CN111850722B - Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber - Google Patents
Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
The invention discloses a preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fibers, which comprises the following steps: MPS and SiO Using Pre-hydrolysis2Stabilizing monomer droplets by nano particles, and preparing the strawberry-shaped cross-linked composite microspheres by Pickering emulsion polymerization; the microsphere chemical fiber slices are blended, and the cross-linked composite microspheres are obtained through processes of melt spinning, drafting, winding and the like so as to serve as the oriented filling reinforced modified chemical fiber. The MPS prehydrolysis product of the stable monomer droplets in the Pickering emulsion is anchored on the surface of the inorganic particles, so that the interaction force between the inorganic particles and the polymer matrix is enhanced; the cross-linked structure in the microsphere endows the composite microsphere with deformation in the melt extrusion-stretching process to form a one-dimensional oriented microfiber structure, so that the breaking strength of the microfiber is enhanced, and the radial mechanical defect is reduced.
Description
Technical Field
The invention relates to the technical field of reinforced chemical fibers, in particular to a preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fibers.
Background
With the continuous development of economy and technology in China, the social requirements are increasing and diversified, and higher requirements are provided for the production and preparation of high-performance and specific chemical fibers. At present, although the chemical fiber industry in China develops rapidly, main products are still concentrated in the application field of daily life, the product homogenization is serious, and the price competition is strong. Therefore, the preparation of the high-strength and specific chemical fiber is an effective way for breaking the price war dilemma, forming a core technology and increasing the market competitiveness.
At present, chemical fiber modification and reinforcement methods mainly comprise two types:
one is to change the crystallinity, strength, dyeing property, hydrophilicity and lipophilicity of chemical fiber by chemical modification methods such as grafting and copolymerization. For example, Huxialan and the like [ the journal of composite materials, 2017,34: 694-. Dajun et al (Artificial Crystal school, 2016,45: 2705-. Maryam Tamizifar et al [ J.APPL.POLYM.SCI,2018,135:45590] change the dyeing properties of PET by controlling the affinity of the monomers to the PET during free radical graft polymerization, controlling the degree of modification of the PET surface. The fiber is modified by a chemical modification method, the operation process is complex, more waste water is generated, the cost is higher, and the industrial large-scale production is not facilitated.
The other is that incompatible polymers or inorganic nano particles are mixed with the polymers by means of blending, and then the fibers with various specificities are prepared by a spinning process. For example, Li loyal et al [ Biomacromolecules,2014,15:4045-]The PLA/PBS composite material is prepared by utilizing an in-situ microfibrillar technology, and in the melt extrusion-stretching process, the PBS is subjected to orientation deformation in a PLA matrix to form a microfibrillar form, so that the toughness and the modulus of the PLA/PBS composite material are greatly improved, and the PLA/PBS composite material is expected to be applied to degradable packaging materials. Joyadong et al [ j.appl.pom.sci.2018,135:46286]The change rule of the form of the dispersed phase when different polymers are used as the dispersed phase and the matrix phase polypropylene is blended is researched. It is found that the elastic modulus of the dispersed phase has a large influence on the morphology evolution mechanism and the final morphology, and the dispersed phase with a large elastic modulus is difficult to form microfibers. But as a reinforcing material, the effect of improving the mechanical property of the composite material is better. Chiffon et al [ CN107435171B]During the fiber forming process, polyacrylate microsphere with molecular cross-linking structure is added to form organic/organic blending system to obtain oriented polyacrylate cross-linking structure filled and reinforced chemical fiber. The research clarifies the change rule of the dispersed phase form in the polymer blending and the condition of the formation of the one-dimensional orientation structure, and provides an idea for the preparation of the one-dimensional filling reinforced composite material. Dianthus superbus et al [ AIP Conference Proceedings,2016,1713:120003]The TPU/PBT blend is filled with carbon fibers, so that the thermal stability and the mechanical property of the composite material are improved. Yang Qin et al, Sichuan university [ POLYMER COMPOSITES,2017,38:2718-]SiO with different contents in a PET/PP blending system is analyzed2Influence on the morphology of dispersed phase PET. SiO was found2At a content of less than 8 wt%, the viscosity of the PP phase is increased, thereby promoting the transformation of PET from a droplet state to a fiber state during stretching. When SiO is present2When the content reaches 12 wt%, SiO distributed on the surface of PET2Coalescence between the PET droplets is hindered and the formation of microfibers is suppressed. In these studies, the inorganic particles and the polymer matrix form a composite material mainly by means of physical blending, and the dispersion of the inorganic particles and the problems of the force acting between the inorganic particles and the polymer matrix, the increase of the viscosity of the polymer melt and the like limit the types and processing modes of raw materials. Therefore, it is a feasible idea to solve the above problems to prepare composite materials or composite microspheres in which inorganic particles are uniformly dispersed in a polymer by bulk polymerization or in-situ polymerization. Dajian et al [ New carbon material, 2013,28:101-]And preparing the PMMA/CNT composite material by using an in-situ bulk polymerization method. Then, by electrostatic spinning equipment and a velocity gradient field, the PMMA/CNT composite long fiber is prepared, and the directional arrangement of the CNTs in the PMMA/CNT composite long fiber is realized, so that the conductivity of PMMA is improved by 10 orders of magnitude. These studies provide the basis for the preparation of functional composite fibersHowever, the force between the inorganic particles and the polymer matrix is weak, and defects are easily generated, and the modification effect is not as expected. The dispersed phase for modification is usually obtained by deforming and coalescing polymer melt droplets, and the strength in the direction perpendicular to the stretching direction is reduced to some extent along with the orientation due to a network structure formed by no chemical crosslinking inside the dispersed phase. And the compatibility between two phase polymers is generally poor, so that the acting force of a phase interface is weak, and defects are easily generated in the material. Therefore, the method for preparing the modified chemical fiber by the oriented one-dimensional filling of the composite microsphere containing the cross-linked structure is very important.
On the basis of the research, the invention provides a method for orienting and reinforcing chemical fibers in a melt extrusion-stretching process by adopting chemically crosslinked strawberry-shaped composite microspheres, which strengthens the chemical fibers by introducing a partially compatible crosslinking structure, reduces the defects caused by high orientation, and simultaneously introduces inorganic particles to endow the material with new functional characteristics.
Disclosure of Invention
The invention provides a preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fibers, which has simple operation flow and operation equipment for preparing the chemical fibers, is easy to realize, has higher strength of the prepared chemical fibers, and can obtain various functionalities through inorganic particles.
The method comprises the following steps: preparing the strawberry-shaped composite microspheres with a certain crosslinking degree, and then preparing the reinforced composite chemical fibers by carrying out melt extrusion-stretching process on the strawberry-shaped composite microspheres and chemical fiber slice particles.
The key points of the invention are as follows: firstly, the surface of the inorganic particle is anchored with a silane coupling agent and is connected with the polymer through chemical bonds, so that the acting force of the inorganic particle and the polymer is stronger, and the strength of the composite chemical fiber is improved. Secondly, the crosslinking degree of the composite microspheres is proper so as to ensure that certain deformation can occur in the extrusion and stretching process to form a microfiber shape and increase the chemical fiber strength. Meanwhile, the reduction of radial strength of the chemical fibers caused by orientation is reduced by a certain degree of crosslinking. And thirdly, the barrel temperature, the screw rotating speed, the stretching ratio and the like in the melt extrusion-stretching process are proper, so that the dispersing and stretching effects with proper strength are provided, and the dissociation is reduced while the one-dimensional orientation of the crosslinked composite microspheres is realized.
Compared with the inorganic particle filling and in-situ microfibrillated reinforcing fiber which are commonly adopted, the one-dimensional orientation reinforcing method of the cross-linked composite microsphere disclosed by the invention has the following advantages: firstly, inorganic particles are uniformly dispersed, the acting force between the inorganic particles and the polymer is strong, and the mechanical defects are few. Secondly, the one-dimensional orientation structure with a certain crosslinking degree reduces radial mechanical defects caused by orientation while reinforcing the material. And the glass transition temperature of the dispersed phase with the reinforcing effect is lower, the temperature in the processing process is reduced, the melt viscosity is reduced, and the energy consumption is greatly reduced.
A preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fibers comprises the following specific steps:
1) prehydrolysis of gamma-Methacryloxypropyltrimethoxysilane (MPS) under an acidic condition, adjusting the pH value to 6-7, adding a monomer styrene (St), an auxiliary monomer and an initiator, and performing ultrasonic emulsification to form an emulsion;
2) adding SiO into the emulsion prepared in the step 1)2Sol and Triethylamine (TEA), heating to initiate polymerization reaction after protective gas is introduced, centrifuging, washing and drying the product to obtain dried crosslinking composite microspheres (namely strawberry-shaped organic/inorganic crosslinking microspheres), and placing the microspheres in a dryer for later use.
3) And adding the dried crosslinked composite microspheres and the chemical fiber slices into a double-screw extruder for melt blending, and performing high-speed drafting to obtain the one-dimensional oriented filling reinforced composite chemical fiber.
The conditions of the invention are optimized:
in the step 1), the conditions of prehydrolysis under acidic conditions are as follows: adjusting the pH value to 3-4 by adopting acetic acid, adjusting the prehydrolysis time to 3-10 min, and performing prehydrolysis by adopting an ice water bath at a stirring speed of 100-400 rpm.
And ammonia water is adopted when the pH value is adjusted, and the pH value is adjusted to 6.5-7.5.
The ultrasonic emulsification conditions are as follows: the ultrasonic emulsification time is 30-90 min, and the ultrasonic power is 50-150W (most preferably 100W); the stirring speed is 200-400 rpm.
The dosage ratio of the gamma-methacryloxypropyltrimethoxysilane to the styrene monomer (St) to the auxiliary monomer to the initiator is 0.2-1.6 mL: 3.5-4.5 g: 0.5-1.5 g: 0.01 to 0.1 g.
The auxiliary monomer is one or a mixture of a plurality of auxiliary monomers such as butyl methacrylate (BA), Methyl Methacrylate (MMA), N-dimethylacrylamide, N-diethylacrylamide, vinyl acetate and the like.
The initiator is Azobisisobutyronitrile (AIBN).
In step 2), the SiO2SiO in sol2The mass concentration of (A) is 0.5-2 wt% (most preferably 1 wt%), and the dosage is 10-30 mL, wherein SiO is2The particle size of (A) is 30 to 50 nm.
The adding amount of the TEA is 0.1-1 mL, and the pH value of the system is adjusted to 9-10.
The SiO2The volume ratio of the sol to the triethylamine is 10-30 mL: 0.1-1 mL.
The SiO2And TEA is added by a syringe pump at a rate of 50-200 mL per hour-1The rate of addition.
The polymerization conditions are as follows: the temperature is 60-75 ℃, and the reaction time is 8-24 h.
The washing conditions are as follows: and (3) taking absolute ethyl alcohol as a washing solution, carrying out centrifugation at 10000-14000 rpm for 5-15 min, and washing for three times.
The drying conditions are as follows: the drying temperature is 30-90 ℃, the drying time is 12-48 h, and the polymer degradation caused by moisture in the melt blending process is reduced.
The size of the crosslinked composite microsphere is 0.2-3 mu m, SiO2The content is 10-30 wt%, and the gel fraction is 20-80%.
In the step 3), in order to obtain a dispersed phase with a one-dimensional orientation structure, the blending ratio (mass ratio of the composite microspheres to the polyester chips) is 10/90-50/50, and the rotating speed of a feeder is 10-30 rpm. Namely, the mass ratio of the dried crosslinked composite microspheres to the chemical fiber slices is 10-50: 90-50, and the sum of the mass ratios is 100.
The temperature of the melt blending is 220-280 ℃, and the conditions of the melt extrusion processing process are as follows: the temperature from the feed opening to the extrusion die is set to be 220, 240, 245, 240-260 ℃, 280, 285, 280 ℃, and the screw rotation speed is 10-30 rpm.
The high-speed drafting conditions are as follows: the drawing speed is 1000 to 7000 m.min-1The hot stretch ratio is 2 to 9.
The average size of the strawberry-shaped organic/inorganic composite microspheres is 0.2-3 mu m, and the size of the cross-linked composite microspheres is further optimized to be 0.6-1.5 mu m in order to enable the cross-linked composite microspheres to be uniformly oriented in the processing process. Undersized microspheres require the addition of large amounts of MPS and SiO2The crosslinking degree of the microspheres is too high, and the shear stress and the tensile stress gradient of the microspheres are too small to be oriented and deformed. Oversized microspheres will result in surface-loaded SiO2The total amount is reduced and the enhancement effect is difficult to achieve. And too large microspheres are easy to be stressed unevenly in the melting and blending process, so that the microspheres are broken, and microfibers with high length-diameter ratio cannot be obtained to reinforce chemical fibers.
The MPS is used in an amount of 0.2-1.6 mL, the gel fraction of the prepared strawberry-shaped organic/inorganic crosslinked composite microsphere is 20-80%, and in order to enable the crosslinked microsphere to have high deformability and certain structural strength and not to be easily dissociated, the MPS is further optimized in an amount of 0.4-0.8 mL, and the gel fraction is 30-50%. The low gel fraction results in a low elastic modulus of the microspheres, which are easily broken and broken during the extrusion-stretching process, and thus micro-fibers cannot be formed. And too high gel fraction causes too short average length of cross-linked network chains in the microspheres, dense cross-linked network structure and too large elastic modulus of the microspheres to be difficult to deform, so that the microspheres are difficult to orient and deform in the stretching process to form microfibril and further reinforce chemical fibers.
The temperature in the melt extrusion process is set to 240 ℃, 260 ℃, 265 ℃, 260 ℃ and the screw rotation speed is 30 rpm. Too low a temperature results in too weak a continuous phase flow property and poor dispersion of the dispersed phase. Meanwhile, the dispersed phase is subjected to larger stress in the processing process, so that the dispersed phase is easy to dissociate and break in a charging barrel of an extruder, and micro-fibers with high length-diameter ratio cannot be formed. However, when the temperature exceeds the decomposition temperature of the polymer, the matrix phase is degraded to form mechanical defects, resulting in a decrease in mechanical properties. Too low a screw speed leads to poor dispersion of the dispersed phase and too long a residence time, which tends to cause thermal decomposition of the polymer. And too fast rotating speed can cause too strong shearing effect on the dispersed phase, so that the dispersed phase is easy to dissociate and break, and microfibers with high length-diameter ratio cannot be formed, thereby achieving the effect of reinforcing the chemical fibers.
The stretching speed in the stretching process is 1000-7000 m.min-1The hot stretch ratio is 2 to 9. Further optimizing the drawing speed to 2700-4500 m.min-1The stretch ratio is 2 to 4. Because a certain cross-linked network structure exists in the dispersed phase, the movement capability of the molecular chain is limited to a certain degree, and the response speed to external stress is reduced to a certain extent. When the stretching speed is too fast, the molecular chain movement is too slow in response to external stress, so that the molecular chain cannot be rapidly deformed to reduce the stress intensity, and the dispersed phase is easy to break. However, when the stretching speed is too slow, the molecular chains become gradually rigid as the extrudate is cooled, and become rigid before failing to be stretched to form microfibers, and thus cannot form microfibers. When the hot draw ratio is too small, the drawing effect is weak, and microfibers having a high aspect ratio cannot be formed. When the draw ratio is too large, the tensile stress is too large, resulting in excessive drawing of the dispersed phase, breaking and dissociating the microspheres, and failing to form microfibers having a high aspect ratio.
The blending amount of the strawberry-shaped cross-linked composite microspheres is 10wt% -30 wt% of the chemical fiber mass. When the blending amount is less, the amount of the produced microfibers is too small, and the reinforcing effect on chemical fibers is poor. When the blending amount is too large, a large amount of dispersed phase microspheres are consumed, the cost is increased, the continuity of a continuous phase is easily damaged, and the generation of microfibers is not facilitated.
The invention further preferably relates to a preparation method of the strawberry-shaped organic/inorganic cross-linked composite microsphere oriented filling reinforced chemical fiber, which is characterized by comprising the following specific steps:
1) mixing oil soluble initiator AIBN with monomer St, butyl methacrylate (BA), Methyl Methacrylate (MMA), N-dimethylacrylamide, N-diethylacryloylOne or more of amine, vinyl acetate and other auxiliary monomers are uniformly mixed, added into the prehydrolyzed MPS hydrolysate, and subjected to ultrasonic treatment to form emulsion. Then slowly adding SiO2Sol, further ultrasonic treatment and pH regulation to alkalescence, introducing N2After oxygen is discharged, heating is carried out to initiate polymerization reaction. And finally, washing and drying the product to obtain the crosslinked composite microsphere powder.
2) And mixing the dried powder with chemical fiber slices, and then carrying out melt extrusion-stretching to directly obtain the reinforced composite chemical fiber.
In the step 1), the MPS dosage is 0.4-0.8 mL.
The prehydrolysis conditions are as follows: prehydrolysis for 5-7 min in ice-water bath.
The ultrasonic conditions are as follows: and performing ultrasonic treatment in an ice water bath for 30-60 min at a stirring speed of 200-300 rpm.
The system acid-base adjusting conditions are as follows: adjusting the pH value to 7.1-7.2 by using ammonia water after prehydrolysis, and adding SiO2And adjusting the pH value to 9.3-9.4 by using TEA after sol.
The polymerization reaction conditions are as follows: the stirring speed is 100-300 rpm, the reaction temperature is 65-70 ℃, and the reaction time is 8-12 h.
The drying conditions are as follows: the drying temperature is 70 ℃, and the drying time is 24 h.
The average grain diameter of the strawberry-shaped organic/inorganic crosslinking composite microspheres is as follows: 0.6 to 1.5 μm.
The gel rate of the strawberry-shaped organic/inorganic crosslinked composite microspheres is as follows: 30 to 50 percent.
The melt extrusion conditions are as follows: the temperature was set at 240 ℃, 260 ℃, 265 ℃, 260 ℃ and the screw speed was 30 rpm.
The stretching conditions are as follows: the drawing speed is 2700-4500 m.min-1The Hot Stretch Ratio (HSR) is 2 to 4.
Compared with the prior art, the invention has the following advantages:
the existing method for filling chemical fiber in one-dimensional orientation has the defects that the dispersed phase used as a reinforcing material generally has a higher melting point, so that higher temperature is required in the processing process, and the processing of polymer materials with lower thermal decomposition temperature is limited. Meanwhile, in the traditional processing method, the compatibility of the dispersed phase and the continuous phase is poor, and the interaction force between the phase interfaces is weak in the melt blending process, so that defects are easily formed. The method adopts different auxiliary monomers to adjust the glass transition temperature of the dispersed phase, and obtains the cross-linked composite microspheres with lower working temperature than the continuous phase as the dispersed phase. And the compatibility between the crosslinked microspheres and the continuous phase is adjustable, the interface acting force is stronger, and the enhancement effect is obvious. The invention can process the chemical fiber which can not be processed by the traditional method and has lower thermal decomposition temperature, does not need to use a compatilizer to improve the interface compatibility, has simple processing technology and obtains pure products.
Secondly, the method for filling chemical fibers with strawberry-shaped organic/inorganic composite particle orientation provided by the invention endows the chemical fibers with various specific performances. In the traditional method, the dispersed phase in the commonly adopted blending system has no cross-linking structure, so that anisotropy is generated after orientation, and the mechanical property in the radial direction of the fiber is weakened to a certain extent. In the method provided by the invention, the dispersed phase is the composite microsphere with a cross-linked structure, and after the microsphere is oriented and deformed, the internal cross-linked network structure is deformed to a certain degree, but still has a cross-linked network with a certain density in the radial direction. When the cross-linked structural chemical fiber is subjected to radial stress, the stress can be effectively dispersed, stress concentration is reduced, strain to a certain degree can be borne, and the radial mechanical property of the oriented chemical fiber is obviously improved. Meanwhile, the inorganic particles and the polymeric microspheres are connected through covalent bonds, so that the acting force between the inorganic particles and the polymer is enhanced. In the traditional processing method, the relation between inorganic particles and a polymer matrix is simple blending, and the inorganic particles are easy to agglomerate in the processing process to cause structural defects. The inorganic particles and the polymer microspheres in the invention form strawberry-shaped composite microspheres, and the inorganic particles are dispersed on the surfaces of the microspheres and cannot be agglomerated in the processing process. Meanwhile, the inorganic particles can absorb a large amount of energy, so that the development of cracks is hindered, and the thermal stability of the chemical fibers can be improved.
And thirdly, the processing in the invention can be carried out by adopting conventional fiber processing equipment.
Fourth, MPS prehydrolysis products of stable monomer droplets in the Pickering emulsion are anchored on the surface of the inorganic particles, and the interaction force between the inorganic particles and the polymer matrix is enhanced; the cross-linked structure in the microsphere endows the composite microsphere with deformation in the melt extrusion-stretching process to form a one-dimensional oriented microfiber structure, so that the breaking strength of the microfiber is enhanced, and the radial mechanical defect is reduced.
Drawings
FIG. 1 is a schematic view of composite microsphere orientation in a fiberizing flow field;
FIG. 2 shows the prehydrolysis of MPS and SiO in example 22Optical microscope photographs of emulsion droplets with particles co-stabilized;
FIG. 3 is a graph showing a particle size distribution of the composite microsphere obtained in example 2;
FIG. 4 is typical TEM image a) and SEM image b) of the strawberry-shaped composite microspheres obtained in example 5;
fig. 5 is a thermogravimetric curve of the strawberry-shaped composite microsphere obtained in example 5.
Detailed Description
The core idea of the invention is that as shown in figure 1, organic/inorganic crosslinked composite microspheres with strawberry-shaped structures are used as dispersed phases, and the strawberry-shaped crosslinked composite microspheres are oriented and deformed through a melt extrusion-hot drawing process to form reinforced microfibers with high length-diameter ratio. The oriented microfibers can increase the force between the fibers and the matrix by utilizing the rough strawberry-shaped surface, so that the tensile strength of the fibers is enhanced. Meanwhile, the hard inorganic particles and the cross-linked network structure in the microfiber can enhance the mechanical strength along the axial direction and reduce the structural defects caused by over orientation.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
(1) adding a certain amount of MPS (gamma-methacryloxypropyltrimethoxysilane) into the glacial acetic acid solution, and stirring and pre-hydrolyzing for a certain time under the ice-water bath condition to obtain pre-hydrolyzed solution.
(2) And (2) adjusting the solution to be neutral by ammonia water, weighing a certain amount of monomer St (styrene), auxiliary monomer BA (butyl methacrylate) and initiator, adding into the prehydrolysis solution obtained in the step (1), and carrying out ultrasonic emulsification for a certain time under the conditions of ice water bath and stirring, wherein the ultrasonic power is 100W, so as to form emulsion.
(3) Taking a certain amount of SiO2The dispersion and TEA (triethylamine) were mixed well and then added to the emulsion of step (2) by syringe pump.
(4) And (4) transferring the emulsion obtained in the step (3) into a four-mouth flask, introducing nitrogen to remove oxygen, reacting for 8 hours at 70 ℃, centrifuging and washing the product by using ethanol, and drying to obtain white microsphere powder.
(5) And (4) uniformly mixing the white powder obtained in the step (4) with the dried chemical fiber slices, mixing the white powder and the dried chemical fiber slices through a double-screw extruder, and performing high-speed drafting to obtain the reinforced chemical fiber.
The specific implementation conditions are shown in table 1:
TABLE 1 summary of the examples
Note: the numbers in the table correspond to the specific examples described below
TH: MPS prehydrolysis time;
d: the average grain size of the obtained composite microspheres;
ge: the gel fraction of the obtained composite microspheres;
length-diameter ratio: the average value of the length and the diameter of the oriented deformed microspheres in the obtained modified chemical fibers.
As can be seen from Table 1, the composition ratio of the monomers St and BA has a great influence on the deformability of the organic/inorganic composite microspheres in the spinning process, mainly the BA influences the movement capability of the copolymer molecular chain, and the increase of the BA content promotes the movement capability of the chain segment. The prehydrolysis time mainly affects the particle size of the microspheres, and the increase of the prehydrolysis time increases the number of silicon hydroxyl groups of the MPS, improves the monomer droplet stabilizing ability, and makes the size of the stabilized monomer droplets smaller. The amount of MPS mainly affects the degree of crosslinking of the microspheres, and the condensed oligomer segment of MPS contains a plurality of reactive C ═ C bonds, which act as a crosslinking agent during the free radical polymerization.
Examples 1 to 3
(1) A glacial acetic acid solution of pH 4 (100 mL) was taken in a four-necked flask, 0.4mL MPS was added, and prehydrolysis was carried out in an ice-water bath at a stirring speed of 150rpm for 5 min.
(2) And (2) adding ammonia water into the prehydrolysis liquid obtained in the step (1) to adjust the pH value of the mixed liquid to be about 7.
(3) St and BA were mixed uniformly in the proportions shown in examples 1 to 3 in Table 1, and 0.05g of AIBN was dissolved in the monomer. And (3) adding the monomer into the mixed solution in the step (2), adjusting the stirring speed to 200rpm, and keeping ultrasonic treatment (100w) for 60min under the ice-water bath condition for emulsification.
(4) 20mL of SiO with the content of 1 wt% and the particle size of 30nm is taken2The dispersion was mixed with 0.6mL of triethylamine and passed through a syringe pump (100 mL. h)-1Speed) adding the emulsion obtained in the step (3). Keeping the ultrasonic wave for 30min in ice water bath.
(5) And (4) introducing nitrogen into the emulsion obtained in the step (4), discharging oxygen, heating to initiate free radical polymerization, and reacting for 8 hours at 70 ℃. And (3) carrying out centrifugal washing on the microspheres for 3 times by using ethanol (the centrifugal speed is 12000rpm, and the centrifugal time is 10min), and drying to obtain the composite microspheres.
By observing the emulsion droplets obtained in step (4) of example 2 using an optical microscope, stable micron-sized monomer droplets can be observed as shown in fig. 2. Since the siloxane chains of MPS are hydrolyzed to hydroxyl groups, distributed over the oil/water interface, by controlling the reasonable degree of pre-hydrolysis under conditions where only MPS is used. After adding SiO2And after hydrolytic condensation in an alkaline environment, SiO2Distributed on the surface of the monomer liquid drop through covalent bond action and stabilizes the liquid drop together with the MPS after prehydrolysis.
The particle size distribution of the composite microspheres prepared in example 2 was characterized using a laser particle sizer, as shown in fig. 3. The average grain diameter of the prepared composite microspheres is 2.77 mu m, and the average grain diameter is close to the size of a monomer liquid drop under an optical microscope, which shows that SiO on the surface of the monomer liquid drop2Has better stabilizing effect.
Examples 4 and 5
(1) 0.8-1.2 mL MPS is taken to be pre-hydrolyzed in glacial acetic acid solution with pH value of about 4 in ice-water bath for 5min under the stirring speed of 150 rpm.
(2) And (3) adding ammonia water into the prehydrolysis liquid obtained in the step (1) to adjust the prehydrolysis liquid to be neutral.
(3) 4gSt, 1g BA and 0.05g AIBN are mixed evenly and added into the neutral solution obtained in the step (2), and ultrasonic treatment (100w) is carried out for 60min under ice water bath for emulsification.
(4) By means of a syringe pump (100 mL. h)-1Speed) to the emulsion obtained in step (3) was added 20mL of SiO having a particle size of 30nm and a content of 1 wt%2The dispersion and 0.6mL triethylamine were sonicated for 30 min.
(5) Introducing nitrogen into the stable emulsion obtained in the step (4) for oxygen discharge, adding the stable emulsion into the stable emulsion for initiating free radical polymerization, and reacting for 8 hours at the polymerization condition of 70 ℃. The product was washed with ethanol by centrifugation (centrifugation speed 12000rpm, centrifugation time 10min) for 3 times and dried to give a white powder.
The size and surface morphology of the composite microspheres obtained in example 5 were observed by a transmission electron microscope and a scanning electron microscope, as shown in fig. 4. The prepared composite microsphere has submicron particle size and large amount of SiO distributed on the surface2The granules are distributed in a strawberry shape. SiO of the surface2The bonding with the microsphere through covalent bonds has higher bonding fastness.
FIG. 5 is a thermogravimetric analysis of the composite microsphere produced in example 5. The weight loss curve in the figure can be used for knowing SiO in the composite microsphere2The content is 19.89 wt%, wherein the thermal decomposition starting temperature of the organic part of the composite microsphere is close to 311 ℃, which shows that the upper limit of the processing temperature of the composite microsphere is higher, and the composite microsphere has a higher processing temperature range.
Examples 6 and 7
(1) 0.8mL MPS is taken to be prehydrolyzed in glacial acetic acid solution for 6-7 min. Adding ammonia water to adjust to neutrality after prehydrolysis.
(2) 4g of St and 1g of BA are uniformly mixed with 0.05g of AIBN, added into the neutral solution obtained in the step (1), and emulsified by ultrasonic treatment (100w) for 60min in an ice-water bath.
(3) By means of a syringe pump (100 mL. h)-1Speed) to the emulsion obtained in step (2) was added 20mL of SiO having a particle size of 30nm and a content of 1 wt%2The dispersion and 0.6mL triethylamine were sonicated for 30 min.
(4) Introducing nitrogen into the stable emulsion obtained in the step (3) for oxygen discharge, adding the stable emulsion into the stable emulsion for initiating free radical polymerization, and reacting for 8 hours at the polymerization condition of 70 ℃. The product was washed with ethanol by centrifugation (centrifugation speed 12000rpm, centrifugation time 10min) for 3 times and dried to give a white powder.
(5) And (3) mixing the dried composite microspheres obtained in the step (4) with the dried PET slices, adding the mixture into a double-screw extruder, blending the mixture according to the mass ratio of 20:80 (the composite microspheres: the PET slices), and extruding and drawing the mixture to obtain the modified chemical fibers.
Examples 8 and 9
(1) 0.8mL MPS was prehydrolyzed in glacial acetic acid for 6 min. Adding ammonia water to adjust to neutrality after prehydrolysis.
(2) 4g of St and 1g of BA are uniformly mixed with 0.05g of AIBN, added into the neutral solution obtained in the step (1), and emulsified by ultrasonic treatment (100w) for 60min in an ice-water bath.
(3) By means of a syringe pump (100 mL. h)-1Speed) to the emulsion obtained in step (2) was added 20mL of SiO having a particle size of 30nm and a content of 1 wt%2The dispersion and 0.6mL triethylamine were sonicated for 30 min.
(4) Introducing nitrogen into the stable emulsion obtained in the step (3) for oxygen discharge, adding the stable emulsion into the stable emulsion for initiating free radical polymerization, and reacting for 8 hours at the polymerization condition of 70 ℃. The product was washed with ethanol by centrifugation (centrifugation speed 12000rpm, centrifugation time 10min) for 3 times and dried to give a white powder.
(5) And (3) mixing the dried composite microspheres obtained in the step (4) with dried PET slices, and adding the mixture into a double-screw extruder, wherein the blending mass ratio is 20:80 (composite microspheres: PET slices). The rotating speed of the screw is 30rpm, the temperature of the neck ring of the extruder is set to be 260 ℃, and the drawing speed is 3000m min-1The draft ratio is 3 to 4. As can be seen from table 1, when the draw ratio is 4, the aspect ratio (18.4) of the microfibers formed by orienting the microspheres is reduced by excessive drawing (this value is 23.4 when the draw ratio is 3).
Comparative example 1
(1) A glacial acetic acid solution (100mL, pH 2) was taken in a four-necked flask, 0.8mL MPS was added, and prehydrolysis was carried out in an ice-water bath at a stirring speed of 150rpm for 15 min.
(2) And (2) adding ammonia water into the prehydrolysis liquid obtained in the step (1) to adjust the pH value of the mixed liquid to be about 7.
(3) The mixture of 4gSt and 1g BA was mixed well, and 0.05g AIBN was dissolved in the monomer. And (3) adding the monomer into the mixed solution in the step (2), adjusting the stirring speed to 200rpm, and performing ultrasonic emulsification for 60min under the ice-water bath condition.
(4) 20mL of SiO with the content of 1 wt% and the particle size of 30nm is taken2And (4) uniformly mixing the dispersion liquid with 0.6mL of triethylamine, and adding the emulsion obtained in the step (3) through a syringe pump. Keeping the ultrasonic wave for 30min in ice water bath.
(5) And (4) introducing nitrogen into the emulsion obtained in the step (4), discharging oxygen, heating to initiate free radical polymerization, and reacting for 8 hours at 70 ℃. And centrifugally washing the microspheres for 3 times by using ethanol, and drying the microspheres to obtain the composite microspheres.
(6) And (3) mixing the dried composite microspheres obtained in the step (5) with dried PET slices, and adding the mixture into a double-screw extruder, wherein the blending mass ratio is 20:80 (composite microspheres: PET slices). The rotating speed of the screw is 30rpm, the temperature of the neck ring of the extruder is set to be 260 ℃, and the drawing speed is 3000m min-1The draft ratio was 3. The orientation degree of the microspheres in the obtained modified chemical fiber is low, and the length-diameter ratio is only 1.2.
The obtained composite microspheres are extracted by taking tetrahydrofuran as a solvent, the extraction time is 24h, and the gel fraction calculation method is as shown in formula (1):
Gethe gel fraction of the crosslinked composite microspheres,%;
m1mass g of the dried crosslinked composite microspheres;
m2the mass of the crosslinked composite microspheres after extraction was completed, g.
The strength of the reinforced chemical fiber is measured by a Universal material Testing Machine (Thwing-Albert, EJA series variable NX Universal Testing Machine) under the test conditions of 25 ℃ and the relative humidity of 60% RH.
Claims (7)
1. A preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fibers is characterized by comprising the following specific steps:
1) prehydrolysis of gamma-methacryloxypropyltrimethoxysilane under an acidic condition, adjustment of the pH value to 6.5-7.5, addition of monomer styrene, auxiliary monomer and initiator, and ultrasonic emulsification to form emulsion;
the dosage ratio of the gamma-methacryloxypropyltrimethoxysilane to the monomer styrene to the auxiliary monomer to the initiator is 0.2-1.6 mL: 3.5-4.5 g: 0.5-1.5 g: 0.01-0.1 g;
2) adding SiO into the emulsion prepared in the step 1)2Dissolving sol and triethylamine, introducing protective gas, heating to initiate polymerization reaction, centrifuging, washing and drying the product to obtain dried crosslinking composite microspheres;
the size of the crosslinked composite microsphere is 0.2-3 mu m;
3) adding the dried crosslinked composite microspheres and chemical fiber slices into a double-screw extruder for melt blending, wherein the rotating speed of a screw is 30rpm, and obtaining the one-dimensional oriented filling reinforced composite chemical fiber after high-speed drafting;
the high-speed drafting conditions are as follows: the drawing speed is 1000 to 7000 m.min-1The hot stretch ratio is 2-9;
the blending amount of the dried crosslinked composite microspheres is 10-30 wt% of the mass of the chemical fibers.
2. The method for preparing the strawberric organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber according to claim 1, wherein in the step 1), the prehydrolysis conditions under acidic conditions are as follows: adjusting the pH value to 3-4 by adopting acetic acid, adjusting the prehydrolysis time to 3-10 min, and performing prehydrolysis by adopting an ice water bath at a stirring speed of 100-400 rpm.
3. The method for preparing the strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber according to claim 1, wherein in the step 1), the ultrasonic emulsification conditions are as follows: the ultrasonic emulsification time is 30-90 min, and the ultrasonic power is 50-150W; the stirring speed is 200-400 rpm.
4. The method for preparing the strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber according to claim 1, wherein in the step 1), the auxiliary monomer is one or more of butyl methacrylate, methyl methacrylate, N-dimethylacrylamide, N-diethylacrylamide and vinyl acetate.
5. The method for preparing the strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforcing chemical fiber according to claim 1, wherein in the step 1), the initiator is azobisisobutyronitrile.
6. The method for preparing the strawberric organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber according to claim 1, wherein in the step 2), the SiO is prepared2SiO in sol2Has a mass concentration of 0.5 to 2 wt%, wherein SiO is2The particle size of (A) is 30-50 nm;
the SiO2The volume ratio of the sol to the triethylamine is 10-30 mL: 0.1-1 mL.
7. The method for preparing the strawberric organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber according to claim 1, wherein in the step 2), the polymerization conditions are as follows: the temperature is 60-75 ℃, and the reaction time is 8-24 h.
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