CN1081686C - Wet PVA-crosslinking spinning technology - Google Patents
Wet PVA-crosslinking spinning technology Download PDFInfo
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- CN1081686C CN1081686C CN 98101364 CN98101364A CN1081686C CN 1081686 C CN1081686 C CN 1081686C CN 98101364 CN98101364 CN 98101364 CN 98101364 A CN98101364 A CN 98101364A CN 1081686 C CN1081686 C CN 1081686C
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Abstract
The present invention relates to a polyvinyl alcohol wet crosslinking spinning technology which comprises the steps that polyvinyl alcohol with common molecular weight is used as a raw material, and a composite crosslinking agent is formed from zirconium, boron, titanium and silicon; after the polyvinyl alcohol is watered and dissolved, the polyvinyl alcohol is spun into fiber in a first coagulating bath, and the fiber is dewatered and solidified in a second coagulating bath; then, the fiber is drawn in a damp and heat mode and carries out crosslinking relieving treatment in an acid bath, acid and sodium sulfate in the fiber are removed in a neutralization bath, the fiber is dried and is finally drawn in a dry and heat mode, and the total drawing multiple reaches 15 to 18 times. The strength of the prepared fiber is 15 g/denier, and the modulus is 360 g/denier. The existing vinylon spinning device can be used for the present invention which has the advantages of simple technology, convenient popularization and wide market.
Description
The present invention relates to a kind of method of producing the high-strength and high-modulus synthetic fiber, specifically, is to cooperate crosslinking agent to spin a kind of spinning technique method of high strength high modulus polyvinyl alcohol fiber by polyvinyl alcohol.
The polyvinyl alcohol raw material sources are extensive, have purposes widely, but improve its intensity and modulus, are still one of target that the synthetic fiber worker seek assiduously.For example vinal and cement have good cohesiveness and curable, can replace asbestos to be used to produce cement and strengthen goods, and it requires vinal to have higher intensity and modulus.At present, majority utilizes the vinal of wet spinning spinning high-strength and high-modulus both at home and abroad, generally the common molecular weight polyvinyl alcohol with DP=1750 ± 50 is a raw material, all use boron to make crosslinking agent, open with Chinese patent: CN1031727A " process for manufacturing of polyvinyl alcohol filaments " is an example, it discloses a kind of concentration 14～20% times, adds by weight 0.8～5.5% boric acid and 0.05～1.5% oxirane high polymer in polyvinyl alcohol, makes spinning solution.The order of its technical process is, earlier through coagulating bath, neutralization baths, damp and hot drawing-off, washing and drying then, and the dry heat drafting processing, thus the baked tensile strength that obtained for 6～300,000 dawn was 11.6 gram/dawn, 264 gram/dawn of initial modulus, the high-intensity fiber of degree of stretching 7.7%.But think that through practice its intensity, particularly modulus also have the possibility that improves.In addition, in order to improve the drawing-off performance, fiber mesoboric acid content is no more than 0.3% at most, and this has just increased the time that boric acid is removed in washing, causes fiber swelling and doubling, occurs lousiness and broken end when making dry heat drafting easily, influences the quality of continued operation and product.Similar therewith manufacture method, as the clear 47-42058 of Japan Patent, clear 54-32858, clear 59-43112 etc. all have this shortcoming.
The objective of the invention is to avoid the weak point of above-mentioned existence, provide a kind of employing polyvinyl alcohol common spinning technique, good spinnability, the washing time is short, the Wet PVA-crosslinking spinning technology that fibre strength and modulus are higher.
Purpose of the present invention can realize with the following method, its Wet PVA-crosslinking spinning technology at first is mixed with spinning solution with polyvinyl alcohol and crosslinking agent, its stoste consists of: polyvinyl alcohol concentration is 12～16%, crosslinking agent adds concentration 0.5～5%, used crosslinking agent is made up of in water miscible zirconium compounds, titanium salt, borate, the silicate two or more, the part by weight that adds is 3～5: 2～3.5: 1～2.5: 1～2.5 in turn, 95～98 ℃ of spinning temperatures; Solution sprays into coagulating bath through spinneret orifice and becomes silk, and its coagulating bath is made of first coagulating bath and second coagulating bath, and first coagulation bath composition is: NaOH: 15～50 grams per liters, sodium sulphate: 300～380 grams per liters, control temperature: 40～45 ℃; Second coagulation bath composition is: NaOH: 10～30 grams per liters, and sodium sulphate: 330～410 grams per liters, the control temperature is: 45～50 ℃, carry out 2～4 times of drawing-offs simultaneously; Order obtains the high-strength and high-modulus long filament through damp and hot drawing-off, acid bath, neutralization bath, drying, dry heat drafting then.
This law main purpose is to make fiber keep the uniformity of structure and good drawing-off performance when nascent state, the as-spun fibre outward appearance is similar to rounded cross section, adopt two coagulating baths: in first coagulating bath for this reason, it is certain crosslinked that big molecule is produced, avoided intermolecular random winding, making as-spun fibre keep gel state also slowly solidifies, reduce amount of sodium hydroxide in second coagulating bath, suitably increase sodium sulfate concentration, make the further dehydration, crosslinked of big molecular polyethylene alcohol, form the as-spun fibre of even structure, and carry out drawing-off first.For cooperating this technology, the selection of its crosslinking agent should make polyvinyl alcohol molecule crosslinked easily, and will satisfy the requirement of spinning technique to fiber.Crosslinking agent is used water miscible zirconium compounds, titanium salt, borate and silicate.In addition, owing to adopt two coagulating baths to form the uniform as-spun fibre of structure, good drawing-off performance is arranged among the present invention.
Purpose of the present invention can also realize that fiber enters damp and hot drawing-off bath after drawing-off first, keeps sodium sulfate concentration in the bath with following method: 340～380 grams per liters, and under 80～95 ℃ of temperature, 2～4 times of drawing-offs.Then enter acid bath, keep sodium sulfate concentration in the acid bath: 280～320 grams per liters, sulfuric acid concentration: 10～40 grams per liters, under effect of sulfuric acid, make the big molecule of polyvinyl alcohol produce crosslinked generating unit and decompose crosslinkedly, purpose is to improve the dry heat drafting performance of fiber.The fiber retention time is in neutralization is bathed: 20～90 seconds, purpose is flush away sulfuric acid and sodium sulphate, make fiber be neutral, this process time of staying comparison is shorter than the patented technology washing time, avoid fiber generation swelling, the high drafting that has guaranteed fiber has promptly guaranteed the high powerful feature that high drafting had, though still have certain corsslinking molecular, does not influence the drawing-off performance and can increase the intensity of product.Drying case control temperature is carried out drying for 120～150 ℃ again, and be drying time: 1～5 minute.At last, carry out dry heat drafting under 225～245 ℃, total drafting multiple can reach 15～18 times.Its drying and drawing-off can be adopted prior art, and its equipment therefor adopts the used device of prior art to transform a little and gets final product.
The present invention has the following advantages compared to existing technology: 1, with the homemade common polythene alcohol in DP1750 ± 50 is raw material, adopt zirconium, titanium, boron, silicon type multiple crosslinking agent and two coagulating bath wet method crosslinking spinning technology, can reach 15 gram/dawn high strength, the vinal of 360 gram/dawn high-moduluss, comparison improves 30% and 36% respectively than patented technology; The drawing-off performance is good, can reach 15～18 times, and comparison is than high about 2～5 times of patent.2, remaining crosslinking agent in the flush away fiber painstakingly not in neutralization is bathed not only can be avoided fiber generation swelling, and can keep insignificant, thereby improves the modulus of fiber.3, can be used for processing high-intensity product, as rope, shelter cloth, rotary hose, industrial sewing line, geotextiles, safety belt, lifting bag, conveyer belt, material for core, fire-retardant product etc., can also be as asbestos alternative, be used to produce cement and other refinforced cement composites, have market widely at home and abroad.
The drawing of accompanying drawing of the present invention is described as follows:
Accompanying drawing is a process flow diagram of the present invention.
Following conjunction with figs. illustrates the present invention with embodiment, and for easier popularization, we use the most frequently used degree of polymerization DP 1750 ± 50, and alcoholysis degree 99.9% polyvinyl alcohol is made the aqueous solution of concentration 14%.2% multiple crosslinking agent of polyvinyl alcohol weight is added in the solution, and multiple crosslinking agent is selected zirconium sulfate, sodium tetraborate for use, and it consists of zirconium sulfate: sodium tetraborate=3: 2.Polyvinyl alcohol spin dope is that 0.08 millimeter spinneret orifice 1 is clamp-oned contains sodium sulfate 370 grams per liters, NaOH 30 grams per liters by the aperture, temperature is 45 ℃ first coagulating bath 2, form the gel as-spun fibre, its process flow diagram is seen accompanying drawing, then enter sodium sulphate 400 grams per liters, NaOH 15 grams per liters, second coagulating bath 3 that temperature is 45 ℃, further dewater, solidify, and 2.5 times of drawing-offs.Sodium sulphate 360 grams per liters in 4,90 ℃ of temperature, 2 times of drawing-offs are bathed in damp and hot drawing-off.Enter contains sodium sulfate 280 grams per liters then, the acid bath 5 of sulfuric acid 15 grams per liters, 1.4 times of room temperature drawing-offs make crosslinked releasings a large amount of in the fiber in drawing-off.The neutralization that enters room temperature then bathes 6, and sodium sulphate in the flush away fiber and sulfuric acid stopped 30 seconds in neutralization is bathed.Then dry in 140 ℃ of drying boxes 7, enter 235 ℃ of dry heat drafting casees 8 afterwards and carry out dry heat drafting, make fiber total draft multiple reach 16 times.Make fiber after measured, intensity was 15 gram/dawn, and at the 360 gram/dawn of modulus, extension at break is 6.0%, and fiber number is 1.48 dtexs.Whole technology continued operation since with the spinning technique basically identical of existing homemade polyvinyl, can utilize former polyvinyl process units, change a little and can produce high strength high modulus polyvinyl alcohol fiber.
Annotate: indication of the present invention " % " is all percentage by weight.
Claims (2)
1, a kind of Wet PVA-crosslinking spinning technology, be mixed with spinning solution by polyvinyl alcohol and crosslinking agent, through spinneret orifice (1) Cheng Sihou, enter coagulating bath (2), (3) and drawing-off, bathe (4), acid bath (5), neutralization bath (6), dry (7) through damp and hot drawing-off then, dry heat drafting (8) technical process obtains the high-strength and high-modulus long filament, it is characterized in that: 1. the spinning solution percentage by weight consists of: polyvinyl alcohol concentration is 12-16%, crosslinking agent adds concentration 0.5～5%, 95～98 ℃ of spinning temperatures; 2. its anterior technical process is: spinning solution is behind spinneret orifice (1), and order is bathed (4), acid bath (5), neutralization bath (6) through first, second coagulating bath (2), (3), damp and hot drawing-off; 3. its coagulating bath is made up of first coagulating bath (2) and second coagulating bath (3), and first coagulating bath (2) contains: NaOH: 15～50 grams per liters, sodium sulphate: 300～380 grams per liters, control temperature: 40～45 ℃; Second coagulating bath (3) contains: NaOH: 10～30 grams per liters, and sodium sulphate: 330～410 grams per liters, the control temperature is: 45～50 ℃, the 2-4 of drawing-off simultaneously is doubly; 4. used crosslinking agent is made up of in water miscible zirconium compounds, titanium salt, borate, the silicate two or more, and the part by weight of adding is in turn: 3～5: 2～3.5: 1～2.5: 1～2.5.
2, Wet PVA-crosslinking spinning technology according to claim 1 is characterized in that fiber with the time is: 20～90 seconds in neutralization bath (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101364 CN1081686C (en) | 1998-04-14 | 1998-04-14 | Wet PVA-crosslinking spinning technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101364 CN1081686C (en) | 1998-04-14 | 1998-04-14 | Wet PVA-crosslinking spinning technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197858A CN1197858A (en) | 1998-11-04 |
| CN1081686C true CN1081686C (en) | 2002-03-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98101364 Expired - Fee Related CN1081686C (en) | 1998-04-14 | 1998-04-14 | Wet PVA-crosslinking spinning technology |
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| CN (1) | CN1081686C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422404C (en) * | 2006-07-27 | 2008-10-01 | 中国石化集团资产经营管理有限公司重庆天然气化工分公司 | Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101387014B (en) * | 2000-09-05 | 2015-08-26 | 唐纳森公司 | Polymer, polymer microfiber is tieed up, polymer nanofiber and the purposes comprising filtration device structure |
| US6743273B2 (en) * | 2000-09-05 | 2004-06-01 | Donaldson Company, Inc. | Polymer, polymer microfiber, polymer nanofiber and applications including filter structures |
| FR2828500B1 (en) * | 2001-08-08 | 2004-08-27 | Centre Nat Rech Scient | PROCESS FOR REFORMING COMPOSITE FIBERS AND APPLICATIONS |
| CN100390333C (en) * | 2006-01-17 | 2008-05-28 | 中国石化集团资产经营管理有限公司重庆天然气化工分公司 | Process and apparatus for manufacturing vinylon filament |
| CN103060940B (en) * | 2011-10-18 | 2015-09-30 | 中国石油化工集团公司 | A kind of preparation method of medium modulus vinal |
| CN103276469B (en) * | 2013-05-23 | 2015-02-25 | 永安市宝华林实业发展有限公司 | Production method of concrete reinforced and toughened PVA (polyvinyl alcohol) fiber |
| CN106757403A (en) * | 2015-11-19 | 2017-05-31 | 张家港市宏盛贸易有限公司 | Spinning equipment before water-soluble fibre |
| CN111101219B (en) * | 2018-10-26 | 2022-08-12 | 中国石油化工股份有限公司 | High-strength high-modulus polyvinyl alcohol filament and preparation method thereof |
| CN111636114B (en) * | 2020-06-12 | 2021-08-31 | 东华大学 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
| CN112226840B (en) * | 2020-08-04 | 2021-07-23 | 东华大学 | High-strength high-modulus PVA fiber and preparation method thereof |
| CN112095170B (en) * | 2020-08-04 | 2022-03-25 | 东华大学 | LaCl3Cross-linked high-strength high-modulus polyvinyl alcohol fiber and preparation method thereof |
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1998
- 1998-04-14 CN CN 98101364 patent/CN1081686C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422404C (en) * | 2006-07-27 | 2008-10-01 | 中国石化集团资产经营管理有限公司重庆天然气化工分公司 | Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use |
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| Publication number | Publication date |
|---|---|
| CN1197858A (en) | 1998-11-04 |
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