CN115522275A - High-resilience spandex fiber and preparation method thereof - Google Patents
High-resilience spandex fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-resilience spandex fiber, which comprises the following main raw materials: polyether polyol or polyester polyol, and diisocyanate compounds, chain extenders and blocking agents; the chain extender is lysine cyclic dipeptide or ornithine cyclic dipeptide. The invention also discloses a preparation method of the high-resilience spandex fiber. The invention uses the condensation products of two molecularamino acids, namely lysine cyclic dipeptide and ornithine cyclic dipeptide, as chain extenders, improves the degree of hydrogen bonding in polyurethane fibers, forms more hydrogen bonding cross-linking points, and the prepared spandex fibers have higher resilience. The prepared high-resilience spandex fiber not only has better tensile elongation, but also has higher breaking strength. Compared with the common polyether-based spandex fiber, the breaking elongation strength of the 70D high-resilience spandex fiber exceeds 140cN, and the strength at 300% elongation is larger than that of the common polyether-based spandex fiber and exceeds 35cN.
Description
Technical Field
The invention belongs to the field of chemical materials, and relates to a bio-based spandex fiber and a preparation method thereof.
Technical Field
The Spandex, also known as polyurethane elastic fiber, which is known as Spandex internationally, is a high-elasticity fiber, and in the industrial production in the fifties of the last century, with the improvement of production technology and the popularization of application technology, the production and consumption of Spandex are strongly promoted, and particularly in recent years, the rapid development of the production and consumption of Spandex fibers is further promoted.
The structure of the spandex fiber:
spandex is a trade name for urethane elastic fiber. The macromolecular chain of the polyurethane fiber contains carbamate
A group. The fiber is in an amorphous structure and has lower glass transition temperature. The flexible chain segment of macromolecule is in high elastic state at normal temperature, and the structure characteristic makes the fiber have great extensibility of 400-800% at standard temperature and humidity.
If the polyurethane is made into a homopolymer, the fiber has no elasticity as in the case of a conventional fiber. The spandex is made of segmented copolymer, and the molecular structure of the spandex has soft non-crystalline low-molecular chain segments, such as polyester and polyether chain segments; and hard, rigid segments, such as diisocyanates, which have crystallinity and can produce cross-linking. The two chain segments with different properties are connected in an embedded manner, wherein the flexible chain segment has certain cross-linking to form a net structure, and when the fiber is subjected to external force, the flexible chain segment is easily elongated and deformed due to small interaction force among the molecular chains, which is the reason why the spandex is easily elongated. On the other hand, due to the presence of the rigid segment, the molecules do not slip when subjected to an external force, which in turn imparts sufficient resilience. Furthermore, because a certain network structure is formed between the flexible chain segments, the structure can always keep a certain relative position between molecules, and even if the molecules are stretched for thousands of times, the molecules still have resilience like a rubber band.
A soft segment:
the soft polyurethane segment is generally composed of an oligomeric polyol. The oligomer polyol mainly includes both polyether polyol and polyether polyol. The soft segment has a relatively large content in the polyurethane elastomer, generally forms soft segment crystals, and has a glass transition temperature lower than room temperature.
The soft segment has longer molecular chain length than the hard segment and contains more alkyl structures, so that the soft segment is in an amorphous state at normal temperature. The chemical regularity of the soft segment, the main valence force of the macromolecular chain, the acting force among molecules and the flexibility of the macromolecular chain have great influence on the low temperature resistance, crystallinity, mechanical property, melting point and flexibility of the polyurethane elastomer.
The effect of the soft segment on the polyurethane elastomer or fiber is mainly reflected in that: the type of soft segment, the molecular weight (hydroxyl number) and the functionality. The elastomer with the soft polyester polyol segment has good heat resistance, tensile strength, tearing strength, oil resistance and wear resistance. The elastomer with polyether polyol as the soft segment has better hydrolysis resistance, lower glass transition temperature of the soft segment and good mildew resistance, but has poorer mechanical property.
The polyol provides a soft chain end to the polyurethane elastomer and the physical property exhibited is flexibility. The polyol in the polyurethane elastomer is typically an oligomeric polyol, typically having a functionality of 2 to 3 and a molecular weight typically in the range of 400 to 6000, most typically 1000 to 3000. The lower the soft segment molecular weight, the higher the relative content of hard segments.
Rigid chain segment:
the rigid segment (hard segment) is generally obtained by polymerization reaction or crosslinking reaction of micromolecular diol, micromolecular diamine and diisocyanate, so that the rigidity of the hard segment group is higher, and the cohesive energy is higher. The urethane group or urea group contained in the hard segment can form hydrogen bonds, and hard segment domains are easily formed.
In the polyurethane elastomer produced, the hard segment contains a certain proportion of hard segments. The hard segment contains many urethane structures, ureido structures, and the like. The hard segment also has a great influence on the properties of the polyurethane elastomer, mainly because the imino and carbonyl structures contained in the hard segment form hydrogen bond structures, and the hydrogen bond structures influence the crystallization of the hard segment and the microphase separation of the soft segment and the hard segment. In addition, the hard phase has a large cohesive energy and forms a crystalline structure, and the crystals are generally dispersed in the form of microcrystals in the soft phase and function as crosslinking points. The factors influencing the cohesive energy of the hard segment are mainly: the type of isocyanate, the type of chain extender and the mass fraction of hard segments.
Microphase separation:
to obtain super-elastic fiber, soft segment must not easily enter into the crystal lattice formed by hard segment, that is, hard segment must have increased polarity, hard segment forms crystallization through hydrogen bond or strong polarity bond, and soft segment must be self-formed into a separate system with low polarity. The hard section and the soft section are two independent systems which are not interfered with each other, and the soft section and the hard section are required to be fully expanded respectively to realize the aim, so that the hard section is harder, the soft section is softer, and the hard section and the soft section respectively play their own roles and are separated, and the crystalline area and the amorphous area belong to the microstructure category of fibers, so the system is called microphase separation. Microphase separation means that at room temperature, the hard segment micro-area is not dissolved in the soft segment but distributed in the soft segment to play a role in crosslinking, and has great influence on the performance of the polyurethane product. It is the key point for spandex to obtain super-high elasticity.
The main influence of microphase separation is in addition to the crystallization of the hard segment. There is also hydrogen bonding self-assembly between hard segments as its main driving force. Most of the hard segments contain urethane or allophanate, and-NH in the structure is an electron-donating group, and C = O is an electron-withdrawing group. The self-assembly of the hydrogen bond promotes the formation of hard segment micro-regions between hard segments, plays a role of a skeleton in polyurethane and endows the polyurethane with excellent mechanical properties.
The structure of the soft and soft segments, the molecular weight, the distribution of the segments of the soft and soft segments, the difference in the thermodynamic compatibility of the soft and soft segments, and the change of the overall molecular weight all affect the hydrogen bonding action in polyurethane, thereby affecting the microphase separation in fibers.
Hydrogen bonding:
in polyurethanes, hydrogen bonding forces are ubiquitous and of great importance, and the formation of physically crosslinked networks enhances the mechanical properties of the polyurethane. The formation of hydrogen bonds between the hard segments contributes to the formation of a polyurethane microphase separation structure.
the-NH group in the carbamate (or allophanate) as an electron-donating group can form hydrogen bonding action with an electron-withdrawing carbonyl group and an ether bond, and the hydrogen bonding action is shown as follows:
the magnitude of these hydrogen bonding forces is not the same. The strengths of the hydrogen bonding forces among the urethane-ether bond (a), the urethane-ester bond (b, c) and the urethane-urethane bond (d) were 23.6Kj/mol, 25.6Kj/mol and 46.5Kj/mol, respectively.
The influence of the soft segment (soft segment) on the hydrogen bonding degree of the polyurethane elastomer can be divided into two aspects of soft segment content and soft segment type. The polyester polyol contains ester groups, and carbonyl groups in the ester groups have higher polarity and are easier to form hydrogen bonds, so that the probability of the formation of the hydrogen bonds of the carbonyl groups in the ester groups is higher than that of the ether groups, namely the hydrogen bond degree of the polyether polyurethane is lower than that of the polyester polyurethane. When the soft segment content is increased, the total hydrogen bonding degree is decreased due to the decrease in the relative content of imino groups on the hard segment that can form hydrogen bonds with the soft segment, whereas the hydrogen bonding degree is increased.
Chain extender:
the chain extender is mainly used for connecting short molecular chains, so that the molecular chains are lengthened and cross-linked among molecules. There are two types of chain extenders commonly used today: firstly, a polyalcohol chain extender and secondly, a polyamine chain extender. Diamine compounds such as: 3,3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA) or a mixture of ethylenediamine and 1, 2-propanediamine, and the chain extension conditions are mild and are most widely applied in industry. The glycol chain extender is mostly 1, 4-Butanediol (BDO), ethylene Glycol (EG), 1, 2-propanediol and the like, and has the advantages of mild reaction conditions, liquid state at normal temperature and convenient operation.
The influence of the hard segment on the hydrogen bonding degree of the polyurethane elastomer is mainly reflected in that the chain extender is different from diamine or diol. Diamine is used as a chain extender to form a carbamido structure, contains two imino groups and a carbonyl group, and the imino groups, ether groups and the carbonyl group in an ester group can form hydrogen bonds, so when diamine is used as the chain extender, the total hydrogen bond degree of the elastomer is relatively increased due to the relationship of quantity and degree, the hydrogen bonds are more easily formed, and the micro-phase separation is more easily generated. This has a great influence on the mechanical properties and crystallinity of the elastomer. When glycol is used as a chain extender, an imino group and an ester group are formed, the number of the imino group is less than half of that of a carbamido group structure, the hydrogen bonding degree of a carbonyl group and an ether group is relatively reduced, the total hydrogen bonding degree is reduced, and the mechanical property of the elastomer is changed. (Song Cheng Long, heat resistance modification of elastic fiber with polyurethane research, master academic thesis of university of south China science, 2017)
In patent CN201710663461.0, a high resilience spandex fiber and a preparation method thereof are introduced, wherein the preparation method is only by a conventional polymerization method, and the adopted chain extender is not informed.
CN201810477737.0 discloses a spinning solution, a preparation method thereof and a method for preparing high resilience spandex, wherein caprolactam double-end isocyanate is adopted to enhance the crystallization area and the molecular weight of a hard section.
The preparation method of the high resilience spandex fiber introduced in Chinese patent document CN101555638 adopts oligomeric diols with different molecular weights to carry out prepolymerization in an organic solvent, and the adopted chain extender is a common diamine compound; the high resilience spandex fibers improved by the patents CN102277649 and CN101469463 are improved in resilience mainly by physical crosslinking and MDI chemical crosslinking, and the side effects are that the crosslinking degree is not easy to control and the viscosity of the spinning solution is not stable in storage.
In the high resilience spandex fiber and the preparation method thereof introduced in chinese patent document CN201310375826.1, polyfunctional amine (functionality > 2) is adopted as a chain extender to increase the urea group content and hydrogen bond content in the chain extension process, and the polyfunctional amine is diethylenetriamine. Modified attapulgite is also added in the preparation process of the spandex fiber.
The preparation method of polyether type high resilience spandex fiber introduced in Chinese patent document CN200810116701.6 adopts chain extender common aliphatic diamine, such as ethylenediamine, 2-methyl pentanediamine, propylenediamine or cyclohexanediamine; the blocking agent is a common monofunctional primary or secondary amine, such as dimethylamine, ethanolamine, and the like.
Higher hydrogen bonding degree, more hydrogen bonding cross-linking points are formed, incompatibility between soft and hard chain segments of the system is increased, microphase separation degree is increased, breaking strength of spandex is increased, and the polyurethane has excellent mechanical property. (effect of the molecular weight of the soft segment on the degree of microphase separation and tensile properties of spandex, engineering plastics applications, 2017,45 (12): 88-92).
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a novel high-resilience spandex fiber which can improve the degree of hydrogen bonding in polyurethane fibers and form more hydrogen bonding crosslinking points.
The invention also provides a preparation method of the high-resilience spandex fiber.
The technical problem to be solved by the present invention is achieved by the following technical means. The invention relates to a high-resilience spandex fiber, which is characterized by comprising the following main raw materials: polyether polyol or polyester polyol, and diisocyanate compounds, chain extenders and blocking agents;
the chain extender is lysine cyclic dipeptide or ornithine cyclic dipeptide, and has the following structure:
the invention further discloses a high-resilience spandex fiber, which adopts the preferable technical scheme that: the polyether polyol is polytetrahydrofuran PTMG with the molecular weight of 1000-3000, and the structure is as follows:
wherein n represents the polymerization degree of the PTMG and is a natural number of 10-35.
The invention further discloses a high-resilience spandex fiber, which adopts the preferable technical scheme that: the polyester polyol is poly hydroxyl-terminated polyester with the molecular weight of 1000-3000, and the structure is as follows:
wherein: r 1 Comprises the following steps: - (CH) 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 6 -、-(CH 2 ) 8 -、-(CH 2 ) 9 One or more structures of (a);
R 2 comprises the following steps: - (CH) 2 ) 2 -、-(CH 2 ) 3 -、
-(CH 2 ) 6 -、-(CH 2 ) 8 -、-(CH 2 ) 9 、-(CH 2 ) 10 One ofOr a plurality of structures; n is the polymerization degree of the polyester and is a natural number of 4-10.
The invention further discloses a high-resilience spandex fiber, which adopts the preferable technical scheme that: the diisocyanate compound is: diphenylmethane diisocyanate or toluene diisocyanate.
The invention further discloses a high-resilience spandex fiber, which adopts the preferable technical scheme that: the end capping agent amino acid is selected from: glycine, glutamic acid, sodium taurate, aspartic acid or alanine.
The invention also provides a preparation method of the high-resilience spandex fiber, which is characterized by comprising the following steps:
(1) Pre-polymerization: preparing 1 molar part of polyester or polyether dihydric alcohol into a solution with the concentration of 30% in a reaction kettle filled with a certain amount of organic solvent N, N-dimethylacetamide (DMAc), adding 2.0-2.02 molar parts of diisocyanate compound while stirring, and carrying out prepolymerization for 3-6 hours at the temperature of 40-45 ℃;
(2) Chain extension: adding 1 molar part of chain extender into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2-3 hours at the temperature of 40-45 ℃;
(3) End capping: adding 0.1-0.15 molar part of end capping agent amino acid, capping the polymer prepared in the step (2), and capping for 2-3 hours at 40-45 ℃; .
(4) Curing: and (4) continuously stirring the polyurethane solution prepared in the step (3) at the temperature of 37-45 ℃ for 28-30 hours for curing.
(5) Spinning: and (4) spinning the spinning solution prepared in the step (4) through operations of liquid discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fibers.
The preparation method of the high-resilience spandex fiber provided by the invention has the further preferable technical scheme that: the polyether diol is polytetrahydrofuran diol with molecular weight of 1000-3000 or polyester diol with molecular weight of 1000-3000.
The invention adopts lysine cyclic dipeptide and ornithine cyclic dipeptide as chain extenders to prepare the high-resilience spandex fiber. Lysine cyclic dipeptide is a diamine compound obtained by dehydrating and cyclizing two molecules of lysine, and has a six-membered ring structure containing two amide groups and two primary amines in the molecule:
when the polyurethane elastomer is prepared, the lysine cyclic dipeptide and the ornithine cyclic dipeptide are used as chain extenders and can react with cyanate ester to produce cyclic dipeptide diurea structures, rigid and strong-polarity six-membered ring structures are introduced into a hard segment, and meanwhile, two hydrogen bond amide groups capable of forming with ether bonds, ester groups, carbamate groups and carbamido groups are introduced, so that the rigidity of the hard segment is further increased, and the prepared polyurethane is easier to carry out microphase separation; meanwhile, when the soft segment is stretched to slip, the restoring force of the soft segment is larger when the soft segment rebounds:
hydrogen bond of lysine cyclic dipeptide diurea (dotted line) produced by lysine cyclic dipeptide as chain extender
Similarly, the structural formula of ornithine cyclodipeptide is as follows:
compared with the prior art, the invention has the beneficial effects that:
1. in the application number 202210893718.2 of the applicant, the main concern is that the chain extender amino acid of the spandex fiber in the polymerization stage is lysine, and the end capping agent is one or more of glycine, glutamic acid, sodium taurate, aspartic acid or alanine. The bio-based spandex fiber molecular chain prepared by the method has more anionic dye bases and cationic dye dyeability. On the basis, the invention further utilizes the condensation product of two molecules of amino acid, namely dipeptide (lysine cyclic dipeptide and ornithine cyclic dipeptide), as a chain extender, improves the degree of hydrogen bonding in the polyurethane fiber, forms more hydrogen bonding crosslinking points, and the prepared spandex fiber has higher resilience performance.
2. The chain extender adopted in the invention is obtained by dehydration and cyclization of amino acid, and is safer and more environment-friendly.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited thereto.
Example 1
(1) Pre-polymerization: 200Kg of PTMEG (polytetrahydrofuran, molecular weight 2000, hydroxyl value 56.1, produced by Shanxi three-dimensional mass) was put into a reaction vessel containing 500kg of N, N-dimethylacetamide (DMAc), and then 50kg of diphenylmethane diisocyanate (produced by Passion chemical) was added thereto with stirring, followed by prepolymerization at 40 ℃ for 3 hours;
(2) Chain extension: adding 25.6kg of chain extender lysine cyclic dipeptide (produced by national medicine group) into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2 hours at 40 ℃;
(3) End capping: 13.3kg of aspartic acid (produced by Shandong Rui Yuan Biotech Co.) as a blocking agent was added to block the polymer prepared in step (2), and the block was performed at 40 ℃ for 2 hours.
(4) Curing: the polyurethane solution prepared in step (3) was aged at 45 ℃ for 28 hours with continuous stirring, and the system viscosity was measured to be 3700 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 1#.
Example 2
(1) Pre-polymerization: 200Kg of PTMEG (polytetrahydrofuran, molecular weight 2300, hydroxyl value 48.8, produced by Shanxi three-dimensional group) was prepolymerized at 40 ℃ for 3 hours in a reaction vessel containing 700kg of N, N-dimethylacetamide (DMAc) while stirring with 43.5Kg of diphenylmethane diisocyanate (produced by Pasov's chemical Co., ltd.);
(2) Chain extension: 22.2kg of chain extender ornithine cyclodipeptide (produced by national medicine group) is added into a reaction kettle, the chain extension reaction is carried out on the prepolymer prepared in the step (1), and the chain extension is carried out for 2 hours at 40 ℃;
(3) End capping: 10.5kg of aspartic acid (produced by Shandong Rui Yuan Biotech Co.) as a blocking agent was added to block the polymer prepared in step (2), and the block was performed at 40 ℃ for 2 hours.
(4) Curing: the polyurethane solution prepared in the step (3) was aged at 45 ℃ with continuous stirring for 28 hours, and the system viscosity was measured to be 3450 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 2#.
Example 3
(1) Pre-polymerization: 428kg of bio-based polyester diol was charged in a reaction vessel containing 1000kg of DMAc
1011 (undecanedioic acid undecanediol polysebacate, hydroxyl number 37.4, molecular weight 3000. Nanjing advanced biomaterial and Process Equipment research institute Co., ltd.), and then toluene diisocyanate was added under stirring
T65N (a mixture of 2, 4-and 2, 6-tolylene diisocyanate, manufactured by Korsakow) 49.6kg, prepolymerized at 44 ℃ for 6 hours;
(2) Chain extension: adding 35.5kg of chain extender lysine cyclic dipeptide (produced by national drug group) into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2 hours at the temperature of 45 ℃;
(3) End capping: adding 2.8kg of end capping agent taurine, capping the polymer prepared in the step (2), and capping for 2 hours at 45 ℃.
(4) Curing: the bio-based polyurethane solution prepared in step (3) was aged at 40 ℃ for 28 hours with continuous stirring, and the measured system viscosity was 4200 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 3#.
Example 4
(1) Pre-polymerization: 400Kg of PTMEG (polytetrahydrofuran, molecular weight 2000, hydroxyl value 56.1, produced by Shanxi three-dimensional group) was charged in a reaction vessel containing 700kg of N, N-dimethylacetamide (DMAc) and then toluene diisocyanate was added thereto with stirring
T65N (a mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, manufactured by Korsakow) 69.6kg, prepolymerized at 40 ℃ for 3 hours;
(2) Chain extension: adding 45kg of chain extender ornithine cyclodipeptide (produced by national drug group) into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2 hours at 40 ℃;
(3) End capping: adding 4.5kg of end capping agent aspartic acid, end capping the polymer prepared in step (2), and end capping at 40 ℃ for 2 hours.
(4) Curing: the polyurethane solution prepared in step (3) was aged at 45 ℃ with continuous stirring for 28 hours, and the viscosity of the system was measured to be 3450 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 4#.
Example 5
(1) Pre-polymerization: 540kg of bio-based polyester polyol is taken as bio-based polyester diol in a reaction kettle filled with 1000kg of DMAc
1111 (undecabodianeundecanedioic acid undecanediol ester, hydroxyl number 41.6, molecular weight 2700), and then toluene diisocyanate was added with stirring
T65N (mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, manufactured by Korsakov) 70kg, prepolymerized at 44 ℃ for 6 hours;
(2) Chain extension: adding 45.1kg of chain extender lysine cyclic dipeptide (produced by national medicine group) into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2 hours at 45 ℃;
(3) End capping: 5.6kg of aspartic acid as a blocking agent is added to block the polymer prepared in the step (2), and the blocking is carried out for 2 hours at the temperature of 45 ℃.
(4) Curing: and (4) continuously stirring the bio-based polyurethane solution prepared in the step (3) at 40 ℃ for 28 hours for curing, and measuring the system viscosity to be 5600 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 5#.
Example 6
(1) Pre-polymerization: 540kg of bio-based polyester polyol is taken as bio-based polyester diol in a reaction kettle filled with 1000kg of DMAc
2111 (Polyundecanedioic acid/undecanedioic acid ester, hydroxyl value 38.7, molecular weight 2900, produced by Nanjing advanced biomaterial and Process Equipment institute, ltd.), and then toluene diisocyanate was added under stirring
T65N 60kg, prepolymerization for 6 hours at 44 ℃;
(2) Chain extension: adding 42.1kg chain extender ornithine cyclodipeptide (produced by national medicine group) into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2 hours at the temperature of 45 ℃;
(3) End capping: adding 3.6kg of end capping agent taurine, capping the polymer prepared in the step (2), and capping for 2 hours at 45 ℃.
(4) Curing: and (4) continuously stirring the bio-based polyurethane solution prepared in the step (3) at 40 ℃ for 28 hours for curing, and measuring the system viscosity of 6520 poise.
(5) Spinning: spinning the spinning solution prepared in the step (4) through operations of discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fiber with the number of 6#.
Comparative examples are as follows:
comparative sample No. 1#
This example prepares spandex fiber for a conventional material as a control. The experimental procedure was as in example 3, except that the chain extender used was ethylenediamine and the end-capping agent was taurine. The viscosity of the spinning solution obtained in the step (4) after aging is 4680 poise.
Numbering the prepared spandex fibers: comparative sample # 1.
Comparative sample No. 2#
This example prepares spandex fiber for a conventional material as a control. The experimental procedure was as in example 3, except that PTMEG1500 (polytetrahydrofuran, produced by Dow chemical) was used, the chain extender was 1, 2-propanediamine, and the end-capping agent was taurine. And (4) curing the spinning solution in the step (4) to obtain the viscosity of 4500 poise.
Numbering the prepared spandex fibers: comparative sample # 2.
Performance testing of biofandex fibers
The biobased spandex fiber samples prepared in the examples were tested according to the standard FZ/T50006-2013 (the spandex fiber tensile property test method), FZ/T50007-2012 (the spandex filament elasticity test method). The biochar content of the prepared spandex fiber is tested according to a method of standard GB/T3970.2-2021 (measurement of plastic bio-based content). The results are shown in Table 1.
TABLE 1 mechanical Property test of Spandex fibers
* In table 1, TEN is the breaking strength; ELO (%) is elongation at break; TM2 at 5 th stretch reverts to 200% filament stress.
As can be seen from the above Table 1, the prepared high resilience spandex fiber not only has better tensile elongation, but also has higher breaking strength. Compared with the common polyether-based spandex fiber, the breaking elongation strength of the 70D high-resilience spandex fiber exceeds 140cN, and the strength at 300% elongation is larger than that of the common polyether-based spandex fiber and exceeds 35cN.
Claims (7)
1. The high-resilience spandex fiber is characterized in that the main raw materials of the high-resilience spandex fiber are as follows: polyether polyol or polyester polyol, and diisocyanate compounds, chain extenders and blocking agents;
the chain extender is lysine cyclic dipeptide or ornithine cyclic dipeptide, and has the following structure:
2. the high resilience spandex fiber according to claim 1, characterized in that: the polyether polyol is polytetrahydrofuran PTMG with the molecular weight of 1000-3000, and the structure is as follows:
wherein n represents the polymerization degree of PTMG and is a natural number of 10-35.
3. The high resilience spandex fiber of claim 1, wherein: the polyester polyol is poly hydroxyl-terminated polyester with the molecular weight of 1000-3000, and the structure is as follows:
wherein: r 1 Comprises the following steps: - (CH) 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 6 -、-(CH 2 ) 8 -、-(CH 2 ) 9 One or more structures of (a);
R 2 comprises the following steps: - (CH) 2 ) 2 -、-(CH 2 ) 3 -、
-(CH 2 ) 6 -、-(CH 2 ) 8 -、-(CH 2 ) 9 、-(CH 2 ) 10 One or more structures of (a); n is the polymerization degree of the polyester and is a natural number of 4-10.
4. The high resilience spandex fiber of claim 1, wherein: the diisocyanate compound is: diphenylmethane diisocyanate or toluene diisocyanate.
5. The high resilience spandex fiber of claim 1, wherein: the end capping agent amino acid is selected from: glycine, glutamic acid, sodium taurate, aspartic acid or alanine.
6. A process for the preparation of high resilience spandex fiber according to any one of claims 1 to 5, characterized by the steps of:
(1) Prepolymerization: preparing 1 molar part of polyester or polyether dihydric alcohol into a solution with the concentration of 30% in a reaction kettle filled with a certain amount of organic solvent N, N-dimethylacetamide (DMAc), adding 2.0-2.02 molar parts of diisocyanate compound while stirring, and carrying out prepolymerization for 3-6 hours at the temperature of 40-45 ℃;
(2) Chain extension: adding 1 molar part of chain extender into a reaction kettle, carrying out chain extension reaction on the prepolymer prepared in the step (1), and carrying out chain extension for 2-3 hours at the temperature of 40-45 ℃;
(3) End capping: adding 0.1-0.15 molar part of end capping agent amino acid, capping the polymer prepared in the step (2), and capping for 2-3 hours at 40-45 ℃; .
(4) Curing: and (4) continuously stirring the polyurethane solution prepared in the step (3) at the temperature of 37-45 ℃ for 28-30 hours for curing.
(5) Spinning: and (4) spinning the spinning solution prepared in the step (4) through operations of liquid discharging, spitting, stretching, false twisting, oiling and the like to prepare spandex fibers.
7. The method for preparing the high resilience spandex fiber according to claim 6, characterized in that: the polyether diol is polytetrahydrofuran diol with the molecular weight of 1000-3000 or polyester diol with the molecular weight of 1000-3000.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013142969A1 (en) * | 2012-03-28 | 2013-10-03 | Jian Ping Gao | Urethanes and ureas and processes |
| CN106757485A (en) * | 2016-11-23 | 2017-05-31 | 华峰重庆氨纶有限公司 | A kind of preparation method of high drawing spandex fibre |
| CN109196012A (en) * | 2016-03-31 | 2019-01-11 | 路博润先进材料公司 | Biodegradable and/or biological absorbable thermoplastic polyurethane |
| CN111379045A (en) * | 2020-05-15 | 2020-07-07 | 中原工学院 | Elasticity-controllable spandex and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013142969A1 (en) * | 2012-03-28 | 2013-10-03 | Jian Ping Gao | Urethanes and ureas and processes |
| CN109196012A (en) * | 2016-03-31 | 2019-01-11 | 路博润先进材料公司 | Biodegradable and/or biological absorbable thermoplastic polyurethane |
| CN106757485A (en) * | 2016-11-23 | 2017-05-31 | 华峰重庆氨纶有限公司 | A kind of preparation method of high drawing spandex fibre |
| CN111379045A (en) * | 2020-05-15 | 2020-07-07 | 中原工学院 | Elasticity-controllable spandex and preparation method thereof |
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