section polyamide oligomer melt into the hard-section polyamide oligomer melt, heating to 265 ℃, reacting for 2 hours under the vacuum degree of 0.06MPa to obtain polyamide fiber-forming polymer, measuring the relative viscosity of the polyamide fiber-forming polymer to be 2.92, cooling and dicing to obtain polyamide fiber-forming polymer chips.
iv) preparation of Polyamide fibers
The polyamide fiber-forming polymer slices are extracted in boiling water at 100 ℃, then are dried by hot air at 110 ℃, and finally are dried in a vacuum drum at 150 ℃ to ensure that the water content of the dry slices is less than 30 ppm.
And (3) carrying out melt extrusion on the dried polyamide fiber-forming polymer slices through a screw extruder, carrying out extrusion molding from a spinneret plate through a metering pump and a spinning assembly, wherein the temperature of a spinning box body is 265 ℃, the number of holes of the spinneret plate is 36, and carrying out stretching and shaping to obtain the FDY fiber. The obtained polyamide fiber had a high three-dimensional spiral crimp characteristic, and the performance index of the obtained polyamide fiber was as shown in table 2.
TABLE 2 Properties of the Polyamide fibers obtained
The above examples have shown: the invention realizes the purpose of adjusting the elasticity of the fiber by respectively adjusting the rigid chain segment and the flexible chain segment in the soft segment and the hard segment.
Although a few aspects of the present invention have been shown and discussed, it would be appreciated by those skilled in the art that changes may be made in this aspect without departing from the principles and spirit of the invention, the scope of which is therefore defined in the claims and their equivalents.
Claims (11)
1. A process for preparing polyamide fiber-forming polymers, characterized in that it comprises the following steps:
i) preparation of "soft block" polyamide oligomer: polymerizing caprolactam, adipic acid, and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to obtain a "soft-block" polyamide oligomer having a relative viscosity of 0.6 to 0.8;
ii) preparation of "hard-stage" polyamide oligomers: reacting caprolactam with NH2-R-COOH, wherein R is selected from phenylene and naphthylene, to obtain a "hard-block" polyamide oligomer with a relative viscosity of 0.8 to 1.0; and
iii) preparation of polyamide fiber-forming polymers: the melt of the polyamide oligomer of the "soft block" and the melt of the polyamide oligomer of the "hard block" are mixed and reacted to give a polyamide fiber-forming polymer with a relative viscosity of 2.5 to 3.0.
2. The method of claim 1,
step i) is carried out by: reacting adipic acid and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane in the presence of caprolactam, followed by hydrolysis of the caprolactam and subsequent polymerization in vacuo; and/or
Step ii) is carried out by: at NH2In the presence of R-COOH, using water as a ring-opening agent to open and hydrolyze caprolactam, and then vacuumizing for polymerization.
3. The process according to claim 1 or 2, characterized in that the molar ratio between adipic acid and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is 1: 1.
4. A process according to claim 1 or 2, characterized in that in the preparation of the "soft block" polyamide oligomer, the weight of adipic acid is 5-20% of the weight of caprolactam.
5. Process according to claim 1 or 2, characterized in that during the preparation of the "hard block" polyamide oligomer, NH is added2-R-COOH in an amount of 5% to 10% based on the weight of caprolactam.
6. The process according to claim 1 or 2, characterized in that the weight ratio of the melt of the "soft-block" polyamide oligomer to the "hard-block" polyamide oligomer is from 1:2 to 2: 1.
7. The process according to claim 1 or 2, characterized in that the weight ratio of the melt of the "soft-block" polyamide oligomer to the "hard-block" polyamide oligomer is 1: 1.
8. Polyamide fibre, characterized in that it is melt spun from a polyamide fibre-forming polymer prepared by the process according to any one of claims 1-7.
9. Polyamide fibre according to claim 8, characterized in that it has a cross-sectional shape selected from the group consisting of circular, dumbbell, elliptical, near-circular.
10. A process for the preparation of a polyamide fibre according to claim 8 or 9, characterized in that it comprises melt spinning a polyamide fibre-forming polymer prepared by a process according to any one of claims 1 to 7.
11. The method as claimed in claim 10, wherein the spinning temperature is 260-270 ℃.
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| CN107033345A (en) * | 2017-05-17 | 2017-08-11 | 东华大学 | A kind of resin of Environmentally-frieflame-retardant flame-retardant nylon 6 and preparation method thereof |
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| CN102653594A (en) * | 2011-03-02 | 2012-09-05 | 骏马化纤股份有限公司 | Block type high-temperature-resistant copolyamide and preparation method thereof |
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