CN100386362C - Catalyst composition and preparation method of fluorine silicon contained polymer - Google Patents
Catalyst composition and preparation method of fluorine silicon contained polymer Download PDFInfo
- Publication number
- CN100386362C CN100386362C CNB2005100266896A CN200510026689A CN100386362C CN 100386362 C CN100386362 C CN 100386362C CN B2005100266896 A CNB2005100266896 A CN B2005100266896A CN 200510026689 A CN200510026689 A CN 200510026689A CN 100386362 C CN100386362 C CN 100386362C
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- fluorine
- catalyst composition
- polymkeric substance
- monomer
- 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.)
- Active
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention discloses a catalyst composition which comprises a silanolate compound and a fluorine containing organosilicon oligomer, wherein the silanolate compound has a general formula disclosed in the specification, and in the formula, n is an integer of 40 to 60; the fluorine containing organosilicon oligomer is selected from methyl fluoride silicon oil, hydroxyl fluoride silicone oil and vinyl fluoride silicon oil; the weight ratio of the silanolate compound to the fluorine containing organosilicon oligomer is from 1:1 to 50:1. The present invention also discloses a method for preparing fluorine containing silanol from the catalyst composition.
Description
Technical field
The present invention relates to the preparation method of the fluorine silicon polymkeric substance of a kind of catalyst composition and this catalyst composition of use.
Background technology
The silicon-fluorine polymer thing is a kind of brand-new material that grows up on the basis of organosilicon material and organic fluorine material, its main chain is for containing the silicon structure side chain for containing fluorine structure, this makes that the silicon-fluorine polymer thing has the good property at high and low temperature of silicon rubber concurrently and viton is high temperature resistant, resistance to chemical attack, oil resistance, thereby become transportation industry, petrochemical industries such as modern military industry, aerospace industry, automobile boats and ships, and the requisite special materials of medical and health industry such as artificial organ and medicine equipment.Described silicon-fluorine polymer thing is normally by 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (following abbreviation D
3 F) and methyl ethylene cyclotetrasiloxane monomer (following abbreviation D
4 MeVi), dimethyl siloxane monomer (following abbreviation D
3 MeOr D
4 Me) in one or both copolymerization form.
For example, United States Patent (USP) 6,610,778 disclose a kind of fluorine silicon polymkeric substance, and its composition comprises: the organopolysiloxane that 1) has trifluoro propyl; 2) silica filler; 3) as the full carbon type organo-peroxide of linking agent; 4) surpass 10,000 compound as a kind of molecular weight of co-crosslinker, have in allyl group, acryloyl, methacryloyl, epoxy and the alkoxyl group at least two kinds in its molecule as substituting group.This United States Patent (USP) reduces the cost in rubber production by shortening curing time.
The polyreaction of prior art for preparing fluorine silicon polymkeric substance, main still based on still reaction.The subject matter of this polymerization process is that polymerization rate is too fast, the fluorine silicon polymkeric substance is in polymerization process, in a short period of time, quick growth along with polymer molecular chain, viscosity increases fast, make mass transfer, the very difficulty that becomes of conducting heat, the problem of cause polymericular weight to be difficult to control, molecular weight distribution is wide influences the performance of trifluoropropyl siloxane.
In addition, described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer, methyl ethylene cyclotetrasiloxane monomer and/or the monomeric purity requirement of dimethyl siloxane polymer of monomers reaction pair are very high.When monomeric purity can not reach a certain threshold value (for example 99.0%), or copolyreaction can not carry out, or obtains low-molecular-weight multipolymer.As a result, the molecular weight and the molecular weight distribution that can not adopt conventional catalyzer and molecular weight regulator to come controlling polymers.Otherwise this catalyzer and/or molecular weight regulator can play impurity, influence the process of polyreaction and/or the performance of the finished product.
It is too fast that the disclosed fluorine silicon polymkeric substance of prior art all fails to solve polymerization rate from the polymerization angle, the problem that mass transfer, the difficulty of conducting heat, polymericular weight are difficult to control, molecular weight distribution is wide.
Therefore, need to seek a kind of catalyst composition, it can be brought into play the effect of catalyzer and can play molecular weight regulator, can the performance of final copolymer not had a negative impact again.
The preparation method who also needs a kind of fluorine silicon polymkeric substance, the product that it makes has higher molecular-weight average, moderate molecular weight distribution, this fluorine silicon polymkeric substance has the higher transparency simultaneously, characteristics such as molecular weight size is easy to control, thus solve that this silicon-fluorine polymer amount stability fluctuation is serious, problem such as lack of homogeneity, qualification rate are lower.
Summary of the invention
Purpose of the present invention is exactly in order to overcome the shortcoming that above-mentioned prior art exists, a kind of compound to be provided, and it can play molecular weight regulator, can the performance of final copolymer not had a negative impact again.A kind of preparation method of fluorine silicon polymkeric substance also is provided, 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 solves that the fluctuation of this silicon-fluorine polymer amount stability is serious, problem such as lack of homogeneity, qualification rate are lower.
Therefore, the invention provides a kind of catalyst composition, it comprises:
A) have the silicon alkoxide compound of following general formula:
Wherein, n is the integer of 40-60; M is the alkali metal that is selected from Na or Li.
B) fluorine-containing organosilicon oligopolymer, it is selected from methyl fluoride silicone oil, hydroxyl fluorosilicon oil, vinyl fluoride silicone oil;
The weight ratio of described silicon alkoxide compound and described fluorine-containing organosilicon oligopolymer is 1: 1 to 50: 1, is preferably 20: 1-40: 1.
The present invention also provides a kind of preparation method of fluorine silicon polymkeric substance, and it comprises the steps:
(a) provide 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) and one or more can be with described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer carries out the organosilicon ring body compound (D that contains vinyl of ionic ring-opening copolymerization reaction
4 MeVi) monomer mixture, 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-;
B) add catalyst composition of the present invention in described monomer mixture, the amount that catalyst composition adds accounts for the 0.004%-0.010% of described monomer mixture gross weight;
Under negative pressure, under 100-145 ℃ temperature, make described monomer copolymerization.
In a better example of the present invention, the described organosilicon ring body compound (D that contains vinyl
4 MeVi) have a following structural formula:
In the formula, Me represents CH
3-.
The present invention also provides a kind of fluorine silicon polymkeric substance, and its characteristic molecular weight is 40～2,000,000, is preferably 60-150 ten thousand; Its molecular weight distribution coefficient is 3-8; Its fugitive constituent＜1%; Its vinyl chain link content is between 0.3～0.8%.
Embodiment
The invention provides a kind of preparation method of fluorine silicon polymkeric substance.The inventive method is at first selected polymerization catalyst component, and the anionic catalyzer is generally all used in the ring-opening polymerization of organosilicon macromolecule polymkeric substance, i.e. basic catalyst such as quaternary phosphonium alkali, quaternary ammonium hydroxide, alkali-metal oxyhydroxide and silicon alkoxide thereof.The strong and weak order of its alkalescence is as follows: quaternary phosphonium alkali＞quaternary ammonium hydroxide 〉=cesium hydroxide (CsOH)＞potassium hydroxide (KOH)＞sodium hydroxide (NaOH)＞lithium hydroxide (LiOH).In general, alkalescence is strong more, and the temperature of ring-opening polymerization is low more, and it is short more to reach balance time.Bibliographical information is crossed D
3 FThe anionic ring-opening polymerization process is as follows:
Is non-reversible process by A to B, and B is a reversing process to C, when balance arrives.99% one-tenth oligomerization ring body D
1 F, simple linear polymer B but seldom even exists hardly.Therefore fluorine silicon superpolymer is D
3 FThe product of thermodynamics nonequilibrium situations in the ring-opening polymerization so must just stop or making B to carry out to this process of C is the least possible in the B stage before reaction reaches balance.In order to obtain high-molecular weight silicon-fluorine polymer thing, generally all use comparatively gentle catalyzer such as sodium hydroxide or lithium hydroxide.
In an example of the present invention, use LiOH as basic catalyst, the reaction monomers of using this moment surpasses 99% as purity, better surpasses 99.5% high-purity monomer, and temperature of reaction is 125-145 ℃.
Because lithium hydroxide makes D
3 FThe temperature of ring-opening polymerization is 125～145 ℃, under this temperature and negative pressure, and D
3 FAnd other monomers are very likely partly extracted out, if monomer purity is a little bit poorer again, and very likely not polymerization or generate oligopolymer.Therefore, in a better example of the present invention, select for use NaOH to make polymerization catalyst component (100～120 ℃ of polymerization temperatures).
In order to improve catalyzer at D
3 FMiddle dispersed, make the polymeric molecular weight distribution more even, be convenient to accurately and convenient the metering, usually described catalyst component is made the silicon alkoxide form with following general formula:
Wherein, n=40-60, M are the alkali metals that is selected from Na or Li.
But the inventor finds, only uses above-mentioned silicon alkoxide catalyst component, also is not enough to control on demand in the building-up process of fluorine silicon polymkeric substance the molecular weight and the molecular weight distribution of this polymkeric substance.
Through big quantity research, the inventor finds that the catalyst composition of formation can be controlled the molecular weight and the molecular weight distribution of this polymkeric substance on demand in the building-up process of fluorine silicon polymkeric substance when adding in above-mentioned silicon alkoxide catalyst component is selected from the fluorine-containing organosilicon oligopolymer of methyl fluoride silicone oil, hydroxyl fluorosilicon oil, vinyl fluoride silicone oil; It is also important that these fluorine-containing organosilicon oligopolymer can not influence the performance of the polymerization activity and the finished product of comonomer.
The contriver thinks, described fluorine-containing organosilicon oligopolymer plays molecular weight regulator in polyreaction of the present invention, but be different from conventional molecular weight regulator again, promptly it can not have a negative impact to the polymerization activity of comonomer, can't the performance of the finished product be exerted an influence.
In the catalyst composition of the present invention that comprises described silicon alkoxide compound and fluorine-containing organosilicon oligopolymer, the weight ratio of described silicon alkoxide compound and described fluorine-containing organosilicon oligopolymer is 1: 1 to 50: 1; Be preferably 20: 1-40: 1.
The silicon alkoxide compound that uses in the catalyst composition of the present invention can make by following reactional equation:
Wherein, M is the alkali metal that is selected from Na or Li.
In a better example of the present invention, described silicon alkoxide compound is with the sodium hydroxide fine powder of high purity (purity＞99.5%) and stoichiometric D through processed
3 FMix mutually, what polymerization 5-30 minute made under the condition of 90 ℃/10mmHg.
The fluorine-containing organosilane monomer that uses in the catalyst composition of the present invention is a compound known in the art, and it is commercially available.For example, it can be available from Shanghai Sanaifu New Material Co., Ltd (going up sea otter Wu Lu No. 4411).
The present invention also provides a kind of preparation method of fluorine silicon polymkeric substance.The preparation method of fluorine silicon polymkeric substance of the present invention uses 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer (D
3 F) and one or more can be with described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer and optional dimethyl siloxane monomer carry out the organosilicon ring body compound (D that contains vinyl of ionic ring-opening copolymerization reaction
4 MeVi) monomer mixture that forms prepares described fluorine silicon polymkeric substance.
In the monomer mixture of the present invention, 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-.This comonomer is the monomer commonly used that this area is used to make the fluorine silicon polymkeric substance, and it is commercially available, and for example, it can be available from Sunhuan Chemical Co., Ltd., Zhejiang.
In a better example of the present invention, the described organosilicon ring body compound (D that contains vinyl
4 MeVi) have a following structural formula:
In the formula, Me represents CH
3-.It can be with described 3,3, and 3-trifluoro propyl methyl cyclotrisiloxane monomer carries out the reaction of ionic ring-opening copolymerization.This comonomer is the monomer commonly used that this area is used to make the fluorine silicon polymkeric substance, and it is commercially available, and for example, it can be available from spark chemical plant, Jiangxi.
Each monomeric ratio should make D in the final copolymer during described comonomer mixed
3 FThe content of monomeric unit account for 97 moles of % or more than, better account for 99 moles of % or more than.Remove D
3 FThe kind of other comonomer in addition and consumption depend on the performance that final polymkeric substance is required.Those of ordinary skill in the art can easily determine the content of other comonomer described in the monomer mixture according to final polymer properties after having read content disclosed by the invention.
In a better example of the present invention, in the multipolymer that finally makes from D
3FMonomeric unit accounts for 97-99.9 mole %.
The preparation method of fluorine silicon polymkeric substance of the present invention also comprises adding catalyst composition of the present invention in described monomer mixture, and the amount that catalyst composition adds accounts for the 0.004%-0.010% of described monomer mixture gross weight, is preferably 0.005-0.006%.
Add the fluorine silicon polymkeric substance that the catalyst composition of the present invention in the above-mentioned amount ranges can obtain to have controlled molecular weight and molecular weight distribution, this catalyst composition can not have a negative impact to final polymer properties again simultaneously.
Copolyreaction of the present invention is under negative pressure, at 100-145 ℃, better carries out under 100-120 ℃ the temperature.The concrete pressure of described negative pressure does not have special restriction, as long as can control the molecular weight and the molecular weight distribution of final copolymer.In a better example of the present invention, described negative pressure is 2000-4000Pa, is preferably 2500-3000Pa, is preferably 2658Pa.
The present invention has also carried out experimental study to trace impurity to the influence of molecular weight.Experimental result shows: D3F shows that on analysis of thermal conductivity 2 peak face purity are during greater than 99.5% left and right sides, to producing the essentially no detrimentally affect of high molecular weight polymers, the impurity of trace has significantly caused molecular weight and molecular weight when purity is 99～99.5% left and right sides, if 3 peaks, and purity was less than 99% o'clock, and polymericular weight descends especially greatly.D
3 FIn when containing two peaks, impurity peaks content is not more than at 0.5% o'clock does not have tangible detrimentally affect to polyreaction; Impurity peaks content is less than 1%, the D greater than 0.5%
3 FIt also is the polymkeric substance that can prepare higher molecular weight that monomer prolongs polymerization time; When impurity peaks quantity is 3 peaks, then can not prepare high molecular weight polymers.
In addition, micro-moisture mainly shows the growth that influences reactive bond to the influence of this polyreaction, and it is little that molecular weight is increased, and secondly is to have reduced activity of such catalysts, makes open loop speed slack-off.
NaOH silicon alkoxide that the inventive method is selected for use or LiOH silicon alkoxide be as polymerization catalyst component, comparatively speaking activity a little less than, and consumption is in ppm level scope.If lost activity, often make the polyreaction failure.Experiment shows, the interior or interior contained micro-moisture of catalyzer of monomer, and the trace catalyst NaOH silicon alkoxide that uses during the divided ring polymerization or the activity influence of LiOH silicon alkoxide are very big, when serious, even the carrying out that stops polyreaction, therefore get rid of micro-moisture to D
3 FIt is one of key issue that monomer polymerization becomes simple linear polymer.
In a better example of the present invention, the preparation method of described fluorine silicon polymkeric substance also comprises in advance the step of catalyst composition and monomer mixture being carried out processed.
In another better example of the present invention, described preparation method is included in and adds polymeric monomer intermixture and an amount of fluorine-containing organosilicon oligopolymer as molecular weight regulator in the polymerization reaction kettle, in dripping bottle, add the silicon alkoxide catalyst component, dehydration respectively under certain temperature, vacuum; Then catalyst component is added mixed dehydration in the polymerization reaction kettle, under vacuum, heat up again with initiated polymerization; Come telo merization speed by controlled polymerization temperature, vacuum tightness, discharging behind the last devolatilization.
The preparation method of fluorine silicon polymkeric substance of the present invention is included in the fluorine-containing organosilicon oligopolymer that adds when polyreaction begins as molecular weight regulator, with the molecular weight distribution of controlling polymers, makes it to be unlikely to wide; And in reaction system, add basic metal silicon alkoxide catalyst component, initiated polymerization under certain temperature, vacuum tightness; The initial stage of polyreaction is with D
3 F, D
4 MeViRing-opening polymerization be principal reaction.Because ring-opening reaction is thermopositive reaction, therefore the temperature of whole polymerization system rises, and polymericular weight progressively increases.Along with the carrying out of polyreaction, the progressively decline of amount of monomer forms a part of high-molecular weight polymer in the polymerization system, the possibility of polycondensation between the chain is increased, thereby the molecular weight of polymkeric substance is increased fast.In the methods of the invention, the purpose of adding molecular weight regulator is control D
3 F, D
4 MeViOpen loop speed, and the suitable condensation polymerization speed in controlled polymerization reaction later stage improve the quality that mixes of polymkeric substance, and final control generates the molecular weight distribution of polymkeric substance.
In a better example of the present invention, the fluorine silicon polymkeric substance that makes with the inventive method has following structure:
Wherein, Me represents CH
3-, Rf represents CF
3CH
2CH
2-, n/m=1～10/1000 wherein, the characteristic molecular weight is 40～2,000,000, is preferably 60-150 ten thousand, the molecular weight distribution coefficient is 3-8, fugitive constituent＜1%.
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.
Embodiment
Preparation silicon alkoxide catalyst component:
A)
Preparation silanol lithium salts catalyst component:
The LiOH of content＞99.5%, under the infrared lamp irradiation, be ground into fine powder, take by weighing the B pipe that 1g puts into polyreaction, in the A pipe, add 100g D
3 F, utilize down at 70 ± 3 ℃/10mmHg (overbottom pressure) respectively and feed dry N capillaceous
2Stream stirs, and sloughs the moisture two hours of absorption, again D
3 FPut into the B pipe, be warming up to rise about 125 ℃/10mmHg (overbottom pressure) poly-, polymerization 5～30 minutes, stopped reaction, the alkali content of measuring gained silanol lithium salts is about 0.85%, viscosity is 10～80PaS, it is standby that the moisture eliminator inner drying is put in sealing.
B) preparation sodium silanolate salt catalyst component:
n＝40～60
The NaOH of content＞99.5%, under the infrared lamp irradiation, be ground into fine powder, take by weighing 1g and put into the B pipe of polyreaction, in the A pipe, add 100g D3F, utilize down at 70 ± 3 ℃/10mmHg (overbottom pressure) respectively and feed dry N2 stream capillaceous stirring, slough the moisture two hours of absorption, again D3F is put into the B pipe, being warming up to 90 ℃/10mmHg (overbottom pressure) rises poly-, polymerization 5～30 minutes, stopped reaction, the alkali content of measuring gained silanol sodium salt is about 0.85%, viscosity is 10～80PaS, and it is standby that the moisture eliminator inner drying is put in sealing.
Embodiment 1
With 10kg D
3 FMonomer (available from Sunhuan Chemical Co., Ltd., Zhejiang, purity＞99.0%), 2g are as the methyl fluoride silicone oil (liking fluorine novel material company limiteds available from Shanghai three) and the 50g D of molecular weight regulator
4 MeViFilter through the 2# sand core funnel, add in the pre-dry 20L stainless steel polymerization reaction kettle.The sodium silanolate catalyst component (polymerization degree is about 55) that 40 grams are made above adds in the catalyzer water trap, stay the monomer mixture about 500g above,, use steam heating in the still with the infrared lamp heating, 70 ± 3 ℃/1333.22～2666.44Pa of controlled temperature uses dry N
2The 1.5hr that dewaters in advance is again with top D
3 FPut on a small quantity in the catalyzer water trap, soak molten alkali dehydration 0.5hr, catalyst component is put into still in 15min, with the monomer washing of staying top, all will wash monomer in the 15min and put into still, remix dehydration 0.5hr, degree of intensification to polymerization temperature rises poly-for about 120 ℃ then, observed molecular weight increases degree, takes off low-boiling-point substance then, polymerization 25 minutes, get water white transparency high molecular rubber, resampling analysis after cooling, weighing and bagging are dug out in cooling while hot immediately.
Adopt the characteristic molecular weight of Ubbelohde viscometer method test fluorine silicon multipolymer.Solvent uses ethyl acetate (AR), and probe temperature is 25 ℃.
Adopt the contents of ethylene in the chemistry titration method test fluorine silicon multipolymer.Solvent uses butylacetate (AR), and probe temperature is 25 ℃.
Measure the fugitive constituent of fluorine silicon multipolymer by Shanghai City company standard Q/GHAC12-2002.
The results are shown in table 1.
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 2
Repeat embodiment 1 described step, just the consumption of sodium silanolate catalyst component is 60 grams.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 80 grams.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, fluorine-containing organosilicon oligopolymer as molecular weight regulator makes hydroxyl fluorosilicon oil (available from Shanghai Sanaifu New Material Co., Ltd) into, and its add-on is 50 grams, the results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, fluorine-containing organosilicon oligopolymer as molecular weight regulator makes vinyl fluoride silicone oil (available from the Shanghai rich novel material of three love company limited) into, and its add-on is 10 grams, the results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, is 3 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, the results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams (polymerization degree n=40), add-on as the fluorine-containing organosilicon oligopolymer of molecular weight regulator is 2 grams, and adds 10 gram dimethyl siloxane comonomers, the results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams (polymerization degree n=50), is 2 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, and polymerization time is reduced to 15 minutes.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams (polymerization degree n=60), is 2 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, and polymerization time is reduced to 20 minutes.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, is 2 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, and polymerization time was kept 25 minutes.The results are shown in table 1.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, only be to use the silanol lithium catalyst component (polymkeric substance is about 55) that makes above, the consumption of silanol lithium catalyst component is 60 grams, playing poly-temperature is 125 ℃, add-on as the fluorine-containing organosilicon oligopolymer of molecular weight regulator is 2 grams, and polymerization time increased to 30 minutes.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, is 20 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, and polymerization time increased to 35 minutes.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, is 2 grams as the add-on of the fluorine-containing organosilicon oligopolymer of molecular weight regulator, and polymerization time increased to 40 minutes.The results are shown in table 1.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 embodiment 1 described step, just the consumption of sodium silanolate catalyst component is 60 grams, does not add the fluorine-containing organosilicon oligopolymer as molecular weight regulator, and polymerization time is reduced to 10 minutes.The results are shown in table 1.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 embodiment 1 described step, just the sodium silanolate catalyst levels is 60 grams, does not add the fluorine-containing organosilicon oligopolymer as molecular weight regulator, and polymerization time is reduced to 20 minutes.The results are shown in table 1.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 embodiment 1 described step, just the consumption of sodium silanolate catalyst component is 60 grams, does not add molecular weight regulator, and polymerization time was kept 25 minutes.The results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, and adds 2 gram molecular weight conditioning agent methyl-silicone oils, the results are shown in table 1.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 the consumption of sodium silanolate catalyst component is 60 grams, polymerization single polymerization monomer D
3 FPurity be 95%, the results are shown in table 1.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 6
Repeat the step of embodiment 1, just the consumption of sodium silanolate catalyst component is 60 grams, polymerization single polymerization monomer D
3 FPurity be 98%, the results are shown in table 1.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 as seen, by the weight of monomer mixture, the consumption of silicon alkoxide catalyst component under the similar substantially situation of polymerization temperature and time, all can obtain the close full-bodied polymer of molecular weight in 0.004～0.010% scope.In certain catalyst levels scope, catalyst levels does not have obvious influence to polymericular weight.
Consider polymer inner catalyst residue to Effect on Performance, catalyst consumption is as far as possible few, but catalyst consumption should not be very little, otherwise often because of the influence of introduced contaminants, makes catalyst failure cause the polyreaction failure.
By embodiment 4,5,6,7 as seen, adding is as the fluorine-containing organosilicon oligopolymer of molecular weight regulator, polymerization rate obviously reduces, molecular weight does not increase by geometric progression, that is to say can the controlled polymerization speed of response with molecular weight regulator, thereby can prolong polymerization reaction time, molecular weight that can indirect regulation silicon-fluorine polymer thing.In addition, behind the adding molecular weight regulator, apparent homogeneity improves a lot relatively, and molecular weight distribution is more even.In addition, molecular weight regulator is to not influence of polymerisate, because also need to add a certain amount of molecular weight regulator in the silicon-fluorine polymer thing course of processing.But molecular weight regulator is small molecules after all, though too much can make the molecular weight distribution of silicon-fluorine polymer thing more even, the mechanical property after polymer sulfuration is processed is decreased.
By embodiment 7 as seen, add other comonomers of a certain amount of structural similitude, can't change final polymer properties; By embodiment 7,8,9 as seen, when polymerization degree n=40 of catalyst composition, n=50, n=60, it is poly-all monomer to be risen, and its polymerization degree size does not have influence substantially to the performance of final product.If but the polymerization degree of catalyst composition is excessive, can influence its dispersed uniform in polymerization single polymerization monomer.In better example of the present invention, the polymerization degree n=50-60 of selecting catalyst composition is preferably 50.
In sum, in the preparation process of fluorine silicon polymkeric substance, the add-on of catalyst composition of the present invention should account for 0.004～0.010% of monomer mixture gross weight
By embodiment 8,9,10,11,12,13 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 comparative example 1,2,3 as seen, owing to do not add molecular weight regulator, the silicon-fluorine polymer speed of response is too fast, and real polymerization time is about general ten minutes (comprising that the heating-up time at most can be above 30 minutes), in case arrive required range estimation molecular weight, it is slow to open still speed, that molecular weight just increases a lot, and molecular weight is difficult to control, in addition, polymer molecular weight distributes wide, and the fugitive constituent of polymerisate is higher.Be unfavorable for the sulfuration processing of polymerisate.In addition, the fugitive constituent of comparative example product will be apparently higher than the polymerization example.
By comparative example 4 as seen, add and the relatively poor molecular weight regulator of polymerization single polymerization monomer consistency, under the identical prerequisite of other conditions, final polymericular weight is less, and fugitive constituent is higher, and transformation efficiency is less.
By comparative example 5,6 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.
Table 2
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Mean value | Standard deviation |
| 1 | 120 | 126 | 117 | 127 | 123 | 125 | 123 | 3.84 |
| 2 | 110 | 114 | 124 | 118 | 120 | 122 | 118 | 5.22 |
| 3 | 109 | 113 | 115 | 116 | 118 | 119 | 115 | 3.63 |
| 4 | 39.5 | 39.8 | 39.3 | 40.2 | 40.4 | 40.8 | 40 | 0.56 |
| 5 | 89 | 92 | 94 | 96 | 98 | 101 | 95 | 4.29 |
| 6 | 108 | 111 | 114 | 116 | 119 | 122 | 115 | 5.14 |
| 7 | 116 | 120 | 125 | 129 | 131 | 135 | 126 | 7.10 |
| 8 | 91 | 94 | 95 | 98 | 99 | 99 | 96 | 3.22 |
| 9 | 111 | 113 | 114 | 118 | 119 | 121 | 116 | 3.90 |
| 10 | 116 | 117 | 119 | 123 | 125 | 126 | 121 | 4.24 |
| 11 | 122 | 126 | 128 | 131 | 133 | 134 | 129 | 4.56 |
| 12 | 121 | 127 | 128 | 133 | 135 | 136 | 130 | 5.74 |
| 13 | 135 | 143 | 149 | 155 | 158 | 160 | 150 | 9.63 |
| C1 | 74 | 113 | 124 | 134 | 147 | 158 | 125 | 29.66 |
| C2 | 80 | 118 | 148 | 155 | 164 | 175 | 140 | 35.14 |
| C3 | 104 | 139 | 168 | 173 | 179 | 185 | 158 | 30.89 |
| C4 | 46 | 56 | 60 | 70 | 80 | 86 | 70 | 16.89 |
| C5 | - | - | - | - | - | - | - | - |
| C6 | 19 | 21 | 24 | 26 | 28 | 30 | 25 | 4.43 |
Can see that by table 2 homogeneity that the silicon-fluorine polymer thing of adding molecular weight regulator distributes is significantly better than the silicon-fluorine polymer thing that does not add molecular weight regulator.
In sum, in the still reaction process, the selection by to polyalcohol catalyst and consumption thereof, polymeric reaction temperature has particularly added molecular weight regulator, makes polyreaction to carry out more reposefully.It is too fast to have solved polymerization rate, and in a short period of time, along with the quick growth of polymer molecular chain, polymer viscosity increases fast, makes mass transfer, the very difficulty that becomes of conducting heat, the problem of cause polymericular weight to be difficult to control, molecular weight distribution is wide; And be more conducive to the sulfuration processing of polymkeric substance.
Claims (16)
1. catalyst composition, it comprises;
A) have the silicon alkoxide compound of following general formula:
Wherein, n is the integer of 40-60; M is the alkali metal that is selected from Na or Li;
B) fluorine-containing organosilicon oligopolymer, it is selected from methyl fluoride silicone oil, hydroxyl fluorosilicon oil, vinyl fluoride silicone oil;
The weight ratio of described silicon alkoxide compound and described fluorine-containing organosilicon oligopolymer is 1: 1 to 50: 1.
2. catalyst composition as claimed in claim 1, the weight ratio that it is characterized in that described silicon alkoxide compound and described fluorine-containing organosilicon oligopolymer is 20: 1 to 40: 1.
3. catalyst composition as claimed in claim 1 or 2 is characterized in that described silicon alkoxide compound is by 3,3, and 3-trifluoro propyl methyl cyclotrisiloxane makes with the alkali metal hydroxide reaction that is selected from Na or Li.
4. catalyst composition as claimed in claim 1 or 2 is characterized in that described M is Na.
5. the preparation method of a fluorine silicon polymkeric substance, it comprises the steps:
(a) provide 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer and one or more and described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer carries out the monomer mixture of the organosilicon ring body compound that contains vinyl of ionic ring-opening copolymerization reaction, described 3,3,3-trifluoro propyl methyl cyclotrisiloxane monomer has following structural formula:
In the formula, Me represents CH
3-, Rf represents CF
3CH
2CH
2-;
B) add catalyst composition as claimed in claim 1 or 2 in described monomer mixture, the amount that catalyst composition adds accounts for the 0.004%-0.010% of described monomer mixture gross weight;
Under negative pressure, under 100-145 ℃ temperature, make described monomer copolymerization.
6. method as claimed in claim 5 is characterized in that the described organosilicon ring body compound that contains vinyl has following structural formula:
In the formula, Me represents CH
3-.
7. as claim 5 or 6 described methods, it is characterized in that it also comprises the step that described monomer mixture and catalyst composition are dewatered in advance.
8. as claim 5 or 6 described methods, it is characterized in that each monomeric purity is greater than 99.0% in the monomer mixture.
9. as claim 5 or 6 described methods, it is characterized in that the present invention is a negative reaction, polymerization pressure is 2000-4000Pa.
10. as claim 5 or 6 described methods, it is characterized in that described in the monomer mixture 3,3, the monomeric content of 3-trifluoro propyl methyl cyclotrisiloxane makes in the multipolymer that makes and is not less than 99 moles of % from this monomeric unitary amount.
11. as claim 5 or 6 described methods, it is characterized in that described M is Na, polymerization temperature is 100-120 ℃.
12., it is characterized in that also containing in the described monomer mixture dimethyl siloxane as claim 5 or 6 described methods.
13., it is characterized in that the amount of catalyst composition adding accounts for the 0.005%-0.006% of described monomer mixture gross weight as claim 5 or 6 described methods.
14. a fluorine silicon polymkeric substance that makes with each described method among the claim 5-13, its characteristic molecular weight is 40～2,000,000, and the molecular weight distribution coefficient is 3-8, fugitive constituent＜1%.
15. fluorine silicon polymkeric substance as claimed in claim 14 is characterized in that its molecular weight is 60-150 ten thousand.
16., it is characterized in that its vinyl chain link content is between 0.3～0.8% as claim 14 or 15 described fluorine silicon polymkeric substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266896A CN100386362C (en) | 2005-06-13 | 2005-06-13 | Catalyst composition and preparation method of fluorine silicon contained polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266896A CN100386362C (en) | 2005-06-13 | 2005-06-13 | Catalyst composition and preparation method of fluorine silicon contained polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1724580A CN1724580A (en) | 2006-01-25 |
| CN100386362C true CN100386362C (en) | 2008-05-07 |
Family
ID=35924221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100266896A Active CN100386362C (en) | 2005-06-13 | 2005-06-13 | Catalyst composition and preparation method of fluorine silicon contained polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100386362C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412112C (en) * | 2006-04-29 | 2008-08-20 | 广东信力特种橡胶制品有限公司 | Polymerization method for crude rubber of fluorinated silicone rubber |
| CN102775613B (en) * | 2012-08-10 | 2014-08-20 | 广州天赐高新材料股份有限公司 | Method for preparing alpha, omega-bis(aminopropyl)polydimethylsiloxane |
| CN103012801B (en) * | 2012-12-22 | 2017-12-19 | 威海新元化工有限公司 | Preparation method of fluorosilicone raw rubber with controllable molecular weight |
| CN103739845B (en) * | 2013-12-30 | 2016-07-06 | 山东华夏神舟新材料有限公司 | A kind of preparation method of high molecular weight fluorine silicon raw rubber |
| CN103739844B (en) * | 2013-12-30 | 2016-06-15 | 山东华夏神舟新材料有限公司 | The preparation method of a kind of hot sulfurization crude rubber of fluorinated silicone rubber |
| CN104119535B (en) * | 2014-03-06 | 2016-09-07 | 杭州师范大学 | A kind of preparation method of hydroxy-end capped fluorine silicon raw rubber |
| CN107619479B (en) * | 2017-08-23 | 2021-01-12 | 无锡龙驰氟硅新材料有限公司 | Fluorosilicone release agent and preparation method thereof |
| CN109608639A (en) * | 2018-11-30 | 2019-04-12 | 万华化学集团股份有限公司 | A kind of organopolysiloxane catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106770A (en) * | 1984-07-20 | 1987-03-11 | Bp化学有限公司 | Polymer composition |
| CN1456564A (en) * | 2003-05-28 | 2003-11-19 | 中国科学院上海有机化学研究所 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
| US6867323B2 (en) * | 2000-06-06 | 2005-03-15 | The Board Of Trustees Of The University Of Illinois | Cross-coupling reaction of organosilicon nucleophiles |
-
2005
- 2005-06-13 CN CNB2005100266896A patent/CN100386362C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106770A (en) * | 1984-07-20 | 1987-03-11 | Bp化学有限公司 | Polymer composition |
| US6867323B2 (en) * | 2000-06-06 | 2005-03-15 | The Board Of Trustees Of The University Of Illinois | Cross-coupling reaction of organosilicon nucleophiles |
| CN1456564A (en) * | 2003-05-28 | 2003-11-19 | 中国科学院上海有机化学研究所 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1724580A (en) | 2006-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100386362C (en) | Catalyst composition and preparation method of fluorine silicon contained polymer | |
| CN101250266B (en) | Fluorine-silicon copolymer rubber and preparation method thereof | |
| CN101768266B (en) | Method for preparing semi-aromatic nylon | |
| CN101880396A (en) | Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation | |
| CN102220014A (en) | High-strength fluorinated silicone rubber gross rubber and preparation method thereof | |
| CN106750312A (en) | Phenyl DT silicones and preparation method thereof | |
| CN103923318A (en) | Amino-containing crosslinkable polyether sulfone as well as preparation method and applications thereof | |
| TW202221056A (en) | Polyether ether ketone, composition, and sheet | |
| CN113024803A (en) | Fluorine-containing water-resistant polyamide 6 and preparation method thereof | |
| CN105969301A (en) | Organic silicone for high-power LED packaging and methods of preparing and using same | |
| CN104327268B (en) | Siloxane copolymer containing ethyl phenyl silica chain links and preparation method thereof | |
| Feng et al. | Facile and rapid synthesis of flexible PEG porous polymers as substrates for functional materials by thiol-ene click chemistry | |
| CN113185689B (en) | Low-water-absorption copolymerized nylon resin and preparation method thereof | |
| CN103289095A (en) | A synthesis method of high viscosity alpha, omega-dihydroxy polydimethylsiloxane | |
| CN107090262A (en) | A kind of good composition epoxy resin of transparency and its applied in automotive field | |
| CN110628085B (en) | Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof | |
| CN108264765A (en) | A kind of preparation method of toughening heat conductive insulating cyanate resin base composite material | |
| WO2024055772A1 (en) | Modified evoh resin and method for preparing same | |
| CN101302263B (en) | Ethylene-tetrafluoroethylene copolymer | |
| CN103739845B (en) | A kind of preparation method of high molecular weight fluorine silicon raw rubber | |
| CN106398193B (en) | Heat resistant polyamide 6T/11 composition and preparation method thereof | |
| CN103739844A (en) | Preparation method of heat curing fluorosilicone raw rubber | |
| CN114106243A (en) | Preparation method of low-viscosity low-monomer-residue dry strength agent | |
| Xiang et al. | Synthesis and Characterization of Comb‐like P (MPEGA‐co‐AM) Copolymer as Phase Change Materials | |
| CN113117455A (en) | Application of choline chloride-glycerol eutectic solvent in absorbing HCl gas |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180524 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 |
|
| CP03 | Change of name, title or address | ||
| 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. |