CN116043360B - Hydroxyl polypropylene copolymer fiber with surface concave-convex structure and preparation method thereof - Google Patents
Hydroxyl polypropylene copolymer fiber with surface concave-convex structure and preparation method thereof Download PDFInfo
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- CN116043360B CN116043360B CN202211592903.4A CN202211592903A CN116043360B CN 116043360 B CN116043360 B CN 116043360B CN 202211592903 A CN202211592903 A CN 202211592903A CN 116043360 B CN116043360 B CN 116043360B
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 171
- 239000000835 fiber Substances 0.000 title claims abstract description 141
- 229920005606 polypropylene copolymer Polymers 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000004743 Polypropylene Substances 0.000 claims abstract description 140
- 229920001155 polypropylene Polymers 0.000 claims abstract description 140
- -1 polypropylene Polymers 0.000 claims abstract description 139
- 229920000642 polymer Polymers 0.000 claims abstract description 132
- 238000009987 spinning Methods 0.000 claims abstract description 97
- 238000002156 mixing Methods 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims description 39
- 238000001125 extrusion Methods 0.000 claims description 37
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229920001410 Microfiber Polymers 0.000 claims description 10
- 239000003658 microfiber Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 229920002959 polymer blend Polymers 0.000 claims description 4
- 230000005251 gamma ray Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims 1
- 238000010128 melt processing Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000009998 heat setting Methods 0.000 description 8
- 238000007781 pre-processing Methods 0.000 description 8
- 239000002352 surface water Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002074 melt spinning Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 108700005457 microfibrillar Proteins 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure and a preparation method thereof, wherein the preparation method comprises the following steps: mixing polypropylene and disperse phase polymer to obtain mixture, melt blending and spinning, and controlling interfacial tension between the disperse phase polymer and polypropylene to be not lower than 0.5X10 ‑3 N/m is used for preparing the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure; the disperse phase polymer is obtained by pre-treating a hydroxyl polypropylene copolymer; the pretreatment process is the reaction process of the hydroxyl polypropylene copolymer and the hydrogen bond capturing agent; the product of the invention is composed of a fiber body and bulges or grooves distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body, and the grooves are parts recessed relative to the surface of the fiber body. The method is simple, the problem of difficult melt processing of the hydroxyl polypropylene copolymer is solved, and the prepared product has an adjustable concave-convex structure.
Description
Technical Field
The invention belongs to the technical field of spinning, and relates to a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure and a preparation method thereof.
Background
Polypropylene (PP) is a polymer obtained by polymerization of propylene, and has very wide application in various industries, and has been increasingly demanded in the industrial fields of civil and household textiles, sanitary materials, construction engineering, separation filtration, and the like due to its unique characteristics of light weight, warmth retention, hydrophobicity, moisture transfer, acid and alkali resistance, and the like. The structure of polypropylene backbone-perfluoroalkanes, however, limits further improvement in performance in the face of increasing application demands.
The main chain of polypropylene fiber has two main methods of introducing polar group, graft modification and copolymerization modification.
The grafting modification further realizes the grafting of the polar groups into the molecular main chain by utilizing the free radicals by means of leading out the free radicals to the polypropylene resin or the fiber. The grafting modification needs free radicals as an intermediary, and the preparation process is complicated, the process is complex and the efficiency is low. In addition it requires a break in the backbone structure and thus has a negative impact on the final fiber and the groups introduced are often only on the polymer surface. The patent CN110886087B obtains the hydroxyl modified polypropylene fiber by carrying out sulfuric acid and gradient hydrogen peroxide solution soaking treatment on the raw material polypropylene fiber, but the method has erosion damage effect on the fiber, and the generated hydroxyl is mainly concentrated on the surface, so that polar groups are difficult to exist in the center of the fiber.
The copolymerization modification is directly carried out by copolymerizing propylene monomer and alpha-olefin monomer with polar group, thus directly obtaining the polypropylene copolymer with polar group, which can completely avoid the damage of grafting modification to the main chain, and can be designed to be stronger and higher in efficiency. Although the functionalized polypropylene copolymer has wide application potential, the melt processing of the functionalized polypropylene copolymer has difficulties. Document (Influence of hydrogen bonding on the melt rheology of polypropylene, 2016, 107:223-232.) discloses a melt processing method of hydroxyl group-containing hydroxy polypropylene, which shows that the melt shear viscosity of the hydroxyl group-containing hydroxy polypropylene copolymer is far higher than that of the conventional polypropylene homopolymer under the condition of the same order of magnitude relative molecular mass, so that the melt fluidity is poor, the melt is difficult to blend with polypropylene to prepare melt-spun polypropylene fibers, and the main reason is that the internal hydroxyl hydrogen bonding forms a physical crosslinking structure, and the complete elimination of the structure is close to the decomposition temperature of the copolymer.
Therefore, the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure and the preparation method thereof are studied, so that the problem of difficult melt processing of the hydroxyl polypropylene copolymer is very significant.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a hydroxyl polypropylene copolymer polypropylene fiber with a surface concave-convex structure and a preparation method thereof.
As shown in fig. 1, the dispersed phase polymer of the present invention is a hydroxyl polypropylene copolymer subjected to pretreatment, wherein the hydroxyl polypropylene copolymer is first dissolved during the pretreatment, and the distance between polymer molecular chains is increased by a solvent, so as to ensure complete elimination of the crosslinked structure of (b); then adding a hydrogen bond capturing agent, and uniformly mixing to ensure uniform dispersion in the polymer solution; finally, the solvent is removed, and the inter-molecular chain distance of the polymer is gradually and synchronously reduced along with the reduction of the solvent.
The pretreatment converts part of the structure (b) in the copolymer into the structure (a) (see FIG. 1) to reduce the degree of physical cross-linking between hydroxyl groups of the molecular chain prior to melt processing. The formation of a physical crosslinked structure by inter-hydroxyl hydrogen bonding within the hydroxypolypropylene copolymer is the most important reason for impeding melt spinning processing, and it is more difficult to attenuate the degree of crosslinking by melt blending (already mentioned in the background). When the hydroxyl polypropylene copolymer is pretreated, the hydrogen bond capturing agent has stronger small molecular movement binding capacity, and can preferentially react with hydroxyl groups on molecular chains to form a stable structure, so that the physical crosslinking structure formed by the interaction of the hydroxyl hydrogen bonds on the molecular chains is effectively avoided, and meanwhile, the content of the structure (b) can be controlled, so that the melt spinning processing requirement can be met.
In addition, the invention can control the content of the structure (a) in the figure 1 to ensure that the copolymer has the structure (a) with better compatibility with polypropylene and the structure (b) with poorer compatibility with polypropylene so as to meet the requirements of melt spinning and surface concave-convex structure construction on a disperse phase, and the zero-cut viscosity of the hydroxyl polypropylene copolymer after pretreatment at the spinning temperature can be reduced to 60-4.0x10 3 Pa·s range.
The invention directly controls the viscosity of polypropylene, the kind of disperse phase polymer and the spinning temperature to control the interfacial tension between the disperse phase polymer and polypropylene to reach a specific value in the spinning forming process without any post-treatment, and simultaneously controls the shape and the size of the surface concave-convex structure of the hydroxyl polypropylene copolymer fiber by controlling the stretching ratio, the stretching temperature, the spinning speed, the aperture of a spinneret orifice and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for preparing the hydroxy polypropylene copolymer fibre with surface concave-convex structure includes such steps as mixing polypropylene with dispersed phase polymer to obtain a mixture, melt blending, spinning, and controlling the viscosity of polypropylene, the type of dispersed phase polymer and the interfacial tension between dispersed phase polymer and polypropylene to be not less than 0.5×10 -3 N/m, and preparing the hydroxyl polypropylene copolymer fiber with a surface concave-convex structure;
the interfacial tension of the blending system is measured by an experimental method, the interfacial tension measuring method is combined with an embedded fiber shrinking method and a deformation liquid drop shrinking method, the numerical value of the interfacial tension is obtained by utilizing small deformation model fitting through observing the shrinking process of the embedded fiber shape, and the interfacial tension and temperature, the molecular weight and the interfacial tension in the distribution range are established by measuring the interfacial tension of different molecular weights and distributions and different temperatures, so that the interfacial tension in a wider temperature, molecular weight and the distribution range is researched;
the spinning part includes: melt blending of disperse phase polymer and polypropylene, melt conveying and spinning, multistage winding of fiber and post-drawing;
the disperse phase polymer is obtained by pre-treating a hydroxyl polypropylene copolymer; the pretreatment process is the reaction process of the hydroxyl polypropylene copolymer and the hydrogen bond capturing agent;
the structural formula of the hydrogen bond capturing agent is as follows:
wherein R is 1 Is an alkane structure with 12-20 carbon atoms, R 2 Is an alkane structure with 10-15 carbon atoms;
the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges or grooves distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body, and the grooves are parts recessed relative to the surface of the fiber body.
As a preferable technical scheme:
the preparation method of the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure comprises the following specific steps of:
(i) Adding the hydroxyl polypropylene copolymer into a solvent with the temperature of 105-110 ℃ to prepare a solution with the solid content of 10-30wt%, stirring and dissolving for 2-5 h, and then keeping the temperature to 90-100 ℃;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 0.5-2 h, wherein the mass percent of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value range of (2) is 5-20wt%;
(iii) The solvent was removed and the product was crushed and dried.
The preparation method of the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure comprises the steps of adjusting the value of a constant a and controlling a constant C<1 adjusting the type and the length-diameter ratio of the bulge, wherein the bulge type comprises a spherical bulge, an ellipsoidal bulge, a short microfiber bulge and a long microfiber bulge, the length-diameter ratio of the bulge is the ratio of the length of the bulge in the fiber axial direction to the length of the bulge in the fiber transverse direction, and the value range is 1-1 multiplied by 10 6 ；
The calculation formula of the constant a is as follows:
wherein eta is m The viscosity of polypropylene is expressed as Pa.s; Is the stress strain rate, the unit is s -1 ；D d The initial diameter of the dispersed phase polymer in m is the initial diameter of the polymer blend before flowing into the spinneret orifice; Γ is the interfacial tension between the dispersed phase polymer and the polypropylene in N/m; p is the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene; the viscosity of the polymer is measured by a capillary rheometer, and the pressure drop delta P of the flow of a convergent flow field of an inlet area of the capillary rheometer is utilized 0 Calculating the viscosity of the melt in the stretching flow field;
the calculation formula of the constant C is as follows:
W a ＝γ d +γ m -Γ；
wherein F is the tensile stress of the fiber during melt blending spinning, the unit is N, and F is measured by an online tensiometer; d is the diameter of the dispersed phase (where diameter is equivalent diameter when the shape is a non-standard circle) in m; a is the cross-sectional area of the hydroxyl polypropylene copolymer fiber with a surface concave-convex structure, and the unit is m 2 ；W a The unit of interfacial bonding work between polypropylene and disperse phase polymer is N/m; gamma ray d And gamma m The surface energy of the disperse phase polymer and the polypropylene respectively can be referred to by manual, and the unit is N/m and W a Can also be obtained by experimental measurement;
the constant a has a value of (0,0.1)]When the convex type is a spherical convex, the length-diameter ratio of the convex is 1; the constant a has a value interval of (0.1, 1) ]When the protrusion is protrudedThe type of the (B) is spherical and ellipsoidal bulges, and the length-diameter ratio of the bulges is 1-10; the constant a has a value interval of (1, 4)]When the protrusion is of a short microfiber protrusion type, the length-diameter ratio of the protrusion is 3-100; the constant a has a value of (4,1.5 ×10) 5 ) When the projections are long microfibrous projections, the aspect ratio of the projections is 10-1×10 6 The reason why the aspect ratio of the short microfibrillar projections partially overlaps with the numerical range of the aspect ratio of the long microfibrillar projections is that the melt blending system is a system in which the dispersed phase is distributed in a plurality and the size is dispersed in a plurality.
The value of the constant a is controlled by adjusting the viscosity and the molecular weight and the distribution of the polypropylene, the type and the molecular weight of the disperse phase polymer and the distribution thereof, the speed of a melt, the spinning temperature, the stretching temperature and the spinning speed;
wherein the viscosity and molecular weight of the polypropylene and its distribution, spinning temperature anddetermining eta m Is determined by the melt extrusion speed and the spinning temperature during extrusion>The values of (2) the drawing temperature and the spinning speed determine +.>Wherein the spin temperature, the viscosity of the polypropylene and the type of the dispersed phase polymer determine the value of Γ together, the viscosity of the polypropylene and the type and molecular weight of the dispersed phase polymer and the distribution thereof determine the value of p, " >η m Γ jointly determine D d The value of the value is generally obtained through actual measurement; the processing technology of the fiber in the invention comprises a POY technology and an FDY technology, and the POY technology does not contain a stretching procedure, so when the processing technology is PThe value of the constant a is controlled by adjusting the viscosity and molecular weight and distribution of the polypropylene, the type and molecular weight and distribution of the disperse phase polymer, the speed of the melt, the spinning temperature and the spinning speed, and the spinning speed is determined in the stretching process>Is a value of (2);
wherein the kind and molecular weight of the dispersed phase polymer and the distribution thereof depend on the carbon number of the hydroxy branched alkane of the hydroxy polypropylene copolymer, the hydroxy content of the hydroxy polypropylene copolymer, the structure of the hydrogen bond scavenger and M P The number average molecular weight of the hydroxypolypropylene copolymer and the molecular weight distribution index of the hydroxypolypropylene copolymer.
According to the preparation method of the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure, the length-diameter ratio of the groove is adjusted by controlling the constant a to be more than 4 and the constant C to be more than or equal to 1 and adjusting the value of the constant C, the length-diameter ratio of the groove is the ratio of the length of the groove in the fiber axial direction to the length of the groove in the fiber transverse direction (the value of the length depends on the size of a disperse phase of the fiber at the corresponding axial position), and the value range is 1-infinity;
When the value interval of the constant C is [1,5], the length-diameter ratio of the groove is 1-20; when the value interval of the constant C is (5, 50), the length-diameter ratio of the groove is 20 to infinity.
The value of the constant C is controlled by adjusting the stretching ratio, the stretching temperature, the spinning speed, the viscosity of polypropylene, the type of disperse phase polymer, the spinning temperature and the aperture of a spinneret orifice; wherein the drawing ratio, the drawing temperature and the spinning speed jointly determine the value of F, the drawing ratio, the spinning speed, the viscosity of polypropylene, the type of disperse phase polymer, the spinning temperature and the aperture of a spinneret orifice jointly determine the values of D and A, the A value and the D value of different spinning positions can be obtained through experimental measurement, the D value can also be based on the initial value of the blend melt after exiting the spinneret orifice, and then based on calculation and prediction of an affine deformation model, the viscosity of polypropylene and the disperse phase polymerThe kind, spinning temperature and drawing temperature determine W together a Is a value of (a).
The preparation method of the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure comprises the steps that the value range of the content of the disperse phase polymer in the mixture is 5-30wt%;
The value range of zero-cut viscosity of polypropylene at the spinning temperature is 5.0X10 2 ～2.0×10 3 Pa·s；
The number average molecular weight of the polypropylene is 8.0X10 4 ～20×10 4 g/mol, wherein the value range of the molecular weight distribution index is 3-5;
the zero-cut viscosity of the hydroxyl polypropylene copolymer at the spinning temperature is in the range of 5.0x10 2 ～20×10 4 Pa·s, (i.e., viscosity at shear rate 0, zero shear viscosity measured by a rheometric curve measured by a rotational rheometer, combined with three-parameter Bird-Carreau-Yasuda model regression);
the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has a carbon number of 6-9 and a number average molecular weight of 1.0X10 4 ～4.0×10 4 g/mol, the molecular weight distribution index is 2.1-4, and the hydroxyl molar content is 0.5-2.0 mol%;
the value range of the ratio of the viscosity of the disperse phase polymer to the viscosity of the polypropylene is 0.05-4;
the melt extrusion speed was in the range of 2.5X10 -11 ～1.5×10 -8 m 3 /s；
The value range of the spinning temperature is 200-240 ℃;
the value range of the stretching temperature is 60-140 ℃;
the value range of the spinning speed is more than 10 m/min;
the value range of the stretching ratio is 2-5;
the range of the aperture of the spinneret orifice is 0.25X10 -3 ～0.3×10 -3 m；
The parameters can influence the values of some parameters in the calculation formulas of the constant a and the constant C, thereby influencing the constant a And a constant C, e.g., the parameters described above result in an initial diameter D of the dispersed phase polymer of the polymer blend prior to flowing into the orifice d The range of the value of (2) is 0.01X10 -6 ～10×10 -6 m, the above parameters result in a specific value A for the cross-sectional area of the hydroxyl polypropylene copolymer fiber having a surface relief structure (since the above parameters result in a range of 10X 10 for the fiber diameter) -6 ～3000×10 -6 m), the abovementioned parameters (spinning temperature, viscosity ratio) result in an interfacial tension Γ between the disperse phase polymer and the polypropylene in the range of 0.7X10 -3 ～7.6×10 -3 N/m, the above parameters lead to an interfacial bonding work W between polypropylene and the dispersed phase polymer a The range of the value is 1 to 20 multiplied by 10 -2 N/m, the above parameters lead to stress strain rateThe value range of (2) is (0-20000)]s -1 。
"hydroxypolypropylene copolymer" as used herein refers to a hydroxypolypropylene copolymer that has not been pretreated unless otherwise specified.
The invention also provides a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure, which is prepared by adopting the preparation method according to any one of the above; the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges or grooves distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body, and the grooves are parts recessed relative to the surface of the fiber body.
As a preferable technical scheme:
the hydroxy polypropylene copolymer fiber with the surface concave-convex structure has the convex diameter of 0.1 multiplied by 10 -7 ～2×10 -6 m, the diameter of the protrusion is the length of the protrusion in the transverse direction of the fiber, where the diameter is the equivalent diameter when the protrusion is in the shape of a non-standard circle.
The hydroxyl polypropylene copolymer fiber with the surface concave-convex structure has the groove width of 0.05X10 -6 ～1.0×10 -6 m。
The principle of the invention is as follows:
according to the invention, an incompatible disperse phase polymer is introduced into polypropylene by using a melt blending spinning method, and the hydroxyl polypropylene copolymer fiber with a surface concave-convex structure is prepared by using morphological fluctuation caused by phase separation and interface separation, so that the control of viscosity force, interfacial tension, tensile stress and interfacial binding force of the disperse phase is realized based on the adjustment of raw materials and processing parameters such as polymer types, spinning speed, spinning temperature and the like, and finally the regulation of the surface concave-convex structure is realized.
Wherein the generation of the concave-convex structure on the surface of the fiber is required to satisfy the interfacial tension of 0.5X10 -3 More than N/m can be obviously separated, and the larger the interfacial tension value is, the more obvious the phase separation is, thus providing a necessary condition for the adjustment of the disperse phase. Adjusting the viscosity and interfacial tension of the disperse phase by adjusting the value of the constant a >When the viscosity of the disperse phase is more than 0.1, the viscous force is dominant to the interfacial tension, and the disperse phase deforms to form an ellipsoidal shape and a microfiber shape, and the larger the value of a, the larger the deformation is, and the more easily microfiber shape is formed; when the constant a is 0.1 or less, interfacial tension exerted on the dispersed phase is dominant relative to viscous force, and the dispersed phase is not deformed, so that the spherical shape is maintained. Due to interfacial tension of 0.5X10 -3 Above N/m, the disperse phase and the polypropylene are subjected to phase separation, and according to the principle of energy minima, the disperse phase interface always tends to be round so as to keep the energy minima; meanwhile, as different polymers have different specific heat capacities and densities, the volume difference of a disperse phase and polypropylene is larger in the cooling process, and certain morphological fluctuation is generated in the phase separation process, so that the formation of a surface concave-convex structure is promoted. In the fiber forming process, the fiber receives axial tensile stress and transmits the tensile stress to a disperse phase in polypropylene, and the disperse phase has interfacial bonding force with the polypropylene, so that the balance between the tensile stress and the interfacial bonding force of the disperse phase is realized by the balance of the tensile stress and the interfacial bonding force, and when the constant C is more than 1, the tensile stress of the disperse phase is dominant compared with the interfacial bonding force, the interface can be separated, the larger the C value is, the more obvious the separation is, and the longer the formed groove is 。
Under the condition of no need of any post-treatment, in the melt spinning process, an uneven structure is constructed on the surface of the hydroxy polypropylene copolymer fiber by adjusting interfacial tension, constant a and constant C between blending phases, and the size of the uneven structure is regulated, so that the hydroxy polypropylene copolymer fiber with the surface uneven structure is directly prepared in one step.
In the prior art, more than two incompatible polymers are melt-blended to prepare fibers, which are based on 'phase separation and interfacial separation' to form concave-convex structures; although more than two incompatible polymers are melt blended to prepare the fiber, the invention is based on the fact that grooves are formed by interfacial separation between two phases; the invention effectively solves the problems of long and difficult control of the disperse phase migration process, environmental pollution caused by the adoption of a solvent in post-treatment and the like in the prior art.
The beneficial effects are that:
(1) The invention provides a technical solution for solving the melt spinning processing of a hydroxyl polypropylene copolymer;
(2) The invention utilizes the limited interface separation between the disperse phase of the fiber surface area and the polypropylene under the spinning condition to construct a micro-nano bulge or groove structure;
(3) The polymer fiber with the surface concave-convex structure has adjustable and controllable protrusion and groove sizes;
(4) The method is simple, effectively solves the problem that the fiber is damaged by the prior modification technology, and realizes the introduction of the main chain hydroxyl while ensuring the mechanical property of the polypropylene fiber by the copolymerization modification technology.
Drawings
FIG. 1 is a schematic view of a hydroxy polypropylene copolymer pretreatment;
FIG. 2 is a spin flow curve (zero shear viscosity measured by a spin rheometer, combined with three parameter Bird-Carreau-Yasuda model regression) of the hydroxy polypropylene copolymer of example 4 at 220℃before and after treatment, respectively;
FIG. 3 is an electron microscopic image of a hydroxy polypropylene copolymer fiber having a surface relief structure prepared in example 2.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
In the following examples:
the calculation formula of the constant a is as follows:
wherein eta is m The viscosity of polypropylene is expressed as Pa.s;is the stress strain rate, the unit is s -1 ；D d The initial diameter of the dispersed phase polymer in m is the initial diameter of the polymer blend before flowing into the spinneret orifice; Γ is the interfacial tension between the dispersed phase polymer and the polypropylene in N/m; p is the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene;
the value of the constant a is controlled by adjusting the viscosity and the molecular weight and the distribution thereof of the polypropylene, the type and the molecular weight and the distribution thereof of the dispersed phase polymer, the speed of melt extrusion, the spinning temperature, the stretching temperature and the spinning speed, wherein the type and the molecular weight of the dispersed phase polymer and the distribution thereof depend on the carbon of the hydroxy branched alkane of the hydroxy polypropylene copolymerNumber of atoms, hydroxyl content of the hydroxyl polypropylene copolymer, structure of the hydrogen bond scavenger, M P Number average molecular weight of the hydroxypolypropylene copolymer and molecular weight distribution index of the hydroxypolypropylene copolymer;
the calculation formula of the constant C is as follows:
W a ＝γ d +γ m -Γ；
wherein F is the tensile stress of the fiber during melt blending spinning, and the unit is N; d is the diameter of the bulge, and the unit is m; a is the cross-sectional area of the hydroxyl polypropylene copolymer fiber with a surface concave-convex structure, and the unit is m 2 ；W a The unit of interfacial bonding work between polypropylene and disperse phase polymer is N/m; gamma ray d And gamma m The surface energy of the disperse phase polymer and the surface energy of the polypropylene are respectively N/m;
the value of the constant C is controlled by adjusting the draw ratio, the draw temperature, the spinning speed, the viscosity of the polypropylene, the type of the dispersed phase polymer, the spinning temperature and the aperture of the spinneret orifice.
In the following examples, the structural formula of the hydrogen bond scavenger is as follows:
wherein R is 1 Is an alkane structure with 12-20 carbon atoms, R 2 Is an alkane structure with 10-15 carbon atoms.
Example 1
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; 1.2X10 of zero shear viscosity of Polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 16X 10 4 g/mol, molecular weight distribution index of 3.5;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (toluene) with the temperature of 105 ℃ to prepare a solution with the solid content of 14 weight percent, stirring and dissolving for 2 hours, and then keeping the temperature to 90 ℃; the zero-shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of the step (2) is 5.0X10 2 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has 6 carbon atoms and 1.0X10 number average molecular weight 4 g/mol, molecular weight distribution index of 4, hydroxyl mole content of 1.5mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 0.5h, wherein the mass percent of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 20wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 12 carbon atoms, R 2 Is an alkane structure with 10 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 0.05;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 5wt%; melt extrusion speed was 4.6X10 -9 m 3 S; the spinning temperature is 230 ℃; the stretching temperature is 80 ℃; the heat setting temperature is 120 ℃; spinning speed is 1000m/min; the draw ratio was 2; the aperture of the spinneret orifice is 0.3 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene at N/m depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 2.7X10 -3 N/m；
The type of the bulge is a spherical bulge; the length-diameter ratio of the bulge is 1; the diameter of the protrusions was 2.0X10 -6 m; constant C in this embodiment<1, the type and aspect ratio of the protrusions depend on the value of the constant a, which is 0.01 in this embodiment.
Example 2
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
Polypropylene; 5.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 2 Pa·s; the polypropylene has a number average molecular weight of 8.0X10 4 g/mol, molecular weight distribution index 3;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (toluene) with the temperature of 108 ℃ to prepare a solution with the solid content of 30wt%, stirring and dissolving for 4 hours, and then keeping the temperature to 95 ℃; the zero-shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of the step (2) is 8.0X10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has the carbon number of 9 and the number average molecular weight of 2.2 multiplied by 10 4 g/mol, molecular weight distribution index of 2.6, hydroxyl mole content of 0.5mol%;
(ii) Adding to the solutionStirring for 1.5h after the hydrogen bond scavenger, wherein the mass percentage of the hydrogen bond scavenger to the hydroxy polypropylene copolymer is M P ，M P The value of (2) is 11wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 16 carbon atoms, R 2 Is an alkane structure with 12 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
The ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 1;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 10wt%; melt extrusion speed was 4.6X10 -9 m 3 S; the spinning temperature is 200 ℃; the stretching temperature is 85 ℃; the heat setting temperature is 120 ℃; spinning speed is 1000m/min; the draw ratio was 3; the aperture of the spinneret orifice is 0.25 multiplied by 10 -3 m；
As shown in fig. 3, the finally produced hydroxyl polypropylene copolymer fiber having a surface relief structure is composed of a fiber body and protrusions distributed on the surface of the fiber body, the protrusions being portions protruding with respect to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene, N/m, depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 1.0X10 -3 N/m；
The type of the bulge is an ellipsoidal bulge; the length-diameter ratio of the bulge is 5; protrusionsIs 1.5X10 diameter -6 m; constant C in this embodiment<1, the type and aspect ratio of the protrusions depend on the value of the constant a, which is 0.5 in this embodiment.
Example 3
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; 2.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 20X 10 4 g/mol, molecular weight distribution index 5;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (the solvent is dimethylbenzene) with the temperature of 110 ℃ to prepare a solution with the solid content of 15wt%, stirring and dissolving for 5 hours, and then keeping the temperature to 100 ℃; the zero-shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of the step (2) is 20 multiplied by 10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has 6 carbon atoms and 3.5X10 number average molecular weight 4 g/mol, molecular weight distribution index of 2.4, hydroxyl mole content of 1.2mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 2 hours, wherein the mass percentage of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 6wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 14 carbon atoms, R 2 Is an alkane structure with 11 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 2; a step of
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 20wt%; melt extrusion speed was 9.3X10 -9 m 3 S; the spinning temperature is 240 ℃; the stretching temperature is 90 ℃; the heat setting temperature is 120 ℃; spinning speed is 2000m/min; the draw ratio was 4; the aperture of the spinneret orifice is 0.3 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene, N/m, depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 5.0X10 -3 N/m；
The type of the bulge is a short microfiber bulge; the aspect ratio of the protrusions is 60; the diameter of the protrusions was 1.2X10 -6 m; constant C in this embodiment<1, the type and aspect ratio of the protrusions depend on the value of the constant a, which in this embodiment is 3.5.
Example 4
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
Polypropylene; 1.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 15X 10 4 g/mol, molecular weight distribution index of 3.5;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (the solvent is dimethylbenzene) with the temperature of 110 ℃ to prepare a solution with the solid content of 10wt%, stirring and dissolving for 5 hours, and then keeping the temperature to 100 ℃; the zero-shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of the step (2) is 20 multiplied by 10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has the carbon number of 9 and the number average molecular weight of 4.0x10 4 g/mol, molecular weight distribution index of 2.1, hydroxyl mole content of 2mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 2 hours, wherein the mass percentage of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 5wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 20 carbon atoms, R 2 Is an alkane structure with 15 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
The ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 4;
as shown in FIG. 2, it was found from the graph that the hydroxy polypropylene used in example 4 was significantly reduced in viscosity at various low shear rates after the treatment compared with the viscosity before the treatment, and the zero cut viscosity obtained by the Carreau model fitting calculation was 20X 10 4 Pa.s is reduced to 4×10 3 Pa·s, the pretreatment step can effectively reduce the zero-cut viscosity of the hydroxyl polypropylene so as to meet the requirement of melt spinning;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 30wt%; melt extrusion speed was 9.3X10 -9 m 3 S; the spinning temperature is 220 ℃; the stretching temperature is 95 ℃; the heat setting temperature is 120 ℃; spinning speed is 2000m/min; the draw ratio was 5; the aperture of the spinneret orifice is 0.25 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene, N/m, depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 1.7X10 -3 N/m；
The type of the bulge is a long microfiber bulge; the aspect ratio of the protrusions is 500; the diameter of the protrusions was 0.1X10 -7 m; constant C in this embodiment<1, the type and aspect ratio of the protrusions depend on the value of the constant a, which is 2000 in this embodiment.
Example 5
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; 1.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 15X 10 4 g/mol, molecular weight distribution index of 3.4;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (toluene) with the temperature of 110 ℃ to prepare a solution with the solid content of 10wt%, stirring and dissolving for 5 hours, and then keeping the temperature to 100 ℃; hydroxy poly (ethylene glycol)The zero shear viscosity of the propylene copolymer at the spinning temperature of step (2) is 20X 10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has the carbon number of 9 and the number average molecular weight of 4.0x10 4 g/mol, molecular weight distribution index of 2.6, hydroxyl mole content of 1.9mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 2 hours, wherein the mass percentage of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 10wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 12 carbon atoms, R 2 Is an alkane structure with 10 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 4;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
Wherein the content of the dispersed phase polymer in the mixture is 5wt%; melt extrusion speed was 2.5X10 -11 m 3 S; the spinning temperature is 230 ℃; the stretching temperature is 90 ℃; the heat setting temperature is 120 ℃; spinning speed is 2400m/min; the draw ratio was 3; the aperture of the spinneret orifice is 0.25 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and grooves distributed on the surface of the fiber body, wherein the grooves are concave parts relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 N/m, between dispersed phase polymer and polypropyleneThe interfacial tension value depends on the viscosity of the polypropylene, the type of the dispersed phase polymer and the spinning temperature, and in this example, the interfacial tension value between the dispersed phase polymer and the polypropylene is 4.7X10 -3 N/m；
The length-diameter ratio of the groove is ≡; the width of the groove is 1.0X10 -6 m; the aspect ratio of the groove depends on the values of the constant a and the constant C, in this embodiment, the value of the constant a is 3000, and in this embodiment, the value of the constant C is 20.
Example 6
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; 1.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 16X 10 4 g/mol, molecular weight distribution index of 3.2;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (toluene) with the temperature of 110 ℃ to prepare a solution with the solid content of 15wt%, stirring and dissolving for 5 hours, and then keeping the temperature to 100 ℃; the zero shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of the step (2) is 18×10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has the carbon number of 9 and the number average molecular weight of 3.0x10 4 g/mol, a molecular weight distribution index of 3, and a hydroxyl group molar content of 1.6mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 2 hours, wherein the mass percentage of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 10wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 16 carbon atoms, R 2 Is an alkane structure with 12 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
The ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 3;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 10wt%; melt extrusion speed was 1.5X10 -10 m 3 S; the spinning temperature is 220 ℃; the stretching temperature is 90 ℃; the heat setting temperature is 120 ℃; spinning speed is 2400m/min; the draw ratio was 3; the aperture of the spinneret orifice is 0.25 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and grooves distributed on the surface of the fiber body, wherein the grooves are concave parts relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene at N/m depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 3.6X10 -3 N/m；
The length-diameter ratio of the groove is ≡; the width of the groove is 0.5X10 -6 m; the aspect ratio of the groove depends on the values of the constant a and the constant C, in this embodiment, the value of the constant a is 3000, and in this embodiment, the value of the constant C is 18.
Example 7
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; spinning temperature of polypropylene in step (2)Zero shear viscosity at degree (i.e. viscosity at shear rate of 0) 1.0X10 3 Pa·s; the polypropylene has a number average molecular weight of 12X 10 4 g/mol, molecular weight distribution index of 4.5;
a dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (the solvent is dimethylbenzene) with the temperature of 108 ℃ to prepare a solution with the solid content of 25wt%, stirring and dissolving for 4 hours, and then keeping the temperature to 95 ℃; the zero shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of step (2) is 1.2X10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has 6 carbon atoms and 1.9X10 number average molecular weight 4 g/mol, molecular weight distribution index of 2.6, hydroxyl mole content of 1.5mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 1.5h, wherein the mass percent of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 15wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 14 carbon atoms, R 2 Is an alkane structure with 11 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 2;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
wherein the content of the dispersed phase polymer in the mixture is 20wt%; melt extrusion speed was 1.5X10 -9 m 3 S; the spinning temperature is 215 ℃; the stretching temperature is 80 ℃; heat setting temperature is 120 ℃; spinning speed is 2400m/min; the draw ratio was 3; the aperture of the spinneret orifice is 0.3 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and grooves distributed on the surface of the fiber body, wherein the grooves are concave parts relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene at N/m depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 2.8X10 -3 N/m；
The length-diameter ratio of the groove is ≡; the width of the groove is 0.08X10 -6 m; the aspect ratio of the groove depends on the values of the constant a and the constant C, in this embodiment, the value of the constant a is 10000, and in this embodiment, the value of the constant C is 15.
Example 8
A preparation method of a hydroxyl polypropylene copolymer fiber with a surface concave-convex structure comprises the following specific steps:
(1) Preparing raw materials;
polypropylene; 1.0X10 of the zero shear viscosity (i.e.the viscosity at shear rate 0) of the polypropylene at the spinning temperature of step (2) 3 Pa·s; the polypropylene has a number average molecular weight of 14X 10 4 g/mol, molecular weight distribution index of 3.5;
A dispersed phase polymer; the dispersed phase polymer is obtained by preprocessing a hydroxyl polypropylene copolymer, and comprises the following specific steps:
(i) Adding the hydroxy polypropylene copolymer into a solvent (the solvent is dimethylbenzene) with the temperature of 105 ℃ to prepare a solution with the solid content of 21wt%, stirring and dissolving for 3 hours, and then keeping the temperature to 95 ℃; the zero shear viscosity of the hydroxy polypropylene copolymer at the spinning temperature of step (2) is 1.0X10 4 Pa·s; the hydroxyl branched alkane of the hydroxyl polypropylene copolymer has 6 carbon atoms and 1.6X10 number average molecular weight 4 g/mol, molecular weight distribution index of 3.5, hydroxyl groupThe molar content of the radicals is 1.6mol%;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 1.5h, wherein the mass percent of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value of (2) is 17wt%;
in the structural formula of the hydrogen bond capturing agent, R 1 Is of an alkane structure with 20 carbon atoms, R 2 Is an alkane structure with 15 carbon atoms;
(iii) Removing the solvent, crushing and drying the product;
the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene was 1;
(2) Mixing polypropylene and a disperse phase polymer, carrying out blending extrusion and granulation in a double-screw extruder to obtain mixture particles with the average length multiplied by the width of 3 multiplied by 3mm, drying the raw materials in a vacuum oven at 80 ℃ for 12 hours before blending extrusion to control moisture, carrying out blending extrusion, removing surface water of the rear particles in the vacuum oven at 80 ℃ for 12 hours, and carrying out melt blending spinning after drying the raw materials to obtain the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
Wherein the content of the dispersed phase polymer in the mixture is 30wt%; melt extrusion speed was 1.5X10 -8 m 3 S; the spinning temperature is 200 ℃; the stretching temperature is 80 ℃; the heat setting temperature is 120 ℃; spinning speed is 2400m/min; the draw ratio was 3; the aperture of the spinneret orifice is 0.3 multiplied by 10 -3 m；
The finally prepared hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and grooves distributed on the surface of the fiber body, wherein the grooves are concave parts relative to the surface of the fiber body.
The surface irregularities are formed because the interfacial tension between the dispersed phase polymer and polypropylene is not less than 0.5X10 -3 The interfacial tension between the dispersed polymer and the polypropylene, N/m, depends on the viscosity of the polypropylene, the type of the dispersed polymer and the spinning temperature, and in this example, the interfacial tension between the dispersed polymer and the polypropylene is 1.7X10 -3 N/m；
The length-diameter ratio of the groove is ≡; the width of the groove is 0.05X10 -6 m; the aspect ratio of the groove depends on the values of the constant a and the constant C, the value of the constant a is 5000 in the embodiment, and the value of the constant C is 15 in the embodiment.
Claims (9)
1. A process for preparing the hydroxy polypropylene copolymer fibre with surface concave-convex structure includes such steps as mixing polypropylene with dispersed phase polymer to obtain a mixture, melt-blending spinning, and controlling the interfacial tension between dispersed phase polymer and polypropylene to be not less than 0.5×10 -3 N/m is used for preparing the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure;
the disperse phase polymer is obtained by pre-treating a hydroxyl polypropylene copolymer; the pretreatment process is the reaction process of the hydroxyl polypropylene copolymer and the hydrogen bond capturing agent;
the specific steps of the pretreatment are as follows:
(i) Adding the hydroxyl polypropylene copolymer into a solvent with the temperature of 105-110 ℃ to prepare a solution with the solid content of 10-30wt%, stirring and dissolving for 2-5 h, and then keeping the temperature to 90-100 ℃;
(ii) Adding a hydrogen bond capturing agent into the solution, and stirring for 0.5-2 h, wherein the mass percent of the hydrogen bond capturing agent to the hydroxyl polypropylene copolymer is M P ，M P The value range of (2) is 5-20wt%;
(iii) Removing the solvent, crushing and drying the product;
the structural formula of the hydrogen bond capturing agent is as follows:
wherein R is 1 Is an alkane structure with 12-20 carbon atoms, R 2 Is an alkane structure with 10-15 carbon atoms;
the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges or grooves distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body, and the grooves are parts recessed relative to the surface of the fiber body.
2. The method for producing a hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 1, wherein the constant C is controlled by adjusting the value of the constant a<1 adjusting the type and the length-diameter ratio of the bulge, wherein the bulge type comprises a spherical bulge, an ellipsoidal bulge, a short microfiber bulge and a long microfiber bulge, the length-diameter ratio of the bulge is the ratio of the length of the bulge in the fiber axial direction to the length of the bulge in the fiber transverse direction, and the value range is 1-1 multiplied by 10 6 ；
The calculation formula of the constant a is as follows:
wherein eta is m The viscosity of polypropylene is expressed as Pa.s;is the stress strain rate, the unit is s -1 ；D d The initial diameter of the dispersed phase polymer in m is the initial diameter of the polymer blend before flowing into the spinneret orifice; Γ is the interfacial tension between the dispersed phase polymer and the polypropylene in N/m; p is the ratio of the viscosity of the dispersed phase polymer to the viscosity of the polypropylene;
the calculation formula of the constant C is as follows:
W a ＝γ d +γ m -Γ；
wherein F is the tensile stress of the fiber during melt blending spinning, and the unit is N; d is the diameter of the disperse phase, and the unit is m; a is the cross-sectional area of the hydroxyl polypropylene copolymer fiber with a surface concave-convex structure, and the unit is m 2 ；W a The unit of interfacial bonding work between polypropylene and disperse phase polymer is N/m; gamma ray d And gamma m The surface energy of the disperse phase polymer and the surface energy of the polypropylene are respectively N/m;
the constant a has a value of (0,0.1)]When the convex type is a spherical convex, the length-diameter ratio of the convex is 1; the constant a has a value interval of (0.1, 1)]When the protrusions are spherical and ellipsoidal, the length-diameter ratio of the protrusions is 1-10; the constant a has a value interval of (1, 4)]When the protrusion is of a short microfiber protrusion type, the length-diameter ratio of the protrusion is 3-100; the constant a has a value of (4,1.5 ×10) 5 ) When the projections are long microfibrous projections, the aspect ratio of the projections is 10-1×10 6 。
3. The method for preparing a hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 2, wherein the value of the constant a is controlled by adjusting the viscosity and molecular weight and distribution thereof, the kind and molecular weight and distribution thereof of the dispersed phase polymer, the melt extrusion speed, the spinning temperature, the stretching temperature and the spinning speed of the polypropylene, wherein the kind and molecular weight and distribution thereof of the dispersed phase polymer depend on the number of carbon atoms of the hydroxyl branched alkane of the hydroxyl polypropylene copolymer, the hydroxyl content of the hydroxyl polypropylene copolymer, the structure of the hydrogen bond scavenger, M P The number average molecular weight of the hydroxypolypropylene copolymer and the molecular weight distribution index of the hydroxypolypropylene copolymer.
4. The method for preparing the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure according to claim 3, wherein the length-diameter ratio of the groove is adjusted by controlling the constant a to be more than 4, the constant C to be more than or equal to 1 and adjusting the value of the constant C, and the length-diameter ratio of the groove is the ratio of the length of the groove in the fiber axial direction to the length of the groove in the fiber transverse direction, and the value range is 1 to infinity;
when the value interval of the constant C is [1,5], the length-diameter ratio of the groove is 1-20; when the value interval of the constant C is (5, 50), the length-diameter ratio of the groove is 20 to infinity.
5. The method for producing a hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 4, wherein the value of the constant C is controlled by adjusting the draw ratio, draw temperature, spinning speed, viscosity of polypropylene, kind of dispersed phase polymer, spinning temperature and spinneret pore diameter.
6. The method for producing a hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 5, wherein the content of the dispersed phase polymer in the mixture is in the range of 5 to 30% by weight;
The value range of zero-cut viscosity of polypropylene at the spinning temperature is 5.0X10 2 ～2.0×10 3 Pa·s；
The number average molecular weight of the polypropylene is 8.0X10 4 ～20×10 4 g/mol, wherein the value range of the molecular weight distribution index is 3-5;
the zero-cut viscosity of the hydroxyl polypropylene copolymer at the spinning temperature is in the range of 5.0x10 2 ～20×10 4 Pa·s；
The hydroxyl branched alkane of the hydroxyl polypropylene copolymer has a carbon number of 6-9 and a number average molecular weight of 1.0X10 4 ～4.0×10 4 g/mol, the molecular weight distribution index is 2.1-4, and the hydroxyl molar content is 0.5-2.0 mol%;
the value range of the ratio of the viscosity of the disperse phase polymer to the viscosity of the polypropylene is 0.05-4;
value of the speed of melt extrusionIn the range of 2.5X10 -11 ～1.5×10 -8 m 3 /s；
The value range of the spinning temperature is 200-240 ℃;
the value range of the stretching temperature is 60-140 ℃;
the value range of the spinning speed is more than 10 m/min;
the value range of the stretching ratio is 2-5;
the range of the aperture of the spinneret orifice is 0.25X10 -3 ～0.3×10 -3 m。
7. A hydroxyl polypropylene copolymer fiber having a surface relief structure, characterized by being produced by the production method according to any one of claims 1 to 6; the hydroxyl polypropylene copolymer fiber with the surface concave-convex structure consists of a fiber body and bulges or grooves distributed on the surface of the fiber body, wherein the bulges are parts protruding relative to the surface of the fiber body, and the grooves are parts recessed relative to the surface of the fiber body.
8. The hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 7, wherein the protrusions have a diameter of 0.1 x 10 -7 ～2.0×10 -6 m。
9. The hydroxyl polypropylene copolymer fiber having a surface relief structure according to claim 7, wherein the grooves have a width of 0.05 x 10 -6 ～1.0×10 -6 m。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113829A (en) * | 1994-08-24 | 1996-05-07 | Toyobo Co Ltd | New polymer blend fiber and its production |
| CN102516655A (en) * | 2011-11-29 | 2012-06-27 | 金发科技股份有限公司 | Strengthening and toughening polypropylene composite and preparation method thereof |
| CN112281229A (en) * | 2020-09-30 | 2021-01-29 | 浙江恒澜科技有限公司 | Preparation method of polyester fiber with special surface structure |
Family Cites Families (2)
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| AU2002248193A1 (en) * | 2000-12-12 | 2002-08-12 | Baker Hughes Incorporated | Low molecular weight isotactic polypropylene polymers, copolymers and derivatives and materials prepared therewith |
| DE102004039451A1 (en) * | 2004-08-13 | 2006-03-02 | Süd-Chemie AG | Polymer blend of incompatible polymers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113829A (en) * | 1994-08-24 | 1996-05-07 | Toyobo Co Ltd | New polymer blend fiber and its production |
| CN102516655A (en) * | 2011-11-29 | 2012-06-27 | 金发科技股份有限公司 | Strengthening and toughening polypropylene composite and preparation method thereof |
| CN112281229A (en) * | 2020-09-30 | 2021-01-29 | 浙江恒澜科技有限公司 | Preparation method of polyester fiber with special surface structure |
Non-Patent Citations (2)
| Title |
|---|
| Surface Structured Polymer Blend Fibers and Their Application in Fiber Reinforced Composite;Dan Pan等;materials;1-13 * |
| 羟基功能化聚丙烯的制备及应用研究;陶梦思;中国优秀硕士学位论文全文数据库(第工程科技Ⅰ辑期);B016-568 * |
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