CN104356276A - Preparation method for preparing type 26 fluororubber from fluoroether sulfonate - Google Patents
Preparation method for preparing type 26 fluororubber from fluoroether sulfonate Download PDFInfo
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- CN104356276A CN104356276A CN201410618549.7A CN201410618549A CN104356276A CN 104356276 A CN104356276 A CN 104356276A CN 201410618549 A CN201410618549 A CN 201410618549A CN 104356276 A CN104356276 A CN 104356276A
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Abstract
The invention provides a preparation method for preparing type 26 fluororubber from a fluoroether sulfonate and belongs to the technical field of synthesis of the high polymer material fluoroelastomers. The preparation method comprises the following steps: 1) blowing nitrogen into an airtight polymerization reaction kettle to remove oxygen, and adding deionized water, an emulsifier, disodium hydrogen phosphate, potassium persulfate, diethyl malonate, vinylidene fluoride and hexafluoropropylene, wherein the emulsifier is the fluoroether sulfonate; 2) reacting under the pressure of 3.0-7.0Mpa and at a temperature ranging from 50 to 120 DEG C, starting a mixing propeller at a rotating speed of 300-700r/min, and ending the reaction after 0.5-2.5 hours, thereby obtaining fluororubber latex; 3) coagulating by use of calcium chloride, washing the coagulated solid particles by use of deionized water until the bubble disappears, and drying in vacuum to obtain the finished product. The preparation method for preparing the type 26 fluororubber from the fluoroether sulfonate has the advantages of increasing the molecular weight of the fluororubber, improving the molecular weight distribution and the mechanical properties of the fluororubber, and protecting the environment.
Description
Technical field
The invention belongs to polymer material fluoroelastomer synthesis technical field, be specially a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton.
Background technology
26 type viton refer to that vinylidene (VDF) and R 1216 (HFP) mix monomer are under emulsifying agent effect, the binary polymer fluoroelastomer of copolymerization according to a certain percentage, there is excellent chemical-resistant, thermotolerance and physical and mechanical properties, be widely used in the fields such as sealing-ring, pad, oil sealing.
At present, Perfluorocaprylic Acid and derivative thereof are used for 26 type viton as emulsifying agent and produce, its Main Function be dispersed viton primary fine particles to ensure stablizing of viton emulsion, be the necessary assistant of suitability for industrialized production 26 type viton.But scientist finds that Perfluorocaprylic Acid and derivative thereof are difficult to degrade from environment, and can biological growth and development be affected, therefore, Perfluorocaprylic Acid and derivative thereof are inhibited in gradually in the production of fluoropolymer and use, and developing green PFOA surrogate becomes the inevitable task of fluoropolymer enterprise.For avoiding using Perfluorocaprylic Acid, domestic viton manufacturing enterprise researchs and develops Perfluorocaprylic Acid substitute one after another, but it is too fast also to there is polymerization rate, viton molecular weight is too little, the viton intensity difference that polymerization is produced, sulfuration is uneven, affects the problems such as the performance of the finished product.
A lot of work has been done selecting in emulsifying agent by domestic and international viton manufacturing enterprise, and the patent related to has:
Patent CN1351616A discloses the method for a kind of fluorine monomer polymerization, and the method for emulsifying agent with PFPE carboxylic acid or its ammonium salt, reduces Emulsion particle size, obtains fluoropolymer dispersion in water of good performance, improve fluoropolymer processing characteristics with this.
Patent US6395848B1 discloses the aqueous dispersion method of employing at least two kinds of fluorochemical surfactant combinations.The method adopts a kind of PFPE carboxylic acid, sulfonic acid or derivatives thereof, can improve mix monomer copolymerization rate and rate of polymerization, improve emulsion particle diameter.
Patent CN101745338A discloses a kind of not containing the preparation method of the fluoropolymer of Perfluorocaprylic Acid, the method adopts the fluorochemical surfactant of one or more non-PFOA/PFOS to be applied to the polymerization technique of fluorine-containing latex, there is certain emulsification and dispersion effect, substantially can reach quality product requirement.
Patent CN103951772A discloses a kind of method being applicable to prepare the fluoropolymer not containing Perfluorocaprylic Acid or perfluorooctane sulfonate.The method adopts poly-polyfluoroalkoxy ether acid as emulsifying agent, can meet environmental requirement, and polymerization reaction time can be made to foreshorten to 4-6 hour, improve the cost benefit of polyreaction.
Patent CN101218264A discloses a kind of aqueous emulsion polymerization of the fluorinated monomer using perfluoropolyether surfactants to carry out.The alternative PFOA/PFOS of the method is used for the letex polymerization of fluorinated monomer, obtains the fluoropolymer dispersion in water of stable dispersion.
Summary of the invention
For the problems referred to above that prior art exists, the object of the invention is to design provides a kind of technical scheme adopting fluorine ether sulfonate to prepare the preparation method of 26 type viton, the method can improve emulsion particle diameter, improves rate of polymerization, shortens polymerization reaction time; Not only can reach the performance of the 26 type viton using Perfluorocaprylic Acid to produce, and avoid the use of Perfluorocaprylic Acid, have a good application prospect.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, is characterized in that comprising the following steps:
1) in airtight polymerization reaction kettle, purge nitrogen deoxygenation, add deionized water, emulsifying agent, Sodium phosphate dibasic, Potassium Persulphate, diethyl malonate, vinylidene, R 1216, described emulsifying agent is fluorine ether sulfonate; The consumption of described deionized water is the 150-350% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 0.1-2.5% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is the 0.1-0.5% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.1-2.0% of vinylidene and R 1216 total mass, and the consumption of described diethyl malonate is the 0.15-2.3% of vinylidene and R 1216 total mass; The mass ratio of R 1216, vinylidene is 3-7:10-14;
Wherein fluorine ether sulfonate, has following general structure:
Wherein R is F, Cl, Br; X is 2-4; Y is 1-3; M is K, Na;
2) reaction pressure is 3.0 – 7.0Mpa, and temperature of reaction is 50 – 120 DEG C, and open stirring rake, rotating speed is 300 – 700r/min, terminates reaction after 0.5-2.5 hour, obtained viton emulsion;
3) condense with calcium chloride, the consumption of calcium chloride is the 0.05-0.55% of quality of the emulsion, and by the solid particulate deionized water wash after gel to lather collapse, washings specific conductivity is down to 4-6 below μ s/cm, and then at 90-100 DEG C vacuum-drying 15-20 hour, obtained finished product.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, it is characterized in that in step 1): the consumption of described deionized water is the 200-300% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 0.5-2.0% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is the 0.2-0.4% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.5-1.5% of vinylidene and R 1216 total mass, the consumption of described diethyl malonate is the 0.2-2.0% of vinylidene and R 1216 total mass, the mass ratio of vinylidene, R 1216 is 4-6:11-13.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, it is characterized in that in step 1): the consumption of described deionized water is the 220-260% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 1.0-1.5% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is 0.3% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.8-1.0% of vinylidene and R 1216 total mass, the consumption of described diethyl malonate is the 0.5-1.5% of vinylidene and R 1216 total mass, the mass ratio of vinylidene, R 1216 is 5:12.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, it is characterized in that step 2) in: reaction pressure is 4.0 – 6.0Mpa, and temperature of reaction is 70 – 100 DEG C, opens stirring rake, rotating speed is 400 – 600r/min, terminates reaction after 1-2 hour.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, it is characterized in that step 2) in: reaction pressure is 4.5-5.5Mpa, and temperature of reaction is 80 – 90 DEG C, opens stirring rake, rotating speed is 450 – 550r/min, terminates reaction after 1.5 hours.
Described a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton, is characterized in that in step 3): washings specific conductivity is down to 5 below μ s/cm, so at 93-95 DEG C vacuum-drying 16-18 hour, obtained finished product.
Above-mentioned fluorine ether sulfonate, can buy from upper Haifeng county longevity Industrial Co., Ltd..
Above-mentioned a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton; adopt fluorine ether sulfonate to be used for 26 type viton as emulsifying agent to produce; improve emulsion particle diameter; improve rate of polymerization; shorten polymerization reaction time, improve viton molecular weight, improve molecular weight distribution and mechanical property; owing to avoiding the use of Perfluorocaprylic Acid in the course of the polymerization process, be therefore conducive to protection of the environment.
Embodiment
It is following that by embodiment and corresponding test, the invention will be further described.
Embodiment 1
6kg deionized water is added in 10L polymerization reaction kettle, then the oxygen in nitrogen replacement reactor is used, to make in still oxygen level lower than 10ppm, add the fluorine ether sulfonate of 20g again, 10g Sodium phosphate dibasic, 0.5kg R 1216, 2kg vinylidene, open stirring rake, rotating speed is 250r/min, be warming up to 90 DEG C, in reactor, 10g Potassium Persulphate initiated polymerization is squeezed into volume pump, constantly add to reactor R 1216/vinylidene mixed gas that mass ratio is 5/12 by medial launder, maintenance reaction pressure is 4MPa, in reactor, diethyl malonate 10g is added after 30min, polyreaction is terminated after 2.5 hours, reclaim unreacted mix monomer, by pressure controlled valve, the emulsion in reactor is delivered in emulsion groove, add 6g calcium chloride powder to condense, then solid matter enters rinse bath and washs, after block finished product sabot after having washed, enter fabric dryer and carry out drying, obtain white particle, carry out mixing more on a mill until, obtain viton, detect qualified rear packaging.This viton molecular weight Mw=7 × 10 are measured through GPC
5, polydispersity coefficient (ratio of weight-average molecular weight and number-average molecular weight) d=1.6, one step cure (temperature 177 DEG C, 10min) back draft intensity is 12.5MPa, and elongation at break is 300%, curing time T10=1'24'', T90=3'07''.One step cure is filled a prescription: 26 type viton 100g, bis-phenol 2g, promotor 0.5g, magnesium oxide 3g, rubber grade carbon black 30g, calcium hydroxide 6g.
Embodiment 2
5.5kg deionized water is added in 10L polymerization reaction kettle, add the fluorine ether sulfonate of 3.5g again, 3.5g Sodium phosphate dibasic, 0.7kg R 1216, 2.5kg vinylidene, open stirring rake, rotating speed is 350r/min, be warming up to 50 DEG C, in reactor, 3.2g Potassium Persulphate initiated polymerization is squeezed into volume pump, constantly add to reactor R 1216/vinylidene mixed gas that mass ratio is 7/25 by medial launder, maintenance reaction pressure is 3MPa, in reactor, diethyl malonate 5g is added after 10min, polyreaction is terminated after 1 hour, reclaim a small amount of unreacted mix monomer, by pressure controlled valve, the emulsion in reactor is delivered in emulsion groove, add 10g calcium chloride powder to condense, then solid matter enters rinse bath and washs, after block finished product sabot after having washed, enter fabric dryer and carry out drying, obtain white viton particle.This viton molecular weight Mw=8 × 10 are measured through GPC
5, polydispersity coefficient (ratio of weight-average molecular weight and number-average molecular weight) d=1.5, one step cure (temperature 177 DEG C, 10min) back draft intensity is 13.5MPa, and elongation at break is 300%, curing time T10=1'20'', T90=3'15''.
Embodiment 3
6kg deionized water is added in 10L polymerization reaction kettle, add the fluorine ether sulfonate of 42.5g, 8.5g Sodium phosphate dibasic, 0.7kg R 1216, 1kg vinylidene, ensure that in still, oxygen level is lower than 10ppm, open stirring rake, rotating speed is 700r/min, be warming up to 120 DEG C, in reactor, 34g Potassium Persulphate initiated polymerization is squeezed into volume pump, constantly add to reactor R 1216/vinylidene mixed gas that mass ratio is 7/10 by medial launder, maintenance reaction pressure is 7MPa, in reactor, diethyl malonate 39g is added after 20min, polyreaction is terminated after 2.5 hours, reclaim a small amount of unreacted mix monomer, by pressure controlled valve, the emulsion in reactor is delivered in emulsion groove, add 9.4g calcium chloride powder to condense, then solid matter enters rinse bath and washs, after block finished product sabot after having washed, enter fabric dryer and carry out drying, obtain white rubber particle.This viton molecular weight Mw=9 × 10 are measured through GPC
5, polydispersity coefficient (ratio of weight-average molecular weight and number-average molecular weight) d=1.5, one step cure (temperature 177 DEG C, 10min) back draft intensity is 14.5MPa, and elongation at break is 350%, curing time T10=1'04'', T90=2'53''.
Embodiment 4
6kg deionized water is added in 10L polymerization reaction kettle, add 38g fluorine ether sulfonate again, 10g Sodium phosphate dibasic, 0.6kg R 1216, 2.4kg vinylidene, open stirring rake, rotating speed is 500r/min, be warming up to 80 DEG C, in reactor, 30g Potassium Persulphate initiated polymerization is squeezed into volume pump, constantly add to reactor R 1216/vinylidene mixed gas that mass ratio is 1/4 by medial launder, maintenance reaction pressure is 5MPa, in reactor, diethyl malonate 35g is added after 15min, polyreaction is terminated after 2 hours, emulsion in reactor is delivered in emulsion groove, add 30g calcium chloride powder to condense, then solid matter enters rinse bath and washs, after block finished product sabot after having washed, enter fabric dryer and carry out drying, obtain white particle.This viton molecular weight Mw=7.5 × 10 are measured through GPC
5, polydispersity coefficient (ratio of weight-average molecular weight and number-average molecular weight) d=1.6, one step cure (temperature 177 DEG C, 10min) back draft intensity is 13.2MPa, and elongation at break is 320%, curing time T10=1'14'', T90=3'30''.
Comparative example 1
Comparative example 1 adopts Perfluorocaprylic Acid as emulsifying agent, and other adopts method in the same manner as in Example 1 to prepare 26 type viton.Both emulsifiers are identical, and implementing procedure is identical.
Above-described embodiment 1 and comparative example 1 are contrasted, refers to table 1.
Shown by table 1: compared with 26 type viton prepared by 26 type viton prepared by the present invention and routine, have outward appearance whiteness good, molecular weight is comparatively large, narrow molecular weight distribution, sulfuration tensile strength and elongation at break high, curing time is short waits excellent properties.Adopt the product that embodiment 2-4 is obtained, also can reach technique effect of the present invention.
Claims (6)
1. adopt fluorine ether sulfonate to prepare a preparation method for 26 type viton, it is characterized in that comprising the following steps:
1) in airtight polymerization reaction kettle, purge nitrogen deoxygenation, add deionized water, emulsifying agent, Sodium phosphate dibasic, Potassium Persulphate, diethyl malonate, vinylidene, R 1216, described emulsifying agent is fluorine ether sulfonate; The consumption of described deionized water is the 150-350% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 0.1-2.5% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is the 0.1-0.5% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.1-2.0% of vinylidene and R 1216 total mass, and the consumption of described diethyl malonate is the 0.15-2.3% of vinylidene and R 1216 total mass; The mass ratio of R 1216, vinylidene is 3-7:10-14;
Wherein fluorine ether sulfonate, has following general structure:
Wherein R is F, Cl, Br; X is 2-4; Y is 1-3; M is K, Na;
2) reaction pressure is 3.0 – 7.0Mpa, and temperature of reaction is 50 – 120 DEG C, and open stirring rake, rotating speed is 300 – 700r/min, terminates reaction after 0.5-2.5 hour, obtained viton emulsion;
3) condense with calcium chloride, the consumption of calcium chloride is the 0.05-0.55% of quality of the emulsion, and by the solid particulate deionized water wash after gel to lather collapse, washings specific conductivity is down to 4-6 below μ s/cm, and then at 90-100 DEG C vacuum-drying 15-20 hour, obtained finished product.
2. a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton as claimed in claim 1, it is characterized in that in step 1): the consumption of described deionized water is the 200-300% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 0.5-2.0% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is the 0.2-0.4% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.5-1.5% of vinylidene and R 1216 total mass, the consumption of described diethyl malonate is the 0.2-2.0% of vinylidene and R 1216 total mass, the mass ratio of vinylidene, R 1216 is 4-6:11-13.
3. a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton as claimed in claim 1, it is characterized in that in step 1): the consumption of described deionized water is the 220-260% of vinylidene and R 1216 total mass, the consumption of described fluorine ether sulfonate is the 1.0-1.5% of vinylidene and R 1216 total mass, the consumption of described Sodium phosphate dibasic is 0.3% of vinylidene and R 1216 total mass, the consumption of described Potassium Persulphate is the 0.8-1.0% of vinylidene and R 1216 total mass, the consumption of described diethyl malonate is the 0.5-1.5% of vinylidene and R 1216 total mass, the mass ratio of vinylidene, R 1216 is 5:12.
4. a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton as claimed in claim 1, it is characterized in that step 2) in: reaction pressure is 4.0 – 6.0Mpa, and temperature of reaction is 70 – 100 DEG C, opens stirring rake, rotating speed is 400 – 600r/min, terminates reaction after 1-2 hour.
5. a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton as claimed in claim 1, it is characterized in that step 2) in: reaction pressure is 4.5-5.5Mpa, and temperature of reaction is 80 – 90 DEG C, opens stirring rake, rotating speed is 450 – 550r/min, terminates reaction after 1.5 hours.
6. a kind of preparation method adopting fluorine ether sulfonate to prepare 26 type viton as claimed in claim 1, is characterized in that in step 3): washings specific conductivity is down to 5 below μ s/cm, so at 93-95 DEG C vacuum-drying 16-18 hour, obtained finished product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105345944A (en) * | 2015-11-13 | 2016-02-24 | 浙江巨圣氟化学有限公司 | Fluororubber washing bucket and automatic fluororubber washing method |
| CN112164497A (en) * | 2020-09-25 | 2021-01-01 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
| WO2022262156A1 (en) * | 2021-06-16 | 2022-12-22 | 浙江巨圣氟化学有限公司 | Method for improving coagulating effect of fluororubber emulsion |
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| CN1671754A (en) * | 2002-07-29 | 2005-09-21 | 3M创新有限公司 | Process for making a fluoroelastomer |
| CN1990515A (en) * | 2005-12-30 | 2007-07-04 | 易会安 | Starch-(methyl) acrylic ester grafted copolymer, oil suction swelling rubber comprising same and oil well packer |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671754A (en) * | 2002-07-29 | 2005-09-21 | 3M创新有限公司 | Process for making a fluoroelastomer |
| CN1990515A (en) * | 2005-12-30 | 2007-07-04 | 易会安 | Starch-(methyl) acrylic ester grafted copolymer, oil suction swelling rubber comprising same and oil well packer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105345944A (en) * | 2015-11-13 | 2016-02-24 | 浙江巨圣氟化学有限公司 | Fluororubber washing bucket and automatic fluororubber washing method |
| CN105345944B (en) * | 2015-11-13 | 2019-01-01 | 浙江巨圣氟化学有限公司 | A kind of fluorubber washing tube and the automatic washing methods of fluorubber |
| CN112164497A (en) * | 2020-09-25 | 2021-01-01 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
| CN112164497B (en) * | 2020-09-25 | 2021-11-23 | 安徽龙庵电缆集团有限公司 | Low-loss phase-stable cable for airborne early warning radar and preparation method thereof |
| WO2022262156A1 (en) * | 2021-06-16 | 2022-12-22 | 浙江巨圣氟化学有限公司 | Method for improving coagulating effect of fluororubber emulsion |
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