CN101724117B - Preparation method for large molded sheet suspended PTFE resin - Google Patents
Preparation method for large molded sheet suspended PTFE resin Download PDFInfo
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- CN101724117B CN101724117B CN 200910249861 CN200910249861A CN101724117B CN 101724117 B CN101724117 B CN 101724117B CN 200910249861 CN200910249861 CN 200910249861 CN 200910249861 A CN200910249861 A CN 200910249861A CN 101724117 B CN101724117 B CN 101724117B
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Abstract
The invention provides a preparation method for a large molded sheet suspended PTFE resin, which comprises the step of adding stabilizing agent which can stabilize polymerization rate into polymerization system. Compared with the prior art, the invention can obtain mould pressing used polytetrafluoethylene fine powder with high average molecular weight and narrow molecular weight distribution. Meanwhile, perfluoroether monomer is added to reduce the crystallinity of polymer, reduce the friction coefficient of the polytetrafluoethylene resin and improve the property of abrasion resistance. The polymer is treated in water to fully hydrolyze the end group of macromolecule, so that the hygroscopicity of polymerized product is reduced. Compared with the traditional common molded polytetrafluoethylene resin, the tensile strength and elongation as well as abrasion resistance performance of the polymer are greatly increased. The polytetrafluoethylene resin produced with the invention has excellent dispersity, thereby having good forming operability and strong product quality reliability.
Description
Technical field
The present invention relates to chemical field, be specifically related to the preparation method of suspended PTFE resin.
Background technology
Teflon resin has good over-all properties, and its high temperature resistant, low temperature are corrosion-resistant, low-friction coefficient, and viscosity not, the physical and mechanical propertiess such as weather-resistant all show very comprehensive and outstanding especially than other engineering plastics and other fluorine resin.Therefore teflon resin output, consumption are in always and increase the situation that does not wane, the all trades and professions such as widespread use Aeronautics and Astronautics, railway, road construction, machinofacture, chemical industry, electronics, electrical equipment, food, instrument, medicine, medical treatment are the important materials that the construction of developing national economy plays a significant role.
Suspending resin is one of present topmost kind in the teflon resin, and present domestic most polytetrafluoroethylsuspending suspending resins all are universal mold pressing resins, belongs to low and middle-grade times rosin products.Abroad instance, take Daikin as example, it is electrical equipment film PP Pipe Compound that suspending resin has M-12, M-14, M-18, M-18F etc. belong to PP Pipe Compound.
Prior art generally is to adopt the oxidation-reduction system of ammonium persulphate thermolysis initiator system or ammonium persulfate-sodium bisulfite, ferrous sulfate catalysis to prepare universal polytetrafluoroethylsuspending suspending powder.Along with the progress with the goods processing technology of widening of polytetrafluoroethylsuspending suspending resin purposes, the inner quality of universal polytetrafluoroethylsuspending suspending resin and goods processing characteristics are not complementary, and be therefore specialized to quality and the processing characteristics of suspension injecting tetrafluoroethylene resin.All belong to the tailored version resin with the Daikin mold pressing with suspending resin M-12, M-18, M-18F etc.Domestic special-purpose suspension tetrafluoroethylene major part is in development, and the resin dedicated domestic demand of polytetrafluoroethylsuspending suspending all will rely on import.
Suspension polymerization, no matter be ammonium persulphate thermolysis polymerization system or ammonium persulfate-sodium bisulfite redox system, its acid number all is constantly to change along with the carrying out of polyreaction in polymerization process, and is very remarkable at reaction middle and later periods auto-acceleration effect.
Summary of the invention
The object of the invention is to provides a kind of method for preparing suspended PTFE resin for above-mentioned deficiency.
The preparation method of suspended PTFE resin of the present invention, it is with tetrafluoroethylene polymerization in initiator system, with polymerisate grind after with water treatment, dry and pulverize and get final product, also add an amount of acid number stablizer in the described initiator system, with the acid number of initiator system in the stable polymerization reaction process.
Above-mentioned initiator system can be: 1) ammonium persulfate-sodium bisulfite, Fe
2+The catalyzed polymerization initiator system; 2) ammonium persulphate thermolysis initiator system; 3) ammonium persulfate-sodium bisulfite initiator system.4) succinic acid peroxide thermal initiation system; 5) potassium permanganate-Catalyzed by Oxalic Acid; 6) ammonium persulphate-hydrochloric acid catalysis initiator system.
Above-mentioned acid number stablizer can be: Sodium phosphate dibasic reagent, SODIUM PHOSPHATE, MONOBASIC, SODIUM PHOSPHATE, MONOBASIC+Sodium phosphate dibasic complex reagent, SODIUM PHOSPHATE, MONOBASIC+sodium hydroxide complex reagent.
The preferred initiator system that adopts is ammonium persulfate-sodium bisulfite, Fe
2+The catalyzed polymerization initiator system, described acid number stablizer is Sodium phosphate dibasic reagent.
Particularly, can carry out in accordance with the following steps in polyreaction: polymerization pressure is 0.6Mpa ± 0.02Mpa, 15 ℃ ± 1 ℃ of polyreaction starting temperature, and 35 ℃ ± 1 ℃ of termination reaction temperature, reaction medium is water, polymkeric substance/water medium is 1: 3～8.
Can add suitable modified monomer when polyreaction, described modified monomer can be R 1216, perfluoroether monomer.
When take perfluoro propyl vinyl ether as modified monomer, tetrafluoroethylene/perfluoro propyl vinyl ether weight ratio is 3500: 0.5～3.5; When take the weight ratio of the initiator system that contains ammonium persulphate ammonium persulphate and Sodium phosphate dibasic during as initiator system as 1: 50～150.
In the present invention, identical with ordinary method outside the agent of the initiator system amount that each component is added in reaction deacidification value stabilization.According to document announcement, tetrafluoroethylene suspension polymerization prepares PTFE suspending resin polymerization system, mainly contain ammonium persulphate-S-WAT redox polymerization system, ammonium persulphate thermolysis polymerization system, the research of succinic acid peroxide class and potassium permanganate-oxalic acid polymerization system etc. is also arranged.
Polymerization process of the present invention adds modified monomer, and its amount is the PPm level.Modified monomer can be R 1216, perfluoroether monomer.Particularly, add perfluoro propyl vinyl ether, its adding can reduce rub sassafras coefficient and abrasion.Further above-mentioned polymerisate is obtained density homogeneous, polymer that hardness is consistent through water treatment, again through smashing, grind, dry, pulverize the suspended PTFE resin that obtains 40～50 μ m to pieces.
Above-mentioned water treatment method is: with adding 2～3 times of deionized waters of polymkeric substance in the polymkeric substance, under agitation condition, 90 ± 5 ℃ of lower processing 0.5 hour.Aftertreatment and traditional aftertreatment difference that reaction obtains the PTFE suspension polymer are characterised in that, polymkeric substance passes through first hot aqueous medium's processing, in polymkeric substance, add 2～3 times of deionized waters, under agitation condition, be heated to 90 ± 5 ℃ from room temperature, and under this temperature, processed 0.5 hour, polymer terminal group fully is hydrolyzed with the polymer particles granule density wants homogeneous, hardness is consistent, carries out resin after the cooling again and smashes essence, grinding, dries and shatter.
The contriver studies discovery, because polymerization process belongs to thermo-sensitivity, and high-level efficiency free radical type polyaddition reaction, in polymerization process, acid number progressively rises in the system, therefore accelerates again polyreaction and carries out, and auto-acceleration effect appears in the speed of response of polymerization process.Control polymerization rate measure: by single ammonium persulphate thermolysis initiator system or single ammonium persulfate-sodium bisulfite initiator system, change over acid number constant initiator system in polymerization process, strict control polymeric reaction temperature is realized Single Parameter Control, eliminates the purpose that polyreaction is accelerated in tetrafluoroethylene suspension polymerization automatically.
The inventive method adds perfluoro propyl vinyl ether class the second monomer, and obtaining the PTFE resin has lower degree of crystallinity, and its configuration changes to the indefiniteness fluorine resin.This polymkeric substance is when ether chain two ends
When linking to each other with perfluoroalkyl and since the strong electron attraction of perfluoroalkyl make Sauerstoffatom not share electron pair be offset, form the ability and the C-O polarity that lose electron donor and show.Therefore perfluor ether no longer has the chemical property of alcohol ether, and it can not generate R with hydrogen ion
F1-O:H-R
F2Ether splitting of chain reaction can not occur, but also have incombustible unreactiveness in salt.Therefore in the TFE polymerization, connect perfluoro propyl vinyl ether class monomer in the polymer molecule propagation process, as be same as interpolation lower molecular weight fluorocarbon oil.Rub the sassafras coefficient and reduce the effect that wears away thereby further reduce.The present invention's research prepares shortcoming for above-mentioned traditional suspended PTFE resin.
The molecular-weight average of the tetrafluoroethylene that the inventive method obtains is high, narrow molecular weight distribution, with the tensile strength of assurance polymkeric substance and the performance requriements of elongation and abrasion performance.The large-scale thin plate mold pressing of the present invention teflon resin has following characteristics: it is a kind of compression molding fine powder material, have better more dispersed than traditional common mold pressing teflon resin, apparent density is high, when the bulk compression molding, can reduce available mold height especially, have advantages of that forming operation is excellent, product quality reliability is strong.
Product of the present invention is and external suitable large molded sheet polytetrafluoroethylsuspending suspending resin.Be used for the goods of railway traffic slide block, railway, road construction basin type support for bridges slide block with the high-grade resin raw material of tetrafluoroethylene, realize the production domesticization of tetrafluoroethylene product resin raw material.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.The poly-fluorine resin process of suspension polymerization preparation is added the acid number stablizer, all belong to this patent invention scope as polymerization process and the polymer water treatment process of the system of elimination auto-acceleration effect.
Embodiment 1
Reactor is cleaned, added deionized water 750L, ammonium persulphate 2g, sodium bisulfite 1g, ferrous sulfate 0.6g, SODIUM PHOSPHATE, MONOBASIC 195g.After the batching, reactor is found time, and with nitrogen replacement 2～3 times, filling gas phase tetrafluoroethylene monomer 0.05Mpa analyzes oxygen level≤30PPM qualified.After oxygen level is qualified, temperature in the kettle is controlled at 15 ℃ ℃.Polyreaction begins to carry out, and the still internal pressure keeps 0.6Mpa until reaction finishes, and the polymerization final temperature is controlled at 35 ℃, and polymerization time 4.5 hours reclaims the residue unconverted monomer, obtains polymkeric substance 90Kg through finding time.Polymkeric substance adds deionized water 700L, and water temperature keeps 90 ± 5 ℃, stirs 30 minutes, add then that deionized water is cleaned, ground, drying and shatter after obtain 45 μ m powder large molded sheet suspended PTFE resins.
Embodiment 2
Reactor is cleaned, added deionized water 750L, ammonium persulphate 2g, sodium bisulfite 1g, ferrous sulfate 0.6g, SODIUM PHOSPHATE, MONOBASIC 195g.After the batching, reactor is found time, and with nitrogen replacement 2～3 times, filling gas phase tetrafluoroethylene monomer 0.05Mpa analyzes oxygen level≤30PPM qualified.After oxygen level is qualified, temperature in the kettle is controlled at 15 ℃ ± 1 ℃.Polyreaction begins to carry out, the still internal pressure keeps 0.6 ± 0.02Mpa, minute three adding perfluor ether vinyl monomer 100g between polymerization period, until reaction finishes, the polymerization final temperature is controlled at 35 ℃ ± 1 ℃, polymerization time 4.5～5 hours reclaims the residue unconverted monomer, obtains polymkeric substance 90 ± 5Kg through finding time.Polymkeric substance adds deionized water 700L, and water temperature keeps 90 ± 5 ℃, stirs 30 minutes, add then that deionized water is cleaned, ground, drying and shatter after obtain 45 ± 5 μ m powder large molded sheet suspended PTFE resins.
Embodiment 3
Reactor is cleaned, added deionized water 750L, ammonium persulphate 2g, ferrous sulfate 0.6g, SODIUM PHOSPHATE, MONOBASIC 195g.After the batching, reactor is found time, and with nitrogen replacement 3 times, filling gas phase tetrafluoroethylene monomer 0.05MPa analyzes oxygen level≤30PPM qualified.After oxygen level is qualified, temperature in the kettle is controlled at 40 ℃.Polyreaction begins to carry out, and the still internal pressure keeps 0.6Mpa, until reaction finishes, the polymerization final temperature is controlled at 55 ℃, and polymerization time 4 hours reclaims the residue unconverted monomer, obtains polymkeric substance 90Kg through finding time.Polymkeric substance adds deionized water 700L, and water temperature keeps 90 ± 5 ℃, stirs 30 minutes, add then that deionized water is cleaned, ground, drying and shatter after obtain 45 μ m large molded sheet suspended PTFE resins.
Embodiment 4
Reactor is cleaned, added deionized water 750L, ammonium persulphate 2g, ferrous sulfate 0.6g, SODIUM PHOSPHATE, MONOBASIC 195g.After the batching, reactor is found time, and with nitrogen replacement 2 times, filling gas phase tetrafluoroethylene monomer 0.05Mpa analyzes oxygen level≤30PPM qualified, after oxygen level is qualified, add perfluoro propyl vinyl ether 80g minutes for three times.Still internal pressure (tetrafluoroethylene) keeps 0.6Mpa, until reaction finishes, temperature in the kettle is controlled at 40 ℃, polyreaction begins to carry out, and the polymerization final temperature is controlled at 55 ℃, polymerization time 4 hours, reclaim the residue unconverted monomer, obtain polymkeric substance 90Kg through finding time.Polymkeric substance adds deionized water 700L, and water temperature keeps 90 ± 5 ℃, stirs 30 minutes, add then that deionized water is cleaned, ground, drying and shatter after obtain 45 μ m powder large molded sheet suspended PTFE resins.
Embodiment 5
Reactor is cleaned, added deionized water 750L, ammonium persulphate 2g, sodium bisulfite 1g, ferrous sulfate 0.6g.After the batching, reactor is found time, and with nitrogen replacement 2～3 times, filling gas phase tetrafluoroethylene monomer 0.05Mpa analyzes oxygen level≤30PPM qualified.After oxygen level is qualified, temperature in the kettle is controlled at 15 ℃ ± 1 ℃.Polyreaction begins to carry out, and the still internal pressure keeps 0.6 ± 0.02Mpa until reaction finishes, and the polymerization final temperature is controlled at 35 ± 1 ℃, and polymerization time 1～1.5 hour reclaims the residue unconverted monomer, obtains polymkeric substance 90 ± 5Kg through finding time.Polymkeric substance adds deionized water 700L/ time, and water temperature keeps 90 ℃ ± 5 ℃, stirs 30 minutes, then adds deionized water and cleans, and obtains 45 ± 5 μ m powders, Universal Die pressing plate suspended PTFE resin through grinding, drying with after shattering.
Above preparation method obtains suspended PTFE resin, and resin property and fabricated product performance see Table one.
Table 1 large molded sheet suspended PTFE resin performance of the present invention
| Sequence number | Performance | Example one | Example two | Example three | Example four | Example five |
| 1 | Tensile strength MPa | 39.7 | 37 | 36.5 | 35 | 32 |
| 2 | Elongation % | 320 | 330 | 310 | 320 | 300 |
| 3 | Granularity d 50 | 46 | 44 | 46 | 47 | 48 |
| 4 | Water content % | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| 5 | Molecular weight | 1.3×10 7 | 1.1×10 7 | 1.25×10 7 | 1.20×10 7 | 2.3×10 6 |
| 6 | Ball indentation hardness | 27.4 | 26.9 | 26.5 | 26.0 | 23 |
| 7 | Rate of wear μ m/Km | 15 | 13 | 18 | 14 | 25 |
| 8 | The goods processing characteristics | The large molded sheet processing characteristics is excellent | The large molded sheet processing characteristics is excellent | The large molded sheet processing characteristics is good | The large molded sheet processing characteristics is excellent | Be fit to general pressing processing |
Claims (10)
1. the preparation method of large molded sheet suspended PTFE resin, it is characterized in that comprising the steps: with tetrafluoroethylene polymerization in initiator system, with polymerisate grind after with water treatment, dry and pulverize and get final product, also add the agent of appropriate amount of acid value stabilization in the wherein said initiator system, acid number with initiator system in the stable polymerization reaction process
Described method with water treatment is: add 2-3 times of deionized water of polymkeric substance in the polymkeric substance, under agitation condition, 90 ± 5 ℃ of lower processing 0.5 hour;
Described initiator system is: 1) ammonium persulfate-sodium bisulfite, Fe
2+The catalyzed polymerization initiator system; 2) ammonium persulphate thermolysis initiator system; 3) ammonium persulphate-sodium bisulfite initiator system; 4) succinic acid peroxide thermal initiation system; 5) potassium permanganate-Catalyzed by Oxalic Acid initiator system; Or 6) ammonium persulphate-hydrochloric acid catalysis initiator system.
2. the method for claim 1 is characterized in that, described acid number stablizer is selected from: Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, SODIUM PHOSPHATE, MONOBASIC+Sodium phosphate dibasic complex reagent, SODIUM PHOSPHATE, MONOBASIC+sodium hydroxide complex reagent.
3. method as claimed in claim 2 is characterized in that, described initiator system is ammonium persulfate-sodium bisulfite, Fe
2+The catalyzed polymerization initiator system, described acid number stablizer is Sodium phosphate dibasic reagent.
4. such as each described method of claim 1～3, it is characterized in that, described polymerization pressure is 0.6 ± 0.02Mpa, 15 ℃ ± 1 ℃ of polyreaction starting temperature, 35 ℃ ± 1 ℃ of termination reaction temperature, reaction medium is water, polymkeric substance and water medium weight ratio are 1:3～8.
5. the method for claim 1 is characterized in that, also is included in tetrafluoroethylene is added modified monomer to carry out modification in the initiator system polyreaction.
6. method as claimed in claim 2 or claim 3 is characterized in that, also is included in tetrafluoroethylene is added modified monomer to carry out modification in the initiator system polyreaction.
7. method as claimed in claim 5 is characterized in that, described modified monomer is R 1216 or perfluoroether monomer.
8. method as claimed in claim 6 is characterized in that, described modified monomer is R 1216 or perfluoroether monomer.
9. method as claimed in claim 8 is characterized in that, described modified monomer is perfluoro propyl vinyl ether, and the weight ratio of tetrafluoroethylene and perfluoro propyl vinyl ether is 3500:0.5～3.5; Ammonium persulphate/Sodium phosphate dibasic weight ratio is 1:100～150.
10. the large molded sheet suspended PTFE resin that is prepared by each described method of claim 1～9.
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| CN103665215B (en) * | 2013-11-29 | 2015-09-30 | 中昊晨光化工研究院有限公司 | A kind of end group fluoridation method of PTFE suspending resin |
| CN105924561A (en) * | 2016-06-16 | 2016-09-07 | 浙江巨圣氟化学有限公司 | Preparation method of modified teflon resin |
| CN106008783A (en) * | 2016-06-16 | 2016-10-12 | 浙江巨圣氟化学有限公司 | Modified polytetrafluoroethylene resin |
| CN114957520A (en) * | 2022-05-09 | 2022-08-30 | 江苏梅兰化工有限公司 | Preparation method of suspended PTFE resin spherical medium particle molding material |
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| CN101125900A (en) * | 2007-10-09 | 2008-02-20 | 上海三爱富新材料股份有限公司 | Method for preparing suspension modified polytetrafluoroethylene |
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