MXPA97002269A - Pulp of poli (p-fenilen tereftalami - Google Patents
Pulp of poli (p-fenilen tereftalamiInfo
- Publication number
- MXPA97002269A MXPA97002269A MXPA/A/1997/002269A MX9702269A MXPA97002269A MX PA97002269 A MXPA97002269 A MX PA97002269A MX 9702269 A MX9702269 A MX 9702269A MX PA97002269 A MXPA97002269 A MX PA97002269A
- Authority
- MX
- Mexico
- Prior art keywords
- poly
- polymerization
- pvp
- phenylene terephthalamide
- pulp
- Prior art date
Links
- 101700058227 POLI Proteins 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 68
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 13
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N Terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000010928 TGA analysis Methods 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 8
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 235000011148 calcium chloride Nutrition 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- -1 for example Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- ZZPLGBZOTXYEQS-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1Cl ZZPLGBZOTXYEQS-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 210000001736 Capillaries Anatomy 0.000 description 1
- 241000048284 Potato virus P Species 0.000 description 1
- 210000002356 Skeleton Anatomy 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L Strontium chloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002469 poly(p-dioxane) polymer Polymers 0.000 description 1
- 229920000470 poly(p-phenylene terephthalate) polymer Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 229940013553 strontium chloride Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002459 sustained Effects 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The present invention relates to a process for producing a fibrous pulp of poly (p-phenylene terephthalamide) and poly (vinyl pyrrolidone), characterized in that it comprises the steps of: (a) establishing a poly (p-phenylene terephthalamide) polymerization system ) with agitation, comprising a solvent for the polymerization components and poly (vinyl pyrrolidone) having an average molecular weight according to the viscosity of at least 100,000 to produce a concentration, in the polymerization system, of from 5 to 30 percent by weight, based on the weight of the polymer to be made, (b) adding stoichiometric amounts of the polymerization components of the poly (p-phenylene terephthalamide) to make reactive contact in the polymerization system, (c) continue the reactive contact of the polymerization components for a sufficient time to (i) achieve an anisotropic polymerization system, (ii) allow the complete reaction of the components of the polymerization of poly (p-phenylene terephthalamide), and (iii) combining poly (p-phenylene terephthalamide) with poly (vinyl pyrrolidone), and (d) separating the combination of poly (p-phenylene terephthalamide) and Poly (vinyl pyrrolidone) of the polymerization system
Description
POLY PULP (p-FENILEN TERE TALAMIDA)
BACKGROUND OF THE INVENTION
Field of the Invention - The present invention relates to the manufacture of an improved form of fibrous pulp using poly (p-phenylene terephthalate) (PPD-T). The pulps have traditionally been made from spun fiber fibers which are mechanically refined and take the form of a skeleton or fiber stem with fibrils that extend along it. The pulp of the present invention is not made from centrifuged fibers and provides beams of pulp particles which have a high proportion of fibrils and a very low proportion of stems.
Description of the Prior Art - U.S. Patent Nos. 5,073,440 and 5,135,687 issued on the KiuSeung Lee applications teach continuous fibers comprising a para-ara and poly (vinyl pyrrolidone) and a method for centrifuging such fibers. European Patent Applications Nos. 381,172 and 396,020, published on September 8, 1990 and November 7, 1990, describe homogeneous alloys of certain aromatic polyamides and poly (vinyl pyrrolidone) and continuous fibers and films made of such alloys. REF: 23916
U.S. Patent No. 4,511,623, issued on the application of H. S. Yoon, teaches the preparation of short aramid fibers by subjecting a solution of the polymerizing wire to a high mechanical cut. U.S. Patent No. 5,028,372, issued on the application of Brierre et al. teaches the manufacture of pulps by submitting anisotropic solutions of para-aramid polymerize to shear forces for the purpose of orienting the polymer chains as they grow.
BRIEF DESCRIPTION OF THE INVENTION
This invention provides a process for producing a fibrous pulp of a combination of PPD-T and poly (vinyl pyrrolidone) (PVP) by the steps of: establishing a polymerization system of PPD-T with stirring comprising a solvent for the polymerization of the components and also comprises a PVP having an average molecular weight according to the viscosity of at least
100,000 at a concentration of at least 5 percent by weight, preferably at least 10 percent by weight, based on the weight of the polymer to be made; add stoichiometric amounts of the polymerization components of the PPD-T to make reactive contact with the
polymerization system; continue the reactive contact of the polymerization components for a sufficient time to achieve an anisotropic polymerization system, allow the reaction of the polymerization components of PPD-T to be completed, and combine the PPD-T with the PVP; and separating the combination of PPD-T and PVP from the polymerization system. I read fibrous pulp made by the process of this invention includes a heterogeneous combination of poly (p-phenylene terephthalamide) and at least 5 weight percent of poly (vinyl pyrrolidone) having an average molecular weight according to viscosity greater than 100,000 , wherein the individual pulp particles are stem free and have a length of 0.5 to 10 millimeters, a diameter of 0.1 to 50 microns, and an aspect ratio greater than 100.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1-5 are photographs of the aramid polymerization products made under a variety of conditions including the process conditions of this invention. Figure 1 shows a product which is not suitably fibrous and Figures 2-5 show the fibrous pulp products of this invention.
Li Figure 6 is a graph of the thermogravimetric analysis of the heterogeneous combination of PPD-T and PVP of this invention; and Figure 7 is a graph of the thermogravimetric analysis of a homogeneous alloy of an aromatic polyamide and PVP of the prior art.
DETAILED DESCRIPTION OF THE INVENTION
The fibrous pulp of this invention is made from a combination of two polymeric components. One component is poly (phenylene terephthala ida) (PPD-T) and the other component is poly (vinyl pyrrolidone) (PVP). By PPD-T is meant the homopolymer resulting from the polymerization mol per mole of p-phenylene diamine and terephthaloyl chloride and, also, the copolymers resulting from the incorporation of small amounts of other diamines with p-phenylene diamine and small amounts of other diacid chlorides with terephthaloyl chloride. As a general rule, other diamines and other diacid chlorides may be used in amounts of up to about 10 mole percent of the p-phenylene diamine or terephthaloyl chloride, or perhaps slightly higher, provided only the other diacids and diacid chlorides do not have reactive groups that
interfere with the polymerization reaction. The PPD-T, also, means the copolymers resulting from the incorporation of small amounts of other aromatic diamines and other aromatic diacid chlorides, such as, for example, 2,6-naphthaloyl chloride or chloro- or dichloroterephthaloyl chloride. The preparation of PPD-T is described in U.S. Patents Nos. 4,308,374 and 4,698,414. PVP is the additive polymer in the pulp fibers of the invention. PVP means the polymer that results from the linear polymerization of monomeric units of N-vinyl-2-pyrrolidone and includes small amounts of co -omers that may be present at concentrations below those that do not interfere with the PVP interaction. with the PPD-T. The combination of the polymeric components is achieved by the polymerization of the PPD-T in the presence of the PVP. The preferred means for polymerizing PPD-T is a completely anhydrous solvent system of N-methyl pyrrolidone (NMP) having a salt, such as calcium chloride, dissolved therein to increase the solubility of PPD-T, once formed. Other salts that can be used to increase the solubility of PPD-T include quaternary ammonium chloride, lithium chloride, magnesium chloride, strontium chloride, and the like, which are soluble in
NMP For the practice of the present invention, the system d ^. solvent, too, has PVP dissolved therein during the progress of the polymerization reaction of the PPD-T. You. PVP was dissolved in the NMP before adding any of the aforementioned salts :} . It has been found that the salt, although it may increase the solubility of the PPD-T in the polymerization system, depresses the initial solubility of the PVP in NMP. It is believed that PVP, present during the polymerization of PPD-T in NMP so that an anisotropic system is established, causes the polymerization of the PPD-T to form oriented or aligned domains of polymer molecules that ultimately result in formation of pulp fiber. In the formation of pulp fiber, due to the anisotropic nature of the system, it is believed that PPD-T and PVP combine in such a way that the domains of the PPD-T are surrounded by PVP to produce particles of pulp of a heterogeneous combination of two materials. Referring to Figure 6, there is shown a graph 'which is the result of thermogravimetric analysis of a material of this invention. Thermogravimetric analysis (TGA) involves heating a sample of the material and recording the residual weight of the sample as a function of temperature. Changes in weight occur at
volatilization temperatures of the sample components. The material shown in the TGA in Figure 6 is a combination of PPD-T and 20 weight percent PVP, prepared in accordance with this invention. The PPD-T had an inherent viscosity of 5.1 and the PVP had an average molecular weight d €: according to the viscosity of 630,000. It should be noted that »the curve in Figure 6 exhibits two gradual bricks. The first run begins at approximately 440 ° C, and represents the volatilization of the PVP component. The PVP is quickly volatilized at a temperature of about 500 ° C and then more slowly at a temperature of about 600 ° C. The second fall begins at "approximately 600 ° C and represents the volatilization of the PPD-T component." The two separate, gradual rises in the TGA curve provide clear evidence of the existence of physically separate components. This invention Referring now to Figure 7, there is shown a graph, which is the result of the TGA of a material described in European Patent Application No.
381,172, which is 2, 2'-bis [4- (4'-aminophenoxy) phenyl] propan. terephthalamide (BAPP-T), which is described as homogeneously combined and alloyed with 20 weight percent PVP. The BAPP-T, polymerized in the presence of PVP, results in a system. isotropic - not anisotropic - of the
components and it appears, as stated in the aforementioned European Patent Application, a tightly bonded, homogeneous alloy of the component materials, It should be noted that the curve of Figure 7 exhibits a single, gradual drop, which starts at about 380 ° C and proceeds through approximately 600 ° C, which represent the volatilization of the homogeneous alloy of BAPP-T and PVP. The only gradual drop of the TGA curve provides clear evidence of the existence of a homogeneous, united combination of prior art materials. It has been determined that the PVP has an average molecular weight according to the viscosity of more than about 100,000 and a concentration of at least 5 percent, preferably of at least 10 percent, based on the weight of the PPD -T, it is necessary for the practice of; this invention. The PVP having an average molecular weight according to the viscosity of less than about 100,000 does not seem to provide adequate support for the orientation of the polymer chains of growing PPD-T and, as a consequence, does not produce an effective result. PVP having average molecular weights according to viscosity greater than about 2,000,000 are only hardly soluble and can not produce solutions that are useful for the
orientation to the required PVP concentrations. PVPs having average molecular weights according to viscosity greater than 100,000 have been found useful for the practice of the present invention. For the purposes of practicing this invention, the molecular weight environment of the appropriate PVP can be obtained by a combination of PVP materials of different molecular weights. For example, the PVP of average molecular weight according to the viscosity of 50,000 can be combined with the PVP of average molecular weight according to the viscosity of 500,000 in amounts such that the average molecular weight according to the total viscosity of the PVP in the polymerization system is greater than 100,000, calculated on a molar basis. The PVP must be present in an amount that is at least 5 percent of the weight of the PPD-T to be formed and a larger amount can be used if desired. Less than 5 percent of PVP does not seem to provide enough PVP to achieve the desired result. The upper limit for the concentration of PVP is a matter of practice. It has been determined that the size and quality of the fibrous pulp particles of PPD-T increases as the concentration of PVP increases to a concentration of about 20, up to 30, percent of the weight of the PPD-T to be formed Concentrations of PVP greater than 30 per
The percentage does not seem to impede the results, but neither does it seem to appreciably improve the size or yield of the pulp product. Polymerization of PPD-T involves the addition, to the polymerization system, of stoichiometric amounts of diamine and diacid chloride. As a general rule, the diamine component is dissolved in the polymerization system and the diacid chloride is added thereto, either all at once, or in more than one portion. The addition of the polymerization components of the PPD-T is conducted under agitation conditions and that agitation generally continues to an anisotropic solution and through the polymerization reaction of the PPD-T until the polymerization reaction is substantially complete. The PPD-T and the polymerization system become extremely viscous during the polymerization reaction and it is preferred to continue the stirring in order to maintain the contact between the components of the reaction. It will not be necessary, however, to provide agitation or shear forces to the polymerization system; and, indeed, the agitation is not necessary once: the components of the reaction have been put in reactive contact. Although agitation is useful for the practice of the present invention, it should be understood that the length and
The quality of the pulp product depends on the concentration and molecular weight of the PVP that is present in the polymerization system. The heart of this invention and which is considered to give patentable meaning is the discovery that the pulp is the heterogeneous product of a polymerization of PPD-T conducted in the presence of PVP under the conditions described herein, using an anisotropic polymerization system. After completing the polymerization of the PPD-T, the pulp of fibrous PPD-T was separated from the polymerization system by breaking the solids of the polymerization system in water through several washes and filtering or centrifuging the pulp of the liquid. The resulting fibrous pulp is the PPD-T polymer with 5 to 30, preferably 10-25, percent PVP, based on the weight of the PPD-T. The concentration of PVP in the pulp is, to some degree, a function of the concentration of PVP in the polymerization system. For example, PPD-T with approximately 10 percent PVP will result from a polymerization system that has a PVP concentration of 10 percent. However, it appears that, under equilibrium conditions, approximately 20 percent is the maximum EVP concentration in the pulp, regardless of how high the concentration of PVP is in the polymerization system. It is believed that the PVP is somehow combined with the PPD-T to a
concentration of about 20 percent and, beyond that concentration, any excess of PVP is washed out of the pulp during the separation step. Of course, it is possible to make a pulp with more than 20 percent PVP by polymerizing the PPD-T in a PVP solution with a concentration greater than 20 percent and then taking care to wash the pulp incompletely. As established, the PVP present in the pulp in an excess of about 20 percent will not be a combined part of the PPD-T / PVP material; nor will it have a significantly adverse effect on the properties of the pulp. The pulp particles of this invention have an average length of about 0.5 to about 10 mm, or perhaps slightly greater, a diameter of only about 0.1 to 50 microns, and an aspect ratio greater than 100. By "aspect ratio" it is understands the relationship of the length to the diameter of the individual pulp particle. Because they are not refined from centrifuged fibers, those pulp particles are free of fiber stems.
TEST METHODS
Pulp Form Factor - Although the amount of pulp particles can be somewhat difficult to describe,
help can be obtained by referring to the Figures which show the fibrous pulp particles of various qualities at an amplification of approximately 40X: The Grade 1 Form is described in Figure 1 and represents the gritty particles of PPD-T which are made without use PVP additive. The Grade 1 Form particles do not exhibit fibrous character. The Grade 2 Form is described in Figure 2 and represents a lower form of fibrous pulp in this invention. The Grade 2 Shape pulp is mainly fibrous and includes fibers up to about 2 millimeters in length. The Grade 3 Form is described in Figure 3 and represents a fibrous pulp of an average grade. The Form d € 'Grade 3 pulp is fibrous and includes fibers up to approximately 3 millimeters in length. The Grade 4 Form is described in Figure 4 and represents a pulp willingly with fibers up to about 5 millimeters in length. The Grade Form 5 is described in Figure 5 and represents an excellent grade pulp with fibers up to about 7 millimeters and more in length.
Inherent Viscosity of PPD-T - Inherent Viscosity (IV) is defined by the equation:
IV = ln (? Re?) / C
in which c is the concentration (0.5 grams of polymer in
100 ml of solvent) of the PPD-T in the polymer solution and? Rß? (Relative viscosity) is the ratio between the flow times of the polymer solution and the solvent measured at 30-30 ° C in a capillary viscometer. The inherent viscosity values reported and specified here were determined using concentrated sulfuric acid (96% H2SO4).
Average Molecular Weight According to Viscosity of PVP - The molecular weight of PVP, as used herein, is the average molecular weight according to the viscosity described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 23 , John Wiley & Sons, on page 968 under "Vinyl Polymers (N-Vinyl)". The average molecular weight according to the viscosity, M ?, is related to the known intrinsic viscosity:
The intrinsic viscosity was determined by the well-known method of measuring the viscosities relative to various concentrations of polymer and extrapolating for the viscosity at zero concentration (the intrinsic viscosity). PVP suppliers often identify the PVP product by means of a "K number", which is associated with Intrinsic viscosity by the following equation:
? ,, lt = 2.303 (0.001K + 0.000075K '').
The average molecular weights according to the viscosity for the PVP can be calculated from the "K-values" using the equation discussed above.
Thermogravimetric Analysis - The TGAs for the tests herein were conducted in accordance with the procedures set forth in ASTM D 3850-84 using nitrogen.
EXAMPLES
Example 1 - In a reaction vessel, a polymerization system of PPD-T was established with stirring, dissolving 12.5 parts of calcium chloride in 147.5 parts of N-methyl pyrrolidone (NMP). The calcium chloride and the NMP were carefully and completely dried. HE
9.329 parts of p-phenylene diamine were dissolved in the polymerization system and 24.2 parts of a solution of 15 parts of PVP in 85 parts of NMP were added to the polymerization system. The PVP had a molecular weight of 630,000 and was distributed by International Specialty Products in Wayne, New Jersey, E.U.A. With sustained stirring, the system was cooled to about 5 ° C, and 17,670 parts of terephthanoyl chloride were added to the polymerization system. In a very short time, the system became opaque to indicate anisotropy; and in about 2 minutes, the system reached a maximum viscosity as a very viscous gel. You. agitation was maintained and the gel broke into highly fibrous particles during continuous agitation for an additional 15 minutes. The resulting fibrous pulp was washed several times with water er. a mixture to remove the NMP, CaCl2, and HCl generated during the polymerization. The polymer had an inherent viscosity of 5.7 and the pulp had a Grade 5 shape with individual fibers having a length of about 5-7 mm.
Comparison Example 1C An identical polymerization was conducted to that of Example 1, above, except that PVP having a weight was used
molecular weight of only 38,000. The resulting product was a lumpy structure of PPD-T without fibrous characteristics. The PPD-T had an inherent viscosity of 5.8.
Example 2-6 - In those examples, the same polymerization process as used in Example 1 was used, except that the PVP was a combination of two materials having different molecular weights. PVP having molecular weights of 38,000 and 630,000 were used to generate PVP with a variety of equivalent molecular weights; and a total of 15 percent PVP was used in each example. Table 1, below, contains the details on the PVP as well as the data on the resulting fibrous pulp.
TABLE 1 Factor of
PVP Example < g) * P. M. Viscosity Shape of the
Number 38 M 630 M Inherent Polymer Equivalent
1C 24.16 0 38,000 5.8 1
2 19.63 4.53 149,000 3.5 2
3 15.85 8.30 241,000 4.9 2
4 12.08 12.08 334,000 3.5 4 5 8.30 15.85 426,000 3.8 5 6 4.53 19.63 519,000 3.6 5 1 0 24.16 630,000 5.7 5 Concentration of the PVP solution in NMP: 15% (w / w), Drying by distillation.
Examples 7-11 In those examples, the same polymerization procedure as in Example 1 was used, except that the PVP was added in several different amounts. The PVP of those examples had a molecular weight of approximately 630,000. Table 2, below, contains the details of the examples including the data on the resulting pulp products.
TABLE 2 Example PVP * Percent Viscosity Length of
Number (g) of PVP Inherent Fiber 7 7.20 5.0 3.03 0.5 mm 8 15.21 10.0 4.08 2 mm 9 24.16 15.0 5.10 5 mm 10 34.33 20.0 4.40 7 mm 11 45.64 25 ** 4.00 6 mm
* Concentration of the PVP Solution in NMP: 15% (weight / pwso). Dried by distillation. ** • The pulp is washed to retain the excess of PVP in the pulp. Example 12 - This example demonstrates that continuous agitation is not necessary to practice the present invention. As in Example 1, above,
established a PPD-T polymerization system by dissolving 12.5 parts of calcium chloride in 147.5 parts of N-methyl pyrrolidone (NMP), with stirring. 9.329 parts of p-phenylene diamine were dissolved in the polymerization system and 24.2 parts of a solution of 15 parts of PVP in 85 parts of NMP were added to the polymerization system. The PVP had a molecular step of 630,000. Maintaining it to agitation, the system was cooled to about 5 ° C, and 17,670 parts of terephthaloyl chloride were added to the polymerization system. In a very short time, the system became opaque to indicate anisotropy; and the agitation stopped. The system was left to rest during the night. The. The resulting fibrous pulp was washed several times with water in a mixer to remove the NMP, CaCl2, and HCl generated during the polymerization. The polymer had an inherent viscosity of 3.84 and the pulp had a Grade 3 shape with individual fibers having a length of about 2 mm. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:
Claims (6)
1. A process for producing a fibrous pulp of poly (p-phenylene terephthalamide) and poly (vinyl pyrrolidone), characterized in that it comprises the steps of: (a) establishing a polymerization system of poly (p-phenylene terephthalamide) with agitation, comprising a solvent for the polymerization components and poly (vinyl pyrrolidone) having an average molecular weight according to the viscosity of at least 100,000 to produce a concentration, in the polymerization system, of 5 to 30 percent by weight, in based on the weight of the polymer to be made; (b) adding stoichiometric amounts of the polymerization components of the poly (p-phenylene terephthalamide) to make reactive contact in the polymerization system; (c) continuing the "reactive" contact of the polymerization components for a sufficient time to (i) achieve an anisotropic polymerization system, (ii) allow the complete reaction of the polymerization components of the poly (p-phenylene terephthalamide), and (iii) combine the poly (p-phenylene terephthalamide) with the poly (vinyl pyrrolidone <; () separating the combination of poly (p-phenylene terephthalamide) and poly (vinyl pyrrolidone) from the polymerization system.
2. The process according to claim 1, characterized in that the stirring is continued to step (c).
3. The process according to claim 1, characterized in that the components of the polymerization are p-phenylene diamine and terephthaloyl chloride.
4. The process according to claim 1, characterized in that the poly (vinyl pyrrolidone) is a single polymer with an average molecular weight according to the viscosity of at least 100,000.
5. The process according to claim 1, characterized in that the poly (vinyl pyrrolidone) is a combination of polymers with an average molecular weight according to the viscosity of at least 100,000.
6. The fibrous pulp of poly (p-phenylene terephthalamide), characterized in that it comprises a combination of 70 to 95 weight percent of poly (p-phenylene terephthalamide) and 5 to 30 weight percent of poly (vinyl pyrrolidone) having a average molecular weight according to viscosity greater than 100,000 where the individual pulp particles are free of stems and have a length of 0.5 to 10 millimeters, a diameter of 0. 1 to 50 microns, and an aspect ratio greater than 100 .
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/315,180 US5532059A (en) | 1994-09-29 | 1994-09-29 | Poly(p-phenylene terephthalamide) pulp |
| US08315180 | 1994-09-29 | ||
| PCT/US1995/011774 WO1996010105A1 (en) | 1994-09-29 | 1995-09-22 | POLY(p-PHENYLENE TEREPHTHALAMIDE) PULP |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA97002269A true MXPA97002269A (en) | 1997-06-01 |
| MX9702269A MX9702269A (en) | 1997-06-28 |
Family
ID=23223254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9702269A MX9702269A (en) | 1994-09-29 | 1995-09-22 | POLY(p-PHENYLENE TEREPHTHALAMIDE) PULP. |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5532059A (en) |
| EP (1) | EP0783604B1 (en) |
| JP (1) | JP3734269B2 (en) |
| CN (1) | CN1065930C (en) |
| AU (1) | AU687261B2 (en) |
| BR (1) | BR9509163A (en) |
| CA (1) | CA2200184C (en) |
| DE (1) | DE69524111T2 (en) |
| MX (1) | MX9702269A (en) |
| RU (1) | RU2151829C1 (en) |
| UA (1) | UA28079C2 (en) |
| WO (1) | WO1996010105A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968974A (en) | 1995-07-19 | 1999-10-19 | Merck & Co., Inc. | Method of treating colonic adenomas |
| US6593361B2 (en) | 1995-07-19 | 2003-07-15 | Merck & Co Inc | Method of treating colonic adenomas |
| US5827610A (en) * | 1997-01-10 | 1998-10-27 | E. I. Du Pont De Nemours And Company | Chitosan-coated pulp, a paper using the pulp, and a process for making them |
| US5830395A (en) * | 1997-08-12 | 1998-11-03 | E. I. Du Pont De Nemours And Company | Process for making a uniform dispersion of aramid fibers and polymer |
| US6303221B1 (en) * | 2000-12-07 | 2001-10-16 | E. I. Du Pont De Nemours And Company | Two-component pulp reinforcement |
| US6436236B1 (en) | 2001-03-05 | 2002-08-20 | E. I. Du Pont De Nemours & Company | Electrically-conductive para-aramid pulp |
| US7201688B2 (en) * | 2004-03-09 | 2007-04-10 | The Gates Corporation | Power transmission belt |
| AU2006280019A1 (en) * | 2005-08-09 | 2007-02-22 | Soane Labs, Llc | Hair hold formulations |
| EP1984564A4 (en) | 2006-02-03 | 2013-04-03 | Nanopaper Llc | Functionalization of paper components |
| US20090165976A1 (en) * | 2006-02-03 | 2009-07-02 | Nanopaper, Llc | Expansion agents for paper-based materials |
| US7820563B2 (en) * | 2006-10-23 | 2010-10-26 | Hawaii Nanosciences, Llc | Compositions and methods for imparting oil repellency and/or water repellency |
| CN109642398B (en) * | 2016-08-24 | 2022-07-22 | 帝人芳纶有限公司 | Friction material comprising aramid |
| EP3504377B1 (en) | 2016-08-24 | 2020-11-04 | Teijin Aramid B.V. | Method for manufacturing aramid pulp comprising pvp |
| EP3401355A1 (en) | 2017-05-12 | 2018-11-14 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Polyamide material |
| US10767316B2 (en) | 2017-11-01 | 2020-09-08 | Dupont Safety & Construction, Inc. | Paper comprising aramid pulp and a friction paper made therefrom |
| US11193240B2 (en) * | 2017-11-01 | 2021-12-07 | Dupont Safety & Construction, Inc. | Paper comprising aramid pulp suitable for electrochemical cells, and electrochemical cells made therefrom |
| US20210296685A1 (en) * | 2020-03-17 | 2021-09-23 | Dupont Safety & Construction, Inc. | Solid-state composite electrolytes comprising aramid polymer fibrils |
| JP2023542068A (en) | 2020-08-04 | 2023-10-05 | デュポン セイフティー アンド コンストラクション インコーポレイテッド | Paper containing aramid pulp suitable for electrochemical cells, and electrochemical cells made from them |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL250256A (en) * | 1959-04-07 | |||
| US3287441A (en) * | 1959-04-07 | 1966-11-22 | Du Pont | Melt-spinnable composition of a poly (nu-vinyl amide) and a polymer from the class consisting of polyamides, polyureas, and polyurethanes |
| US3211807A (en) * | 1962-04-03 | 1965-10-12 | Du Pont | Process for obtaining a blend of a polyamide and a poly(n-vinyl amide) |
| US3564075A (en) * | 1969-03-07 | 1971-02-16 | Bayer Ag | Polyamides with improved transparency containing polyvinyl pyrrolidone |
| KR840000726B1 (en) * | 1982-08-30 | 1984-05-24 | 전학제 | Method of preparing for monofilament from aromatic polyamide |
| US5028372A (en) * | 1988-06-30 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Method for producing para-aramid pulp |
| RU2059027C1 (en) * | 1988-06-30 | 1996-04-27 | Е.И.Дюпон Де Немур Энд Компани | Pulp and a method of its producing |
| DE3903099A1 (en) * | 1989-02-02 | 1990-08-16 | Hoechst Ag | HOMOGENOUSLY MIXED ALLOYS OF AROMATIC POLYAMIDES AND POLY-N-VINYLPYRROLIDONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US4959453A (en) * | 1989-04-03 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Process for the preparation of a poly(paraphenylene terephthalamide)fibrous gel composition and a process to produce poly(paraphenylene terephthalamide) paper from the composition |
| DE3914226A1 (en) * | 1989-04-29 | 1990-10-31 | Hoechst Ag | FIBER MATERIALS FROM HOMOGENEOUS ALLOYS FROM AROMATIC POLYAMIDES AND POLY-N-VINYLPYRROLIDONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US5073440A (en) * | 1989-06-05 | 1991-12-17 | E. I. Du Pont De Nemours And Company | Poly(vinyl pyrrolidone)/p-phenylene terephthalamide composite fibers (pvp/ppd-t) |
| US5135687A (en) * | 1989-06-05 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Process for making PVP/para-aramid fibers |
| US5084136A (en) * | 1990-02-28 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Dispersible aramid pulp |
| US5106560A (en) * | 1990-08-09 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Producing para-aramid pulp by means of gravity-induced shear forces |
| CN1068831A (en) * | 1991-07-25 | 1993-02-10 | 范铜波 | The manufacture method of high molecular aromatic polyamide |
| US5416164A (en) * | 1993-04-12 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Solution of PPD-T and PVP and articles made therefrom |
-
1994
- 1994-09-29 US US08/315,180 patent/US5532059A/en not_active Expired - Lifetime
-
1995
- 1995-09-22 WO PCT/US1995/011774 patent/WO1996010105A1/en active IP Right Grant
- 1995-09-22 BR BR9509163A patent/BR9509163A/en not_active IP Right Cessation
- 1995-09-22 RU RU97107091/04A patent/RU2151829C1/en not_active IP Right Cessation
- 1995-09-22 CN CN95195418A patent/CN1065930C/en not_active Expired - Fee Related
- 1995-09-22 DE DE69524111T patent/DE69524111T2/en not_active Expired - Fee Related
- 1995-09-22 MX MX9702269A patent/MX9702269A/en unknown
- 1995-09-22 JP JP51184196A patent/JP3734269B2/en not_active Expired - Fee Related
- 1995-09-22 AU AU36769/95A patent/AU687261B2/en not_active Ceased
- 1995-09-22 EP EP95934431A patent/EP0783604B1/en not_active Expired - Lifetime
- 1995-09-22 CA CA002200184A patent/CA2200184C/en not_active Expired - Fee Related
- 1995-09-22 UA UA97052089A patent/UA28079C2/en unknown
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