CN101250266A - Fluorine-silicon copolymer rubber and preparation method thereof - Google Patents
Fluorine-silicon copolymer rubber and preparation method thereof Download PDFInfo
- Publication number
- CN101250266A CN101250266A CNA2008100352274A CN200810035227A CN101250266A CN 101250266 A CN101250266 A CN 101250266A CN A2008100352274 A CNA2008100352274 A CN A2008100352274A CN 200810035227 A CN200810035227 A CN 200810035227A CN 101250266 A CN101250266 A CN 101250266A
- Authority
- CN
- China
- Prior art keywords
- monomer
- fluorine
- silicon
- copolymer rubber
- trifluoro propyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses a fluorine-containing silicon copolymer which comprises the fluorine-containing silicon copolymer which has the following general formula, wherein Me represents CH3-, Rf represents CF3 CH2 CH2-, wherein X/Y/Z=400-500/600-400/1-10, property molecular weight is 10-100 ten thousand, better is 30-80 ten thousand, molecular distribution parameter is 1-3, better is 1.2-1.8, and volatilization parts are less than 3%, and ethenyl chain link content is within 0.3-0.8%. And a preparation process of fluorine-containing silicon copolymer is disclosed.
Description
Technical field
The present invention relates to a kind of fluorine-silicon copolymer rubber and preparation method thereof.Relating in particular to a kind of high temperature and low-temperature stability, to reach cost well low, is easy to industrialized fluorosilicone copolymer rubber and preparation method thereof.
Background technology
Fluorine silicon homopolymerization rubber (for example poly-methyl trifluoro propyl siloxanes) has good oil resistant, low temperature resistant, weathering resistance and erosion resistance, as a kind of high performance elastomer, in aircraft industry, automotive industry important use is arranged.But the main drawback of fluorine silicon homopolymerization rubber (for example poly-methyl trifluoro propyl siloxanes) is the price height, and decomposes the low-molecular-weight ring body of generation easily under high temperature and sealed state, thereby has limited its application.In addition, along with the development of aeronautical technology, the resistance to low temperature of fluorine silicon homopolymerization rubber is had higher requirement, fluorine silicon homopolymerization rubber is difficult to satisfy the low temperature requirement of this higher category.
The price of fluorine silicon homopolymerization rubber is higher than no trifluoropropyl siloxane (for example methyl vinyl silicone rubber) far away, but the oil-proofness of not having trifluoropropyl siloxane is poor.Characteristic such as chain cracking easily takes place under high temperature and sealed state and reduce its cost for improving fluorine silicon homopolymerization rubber, simultaneously in order to solve the not grease-proof problem of no trifluoropropyl siloxane, the method that prior art has proposed not have trifluoropropyl siloxane and trifluoropropyl siloxane formation blend solves the oil-proofness of no trifluoropropyl siloxane and the high thermal resistance and the cost problem of fluorine silicon homopolymerization rubber.But there is the shortcoming of the easy layering of its cross-linked rubber, poor fatigue properties in this no trifluoropropyl siloxane/trifluoropropyl siloxane blend.
Therefore, it is not very high and under to high temperature resistant and situation that low temperature properties is had relatively high expectations, will not have trifluoropropyl siloxane and trifluoropropyl siloxane copolymerization formation fluorine-silicon copolymer rubber usually at some oil resistance being required.Because this moment is if select for use simple no trifluoropropyl siloxane then can not satisfy the requirement of oil resistance; And select for use simple trifluoropropyl siloxane can not make full use of its oil resistance, cause the unnecessary wasting of resources, and cost is too high.Adopt fluorine-silicon copolymer rubber both can reduce material cost, can overcome the shortcoming of no trifluoropropyl siloxane/easy layering of trifluoropropyl siloxane blend cross-linked rubber, poor fatigue properties again.
Known fluorine-silicon copolymer rubber has medium oil resistance and good heat-resistant, can also can be used in the environment that may be subjected to a small amount of fuel oil pollution uses such as elastic sealing element as uses such as gasket, oil sealings in the environment of the oily vapour of contact as the aviation electric connector.
But, be not arbitrarily fluorine-silicon copolymer rubber all can have the performance of two kinds of cosegments itself simultaneously.For example, in order to reduce cost and to improve high temperature, the low-temperature stability of fluorine silicon homopolymerization rubber, method with methyl trifluoro propyl cyclotrisiloxane and octamethylcyclotetrasiloxane copolymerization (promptly introducing the dimethyl silica alkyl structure in poly-methyl trifluoro propyl siloxane molecule chain) has been proposed, this method can reduce cost 40～50%, and obtains the fluorine-silicon copolymer rubber of the suitable high temperature of polymerization, low-temperature performance.But this method only is only applicable to this two kinds of certain monomers multipolymers, prior art all do not mention floride-free silicon monomer and other fluorine silicon monomer commonly used or do not have trifluoropropyl siloxane with the blend of other trifluoropropyl siloxane of using always in all have such characteristic.In fact when hexamethyl cyclotrisiloxane (floride-free silicon monomer) and methyl trifluoro propyl cyclotrisiloxane (fluorine silicon monomer) copolymerization, the multipolymer that obtains but has relatively poor low-temperature performance.
Although prior art has proposed some and has been applicable to the fluorine-silicon copolymer rubber of specific end use, but still need a kind of like this fluorine-silicon copolymer rubber of exploitation, it can be mainly used in to resistance toheat requirement height and to the oil resistance requirement is not very high position, for example, various types of vehicles wear ring, diaphragm, conduit, valve lining etc. in automotive industry; Equipment sealing products such as all kinds of high temperature resistant, low temperature, valve, oil tank in petrochemical industry; In aircraft industry, then can recommend to replace silicon rubber on the position of oily vapour of contact or industrial naptha clean-out system, to use.
Summary of the invention
One object of the present invention just provides a kind of fluorine-silicon copolymer rubber that has good low-temperature resistance, resistance toheat, weathering resistance and erosion resistance and have certain oil-proofness, it has higher molecular-weight average, moderate molecular weight distribution, has the higher transparency simultaneously, thereby solve fluorine silicon homopolymerization rubber and under high temperature and sealed state, decompose the low-molecular-weight ring body of generation easily, the problem of resistance to low temperature difference, and greatly reduce cost, so this fluorine-silicon copolymer rubber is more suitable for the commercial market except military.
Another object of the present invention provides a kind of preparation method of described fluorine-silicon copolymer rubber, and not only polymerization technique is simple for it, and synthesis of product molecules amount size is easy to control.
Therefore, one aspect of the present invention provides a kind of preparation method of fluorine-silicon copolymer rubber, and it comprises the steps:
(1) provides 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (following abbreviation D
3 F), described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) have a following structural formula:
In the formula, Me represents CH
3-, Rf represents CF
3CH
2CH
2-;
(2) provide octamethylcyclotetrasiloxane monomer (following abbreviation D
4 Me), described octamethylcyclotetrasiloxane monomer (D
4 Me) have a following structural formula:
Wherein, Me represents CH
3-;
(3) provide a kind of can be with described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer and octamethylcyclotetrasiloxane monomer carry out organosilicon ring body compound (the following abbreviation D that contains vinyl of ionic ring-opening copolymerization reaction
4 MeVi), the described organosilicon ring body compound that contains vinyl has following structural formula:
In the formula, Me represents CH
3-;
(4) provide a kind of catalyst component, described catalyst component is selected from the silicon alkoxide of potassium hydroxide, the silicon alkoxide of quaternary ammonium hydroxide or the silicon alkoxide of quaternary phosphonium alkali;
(5) in the presence of described catalyst component, make 3,3,3-trifluoro propyl methyl cyclotrisiloxane, octamethylcyclotetrasiloxane monomer and organosilicon ring body compound polymerase 10 .5～3 hour under 60～100 ℃ temperature.
The present invention also provides a kind of fluorine-silicon copolymer rubber that makes with aforesaid method, and this fluorine-silicon copolymer rubber has following structure:
Wherein, Me is CH
3-;
Rf is CF
3CH
2CH
2-;
X＝400～500；
Y＝600～400；
Z＝1～10；
Its characteristic molecular weight is 10～1,000,000, is preferably 30～800,000; Its molecular weight distribution coefficient is 1～3, is preferably 1.2～1.8; Its fugitive constituent＜3%; Its vinyl chain link content is between 0.3～0.8%.
Embodiment
The invention provides a kind of preparation method of fluorine-silicon copolymer rubber, it comprises provides 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (following abbreviation D
3 F) step, described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) have a following structural formula:
In the formula, Me represents CH
3-, Rf represents CF
3CH
2CH
2-.
Described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) be commercially available, for example it can be available from Sunhuan Chemical Co., Ltd., Zhejiang.
In polymerization reactant, described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) add-on be 100 weight parts.
In a better example of the present invention, before polymerization, need to 3,3 3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) dewater.Concrete dehydrating step comprises 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) join in the reinforced bottle, dewatered 1～3 hour down at negative pressure 1329～9303Pa (negative pressure 3000-7500Pa more fortunately), 60-90 ℃ (better 80 ℃).
The inventive method also comprises provides octamethylcyclotetrasiloxane monomer (following abbreviation D
4 Me) step, described octamethylcyclotetrasiloxane monomer (D
4 Me) have a following structural formula:
Wherein, Me represents CH
3-.
Described octamethylcyclotetrasiloxane monomer (D
4 Me) be commercially available, for example, described octamethylcyclotetrasiloxane monomer (following abbreviation D
4 Me) can be available from chemical industrial company of Japanese SHIN-ETSU HANTOTAI.
In polyblend, by 100 weight parts 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) meter, described octamethylcyclotetrasiloxane monomer (D
4 Me) add-on be the 60-100 weight part, be preferably the 65-90 weight part.
In a better example of the present invention, polymerization is preceding to octamethylcyclotetrasiloxane monomer (D
4 Me) dehydration, for example, can be with octamethylcyclotetrasiloxane monomer (D
4 Me) in the 30L stainless steel cauldron, dewater, dehydration conditions is that negative pressure 1329～9303Pa (negative pressure 3000-7500Pa more fortunately), 60-90 ℃ (better 80 ℃) dewatered 1～3 hour down.
The inventive method also comprise provide a kind of can be with described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer and octamethylcyclotetrasiloxane monomer carry out organosilicon ring body compound (the following abbreviation D that contains vinyl of ionic ring-opening copolymerization reaction
4 MeVi), the described organosilicon ring body compound that contains vinyl has following structural formula:
In the formula, Me represents CH
3-.
Described organosilicon ring body compound (D
4 MeVi) be commercially available.For example, it can be available from the Jiangxi Xinghuo Organic Silicone Plant.
Organosilicon ring body compound (D
4 MeVi) monomer plays the effect of sulfuration point in fluorine-silicon copolymer rubber, its consumption can have influence on the product properties of fluorine-silicon copolymer rubber.Therefore, by 100 weight parts 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer meter, D in the polyblend
4 MeViThe general 0.2-0.8 weight part of monomeric amount is preferably the 0.3-0.6 weight part.
In an example of the present invention, need before the polymerization organosilicon ring body compound (D
4 MeVi) monomer dewaters, for example, can be with D
4 MeViMonomer dewaters in the 30L stainless steel cauldron, and dehydration conditions is that negative pressure 1329～9303Pa (negative pressure 3000-7500Pa more fortunately), 60-90 ℃ (better 80 ℃) dewatered 1～3 hour down.
The silicon alkoxide that provides a kind of catalyst component, described catalyst component to be selected from potassium hydroxide, the silicon alkoxide of quaternary ammonium hydroxide or the silicon alkoxide of quaternary phosphonium alkali also are provided the inventive method.
In reaction mixture, the consumption of described catalyst component accounts for the 0.002-0.008 weight % of other component total amount, better accounts for 0.004-0.006 weight %.
First-selected silanol ammonium salt (be the silicon alkoxide of quaternary amine alkali, be called for short ammongelatine below) of described catalyst component or silanol sylvite (be the silicon alkoxide of potassium hydroxide, be called for short potassium glue below).Be applicable to that silanol ammonium salt of the present invention or silanol sylvite can be made by following reaction method respectively:
Perhaps
In above-mentioned catalyzer building-up process, its alkali ((CH for example
3)
4NOH or KOH) content generally is controlled at 0.5～1wt%, and its viscosity controller is at 20～60PaS, silanol ammonium salt/D
3 FRatio or silanol sylvite/D
3 FRatio control at 0.5～1wt%.
The inventive method also is included under the existence of described catalyst component and makes 3,3, the step of 3-trifluoro propyl methyl cyclotrisiloxane, octamethylcyclotetrasiloxane monomer and organosilicon ring body compound polymerase 10 .5～3 hour under 60～100 ℃ temperature.
In an example of the present invention, described method comprises dewaters respectively earlier to polymerization single polymerization monomer, is about to 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) join in the reinforced bottle, dewatered 1～3 hour down at negative pressure 1329～9303Pa (negative pressure 3000-7500Pa more fortunately), 60-90 ℃ (better 80 ℃); With D
4 MeMonomer and D
4 MeViMonomer dewaters in the 30L stainless steel cauldron, and dehydration conditions is negative pressure 1329～9303Pa, 60～90 ℃, dewaters 1～3 hour; Add catalyst component (ammongelatine) then and continue dehydration 0.5～2 hour under normal pressure in described 30L stainless steel cauldron, begin the polymerization that heats up, concrete polymerizing condition is 60～100 ℃ of temperature, 1～20 minute time, drips the D through dehydration then
3 F, drip off the back copolymerization about 0.5～3 hour.Can control the viscosity of multipolymer relatively by the rotating speed of whipping appts, mixing speed is generally 10～100 rev/mins.In the polymerization process by adding exsiccant nitrogen in time to take away the micro-moisture that the small amount of hydroxyl groups condensation reaction is produced.
Because the viscosity of polymer material can surpass 100Pas under polymerization temperature, and this multipolymer is viscoelastic fluid, and in order to strengthen the mass-and heat-transfer effect of polyreaction, the present invention adopts the 30L stainless steel polyreaction of discharging at the bottom of the still of being with helical ribbon agitator.Can control the viscosity of multipolymer relatively by the rotating speed of whipping appts, mixing speed is generally 10～100 rev/mins.
In another example of the present invention, described polyblend has following composition:
3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F): the 500-600 weight part;
Octamethylcyclotetrasiloxane monomer (D
4 Me): 300-550 weight part, better 400～500 weight parts;
Methyl ethylene cyclotetrasiloxane monomer (D
4 MeVi): 1～8 weight part is preferably 3～6 weight parts;
The silanol ammonium salt of 1 weight % concentration (or silanol sylvite): 2～8 weight parts are preferably 3～6 weight parts.
Because fluorine-silicon copolymer rubber is the product of thermodynamics nonequilibrium situations, usually after monomer conversion is greater than 95%, promptly reaches before the molecular weight maximum value stopped reaction immediately, so must contain unconverted monomer and polymer degradation products etc. in the polymkeric substance.Fugitive constituent is the important indicator of rubber quality, if volatile content is too high, then influences the dimensional stability and the electrical performance indexes of goods, therefore must to polymkeric substance in addition aftertreatment to remove fugitive constituent.In general, described post-treating method can have two kinds of methods:
A) remove fugitive constituent earlier in reactor, be rapidly heated then to 150 ℃ of half an hour, remove catalyzer, multipolymer passes through the nitrogen discharging from the reactor lower discharge port; Perhaps
B) after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.
Generally speaking, two kinds of methods all can obtain fluorine-silicon copolymer rubber of the present invention, and the test of gained rubber performance is also similar, but the molecular weight distribution of the co-polymer that a kind of method in back obtains is even relatively.
The synthetic method of fluorosilicone of the present invention-dimethyl siloxane copolymer rubber adopts 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F), octamethylcyclotetrasiloxane monomer (D
4 Me) be principal monomer, under catalyst action and a small amount of methyl ethylene cyclotetrasiloxane (D
4 MeVi) carry out copolymerization, by suitable polymerization process, can obtain the fluorosilicone-dimethyl siloxane copolymer rubber of molecular weight adjustable excellent performance in 10～1,000,000 scopes.
The invention solves above-mentioned existing technical problem, and have the following advantages than the polymerization process of fluorine silicon homopolymerization rubber:
A. polymeric segment adopts the ribbon stirring to make polymerization system obtain mixing relatively fully and Surface Renewal.Can control the viscosity of multipolymer relatively by the rotating speed of whipping appts.
B. the bottom discharge mode can reduce out the still number of times, has improved working efficiency.
C. the catalyzer ammongelatine is temporary catalyzer, can remove catalyzer easily through 15～30 minutes under certain temperature, negative pressure.
D. after polymerization is finished, polymkeric substance is placed on enters baking oven catalyzer through removing in the polymkeric substance in 15～30 minutes under certain temperature, negative pressure in the enamel tray, advantage has been to increase the specific surface area of material, both can remove catalyzer fast, can remove residual volatile component fast again, improve the homogeneity of product.
From the polymerization angle, institute's synthetic polymer water white transparency does not have thing to be drawn out of under high temperature, high vacuum substantially, proves the complete copolymerization of this polymkeric substance.With this understanding, then extract out already if any monomer, and product yield is more than 96%, simultaneously, if two kinds of monomers polymerization or part copolymerization respectively, then polymkeric substance presents oyster white.
Product testing dynamic thermomechanometry (DMA) behind institute's synthetic fluorine-silicon copolymer rubber post vulcanization: have only a peak on the spectrogram, prove copolymerization.Transition temperature: between-93 ℃～-116 ℃.Fluorine silicon homopolymerization rubber two-stage vulcanizes back product testing DMA in addition.Has only a peak on the spectrogram, transition temperature: about-64 ℃.
Product testing dsc DSC behind institute's synthetic fluorine-silicon copolymer glue post vulcanization.Second-order transition temperature (D
3 F: D
4 Me=500: 500) between-104 ℃～-116 ℃, (D
3 F: D
4 Me=600: 400) between-93 ℃～-103 ℃, prove copolymerization.Because reaction is random copolymerization, so the composition of different sites is not quite identical, so second-order transition temperature is an interval, rather than a point.
The present invention also provides a kind of usefulness fluorine-silicon copolymer rubber that above-mentioned the inventive method makes, and this fluorine-silicon copolymer rubber has following structure:
Wherein, Me is CH
3-;
Rf is CF
3CH
2CH
2-;
X＝400～500；
Y＝600～400；
Z＝1～10；
Its characteristic molecular weight is 10～1,000,000, is preferably 30～800,000; Its molecular weight distribution coefficient is 1～3, is preferably 1.2～1.8; Its fugitive constituent＜3%; Its vinyl chain link content is between 0.3～0.8%.
The fluorine-silicon copolymer rubber that makes with the inventive method is a kind of rubber, of the present invention some preferably in the example, the performance of the ripe glue that this fluorine-silicon copolymer rubber sulfuration processing forms later is as shown in table 1 below:
Table 1
| Hardness/degree | Tensile strength/MPa | Elongation rate of tensile failure/% | Rebound degree | Anti-with reference to fuel oil B (23 ℃, 24h) quality change | Tear strength KN/m | Second-order transition temperature (℃) |
| 70 | 8.3 | 321 | 30 | 78 | 13.26 | -108 |
| 68 | 6.9 | 314 | 30 | 53 | 14.21 | -95 |
| 70 | 7.4 | 368 | 31 | 58 | 14.54 | -98 |
| 69 | 7.9 | 314 | 30 | 59 | 13.88 | -99 |
| 67 | 7.0 | 315 | 28 | 60 | 12.86 | -101 |
| 69 | 7.5 | 357 | 28 | 65 | 14.28 | -103 |
| 68 | 8.3 | 413 | 30 | 51 | 15.32 | -93 |
As known from Table 1:
The processing characteristics of a fluorine-silicon copolymer rubber rubber is identical with fluorine silicon homopolymerization rubber raw rubber, can satisfy the requirement of rubber processing;
B fluorine-silicon copolymer rubber cross-linked rubber is compared with fluorine silicon homopolymerization vulcanization of rubber glue, the fluorine-silicon copolymer rubber mechanical properties of vulcanizate and the fluorine silicon homopolymerization vulcanization of rubber are gluedd joint near, particularly the low-temperature performance of fluorine-silicon copolymer rubber is more much better than fluorine silicon homopolymerization rubber, can be at-60 ℃ of following life-time service.
Though the oil resistance of c fluorine-silicon copolymer rubber cross-linked rubber is more less better than fluorine silicon homopolymerization vulcanization of rubber glue, anti-as fluorine-silicon copolymer rubber cross-linked rubber at room temperature 24 hours is 51～78% with reference to the quality change behind the fuel oil B, and fluorine silicon homopolymerization vulcanization of rubber glue only is 12%, but still can satisfy the oil resistant requirement of general grade.
D compares with fluorine silicon homopolymerization rubber raw rubber because of the price of fluorine-silicon copolymer rubber rubber, can reduce near half, have the good ratio of performance to price.
Below, further specify the present invention in conjunction with the embodiments.In an embodiment, except as otherwise noted, otherwise all part and percentage number average are benchmark with weight.
Preparation embodiment
A)
Preparation silanol ammonium salt in catalysis agent component (ammongelatine):
With 3.2g (N (CH
3)
4OHnH2O 25%) be put in the 500ml there-necked flask,, then that catalyzer is fine ground with infrared lamp according to the moisture of removing 90%, add 80g D
4 Me, in 55 ℃ of dehydrations 1 hour, be warming up to 65～80 ℃ then, polymerization discharging about 5～30 minutes, bottling is weighed, and the alkali content of measuring gained silanol ammonium salt is about 0.85%, and viscosity is 10～80Pas.It is standby that the moisture eliminator inner drying is put in sealing.
B) preparation silanol sylvite catalyst component (potassium glue):
1gKOH (content 〉=99.9%) is put in the 500ml there-necked flask,, then that catalyzer is fine ground with infrared lamp according to removing moisture, add 100g D
4 Me, in 70～100 ℃ of dehydrations 1 hour, be warming up to 110～140 ℃ then, polymerization discharging about 5～30 minutes, bottling is weighed, and the alkali content of measuring gained silanol ammonium salt is about 0.85%, and viscosity is 10～80Pas.It is standby that the moisture eliminator inner drying is put in sealing.
Test method
1. test the molecular weight of trifluoropropyl siloxane
Adopt the absolute molecular weight of light-scattering photometer and gel permeation chromatography (GPC) coupling test hot sulfurization trifluoropropyl siloxane.
Light-scattering photometer: instrument model: DAWN HELEOS optical maser wavelength: 658.0nm; Calibration constants: 2.3368e-4 l/ (V cm); Flow rate: 1.000ml/min; Concentrate wave-detector: RI;
GPC: instrument model: Waters515; Probe temperature: 25 ℃; Solvent is tetrahydrofuran (THF) (THF).
2. test the contents of ethylene in the fluorine-silicon copolymer thing
Adopt the contents of ethylene in the chemistry titration method test fluorine silicon multipolymer.Solvent uses butylacetate (AR), and probe temperature is 25 ℃.
3. test the content of fugitive constituent
Measure the fugitive constituent of fluorine silicon multipolymer by Shanghai City company standard Q/GHAC12-2002.
Embodiment 1
Polymerization procedure
With 5kg octamethylcyclotetrasiloxane monomer (D
4 Me), 30g methyl ethylene cyclotetrasiloxane monomer (D
4 MeVi) filter through the 2# sand core funnel, add in the pre-dry 30L stainless steel polymerization reaction kettle.With 5kg D
3 FAdd in the water trap,, use electrically heated in the still with the infrared lamp heating.
Need before the material polymerization to dewater respectively earlier, dewater in advance with dry N2, i.e. D
4 MeMonomer and D
4 MeViMonomer dewaters in the 30L stainless steel cauldron, and dehydration conditions is negative pressure 9303Pa, 70 ℃, dewaters D 2 hours
3 FJoin in the reinforced bottle and dewater, dehydration conditions is negative pressure 7974Pa, 80 ℃ of following dehydrations 2 hours, catalyst component (ammongelatine) 60g that makes above adding under normal pressure then continues dehydration 1 hour in the 30L stainless steel cauldron, begin the polymerization that heats up, concrete polymerizing condition is 68 ℃ of temperature, 2 minutes time, drip D then
3 F, drip off the back copolymerization temperature: 120 ℃, the time: 60 minutes.In the polymerization process by adding exsiccant nitrogen in time to take away the micro-moisture that the small amount of hydroxyl groups condensation reaction is produced.
Post-processing step
After polyreaction finishes, remove fugitive constituent earlier in reactor, be rapidly heated then to 150 ℃ of half an hour, remove catalyzer, under the pushing effect of nitrogen and helical ribbon agitator, multipolymer passes through the nitrogen discharging from the reactor lower discharge port.
Test the absolute molecular weight of hot sulfurization trifluoropropyl siloxane, contents of ethylene in the fluorine silicon multipolymer and the fugitive constituent of fluorine silicon multipolymer respectively with top method, the results are shown in table 2.
Embodiment 2
Repeat embodiment 1 described step, just polymerization time is 40 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 3
Repeat embodiment 1 described step, just polymerization time is 80 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 4
Repeat embodiment 1 described step, just polymerization time is 100 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 5
Repeat embodiment 1 described step, just polymerization time is 120 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 6
Repeat embodiment 1 described step, just polymerization time is 60 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 7
Repeat embodiment 1 described step, just polymerization time is 80 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 8
Repeat embodiment 1 described step, just polymerization time is 100 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 9
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 60 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 10
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 80 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 11
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 100 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 12
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 60 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 13
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 80 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 14
Repeat embodiment 1 described step, just polymerization single polymerization monomer D
3 FConsumption be 6kg, D
4 MeConsumption be 4kg, polymerization time is 100 minutes.Post processing mode: after polyreaction finishes, remove earlier fugitive constituent in reactor, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, is rapidly heated then to 150 ℃ of half an hour, removes catalyzer.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 15
Repeat embodiment 1 described step, just catalyst component is a potassium glue, and its consumption is 60 grams, and polymerization time is 60 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 16
Repeat embodiment 1 described step, just catalyst component is a potassium glue, and its consumption is 60 grams, and polymerization time is 80 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Embodiment 17
Repeat embodiment 1 described step, just catalyst component is a potassium glue, and its consumption is 60 grams, and polymerization time is 100 minutes.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Comparative example 1
Repeat the step of embodiment 1, just polymerization single polymerization monomer D
3 FPurity be 95%.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Comparative example 2
Repeat the step of embodiment 1, just polymerization single polymerization monomer D
3 FPurity be 98%.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Comparative example 3
Repeat the step of embodiment 1, just polymerizing catalyst is an ammongelatine, and consumption is 40g.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Comparative example 4
Repeat the step of embodiment 1, just polymerizing catalyst is an ammongelatine, and consumption is 80g.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
Comparative example 5
Repeat the step of embodiment 1, just polymerizing catalyst is an ammongelatine, and consumption is 100g.Respectively get 6 comparisons of carrying out molecular weight distribution at the different sites of the polymkeric substance that makes, the results are shown in table 2.
By embodiment 1,2,3,4,5 as seen, under the identical prerequisite of other conditions, polymerization reaction time is long more, and the molecular weight of polymkeric substance is big more.
By embodiment 6,7,8 as seen, after polyreaction finishes, in reactor, remove earlier fugitive constituent, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, be rapidly heated then, remove catalyzer to 150 ℃ of half an hour.After advancing the baking oven aftertreatment, the fugitive constituent of co-polymer greatly reduces.
By embodiment 9,10,11 as seen, reaction monomers changes to some extent, monomer D
4 MeConsumption becomes 4kg by 5kg, monomer D
3 FConsumption becomes 6kg by 5kg, and this mainly is that co-polymer is found this other better performances of multipolymer sulfuration back when vulcanizing the processing characteristics test, but oil resistance is relatively poor relatively, because fluorochemical monomer has excellent oil resistance, therefore, suitably improves monomer D
3 F, this co-polymer sulfuration back oil resistance before is greatly improved.
By embodiment 12,13,14 as seen, monomer D
4 MeConsumption becomes 4kg by 5kg, monomer D
3 FAfter consumption becomes 6kg by 5kg, advance the baking oven aftertreatment after, the fugitive constituent of co-polymer greatly reduces, cured properties is better.
By embodiment 15,16,17 as seen, be catalyzer with potassium glue, copolyreaction speed is more steady, by regulating polymerization temperature, vacuum tightness and dripping D
3 FThe monomer time, institute's synthetic fluorine-silicon copolymer rubber is more and more transparent.But because this reaction is the anionic ring-opening polymerization reaction, ability ring-opening polymerization under negative pressure condition, D
4 MeBoiling point be 175.8 ℃/760mmHg, and play poly-temperature more than 128 ℃, the big slightly monomer of vacuum tightness just is drawn out of reaction system, so polymericular weight is done not quite.Therefore,, want the fluorine-silicon copolymer rubber of synthetic macromolecule amount, more highly active catalyzer must be arranged though catalyzer potassium glue can synthesize fluorine-silicon copolymer rubber.
By comparative example 1,2 as seen, as monomer D
3 FPurity is 95% o'clock, and polyreaction then can not be carried out; As monomer D
3 FPurity is 98% o'clock, and final resulting polymers is that molecular weight is very little.
By comparative example 3,4,5 and embodiment 1 as seen, weight by monomer mixture, the consumption of silanol ammonium salt in catalysis agent component under the similar substantially situation of polymerization temperature and time, all can obtain the close full-bodied polymer of molecular weight in 0.002～0.008% scope.In certain catalyst levels scope, catalyst levels does not have obvious influence to polymericular weight.But catalyst consumption should not be very little, otherwise often because of the influence of introduced contaminants, make catalyst failure cause the polyreaction failure, catalyzer is too many, and molecular weight of copolymer does not increase, therefore, by repeated experiments, the optimum amount of determining catalyst component is about 0.006%.
Can see by last table, after polyreaction finishes, in reactor, remove earlier fugitive constituent, multipolymer directly passes through the nitrogen discharging from the reactor lower discharge port then, material is placed on enters baking oven in the enamel tray, be rapidly heated then, remove catalyzer to 150 ℃ of half an hour.The co-polymer molecular weight distribution that this method obtains is even relatively.
In sum, in the still reaction process, by selection to polymer monomer, catalyzer and consumption thereof, polymerization reaction time and post processing mode.Obtain a kind of fluorosilicone-dimethyl siloxane copolymer rubber with good low-temperature resistance, resistance toheat, weathering resistance and erosion resistance.Not only polymerization technique is simple for it, and synthesis of product molecules amount size is easy to control, have higher molecular-weight average, moderate molecular weight distribution, the silicon-fluorine polymer thing that makes simultaneously has the higher transparency, thereby solve fluorine silicon homopolymerization rubber and under high temperature and sealed state, decompose low-molecular-weight ring body, the problem of resistance to low temperature difference of producing easily.
Embodiment 18-24
The rubber of embodiment 8-14 is processed into ripe glue through sulfuration, tests its performance, data are listed in table 4 (table 3 provides the performance of embodiment 8-14 rubber):
Table 3
| Embodiment | Form (D 3 F∶D 4 Me) | Polymkeric substance number-average molecular weight (ten thousand) | Fugitive constituent (%) | Contents of ethylene ‰ | The product transparency |
| 8 | 500∶500 | 43 | 1.5 | 3.2 | Water white transparency |
| 9 | 600∶400 | 38 | 2.7 | 3.5 | Water white transparency |
| 10 | 600∶400 | 46 | 2.4 | 3.4 | Water white transparency |
| 11 | 600∶400 | 55 | 2.3 | 3.6 | Water white transparency |
| 12 | 600∶400 | 36 | 1.7 | 3.3 | Water white transparency |
| 13 | 600∶400 | 44 | 1.5 | 3.2 | Water white transparency |
| 14 | 600∶400 | 52 | 1.4 | 3.5 | Water white transparency |
Table 4
| Embodiment | Hardness/degree | Tensile strength/MPa | Elongation rate of tensile failure/% | Rebound degree | Anti-with reference to fuel oil B (23 ℃, 24h) quality change | Tear strength KN/m | Second-order transition temperature (℃) |
| 18 | 70 | 8.3 | 321 | 30 | 78 | 13.26 | -108 |
| 19 | 68 | 6.9 | 314 | 30 | 53 | 14.21 | -95 |
| 20 | 70 | 7.4 | 368 | 31 | 58 | 14.54 | -98 |
| 21 | 69 | 7.9 | 314 | 30 | 59 | 13.88 | -99 |
| 22 | 67 | 7.0 | 315 | 28 | 60 | 12.86 | -101 |
| 23 | 69 | 7.5 | 357 | 28 | 65 | 14.28 | -103 |
| 24 | 68 | 8.3 | 413 | 30 | 51 | 15.32 | -93 |
Claims (8)
1. the preparation method of a fluorine-silicon copolymer rubber, it comprises the steps:
(1) provide 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) have a following structural formula:
In the formula, Me represents CH
3-, Rf represents CF
3CH
2CH
2-;
(2) provide the octamethylcyclotetrasiloxane monomer, described octamethylcyclotetrasiloxane monomer has following structural formula:
Wherein, Me represents methyl;
(3) provide a kind of can be with described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer and octamethylcyclotetrasiloxane monomer carry out the organosilicon ring body compound that contains vinyl of ionic ring-opening copolymerization reaction, and the described organosilicon ring body compound that contains vinyl has following structural formula:
In the formula, Me represents CH
3-;
(4) provide a kind of catalyst component, described catalyst component is selected from the silicon alkoxide of potassium hydroxide, the silicon alkoxide of quaternary ammonium hydroxide or the silicon alkoxide of quaternary phosphonium alkali;
(5) in the presence of described catalyst component, make 3,3,3-trifluoro propyl methyl cyclotrisiloxane, octamethylcyclotetrasiloxane monomer and organosilicon ring body compound polymerase 10 .5～3 hour under 60～100 ℃ temperature.
2. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1, it is characterized in that described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, octamethylcyclotetrasiloxane monomer, contain the purity of organosilicon ring body compound of vinyl all greater than 99.5%.
3. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1, it is characterized in that it also comprises described 3 before polyreaction, 3,3-trifluoro propyl methyl cyclotrisiloxane monomer, octamethylcyclotetrasiloxane monomer, contain the organosilicon ring body compound of vinyl and the step that catalyst component dewaters respectively.
4. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1 is characterized in that, by 100 weight parts 3,3, and 3-trifluoro propyl methyl cyclotrisiloxane monomer meter, described octamethylcyclotetrasiloxane monomer (D
4 Me) add-on be the 60-100 weight part, be preferably the 65-90 weight part.
5. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1, it is characterized in that, by 100 weight parts 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer meter, contain the general 0.2-0.8 weight part of amount of the organosilicon ring body compound of vinyl in the polyblend, be preferably the 0.3-0.6 weight part.
6. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1, it is characterized in that the amount that catalyst component adds accounts for described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, octamethylcyclotetrasiloxane monomer, contain vinyl organosilicon ring body compound gross weight 0.002%～0.8%, better account for 0.005%-0.006%.
7. the preparation method of fluorine-silicon copolymer rubber as claimed in claim 1 is characterized in that described catalyst component is the silanol ammonium salt, and polymerization pressure is 2,000-4,000Pa.
8. fluorine silicon polymkeric substance that makes with each described method among the claim 1-7, this fluorine-silicon copolymer rubber has following structure:
Wherein, Me is CH
3-;
Rf is CF
3CH
2CH
2-;
X＝400～500；
Y＝600～400；
Z＝1～10；
Its characteristic molecular weight is 10～1,000,000, is preferably 30～800,000; Its molecular weight distribution coefficient is 1～3, is preferably 1.2～1.8; Its fugitive constituent＜3%; Its vinyl chain link content is between 0.3～0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100352274A CN101250266B (en) | 2008-03-27 | 2008-03-27 | Fluorine-silicon copolymer rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100352274A CN101250266B (en) | 2008-03-27 | 2008-03-27 | Fluorine-silicon copolymer rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101250266A true CN101250266A (en) | 2008-08-27 |
| CN101250266B CN101250266B (en) | 2011-09-07 |
Family
ID=39953882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100352274A Active CN101250266B (en) | 2008-03-27 | 2008-03-27 | Fluorine-silicon copolymer rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101250266B (en) |
Cited By (16)
| 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 |
| CN102220014A (en) * | 2011-06-01 | 2011-10-19 | 山东大学 | High-strength fluorinated silicone rubber gross rubber and preparation method thereof |
| CN102225997A (en) * | 2011-06-02 | 2011-10-26 | 山东大学 | Preparation method of raw fluorinated silicone rubber with high molecular weight |
| CN102775613A (en) * | 2012-08-10 | 2012-11-14 | 广州天赐高新材料股份有限公司 | Method for preparing alpha, omega-bis(aminopropyl)polydimethylsiloxane |
| CN104436763A (en) * | 2014-11-14 | 2015-03-25 | 衢州氟硅技术研究院 | Fluorosilicone defoaming agent and preparation method thereof |
| CN104927056A (en) * | 2015-06-29 | 2015-09-23 | 深圳市森日有机硅材料有限公司 | Preparation method for synthesizing vinyl fluorosilicone oil through double-component catalytic system |
| CN105384937A (en) * | 2015-12-16 | 2016-03-09 | 江南大学 | Preparation method of hydroxypropylfluorosilicone |
| CN107141480A (en) * | 2017-06-15 | 2017-09-08 | 怀化学院 | A kind of high anti-swelling fluorine silicon raw rubber and preparation method thereof |
| CN107278214A (en) * | 2016-02-01 | 2017-10-20 | 株式会社Lg化学 | New polysiloxane and the Copolycarbonate prepared using the polysiloxane |
| CN107643652A (en) * | 2017-10-31 | 2018-01-30 | 武汉华星光电技术有限公司 | Nano-imprint stamp and preparation method thereof and application |
| CN108373595A (en) * | 2018-03-30 | 2018-08-07 | 长春物恒新技术有限公司 | A kind of copolymerization fluorine silicone grease composition |
| CN108503838A (en) * | 2018-03-18 | 2018-09-07 | 长春物恒新技术有限公司 | A kind of liquid copolymeric fluorine silicon raw rubber based on isopropyl alcohol extraction method |
| CN109851788A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of silicone terminated dose of copoly type fluorine and fluorine silicon liquid glue and preparation method thereof |
| CN109851789A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of add-on type fluorine silicon liquid glue and preparation method thereof |
| CN109943300A (en) * | 2019-04-10 | 2019-06-28 | 北京大德广源石油技术服务有限公司 | Silicon amine base drilling fluids and preparation method thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
Family Cites Families (7)
| 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 |
| JPH05279481A (en) * | 1992-03-31 | 1993-10-26 | Toray Dow Corning Silicone Co Ltd | Fluorosilicon block copolymer and its production |
| WO2004051648A1 (en) * | 2002-12-02 | 2004-06-17 | Matsushita Electric Industrial Co., Ltd. | Adaptive equalization circuit and adaptive equalization method |
| US7084229B2 (en) * | 2003-03-20 | 2006-08-01 | Shin-Etsu Chemical Co., Ltd. | Silicone composition for release agent |
| CN1258194C (en) * | 2003-08-12 | 2006-05-31 | 宋福如 | Application of fluorinated silicone rubber to prepare synthetic insulator |
| DE102004058550A1 (en) * | 2004-12-03 | 2006-06-14 | Sms Demag Ag | CSP continuous caster with roller hearth furnace and swivel ferries |
| 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 |
-
2008
- 2008-03-27 CN CN2008100352274A patent/CN101250266B/en active Active
Cited By (21)
| 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 |
| CN102220014A (en) * | 2011-06-01 | 2011-10-19 | 山东大学 | High-strength fluorinated silicone rubber gross rubber and preparation method thereof |
| CN102220014B (en) * | 2011-06-01 | 2013-04-03 | 山东大学 | High-strength fluorinated silicone rubber gross rubber and preparation method thereof |
| CN102225997A (en) * | 2011-06-02 | 2011-10-26 | 山东大学 | Preparation method of raw fluorinated silicone rubber with high molecular weight |
| CN102775613A (en) * | 2012-08-10 | 2012-11-14 | 广州天赐高新材料股份有限公司 | Method for preparing alpha, omega-bis(aminopropyl)polydimethylsiloxane |
| CN104436763A (en) * | 2014-11-14 | 2015-03-25 | 衢州氟硅技术研究院 | Fluorosilicone defoaming agent and preparation method thereof |
| CN104927056A (en) * | 2015-06-29 | 2015-09-23 | 深圳市森日有机硅材料有限公司 | Preparation method for synthesizing vinyl fluorosilicone oil through double-component catalytic system |
| CN104927056B (en) * | 2015-06-29 | 2017-10-13 | 深圳市森日有机硅材料股份有限公司 | A kind of preparation method of double-component catalyst system synthesis of vinyl fluorosilicon oil |
| CN105384937A (en) * | 2015-12-16 | 2016-03-09 | 江南大学 | Preparation method of hydroxypropylfluorosilicone |
| CN105384937B (en) * | 2015-12-16 | 2018-03-23 | 江南大学 | A kind of preparation method of hydroxypropyl flucride siloxane |
| CN107278214A (en) * | 2016-02-01 | 2017-10-20 | 株式会社Lg化学 | New polysiloxane and the Copolycarbonate prepared using the polysiloxane |
| CN107141480A (en) * | 2017-06-15 | 2017-09-08 | 怀化学院 | A kind of high anti-swelling fluorine silicon raw rubber and preparation method thereof |
| CN107141480B (en) * | 2017-06-15 | 2019-07-12 | 怀化学院 | A kind of high anti-swelling fluorine silicon raw rubber and preparation method thereof |
| CN107643652A (en) * | 2017-10-31 | 2018-01-30 | 武汉华星光电技术有限公司 | Nano-imprint stamp and preparation method thereof and application |
| US10520807B2 (en) | 2017-10-31 | 2019-12-31 | Wuhan China Star Optoelectronics Technology Co., Ltd. | Nanoimprint template, a method of making the same and applications thereof |
| CN108503838A (en) * | 2018-03-18 | 2018-09-07 | 长春物恒新技术有限公司 | A kind of liquid copolymeric fluorine silicon raw rubber based on isopropyl alcohol extraction method |
| CN108373595A (en) * | 2018-03-30 | 2018-08-07 | 长春物恒新技术有限公司 | A kind of copolymerization fluorine silicone grease composition |
| CN109851788A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of silicone terminated dose of copoly type fluorine and fluorine silicon liquid glue and preparation method thereof |
| CN109851789A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of add-on type fluorine silicon liquid glue and preparation method thereof |
| CN109943300A (en) * | 2019-04-10 | 2019-06-28 | 北京大德广源石油技术服务有限公司 | Silicon amine base drilling fluids and preparation method thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101250266B (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101250266B (en) | Fluorine-silicon copolymer rubber and preparation method thereof | |
| CN102220014B (en) | High-strength fluorinated silicone rubber gross rubber and preparation method thereof | |
| CA2100995C (en) | Combinations of polyorganosiloxanes and fluororubbers containing double bonds by si-h addition | |
| CN108976816B (en) | Addition type liquid fluorosilicone rubber composition and preparation method thereof | |
| CN107353871B (en) | High-temperature-resistant bonding sealing silicone resin and preparation method thereof | |
| CN102219907B (en) | Poly(diphenyl-dimethyl siloxane) with terminals sealed by alkyloxy groups, and preparation method thereof | |
| CN101376709A (en) | Preparation of hydroxy end capped poly(methyl(trifluoropropyl) siloxane) | |
| CN104004191A (en) | Fluorosiloxane copolymer and preparing method thereof | |
| CN101177486A (en) | Method for preparing fluorine silicon rubber base glue | |
| CN112280041B (en) | Preparation method of amino silicone oil with low organosilicon ring body content | |
| CN100386362C (en) | Catalyst composition and preparation method of fluorine silicon contained polymer | |
| CN105778104B (en) | A kind of add-on type liquid fluorine silicon rubber base glue and preparation method thereof | |
| CN115181270A (en) | Ternary polymerization fluorosilicone rubber and preparation method thereof | |
| CN104327268A (en) | Siloxane copolymer containing ethyl phenyl silica chain links and preparation method thereof | |
| CN103289095A (en) | A synthesis method of high viscosity alpha, omega-dihydroxy polydimethylsiloxane | |
| CN106753217A (en) | A kind of preparation method of Novel hot vulcanized liquid silicon rubber | |
| CN104628920B (en) | Preparation method of solution polymerized ethylene propylene (EP) rubber | |
| CN115403773B (en) | High-fatigue fluorosilicone rubber compound, anti-fatigue agent and preparation method thereof | |
| CN103739845A (en) | Preparation method for high molecular weight fluorosilicone raw rubber | |
| CN102690417A (en) | Preparation method of crude liquid fluorosilicone rubber by means of room temperature vulcanization | |
| CN110982282B (en) | Fluorosilicone rubber composition and preparation method thereof | |
| CN103739844A (en) | Preparation method of heat curing fluorosilicone raw rubber | |
| CN104263278B (en) | A kind of cross-linking agent used by LED packaging plastic and preparation method thereof | |
| CN114381001B (en) | Preparation method of solvent-resistant fluorosilicone rubber with wide temperature range and composition thereof | |
| CN113336945A (en) | Siloxane polymer with phenylene (phenylene) main chain and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180528 Address after: 200025 Xujiahui Road, Huangpu District, Shanghai, room 1301, room 560 Patentee after: Shanghai 3F new Mstar Technology Ltd Address before: No. 4411 Longwu Road, Shanghai City, Shanghai Patentee before: Sanaifu New Material Co., Ltd., Shanghai |
|
| TR01 | Transfer of patent right | ||
| CP03 | Change of name, title or address |
Address after: Room 801, 560 Xujiahui Road, Huangpu District, Shanghai 200025 Patentee after: Shanghai Huayi sanaifu New Material Co., Ltd Address before: 200025 Xujiahui Road, Shanghai, room 560, No. 1301, room Patentee before: SHANGHAI 3F NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CP03 | Change of name, title or address |