CN117802819A - Preparation method of polyphenylene sulfide fiber paper and product thereof - Google Patents
Preparation method of polyphenylene sulfide fiber paper and product thereof Download PDFInfo
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- CN117802819A CN117802819A CN202410099760.6A CN202410099760A CN117802819A CN 117802819 A CN117802819 A CN 117802819A CN 202410099760 A CN202410099760 A CN 202410099760A CN 117802819 A CN117802819 A CN 117802819A
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- polyphenylene sulfide
- dichlorobenzene
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- sulfide resin
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 143
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 143
- 239000000835 fiber Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 49
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 38
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000009998 heat setting Methods 0.000 claims description 28
- 238000005098 hot rolling Methods 0.000 claims description 28
- 238000009987 spinning Methods 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002074 melt spinning Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 9
- 238000001035 drying Methods 0.000 description 15
- 238000005728 strengthening Methods 0.000 description 11
- 238000003490 calendering Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229920002994 synthetic fiber Polymers 0.000 description 7
- 239000012209 synthetic fiber Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Abstract
The invention discloses a preparation method of polyphenylene sulfide fiber paper, which is prepared by a wet papermaking process and comprises resin raw materials and water, wherein the resin raw materials comprise the following components in percentage by mass: 80-95% of polyphenylene sulfide resin A; 5-20% of polyphenylene sulfide resin B; the polyphenylene sulfide resin A is obtained by polymerizing p-dichlorobenzene and a sulfur source A; the polyphenylene sulfide resin B is obtained by polymerizing p-dichlorobenzene, m-dichlorobenzene and a sulfur source B, and the molar ratio of m-dichlorobenzene is 10-50% based on 100% of the total molar number of p-dichlorobenzene and m-dichlorobenzene monomers. The invention provides the polyphenylene sulfide paper with low production cost, simple process and high mechanical property and chemical resistance and the preparation method thereof.
Description
Technical Field
The invention relates to the field of preparation of polyphenylene sulfide, in particular to a preparation method of polyphenylene sulfide fiber paper and a product thereof.
Background
The fiber paper is a solid lamellar material prepared by a papermaking process, the performance of the fiber paper is determined by the fiber material, the paper structure and the manufacturing process, and the fiber paper can be used as products such as impregnated paper, winding paper, cable paper, diaphragm paper, capacitor paper, high-temperature-resistant paper and the like. The main material of the fiber paper is selected from plant fibers and synthetic fibers, however, plant fibers such as cork have the advantages of high cellulose content and good impregnation property, but have the disadvantages of poor heat resistance, poor fiber uniformity, paper appearance defects and the like. The synthetic fiber paper can select proper synthetic fiber according to specific working conditions, and the synthetic fiber can be prepared by melt spinning or solution spinning and other methods, so that the defects of the plant fiber paper can be overcome, and common synthetic fiber materials comprise polypropylene, polyphenyl ether, polyaramid, polyphenylene sulfide and the like.
At present, synthetic fiber paper making mainly comprises two processes, namely a wet process and a dry process, and the difference of the media is different. Dry papermaking is a papermaking process in which air is used as a carrier for fibers, a thin layer of the fibers is formed on a forming wire, and the resulting paper is bonded in the form of an adhesive, hot rolling, or the like. The wet papermaking technology is a papermaking technology using water as a medium and comprises the procedures of a flow box (defibering pulping), a flow part, a net part (papermaking forming), a pressing part (dewatering), a drying part (drying), hot rolling strengthening, calendaring, coiling, and the like. The method has the advantages of mature process, high yield and the like, but in order to solve the problems of good combination and uniform dispersion among synthetic fibers in the papermaking process, auxiliary agents such as a binder, a dispersing agent and the like are often required to be added, and the process requirement is high.
Polyphenylene Sulfide (PPS) is one of six special engineering plastics, has excellent comprehensive performance, has the advantages of good chemical resistance, high temperature resistance, flame retardance, good dimensional stability, low creep amount and the like, is widely used as a structural polymer material, and more manufacturers begin to apply polyphenylene sulfide fiber paper to insulating paper, heat-resistant paper, diaphragm paper and other purposes. Commercial polyphenylene sulfide fibers are mainly prepared by melt spinning and comprise the procedures of granulating, drying, spinning, winding, barrel dropping, bundling, drafting, heat setting, oiling, curling, cutting, packaging and the like.
The insulating paper is prepared by the steps of pulp preparation, white water mixing, inclined net forming, water needling reinforcement, winding into rolls, alkali liquor treatment, hot rolling reinforcement of a light stick and the like of polyphenyl thioether short fibers, polyphenyl thioether pulp foils and low-crystallinity polyphenyl thioether short fibers. Although the patent adopts the low-crystallinity polyphenylene sulfide fiber, parameters such as melting temperature and the like are mainly determined by the material, and even if the material can be softened at a lower temperature, the problems of insufficient bonding force, interlayer peeling tendency, unstable production and the like can still occur in the thermal bonding process. Secondly, the hot rolling strengthening temperature of the patent is high (240-280 ℃), the energy consumption is high, and meanwhile, the too high hot rolling temperature causes PPS fibers to oxidize, so that the properties of the fiber paper are affected.
The method comprises the steps of preparing crimped short fibers through conventional polyphenylene sulfide melt spinning by CN101148841A of Sichuan Tex, mixing the crimped short fibers with polyvinyl alcohol, inorganic filler and reinforcing fiber for wet papermaking, and carrying out fluffing, papermaking forming, dehydration, drying, hot pressing/hot rolling and the like to obtain the fiber paper. The patent is compounded by polyphenylene sulfide fibers and non-thermally-drawn polyphenylene sulfide precursor fibers or reinforced fibers such as poly-p-phenylene terephthalamide fibers, carbon fibers, graphite fibers and the like; the patent requires a crimping process for producing polyphenylene sulfide fibers, however, the crimped fibers are agglomerated during paper making, and the paper structure is uneven. In addition, a large amount of various auxiliary agents are added in the papermaking process, and the high-temperature resistance, chemical resistance, insulation and other performances of the auxiliary agents are not enough to be comparable with those of polyphenylene sulfide materials, so that the auxiliary agents are greatly limited in use in high-temperature high-humidity and corrosion environments.
When conventional PPS fibers are used for papermaking, the temperature is high at the time of hot rolling/pressing due to its high melting point up to 285 ℃, however, PPS is extremely easily oxidized when treated at high temperature, resulting in a decrease in fiber strength, thereby affecting paper properties. For this purpose, the temperature at the time of hot rolling/pressing is lowered by adding a binder, but this method has another problem in that the chemical resistance of the binder cannot be comparable to that of polyphenylene sulfide, destroying the advantages of PPS itself.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the polyphenylene sulfide paper with low production cost, simple process and high mechanical property and chemical resistance and the preparation method thereof.
The specific technical scheme is as follows:
the preparation method of the polyphenylene sulfide fiber paper is prepared by a wet papermaking process and comprises the following steps of:
80-95% of polyphenylene sulfide resin A;
5-20% of polyphenylene sulfide resin B;
the polyphenylene sulfide resin A is obtained by polymerizing p-dichlorobenzene and a sulfur source A;
the polyphenylene sulfide resin B is obtained by polymerizing p-dichlorobenzene, m-dichlorobenzene and a sulfur source B, and the molar ratio of m-dichlorobenzene to the total molar number of p-dichlorobenzene and m-dichlorobenzene monomers is 10-50% based on 100%.
According to the invention, the polyphenylene sulfide resin B prepared by copolymerization of m-dichlorobenzene, p-dichlorobenzene and a sulfur source is introduced into a paper formula system, and the fiber paper can be treated at a lower hot rolling/hot pressing temperature without adding an adhesive, so that the fiber paper still has excellent adhesive property, and the PPS fiber paper with high mechanical property and chemical resistance is prepared.
The polyphenylene sulfide resin A is a conventional polyphenylene sulfide resin and is obtained by polymerizing p-dichlorobenzene and a sulfur source A, wherein the molar ratio of the p-dichlorobenzene to the sulfur source is (1.0-1.2): 1.0; the sulfur source A is selected from one or more of sodium sulfide, sodium hydrosulfide and hydrogen sulfide. The weight average molecular weight of the polyphenylene sulfide resin A is 3-7 ten thousand.
The polyphenylene sulfide resin B is obtained by polymerizing p-dichlorobenzene, m-dichlorobenzene and a sulfur source B, and the molar ratio of the total dichlorobenzene (comprising the p-dichlorobenzene and the m-dichlorobenzene) to the sulfur source B is (1.0-1.2): 1.0; the sulfur source B is selected from one or more of sodium sulfide, sodium hydrosulfide and hydrogen sulfide. The weight average molecular weight of the polyphenylene sulfide resin B is 3-7 ten thousand.
Experiments show that key factors influencing the hot rolling/hot pressing temperature in the paper making process comprise the feeding mole ratio of m-dichlorobenzene in the polyphenylene sulfide resin B and the mass ratio of the polyphenylene sulfide resin B in the resin raw material.
In the polyphenylene sulfide resin B disclosed by the invention, the feeding mole ratio of m-dichlorobenzene is controlled to be 10-50%. The content of m-dichlorobenzene is too low, and the melting point is not obviously reduced; when the content of m-dichlorobenzene is too large, the molar ratio of the effective dichlorobenzene to sodium sulfide deviates from 1 due to larger steric hindrance during meta-polymerization: 1, it is difficult to form high molecular weight polymers, even leading to an increased probability of depolymerization and polymerization failure; meanwhile, the content of m-dichlorobenzene is too high, the inter-molecule distance of the polymer is enlarged, and the mechanical property of the material is reduced.
Preferably:
the resin comprises the following raw materials in percentage by mass:
90-95% of polyphenylene sulfide resin A;
5-10% of polyphenylene sulfide resin B;
the molar ratio of the m-dichlorobenzene to the m-dichlorobenzene is 20-40 percent based on 100 percent of the total molar number of the p-dichlorobenzene and the m-dichlorobenzene monomers.
Further preferred is:
the molar ratio of the m-dichlorobenzene to the m-dichlorobenzene is 30-40 percent based on 100 percent of the total molar ratio of the p-dichlorobenzene to the m-dichlorobenzene.
More preferably:
the mass ratio of the polyphenylene sulfide resin A to the polyphenylene sulfide resin B is 90:10;
the molar ratio of the m-dichlorobenzene to the m-dichlorobenzene monomer is 40 percent based on 100 percent of the total molar ratio of the p-dichlorobenzene to the m-dichlorobenzene.
Experiments show that with the continuous optimization of the parameters, the hot rolling/pressing temperature in the paper making process can be controlled in a proper range, and the polyphenylene sulfide fiber paper with high mechanical property and chemical resistance can be prepared.
The preparation method of the polyphenylene sulfide fiber paper specifically comprises the following steps:
the method comprises the steps of A, respectively and independently spinning polyphenylene sulfide resin A and polyphenylene sulfide resin B to obtain polyphenylene sulfide fibers A and polyphenylene sulfide fibers B, dispersing the polyphenylene sulfide fibers A and the polyphenylene sulfide fibers B in water, uniformly mixing to prepare slurry, and preparing the polyphenylene sulfide fiber paper through a wet papermaking process;
or the method B is that the polyphenylene sulfide fiber A is prepared after the polyphenylene sulfide resin A is subjected to melt spinning, the polyphenylene sulfide fiber A and the polyphenylene sulfide resin B are dispersed in water and are uniformly mixed to prepare slurry, and the polyphenylene sulfide fiber paper is prepared through a wet papermaking process.
The melt spinning of the polyphenylene sulfide fiber in the present invention adopts the conventional technical means in the art, including the processes of pelletization, drying, spinning, cooling, winding, drawing, heat setting, etc. (refer to CN100999833a for specific details), and then cutting into the desired length.
In the method A, the spinning extrusion temperature of the polyphenylene sulfide resin A for independent spinning is 290-340 ℃, the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber A is 1-15 mm, and the fineness is 0.5-5.0 dtex.
The spinning extrusion temperature of the polyphenylene sulfide resin B is 180-290 ℃, the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber B is 1-15 mm, and the fineness is 0.5-5.0 dtex.
In the method B, only polyphenylene sulfide resin A is adopted for melt spinning.
The spinning extrusion temperature of the melt spinning is 290-340 ℃, the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber A is 1-15 mm, and the fineness is 0.5-5.0 dtex.
The heat setting time is preferably 1-30 s, and the heat setting temperature is preferably 150-250 ℃; insufficient heat setting temperature and time can cause great heat shrinkage of the fiber, the heat shrinkage is increased at high temperature in the papermaking process, and paper wrinkles and bubbles appear; meanwhile, the fiber breaking strength is not improved, so that the paper strength is lower. The heat setting time and the heat setting temperature are too large, so that energy consumption is wasted, production cost is increased, and downstream use is influenced by fiber hardening.
The fineness of the polyphenylene sulfide short fiber prepared by each method is preferably 0.5-5.0 dtex. When the fineness is less than 0.5dtex, the prepared paper is not stiff enough and the spinneret orifices are too small, so that the processing and cleaning are difficult; when the fineness is more than 5.0dtex, the fiber diameter is too thick, so that the fiber bundles are not easy to be uniformly cooled during spinning, the temperature difference between the inside and the outside of the fiber is large, and the spinning yarn breakage is easy to occur.
Further preferably 1.1dtex and 2.2dtex.
In the process of preparing the polyphenylene sulfide short fibers for papermaking, the curling operation is not needed, the fibers are excessively cohesive by curling, the beating dispersion is not facilitated, the fibers are agglomerated, and the fiber paper with uniform paper surface is difficult to obtain.
The cutting length is preferably 1 to 15mm, more preferably 1 to 7mm. The length is less than 1mm, the fiber paper has insufficient toughness, wear resistance and durability and is easy to break, and the working condition requirement is difficult to meet. Too large a length may cause problems such as uneven paper due to entanglement of fibers.
Preferably, the preparation method of the polyphenylene sulfide fiber paper is preferably a method B, and experiments show that the polyphenylene sulfide fiber paper prepared by the method B has more excellent mechanical properties and chemical resistance.
The wet papermaking process adopts the conventional technical means in the field, including a headbox (defibering pulping), a streaming part, a net part (papermaking forming), a pressing part (dewatering), a drying part (drying), hot rolling strengthening, calendaring, coiling, and the like, and can be specifically referred to as CN101148841A.
The concentration of the fiber slurry after the slurry is mixed in a head box is 0.1 to 10 weight percent, and the production efficiency is low due to the too thin concentration; the concentration is too large, which is unfavorable for uniform dispersion and mixing.
The diameter of the filtering mesh hole of the mesh table part is 14-45 mu m, the mesh hole is too small, the filtering is too slow, and the yield is affected; the meshes are too large, the loss of raw material fibers is large, and the yield is low.
The press section can press the wet sheet to dewater, increasing the sheet tightness. The dryness of the wet paper sheet is controlled to be 20-45%.
The moisture in the wet paper sheet can be removed after the drying part is dried, so that the strength and smoothness of the paper are improved. The dryness of the dried paper sheet is controlled to be 90-96 percent. The dryness is too high, the drying time and the drying temperature are too long, and the subsequent hot rolling waste heat is not fully utilized; the dryness is too low, the paper strength is insufficient, and a large amount of heat is used for evaporating water in paper during hot rolling, so that the hot rolling effect is affected.
The hot rolling strengthening temperature is 160-270 ℃, and the temperature can be fused and bonded without reaching the melting point of the conventional polyphenylene sulfide at 285 ℃ due to the addition of the polyphenylene sulfide resin B or the polyphenylene sulfide fiber B, and the specific temperature can be adjusted according to the property and the proportion of the added polyphenylene sulfide resin B.
Preferably, the temperature of the hot-rolled reinforcement is 160-245 ℃, and more preferably 180-210 ℃.
The smoothness and thickness uniformity of the paper can be improved by calendering, and the calendering pressure is 0.5-5.0 Mpa.
Compared with the prior art, the invention has the following advantages:
the invention discloses a preparation method of polyphenylene sulfide fiber paper, which can treat the fiber paper at a lower hot rolling/hot pressing temperature by reasonable design of a formula on the premise of not adding an adhesive, so that the fiber paper still has excellent bonding performance, and PPS fiber paper with high mechanical property and chemical resistance is prepared. The preparation method saves energy consumption, reduces cost and meets the modern production requirements.
Detailed Description
The present invention will be described in detail with reference to examples for further understanding of the present invention, but the present invention is not limited to these examples, and various modifications and adjustments are not essential to the spirit of the present invention, and remain within the scope of the present invention.
Example 1
Step 1, polymerization: paradichlorobenzene and sodium sulfide were mixed in a 1.1:: polymerization is carried out according to the molar ratio of 1.0, so that the conventional polyphenylene sulfide resin A with the weight average molecular weight of 6 ten thousand is prepared and is marked as a component A;
paradichlorobenzene, m-dichlorobenzene and sodium sulfide were mixed at 0.66:0.44:1 to prepare a polyphenylene sulfide resin B with a weight average molecular weight of 5 ten thousand, which is marked as a component B;
step 2, spinning: the component A is processed by melt spinning to prepare conventional polyphenylene sulfide short fibers; wherein the spinning extrusion temperature is 325 ℃, the heat setting temperature is 250 ℃, the heat setting time is 10s, and the fiber is cut into short fibers with 3mm, and the fineness is 1.11dtex;
step 3, papermaking: 90 parts by weight of conventional polyphenylene sulfide short fibers and 10 parts by weight of polyphenylene sulfide resin B were dispersed in water to form 2wt% slurry, the diameter of the filter mesh of the mesh portion was 24 μm, the dryness of the wet paper sheet after extrusion in the press portion was 30%, the dryness of the dried paper sheet after drying was 93%, the hot-rolling strengthening temperature was set at 180℃and the calendering pressure was 2MPa.
Example 2
The preparation process is essentially the same as in example 1, except that in step 1, the molar ratio of p-dichlorobenzene, m-dichlorobenzene and sodium sulfide is replaced with 0.99:0.11:1, the hot-rolling strengthening temperature was set to 270 ℃.
Example 3
The preparation process was essentially the same as in example 1, except that in step 1, the molar ratio of p-dichlorobenzene, m-dichlorobenzene and sodium sulfide was replaced with 0.88:0.22:1, the hot rolling strengthening temperature is set to 245 ℃.
Example 4
The preparation process was essentially the same as in example 1, except that in step 1, the molar ratio of p-dichlorobenzene, m-dichlorobenzene and sodium sulfide was replaced with 0.77:0.33:1, the hot-rolling strengthening temperature was set to 210 ℃.
Example 5
The preparation process was essentially the same as in example 1, except that in step 1, the molar ratio of p-dichlorobenzene, m-dichlorobenzene and sodium sulfide was replaced with 0.55:0.55:1, the hot-rolling strengthening temperature was set to 165 ℃.
Example 6
The preparation process is essentially the same as in example 1, except that in step 3:
dispersing 80 parts by weight of conventional polyphenylene sulfide short fibers and 20 parts by weight of polyphenylene sulfide resin B in water to form 2wt% slurry;
the hot-rolling consolidation temperature was replaced with 170 ℃.
Example 7
The preparation process is essentially the same as in example 1, except that in step 3:
dispersing 95 parts by weight of conventional polyphenylene sulfide short fibers and 5 parts by weight of polyphenylene sulfide resin B in water to form 2wt% slurry;
the hot-rolled consolidation temperature was replaced with 190 ℃.
Example 8
The preparation process is substantially the same as in example 1, except that:
in step 1, the molar ratio of p-dichlorobenzene, m-dichlorobenzene and sodium sulfide was replaced with 0.55:0.55:1, a step of;
in step 3: dispersing 80 parts by weight of conventional polyphenylene sulfide short fibers and 20 parts by weight of polyphenylene sulfide resin B in water to form 2wt% slurry;
the hot-rolling consolidation temperature was replaced with 160 ℃.
Example 9
Step 1 is exactly the same as in example 1;
step 2, spinning: and (3) independently melt-spinning the polyphenylene sulfide resin A and the polyphenylene sulfide resin B.
The spinning extrusion temperature of the polyphenylene sulfide resin A is 325 ℃, the heat setting temperature is 250 ℃, the heat setting time is 10s, and the polyphenylene sulfide resin A is cut into polyphenylene sulfide fibers A with fineness of 1.11dtex and length of 3 mm;
the polyphenylene sulfide resin B was spun separately at a spinning extrusion temperature of 225℃and a heat setting temperature of 160℃for 10s, and was cut into polyphenylene sulfide fibers B having a fineness of 1.11dtex and a length of 3 mm.
Step 3, papermaking: 90 parts by weight of polyphenylene sulfide fibers A and 10 parts by weight of polyphenylene sulfide fibers B were dispersed in water to form a 2wt% slurry, the diameter of the filter mesh of the mesh portion was 24. Mu.m, the dryness of the wet paper sheet after extrusion in the press portion was 30%, the dryness of the dried paper sheet after drying was 93%, the hot-rolled reinforcing temperature was set at 180℃and the calendering pressure was 2MPa.
Comparative example 1
Step 1, polymerization: polymerizing paradichlorobenzene and sodium sulfide according to a molar ratio of 1.1:1.0 to prepare a conventional polyphenylene sulfide resin A (component A) with a weight average molecular weight of 6 ten thousand;
step 2, spinning: the component A is processed by melt spinning to prepare conventional polyphenylene sulfide short fibers; wherein the spinning extrusion temperature is 325 ℃, the heat setting temperature is 250 ℃, the heat setting time is 10s, and the polyphenylene sulfide fiber A with the length of 3mm and the fineness of 1.11dtex is cut into the polyphenylene sulfide fiber A;
step 3, papermaking: 100 parts by weight of conventional polyphenylene sulfide fiber A was dispersed in water to form 2wt% slurry, the diameter of the filter mesh of the mesh portion was 24. Mu.m, the dryness of wet paper sheet after extrusion in the press portion was 30%, the dryness of dry paper sheet after drying was 93%, the hot-rolled reinforcing temperature was set to 295℃and the calendering pressure was 2MPa. In the test, when the calendering pressure is 2MPa and the hot rolling strengthening temperature is lower than 260 ℃, the surface of the prepared fiber paper has cracking and has poor mechanical property.
Comparative example 2
Step 1, polymerization: polymerizing paradichlorobenzene and sodium sulfide according to a molar ratio of 1.1:1.0 to prepare a conventional polyphenylene sulfide resin A (component A) with a weight average molecular weight of 6 ten thousand;
step 2, spinning: the component A is processed by melt spinning to prepare conventional polyphenylene sulfide short fibers; wherein the spinning extrusion temperature is 325 ℃, the heat setting temperature is 250 ℃, the heat setting time is 10s, and the fiber is cut into short fibers with 3mm, and the fineness is 1.11dtex;
step 3, papermaking: 95 parts by weight of conventional polyphenylene sulfide short fibers and 5 parts by weight of polyvinyl alcohol (binder) were dispersed in water to form 2wt% slurry, the diameter of the filter mesh of the mesh portion was 24 μm, the dryness of wet paper sheet after extrusion in the press portion was 30%, the dryness of dry paper sheet after drying was 93%, the hot-rolling strengthening temperature was set to 180 ℃, and the calendering pressure was 2MPa.
The polyphenylene sulfide fibers prepared in the spinning steps of the above examples and comparative examples, respectively, and the finally prepared polyphenylene sulfide fiber paper were subjected to performance tests, and the test data are shown in tables 1 to 2 below.
TABLE 1
Note that: the acid and alkali resistance strength retention rate of the polyphenylene sulfide fiber paper is calculated by referring to the acid and alkali experimental conditions of FZT 52017-2011 and then testing the strength ratio of acid and alkali treatment to acid and alkali treatment according to GB/T1040.3.
TABLE 2
The foregoing is merely a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and the present invention is described by using the specific examples, which are only for aiding in understanding the present invention, and are not limited thereto. Several simple deductions, variations, substitutions or combinations may also be made by those skilled in the art to which the invention pertains based on the inventive concept. Such deductions, modifications, substitutions or combinations are also within the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the polyphenylene sulfide fiber paper is prepared by a wet papermaking process and comprises resin raw materials and water, and is characterized in that the composition of the resin raw materials comprises the following components in percentage by mass:
80-95% of polyphenylene sulfide resin A;
5-20% of polyphenylene sulfide resin B;
the polyphenylene sulfide resin A is obtained by polymerizing p-dichlorobenzene and a sulfur source A;
the polyphenylene sulfide resin B is obtained by polymerizing p-dichlorobenzene, m-dichlorobenzene and a sulfur source B, and the molar ratio of m-dichlorobenzene to the total molar number of p-dichlorobenzene and m-dichlorobenzene monomers is 10-50% based on 100%.
2. The method for producing polyphenylene sulfide fiber paper according to claim 1, wherein the sulfur source a and the sulfur source B are independently selected from one or more of sodium sulfide, sodium hydrosulfide, and hydrogen sulfide.
3. The method for preparing polyphenylene sulfide fiber paper according to claim 1, wherein:
the weight average molecular weight of the polyphenylene sulfide resin A is 3-7 ten thousand;
the weight average molecular weight of the polyphenylene sulfide resin B is 3-7 ten thousand.
4. The method for preparing polyphenylene sulfide fiber paper according to claim 1, wherein:
the resin comprises the following raw materials in percentage by mass:
90-95% of polyphenylene sulfide resin A;
5-10% of polyphenylene sulfide resin B;
the molar ratio of the m-dichlorobenzene to the m-dichlorobenzene is 20-40 percent based on 100 percent of the total molar number of the p-dichlorobenzene and the m-dichlorobenzene monomers.
5. The method for producing polyphenylene sulfide fiber paper according to claim 4, wherein:
the molar ratio of the m-dichlorobenzene to the m-dichlorobenzene is 30-40 percent based on 100 percent of the total molar ratio of the p-dichlorobenzene to the m-dichlorobenzene.
6. The method for producing polyphenylene sulfide fiber paper according to any one of claims 1 to 5, comprising:
the method comprises the steps of A, respectively and independently spinning polyphenylene sulfide resin A and polyphenylene sulfide resin B to prepare polyphenylene sulfide fibers A and polyphenylene sulfide fibers B, dispersing the polyphenylene sulfide fibers A and the polyphenylene sulfide fibers B in water, uniformly blending to prepare slurry, and preparing the polyphenylene sulfide fiber paper through a wet papermaking process;
or the method B is that the polyphenylene sulfide fiber A is prepared after the polyphenylene sulfide resin A is subjected to melt spinning, the polyphenylene sulfide fiber A and the polyphenylene sulfide resin B are dispersed in water and are uniformly mixed to prepare slurry, and the polyphenylene sulfide fiber paper is prepared through a wet papermaking process.
7. The method for producing polyphenylene sulfide fiber paper according to claim 6, wherein in method a:
the spinning extrusion temperature of the polyphenylene sulfide resin A is 290-340 ℃, the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber A is 1-15 mm, and the fineness is 0.5-5.0 dtex.
The spinning extrusion temperature of the polyphenylene sulfide resin B for independent spinning is 180-290 ℃; the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber B is 1-15 mm, and the fineness is 0.5-5.0 dtex.
8. The method for producing polyphenylene sulfide fiber paper according to claim 6, wherein in method B:
the spinning extrusion temperature of the melt spinning is 290-340 ℃, the heat setting temperature is 150-250 ℃, and the heat setting time is 1-30 s;
the length of the polyphenylene sulfide fiber A is 1-15 mm, and the fineness is 0.5-5.0 dtex.
9. The method for preparing polyphenylene sulfide fiber paper according to claim 6, wherein in method a or method B, the wet papermaking process comprises hot-rolling reinforcement, and the temperature of the hot-rolling reinforcement is 160-270 ℃.
10. A polyphenylene sulfide fiber paper made according to the method of any one of claims 1-9.
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