CN1844198A - Polymerization method for crude rubber of fluorinated silicone rubber - Google Patents
Polymerization method for crude rubber of fluorinated silicone rubber Download PDFInfo
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- CN1844198A CN1844198A CN 200610035304 CN200610035304A CN1844198A CN 1844198 A CN1844198 A CN 1844198A CN 200610035304 CN200610035304 CN 200610035304 CN 200610035304 A CN200610035304 A CN 200610035304A CN 1844198 A CN1844198 A CN 1844198A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 66
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 229920002379 silicone rubber Polymers 0.000 title claims description 32
- 239000004945 silicone rubber Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 13
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- -1 silicon alkoxide Chemical class 0.000 claims description 20
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- ZYJKUXGOCSWXQO-UHFFFAOYSA-N ethene;silicon Chemical compound [Si].C=C ZYJKUXGOCSWXQO-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- DODVWSSKXYVHOR-UHFFFAOYSA-N fluoro(hydroxy)silicon Chemical compound O[Si]F DODVWSSKXYVHOR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 238000012952 Resampling Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention relates to a method for aggregation of hydrofluorosilicic crude rubber. The hydrofluorosilicic crude rubber prepared by this invention is of even molecular weight distribution and superior performance, and can exactly control the average molecular weight of the product. The method includes the following steps: first preparing the polymeric materials, in which the polymeric materials can be fluosilicic monomer D3F, vinyl silicon monomer or alkaline agent, mixing and dewatering the raw materials, then inputting the materials into the polymerization kettle, after the polymerization, the materials entering the devolatilization kettle because of pressure differences, then entering the out-feed extrusion machine, and the polymer blendedly discharging by the extrusion machine. The hydrofluorosilicic crude rubber prepared by this invention is of even molecular weight distribution and can exactly control and adjust the average molecular weight of the product, so it can improve the homogeneity of the product.
Description
Technical field
The present invention relates to a kind of polymerization process of rubber raw rubber, relate in particular to a kind of automotive industry and space flight and aviation basin polymerization process with crude rubber of fluorinated silicone rubber.
Background technology
Trifluoropropyl siloxane is that a kind of main chain is that siliceous oxide structure, side chain are the special synthetic rubber material of fluorine-containing alkyl structure.The special chemical structure of this material makes its high temperature performance that had both had the silicon rubber excellence, and high temperature resistant, the resistant to chemical media and the oil resistance that have the viton excellence concurrently are arranged.
Nineteen fifty-one United States Air Force department and Dow Corning company begin joint study, and began to release first trifluoropropyl siloxane commodity in 1956.After this, the product type of trifluoropropyl siloxane and Application Areas have obtained expansion rapidly.Trifluoropropyl siloxane mainly is divided into liquid fluorine silicon rubber and hot sulfurization trifluoropropyl siloxane two classes, is primarily aimed at the hot sulfurization trifluoropropyl siloxane here.
The polymerization process of crude rubber of fluorinated silicone rubber is divided into three phases.Fs, fluorine silicon monomer D3F, vinyl silicon monomer carry out ring-opening polymerization under the effect of alkaline assistant, and molecular weight steadily increases; Subordinate phase, after molecular weight increased to certain limit, the condensation polymerization between molecule segment became main process, and molecular weight becomes geometricprogression to increase.System viscosity increases rapidly; Phase III, after system viscosity was very big, molecular motion was fettered, and polymerization is near stopping.Usually the molecular weight of crude rubber of fluorinated silicone rubber that has actual application value is in 60～1,500,000 scopes.The fluorine silicon raw rubber viscosity height of this molecular weight ranges, heat and mass difficulty in polymerization process, by general kettle-typed polymerization method, be difficult to the molecular weight and the distribution thereof of controlled polymerization product, the deviation of the highest/lowest molecular weight and molecular-weight average has had a strong impact on the processibility of trifluoropropyl siloxane and the performance of vulcanized article generally up to about 300,000 in its product.
A lot of about the patent of trifluoropropyl siloxane both at home and abroad, but about rubber polymeric patent seldom.The Chinese patent of application number CN01126772.0 has proposed a kind of preparation method of fluorine silicon penylene rubber, with D
3F and a kind of fluorine silicon penylene monomer are main raw material, under base catalysis, make number-average molecular weight through negatively charged ion open loop, polycondensation, balanced reaction and are up to 600,000 rubber.This rubber is multipolymer, contains 10～95% fluorine silicon penylene chain link.
The Chinese patent of application number CN200510026689.6 discloses a kind of crude rubber of fluorinated silicone rubber polymeric catalyst composition that is used for, it mainly adopts fluorine-containing organosilicon oligopolymer, as methyl fluoride silicone oil, hydroxyl fluorosilicon oil, vinyl fluoride silicone oil etc., polymerization process to crude rubber of fluorinated silicone rubber is regulated, to reach the inhomogeneity purpose of control molecular weight.This patent represents to be applicable to the polymerization of the crude rubber of fluorinated silicone rubber between molecular weight 60～1,500,000, can be with the deviation control of the highest/lowest molecular weight and molecular-weight average within 3～80,000.But the embodiment that provides from this patent, its product is the highest/and the deviation of lowest molecular weight and molecular-weight average is generally less than 100,000, and for the product of 1,300,000 following molecular weight, deviation is less than 80,000, for the product of 1,300,000 above molecular weight, deviation is between 8～100,000.In addition, this patent still adopts common still reaction, comes the controlled polymerization degree by visual observation, and the artificial discharging method of still is then adopted out in discharging.
Summary of the invention
Problem at the prior art existence, technical problem to be solved by this invention is to adopt new polymerization process, prepare crude rubber of fluorinated silicone rubber even molecular weight distribution, superior performance, can accurately control and regulate the molecular-weight average of crude rubber of fluorinated silicone rubber product.
For reaching above-mentioned purpose, the polymerization process of crude rubber of fluorinated silicone rubber of the present invention is achieved by following technical proposals:
Polymerization process based on crude rubber of fluorinated silicone rubber of the present invention comprises the steps:
1., at first prepare polymer raw, polymer raw adopts fluorine silicon monomer D3F, vinyl silicon monomer, alkaline assistant, and the molar ratio of ethene silicon monomer/D3F is controlled at 1/1000～1/100, and polymer raw comprises following each component by mass fraction:
Fluorine silicon monomer D3F:100, the vinyl silicon monomer: 0.05～0.5,
Alkaline assistant: 0.1～1;
2., need to carry out earlier mixed dehydration before the material polymerization, dehydration conditions is-0.01～-0.02MPa, 60～80 ℃, 1.5～4 hours; Material enters polymeric kettle then, concrete polymerizing condition is 110～140 ℃ of temperature, 10～60 minutes time, need according to molecular weight, come the terminal point of controlled polymerization reaction by the power output valve of whipping appts, stirring velocity generally is controlled at 5～50 rev/mins, feeds the trace water that the exsiccant air is produced in time to take away condensation course in the polymerization process continuously;
3., after polymerization finishes, material enters the devolatilization still by pressure difference, the top of devolatilization still is furnished with sieve plate, material forms fine strip shape after by sieve plate,-0.01～-0.05MPa vacuum tightness under, remove volatile monomers residual in the material and moisture content, the devolatilization temperature is generally 80～110 ℃;
4., in the bottom of devolatilization still, the fine strip shape mixed with polymers enters the discharging forcing machine, polymkeric substance is by forcing machine mixing discharging.
The 1. described alkaline assistant of step is selected corresponding silicon alkoxide such as sodium hydroxide, potassium hydroxide, quaternary ammonium hydroxide, lithium hydroxide, first-selected silanol sodium salt, its alkali content is controlled at 0.1～1wt%, and its viscosity controller is at 10～80Pas, and the ratio control of silanol sodium salt/D3F is at 0.1～1wt%.
The polymerization process of crude rubber of fluorinated silicone rubber of the present invention adopts 3,3,3-trifluoro propyl methyl cyclotrisiloxane (D
3F) be principal monomer, under the alkaline reagents effect, carry out copolymerization with small amount of ethylene base silicon monomer, by suitable polymerization process, can obtain that molecular weight is adjustable in 50～1,500,000 scopes, the deviation of the highest/lowest molecular weight and molecular-weight average is less than the crude rubber of fluorinated silicone rubber of 50,000 excellent combination property.
The invention solves above-mentioned existing technical problem, and have the following advantages than the polymerization process of traditional crude rubber of fluorinated silicone rubber:
(1), polymeric segment adopts stirring of ribbon screw or double-screw type to stir to guarantee that polymerization system is mixed and Surface Renewal fully; The even molecular weight distribution of the crude rubber of fluorinated silicone rubber that polymerization obtains, the deviation of the highest/lowest molecular weight and molecular-weight average is less than 50,000;
(2), come the controlled polymerization reaction end, can accurately control and regulate the molecular-weight average of crude rubber of fluorinated silicone rubber product, the molecular-weight adjusting span of control is 50～1,500,000 by the power output valve of polymeric segment whipping appts;
(3), material enters in the devolatilization still by the form of specific sieve plate with elongate strip, the material table area enlarges markedly, and can remove residual volatile component fast, the fugitive constituent of the finished product is less than 0.1wt%;
(4), adopt forcing machine mixing discharging, further improve the homogeneity of product.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Fluorine silicon monomer D3F, the vinyl silicon monomer, enter behind the mixed dehydrations such as alkaline assistant and react in the polymeric kettle, this polymeric kettle adopts ribbon screw agitator or double-screw type agitator to be mixed fully and Surface Renewal to guarantee polymerization system, polymerization process is carried out under certain vacuum tightness or dry air, when polymerization system reaches the certain viscosity scope, under the pushing effect of pressure difference or agitator, material enters in the devolatilization still with the form of elongate strip by specific sieve plate and removes fugitive constituent, and, obtain crude rubber of fluorinated silicone rubber by forcing machine mixing discharging.
The concrete polymerization process of crude rubber of fluorinated silicone rubber comprises the steps:
(1) preparation raw material:
Polymer raw adopts general fluorine silicon monomer D3F, vinyl silicon monomer, alkaline assistant.Therein ethylene base silicon monomer plays the effect of sulfuration point in fluorine silicon raw rubber, its consumption can have influence on the performance of the vulcanization characteristics and the goods of trifluoropropyl siloxane, the molar ratio of ethene silicon monomer/D3F generally is controlled at 1/1000～1/100, preferably is controlled between 3/1000～8/1000.
Polymer raw comprises following each component by mass fraction:
Fluorine silicon monomer D3F:100; Vinyl silicon monomer: 0.05～0.5, best 0.15～0.4;
Alkaline assistant: 0.1～1, best 0.4～0.8.
Alkaline assistant can be selected sodium hydroxide, potassium hydroxide, quaternary ammonium hydroxide, lithium hydroxide etc. or corresponding silicon alkoxide, and the present invention selects the silanol sodium salt for use.Alkali content generally is controlled at 0.1～1wt% in the silanol sodium salt, is preferably 0.7～0.9wt%, and its viscosity generally is controlled at 10～80Pas; The ratio of silanol sodium salt/D3F generally is controlled at 0.1～1wt%, is preferably in 0.4～0.8wt%.
(2) polymerization procedure:
Because the viscosity of polymer material can be up to 100Pas under polymerization temperature, and belong to viscoelastic fluid, in order to reach the good heat transfer mass transfer effect, the present invention adopts two types polymeric kettle, a kind of for boring end ribbon screw rod stirring polymeric kettle (vertical), a kind of is that twin screw stirs polymeric kettle (horizontal).These two kinds of polymeric kettles all can effectively be realized the mixing and the heat transfer of medium-high viscosity material, thereby improve the molecular weight homogeneity of crude rubber of fluorinated silicone rubber.Stirring velocity generally is controlled at 5～50 rev/mins, is preferably in 10～30 rev/mins.Whipping appts has power output, along with the increase of polymer material viscosity, and the corresponding increase of this power output valve.For different polymeric kettles, its corresponding relation that stirs output power value and material viscosity is different, can measure the relation curve of stirring output rating-material viscosity by the material of examination polymerization or employing known-viscosity.
Needing to carry out earlier mixed dehydration before the material polymerization, dehydration conditions is-0.01～-0.02MPa, 60～80 ℃, 1.5～4 hours.Add polymeric kettle after material can dewater, also can in polymeric kettle, dewater.
Concrete polymerizing condition is: 110～140 ℃ of temperature (best 120～130 ℃), 10～60 minutes time (best 20～40 minutes).According to the molecular weight needs, come the terminal point of controlled polymerization reaction by the power output valve of whipping appts, feed the trace water that the exsiccant air is produced in time to take away condensation course in the polymerization process continuously.
(3) devolatilization step:
Residual a spot of volatile monomers of meeting and moisture content need remove by the devolatilization still in the crude rubber of fluorinated silicone rubber polymerization process.Top at the devolatilization still is furnished with sieve plate, general 0.5～5 millimeter of screen-aperture, best 1～3 millimeter.1～10 millimeter of sieve aperture spacing, best 3～6 millimeters.Material forms fine strip shape after by sieve plate, under the certain vacuum degree (be generally-0.01～-0.05MPa, be preferably-0.01～-0.02MPa), volatile monomers and moisture content residual in the material are easy to remove, the devolatilization temperature is generally 80～110 ℃, is preferably 90～105 ℃.After polymerization finished, material entered the devolatilization still by pressure difference or the promotion by polymerization stirrer.
(4) discharging step:
Bottom at the devolatilization still, the fine strip shape mixed with polymers enters the discharging forcing machine, the discharging forcing machine can play the effect of self-emptying on the one hand, then also plays the effect of mixing of materials on the other hand, thereby can further improve the molecular weight homogeneity of crude rubber of fluorinated silicone rubber product.
Comparative Examples:
10 kilograms of D3F monomers, 2 gram hydroxyl fluorosilicon oils, 50 gram vinyl silicon monomers, 40 restrain the silanol sodium salts, add in pre-dry 20 liters of stainless steel polymerization reaction kettles.70 ± 3 ℃ of controlled temperature ,-0.01～0.02MPa feeds drying nitrogen, dewaters 3 hours.Degree of intensification is to 125 ℃ ± 3 ℃ of polymerization temperatures then, and polymerization process feeds drying nitrogen, and polymerization 25 minutes gets water white transparency high molecular rubber, and resampling analysis after cooling, weighing and bagging are dug out in cooling while hot immediately.
Adopt the limiting viscosity of Ubbelohde viscometer method test fluorine silicon polymkeric substance, obtain corresponding molecular weight, solvent uses ethyl acetate (AR), and probe temperature is 25 ℃.Adopt the contents of ethylene in the chemistry titration method test fluorine silicon polymkeric substance, solvent uses butylacetate (AR), and probe temperature is 25 ℃.Adopt thermal weight loss to send out the mensuration volatile content.
Specific embodiment 1～example 6 (referring to table 1):
Polymer raw is not except using the hydroxyl fluorosilicon oil, and other are identical with Comparative Examples.Dehydration conditions before the polymerization, polymerization temperature are all identical with Comparative Examples.
Example 1～example 6 all adopts dry air rather than nitrogen.
Example 1～example 3 adopts 20 liters of awl end ribbon screws to stir polymeric kettle (vertical), and 20 rev/mins of rotating speeds, polymerization time were respectively 20 minutes, 25 minutes, 30 minutes.
Example 4～example 6 adopts 20 liters of double-screw types to stir polymeric kettle (horizontal), and 20 rev/mins of rotating speeds, polymerization time were respectively 20 minutes, 25 minutes, 30 minutes.
After polymerization time arrives, the polymeric kettle fast cooling, material enters the devolatilization still, 2 millimeters of the screen-apertures of devolatilization still, 4 millimeters of sieve aperture spacings by pressure difference or the promotion by polymerization stirrer.Vacuum tightness is-0.01～-0.02MPa, the devolatilization temperature is 95 ℃.Material entered the devolatilization still and finishes devolatilization in 10 minutes, the material after the devolatilization is expressed in the packing bag by the discharging forcing machine, the sampling analysis and the packing of weighing.
Aspect molecular weight control: prior art adopts visual control, and the present invention can be by the control of agitator power output valve;
The deviation of the highest in the polymerization system/lowest molecular weight and molecular-weight average (ten thousand): prior art 5～30, best level are less than 10, and the present invention is less than 5;
Fugitive constituent (wt%): prior art is greater than 0.1, and the present invention is less than 0.1.
The same Comparative Examples of analytical procedure.
Table 1: during the product analysis data of example 1～example 6 and Comparative Examples are listed in the table below
| Project | Polymerization time (minute) | Contents of ethylene (mol%) | Fugitive constituent (wt%) | Molecular weight (ten thousand) | Molecular weight deviation (ten thousand) |
| Example 1 | 20 | 0.4 | 0.09 | 73 | 1.4 |
| Example 2 | 25 | 0.4 | 0.05 | 108 | 2.5 |
| Example 3 | 30 | 0.4 | 0.06 | 135 | 4.1 |
| Example 4 | 20 | 0.4 | 0.08 | 68 | 0.8 |
| Example 5 | 25 | 0.4 | 0.08 | 97 | 3.2 |
| Example 6 | 30 | 0.4 | 0.04 | 141 | 4.7 |
| Contrast | 25 | 0.4 | 0.15 | 106 | 8.5 |
Claims (8)
1, a kind of polymerization process based on crude rubber of fluorinated silicone rubber is characterized in that, comprises the steps:
1., at first prepare polymer raw, polymer raw adopts fluorine silicon monomer D3F, vinyl silicon monomer, alkaline assistant, and the molar ratio of ethene silicon monomer/D3F is controlled at 1/1000～1/100, and polymer raw comprises following each component by mass fraction:
Fluorine silicon monomer D3F:100, the vinyl silicon monomer: 0.05～0.5,
Alkaline assistant: 0.1～1;
2., need to carry out earlier mixed dehydration before the material polymerization, dehydration conditions is-0.01～-0.02MPa, 60～80 ℃, 1.5～4 hours; Material enters polymeric kettle then, concrete polymerizing condition is 110～140 ℃ of temperature, 10～60 minutes time, need according to molecular weight, come the terminal point of controlled polymerization reaction by the power output valve of whipping appts, stirring velocity generally is controlled at 5～50 rev/mins, feeds the trace water that the exsiccant air is produced in time to take away condensation course in the polymerization process continuously;
3., after polymerization finishes, material enters the devolatilization still by pressure difference, the top of devolatilization still is furnished with sieve plate, material forms fine strip shape after by sieve plate,-0.01～-0.05MPa vacuum tightness under, remove volatile monomers residual in the material and moisture content, the devolatilization temperature is generally 80～110 ℃;
4., in the bottom of devolatilization still, the fine strip shape mixed with polymers enters the discharging forcing machine, polymkeric substance is by forcing machine mixing discharging.
2, in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The 1. described alkaline assistant of step is selected corresponding silicon alkoxide such as sodium hydroxide, potassium hydroxide, quaternary ammonium hydroxide, lithium hydroxide, first-selected silanol sodium salt, its alkali content is controlled at 0.1～1wt%, and its viscosity controller is at 10～80Pas, and the ratio control of silanol sodium salt/D3F is at 0.1～1wt%.
3, in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The 1. described polymer raw of step comprises following each component by mass fraction:
Fluorine silicon monomer D3F:100, the vinyl silicon monomer: best 0.15～0.4,
Alkaline assistant: best 0.4～0.8.
4, in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The 2. described polymeric kettle of step adopts the double-screw type agitator, and polymeric kettle is horizontal.
5. in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The molecular weight of the 2. described polymerization terminal point control of step material is regulated in 50～1,500,000 scope, and the 2. described polymeric kettle of step adopts awl end ribbon screw agitator, and polymeric kettle is vertical.
6. in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
Step is 3. described, and material enters with the form of elongate strip by specific sieve plate and removes the volatilization composition in the devolatilization still.
7. in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The top of the 3. described devolatilization still of step is furnished with sieve plate, general 0.5～5 millimeter of screen-aperture, 1～10 millimeter of sieve aperture spacing.
8. in the polymerization process of crude rubber of fluorinated silicone rubber according to claim 1, it is characterized in that:
The 3. described material of step enters the devolatilization still by the promotion of polymerization stirrer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824151A (en) * | 2010-04-29 | 2010-09-08 | 华东理工大学 | Method for synthesizing fluorine-silicon-oxygen polymer body through anion ring-opening polymerization and reactive extrusion |
| CN102134322A (en) * | 2011-02-08 | 2011-07-27 | 溧阳市利达有机硅科技有限公司 | Raw glue receptor and glue discharging device |
| CN102199291A (en) * | 2011-02-08 | 2011-09-28 | 溧阳市利达有机硅科技有限公司 | Crude rubber production system |
| CN103952079A (en) * | 2014-05-15 | 2014-07-30 | 桂林电器科学研究院有限公司 | Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof |
| CN104045832A (en) * | 2013-03-11 | 2014-09-17 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of vinyl-mono-capped fluorinated silicone raw-rubber |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960811A (en) * | 1989-06-16 | 1990-10-02 | General Electric Company | Fluorosilicone compositions with improved elastic response |
| US5171773A (en) * | 1991-11-13 | 1992-12-15 | Dow Corning Corporation | High strength fluorosilicone rubber |
| AU2001275302A1 (en) * | 2000-06-06 | 2001-12-17 | Board Of Trustees Of The University Of Illinois | Cross-coupling reaction of organosilicon nucleophiles |
| CN100386362C (en) * | 2005-06-13 | 2008-05-07 | 上海三爱富新材料股份有限公司 | Catalyst composition and preparation method of fluorine silicon contained polymer |
| CN1302048C (en) * | 2005-06-13 | 2007-02-28 | 上海三爱富新材料股份有限公司 | Fluorine-silicon compounded rubber stock and method for making same |
-
2006
- 2006-04-29 CN CNB2006100353047A patent/CN100412112C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824151A (en) * | 2010-04-29 | 2010-09-08 | 华东理工大学 | Method for synthesizing fluorine-silicon-oxygen polymer body through anion ring-opening polymerization and reactive extrusion |
| CN102134322A (en) * | 2011-02-08 | 2011-07-27 | 溧阳市利达有机硅科技有限公司 | Raw glue receptor and glue discharging device |
| CN102199291A (en) * | 2011-02-08 | 2011-09-28 | 溧阳市利达有机硅科技有限公司 | Crude rubber production system |
| CN102134322B (en) * | 2011-02-08 | 2012-10-03 | 溧阳市利达有机硅科技有限公司 | Raw glue receptor and glue discharging device |
| CN102199291B (en) * | 2011-02-08 | 2012-10-03 | 溧阳市利达有机硅科技有限公司 | Crude rubber production system |
| CN104045832A (en) * | 2013-03-11 | 2014-09-17 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of vinyl-mono-capped fluorinated silicone raw-rubber |
| CN103952079A (en) * | 2014-05-15 | 2014-07-30 | 桂林电器科学研究院有限公司 | Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof |
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| CN100412112C (en) | 2008-08-20 |
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