CN101547958A - Process for the production of monodisperse and narrow disperse monofunctional silicones - Google Patents
Process for the production of monodisperse and narrow disperse monofunctional silicones Download PDFInfo
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- CN101547958A CN101547958A CNA200680016521XA CN200680016521A CN101547958A CN 101547958 A CN101547958 A CN 101547958A CN A200680016521X A CNA200680016521X A CN A200680016521XA CN 200680016521 A CN200680016521 A CN 200680016521A CN 101547958 A CN101547958 A CN 101547958A
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Abstract
Synthesis and purification of mono and narrow disperse monofunctional polydimethylsiloxane methacrylate derivatives with different molecular weights are disclosed.
Description
The application is according to the preference of 35 USC § 119 (e) requirement respectively at the 60/662nd, 556 and 60/682, No. 410 U.S. Provisional Patent Application of submitting on March 17th, 2005 and on May 19th, 2005.SN 60/662,556 and SN60/682,410 separately full contents are incorporated by reference the application.
Invention field and background
The present invention relates to be used for method synthetic and dispersion of purifying list and narrow dispersion (narrow disperse) polymer composition, described synthetics comprises monofunctional polydimethylsiloxane derivative (this paper is called mPDMS).MPDMS polymkeric substance of the present invention is used for biomaterial and other application.MPDMS polymkeric substance of the present invention is specially adapted to produce contact lens.
Be used to produce and have the method for the more high molecular mPDMS polymkeric substance of more number siloxane units more and used anionic polymerization and for example following solvent: the mixture of tetrahydrofuran (THF) (THF) and hexanaphthene and benzene and THF.
Summary of the invention
The invention provides and be used for synthetic and purifying has free radical reaction, terminally for replacing and the general method of the polydimethylsiloxane synthetics of substituted alkyl not, described method can be used for single low-molecular weight oligo thing and polymolecularity of disperseing near 1 higher molecular weight polymer.Specifically, in one embodiment, the method that the present invention relates to may further comprise the steps:
(a) make hexamethyl cyclotrisiloxane at least a non-polar solvent with the trialkyl silanol (trialkylsilanol) or the trialkyl silicomethane alkoxide of molar excess, perhaps at least a functionalized or not functionalized organometallic compound reaction, the silanol negatively charged ion (silanolate anion) that has single dispersity or low dispersity with generation, described organometallic compound is the alkyl lithium compounds of formula RLi for example, and wherein R is the alkyl of 1 to 8 carbon atom.In other embodiments, described silanol negatively charged ion can be further and the chlorosilane cpd of the formula I of molar excess:
Cl-Si-(CH
3)
2-R
1
Reaction, wherein R
1Be selected from C1 to the C8 alkyl of H, C1 to C8 alkyl or replacement, wherein said substituting group comprises the proton inertia substituting group, for example Bao Hu hydroxyl, free radical reaction group and combination thereof.The end that is generated is that the polydimethylsiloxane compound of silane can further replace with (a) or the reaction of unsubstituted (methyl) vinylformic acid allyl group alkyl ester is the polydimethylsiloxane of alkyl to generate replacement or unsubstituted end, the perhaps epoxide reaction that replaces with (b), this epoxide experience ring-opening reaction is the polydimethylsiloxane of alkyl to generate replacement or unsubstituted end then.
Detailed Description Of The Invention
This paper has described the method that is used to produce the mPDMS derivative, described mPDMS derivative comprises " the single dispersion " and " narrow dispersion ", has free radical reaction, terminal for replacing and the polydimethylsiloxane of substituted alkyl not for example single the dispersion and narrow dispersion hydroxyl mPDMS propyl group glycerine (methyl) acrylate synthetics and mPDMS propyl group (methyl) acrylate synthetics.Abbreviation " mPDMS " refers to monofunctional polydimethylsiloxane.Term " the single dispersion " refers to have the same molecular amount at least about 98% polymkeric substance that exists in the siloxane polymer product.Term " narrow dispersion " refers in the siloxane polymer product to have at least about 85%, at least about 90% described siloxane polymer the molecular weight of hope.(methyl) used herein acrylate comprises acrylate and methacrylic ester.
In the first step of present method, hexamethyl cyclotrisiloxane (D
3) and functionalized or not functionalized organometallic compound or trialkyl silanol reactant salt, described trialkyl silicomethane alkoxide for example has formula MOSiR
2R
3R
4Those, R wherein
2-R
4Independently be selected from alkyl with 1 to 8 carbon atom, and M be can be positively charged the thing class, for example metal and tetraalkyl ammonium ion.Suitable trialkyl silicomethane alkoxide example comprises the tetrabutylammonium salt of trimethyl silyl alcohol.Suitable functionalized or not the functionalized organometallic examples of compounds be included in the alkyl lithium compounds of the formula RLi of at least a non-polar solvent under existing, wherein R is the alkyl of 1 to 8 carbon atom.Suitable non-polar solvent comprises and does not contain the hydrocarbon liquid that can extract proton (abstractable proton).The example of non-polar solvent comprises pentane, hexanaphthene, hexane, heptane, benzene, toluene, high-grade non-polar hydrocarbons and composition thereof etc. more.In one embodiment, described non-polar solvent comprises pentane, hexanaphthene, hexane and composition thereof etc.Initial period in ring-opening reaction uses non-polar solvent to generate single the dispersion or narrow dispersive silanol negatively charged ion.
Hexamethyl cyclotrisiloxane can commercially obtain.In one embodiment, alkyl lithium compounds is selected from n-Butyl Lithium or s-butyl lithium.
Use hexamethyl cyclotrisiloxane and alkyl lithium compounds with stoichiometric quantity based on the dimethyl siloxane repeating unit number in the desirable final mPDMS derivative.For example, have a dimethyl siloxane repeating unit if wish the mPDMS derivative, then the mol ratio of alkyl lithium compounds of Shi Yonging and hexamethyl cyclotrisiloxane for about 1:1.1 to about 1:1.5.When wishing that molecular weight of product improves, then the ratio of alkyl lithium compounds and hexamethyl cyclotrisiloxane reduces.Those skilled in the art can utilize instruction of the present invention to calculate other mol ratio.Be reflected at about 5 ℃ and to about 60 ℃ temperature, carry out, and in some embodiments, to about 30 ℃ temperature, carry out at about 5 ℃.Reaction was carried out about 1 hour to 4 hours.Can environment for use pressure.
When needing the mPDMS derivative of higher molecular weight, finish the back at initial reaction and add polar chain growth solvent, for example THF, Anaesthetie Ether, diox, DMSO, DMF, hexamethylphosphorictriamide, its mixture etc.In one embodiment, THF, diox, DMSO or its mixture increase solvent as polar chain, and in another embodiment, polar chain increases solvent and comprises THF.Polar chain increases solvent and adds under controlled conditions, and makes and be reflected at about 5 ℃ to 60 ℃ and carried out about 2 hours to about 24 hours to about 30 ℃ temperature at about 5 ℃ in some embodiments.Detect the conversion of hexamethyl cyclotrisiloxane by gas chromatographic analysis.
Then, with the chlorosilane cpd of silanol negatively charged ion and formula I:
Cl-Si-(CH
3)
2-R
1
Reaction, wherein R
1Be selected from C1 to the C8 alkyl of H, C1 to C8 alkyl or replacement, wherein said substituting group comprises the proton inertia substituting group, for example Bao Hu hydroxyl, free radical reaction group and combination thereof.As used herein, the free radical reaction group comprises (methyl) acrylate group, styryl, vinyl, vinyl ether group, vinylformic acid C
1-6Alkyl group, acrylamide group, C
1-6Alkyl acrylamide group, N-vinyl lactam group, N-vinylamide group, C
2-12Alkenyl, C
2-12Alkenyl phenyl, C
2-12Alkenyl naphthyl or C
2-6Alkenyl phenyl C
1-6Alkyl.In one embodiment, the free radical reaction group comprises (methyl) acrylate group, acryloxy (acryloxys), (methyl) acrylamide group etc. and composition thereof.In one embodiment, the free radical reaction group is methacrylic ester or acrylate group.
Used excessive chlorosilane.Though chlorosilane cpd can be any mol ratio than the anionic mol ratio of silanol, is economic cause, use extremely about 5 to 1 ratio of about 1.1:1, and use extremely about 2 to 1 ratio of about 1.1:1 in some embodiments.The anionic reaction of chlorosilane and silanol is heat release.Correspondingly, keep temperature of reaction, for example control the temperature of adding chlorosilane or before adding chlorosilane, reducing reaction mixture by currently known methods.This end reaction can be lower than under about 70 ℃ temperature, and carries out about 15 minutes kinds in some embodiments to about 4 hours time under about 0 ℃ to 70 ℃ temperature.
Work as R
1When being not H, end reaction generates and replaces or unsubstituted alkyl-mPDMS derivative the narrow dispersion or single dispersion of wishing.
When chlorosilane was dimethylchlorosilane, it was the polydimethylsiloxane of silane that end reaction generates end.End is that the PDMS of silane can purifying or directly use before further reacting.Can remove impurity by many methods, comprise: filter LiCl; Evaporate excessive Chlorodimethyl silane; With buck (sodium bicarbonate of dilution) wash residual thing to remove residual HCl, with after washing; And dry (anhydrous sodium sulphate) and distillation (using falling-film evaporator or wiped film evaporator or additive method well known by persons skilled in the art) are anhydrated and the D of any residual trace to remove
3Or senior ring compound.When wishing purifying silane end PDMS, any method in can making in many ways, for example distillation is as long as the condition of selecting (for example plate number, vacuum and the temperature of the residence time, use) is enough to provide the silane that has narrow at least dispersing molecule amount as herein defined terminal PDMS.Perhaps, the purifying of the terminal PDMS of silane can be by the evaporation chlorosilane, and water extraction (use buck) LiCl and above-mentioned distillation subsequently finished.
Work as R
1During for hydrogen, the inventive method further comprises hydrosilylation step.The terminal PDMS of silane then can be by the epoxide reaction of hydrosilylation reactions with (methyl) allyl acrylate or replacement, and described hydrosilylation reactions is for example disclosed among the US2006/0047134, and its disclosure is incorporated by reference in their entirety to this paper.Described (methyl) allyl acrylate uses with excessive about 10% to about 100% molar weight.
Suitable (methyl) allyl acrylate example comprises (methyl) allyl acrylate, methacrylic acid allyl group oxygen base hydroxy-propyl ester and vinylformic acid allyl group oxygen base hydroxy-propyl ester.Should be appreciated that allyl oxyglycerol (methyl) acrylate exists as the mixture balance of primary alconol and secondary alcohol.In any reaction disclosed herein, can use the equilibrium mixture of allyl oxyglycerol (methyl) acrylate.
Suitably the epoxide that replaces comprises the single substituted epoxide with terminal ethylenyl groups.Specific examples comprises the epoxide of formula III:
Wherein B is the group that can form hydrogen bond with another group or carboxylic acid derivative.The specific examples of B comprises heteroatoms (comprising O, S, N, P etc.), carbonyl, has the alkylidene group of 1 to 6 carbon atom (described alkylidene group can be unsubstituted or be replaced by hydroxyl), amine, acid amides, ether, ester, aldehyde, ketone, aromatic group, alkyl and combination thereof.
In one embodiment, B is the alkyl that O or the hydroxyl with 1 to 4 carbon atom replace.The specific examples of the epoxide that replaces comprises glycidyl allyl ether.
The terminal PDMS of silane is in the presence of hydrosilylation catalysts, with suitable (methyl) allyl acrylate or the epoxide reaction of replacement.Suitable hydrosilylation catalysts comprises metal halide, comprises muriate, bromide and the iodide of chromium, cobalt, nickel, germanium, zinc, tin, mercury, copper iron, ruthenium, platinum, antimony, bismuth, selenium and tellurium.The specific examples of suitable hydrosilylation catalysts comprises: independent platinum, the catalyzer that solid platinum go up to be formed at carrier (for example alumina, silicon-dioxide and carbon black), Platinic chloride, the mixture of Platinic chloride and alcohol, aldehyde and ketone, platinum-alkene complex { Pt (CH for example
2=CH
2)
2(PPh
3)
2Pt (CH
2=CH
2)
2Cl
2; Platinum-vinylsiloxane mixture { Ptn (ViMe for example
2SiOSiMe
2Vi)
m, Pt[(MeViSiO)
4]
m; Platinum-phosphine mixture { Pt (PPh for example
3)
4, Pt (PBu
3)
4; Platinum-phosphite mixture { Pt[P (OPh) for example
3]
4, Pt[P (OBu)
3]
4(in formula, Me is a methyl, and Bu is a butyl, and Vi is a vinyl, and Ph is a phenyl, and n and m are integer), dicarbapentaborane dichloro platinum is as platinum-hydrocarbon mixture and the platinum-alcoholate catalyst of describing among USP3159601 and the USP 3159662 as describing among the USP3220972.In addition, be effective as platinum chloride-alkene complex of describing among the USP3516946.Operable is not that the example of the catalyzer of platinic compound comprises RhCl (PPh yet
3)
3, RhCl
3, Rh/Al
2O
3, RuCl
3, IrCl
3, FeCl
3, AlCl
3,
, NiCl
2And TiCl
4(Ph represents phenyl).Can also use catalyzer, for example Wilkinson ' s catalyzer based on rhodium.Preferred hydrosilylation (hydrosilation) catalyzer comprises the vinyl complexes (for example Karstedt ' s catalyzer and Ashby ' s catalyzer) of the muriate and the platinum of platinum, and especially effectively hydrosilylation catalysts comprises Karstedt ' s (Pt
2{ [(CH2=CH) Me
2Si]
2O}
3) with as US 4,421,903 and US4,288, the 345 described platinum vinylsiloxane mixtures (Ashby ' s catalyzer) that contain low halogen.
Hydrosilylation catalysts uses with appropriate amount, comprises about 1ppm to about 500ppm, and preferably about 5ppm is to about 100ppm.
Be reflected under the mild conditions and carry out, for example temperature is about 0 ℃ to about 100 ℃, is preferably about 0 ℃ to about 60 ℃, more preferably about 5 ℃ to about 40 ℃.Increase even have been found that the reaction times, these temperature of reaction also can significantly reduce by product.Pressure is not crucial, can use normal atmosphere.The operable reaction times is no more than about 24 hours, preferably is no more than about 12 hours, more preferably about 4 hours to about 12 hours.Those skilled in the art will appreciate that temperature and reaction times is inversely proportional to, and higher temperature of reaction reduces the reaction times, vice versa.Can mix (solvent-free) only or in solvent blending ingredients, described solvent is aliphatic hydrocarbon, aromatic hydrocarbons, ether, ketone, its mixture etc. for example.Suitable examples comprises in all kinds of: aromatic hydrocarbon solvents, for example benzene, toluene and dimethylbenzene; Aliphatic hydrocarbon solvent, for example pentane, hexane, octane or more high-grade stable hydrocarbon; Ether solvents, for example ethyl ether, butyl ether and tetrahydrofuran (THF); Alcohol, for example Virahol and ethanol; With halon solvent, for example trieline; And composition thereof.In one embodiment, hydrosilylation reactions carries out under solvent-free.
If used the epoxide that replaces in the hydrosilylation reactions, then alkyl epoxy-the PDMS of Sheng Chenging can carry out the epoxide ring-opening reaction under the disclosed condition in US sequence number 10/862074.In this embodiment, the epoxide of replacement and at least a vinylformic acid and at least a described acrylic acid lithium salts reaction.Suitable vinylformic acid comprises 1 to 4 carbon atom.In one embodiment, described vinylformic acid is methacrylic acid.The epoxide and the reaction between the vinylformic acid that replace can be equimolar, yet it may be favourable adding excessive vinylformic acid.Therefore, can every mole of about 1 mole of extremely about 3 moles acrylic acid amount of epoxide use vinylformic acid.
Lithium salts comprises lithium and at least a vinylformic acid that contains 1 to 4 carbon atom.In one embodiment, lithium salts is the Li salt of methacrylic acid.The amount that lithium salts adds is enough to catalyzed reaction, preferably reaches about 0.5 equivalent of epoxide.
Can also comprise inhibitor in the reactant.Can use any inhibitor that can reduce rate of polymerization.Suitable inhibitor comprises sulfide, mercaptan, quinine, thiodiphenylamine, sulphur, phenol and phenol derivatives, its mixture etc.Specific examples includes but not limited to hydroquinone monomethyl ether, Yoshinox BHT, its mixture etc.It is about 10 that the addition of described inhibitor can reach, and 000ppm is preferably about 1ppm to about 1,000ppm.
Can also in any other method steps disclosed herein, use an amount of inhibitor, comprise the free radical reaction compound.
Carry out the epoxide ring-opening reaction with the temperature that raises, described temperature preferably is higher than about 60 ℃, more preferably from about between 80 ℃ and about 110 ℃.The suitable reaction times comprises and reaches about 1 day, is about 4 hours to about 20 hours in some embodiments, is about 6 hours to about 20 hours in other embodiments.It should be appreciated by those skilled in the art that described temperature and reaction times is inversely proportional to, higher temperature of reaction can make the reaction times reduce, and vice versa.Yet, in the methods of the invention, wish to make to react completely or near (for example, it is about 95% that the substituted epoxide transformation efficiency surpasses, and preferably surpasses about 98% substituted epoxide transformation efficiency) fully.
Aforesaid method generates single the dispersion or the replacement of narrow dispersive or unsubstituted alkyl-mPDMS derivative.The replacement that can generate by the inventive method or the example of unsubstituted alkyl-mPDMS derivative comprise the polydimethylsiloxane of single normal-butyl end of list-(3-methacryloxy-2-hydroxypropyl oxygen base) the polydimethylsiloxane propyl group end, the monobutyl end and monomethyl acryloxy propyl group end.Can pass through gel permeation chromatography, NMR
1H and
29Si and mass spectrum (MALDI-TOFS) analyses determine that average MW distributes.Can under controlled temperature and vacuum condition, use fractionating method (for example packed column or many plates distillation) and the known additive method of prior art (chromatography for example well known by persons skilled in the art) to be further purified the narrow dispersion product that is generated.
The present invention described above.For illustrating the present invention, added following exemplary reaction design.These exemplary reaction descriptions do not limit the present invention.It only is to show the method for the present invention of implementing.The synthetic those skilled in the art of silicone compounds and other professionals can find to implement additive method of the present invention.Yet these methods are believed to comprise within the scope of the present invention.
Method 1:
The method that is used for parent hydroxy-simple function dimethyl silica alkane derivatives has been described among the flow process 1A.
Flow process 1A:MW is single hydroxyl-alkyl-simple function-dimethyl silica alkane derivatives-method 1 of disperseing of 391g/ mole.
Synthetic and the purifying of step 1:mPDMS-H derivative
Method A: first step is the negatively charged ion ring-opening reaction, is included in the alkyl lithium reagents (for example n-Butyl Lithium or s-butyl lithium) that uses molar excess in the non-polar solvent (for example hexanaphthene or hexane) and makes and can ring-opening reaction about 1 take place to about 4 hours (BuLi:D by the commercial D3 that obtains to about 60 ℃ temperature at about 5 ℃
3Mol ratio be about 1.1:1 to 2:1), use the alkyl dimethyl silanol negatively charged ion endization of excess chlorine dimethylsilane (be generally employed alkyl lithium reagents amount 1.1 times to 5 times) subsequently to generating.The reaction product that purifying generated by the following method: filter LiCl; Evaporate excessive Chlorodimethyl silane; With buck (sodium bicarbonate of dilution) wash residual thing to remove residual HCl, with after washing; And dry (anhydrous sodium sulphate) and distillation (using falling-film evaporator or wiped film evaporator or other distillating methods well known by persons skilled in the art) are anhydrated and any residual D to remove
3Or senior ring compound.The product that is generated is that MW is normal-butyl-or the sec-butyl-simple function dimethyl siloxane dimethyl-silicon alkane derivatives of 190g/ mole.
Method B: for obtaining MW is narrow dispersion and the single mPDMS-H of dispersion synthetics more than the 190g/ mole, uses the D of calculated amount in hexanaphthene or hexane
3And alkyl lithium reagents (for example n-Butyl Lithium or s-butyl lithium) reacted about 1 hour to about 4 hours to about 60 ℃ temperature at about 5 ℃.(time is about 2 hours to about 24 hours, and temperature is about 5 ℃ to about 60 ℃) added polar chain and increased aprotic solvent (for example THF) subsequently under controlled conditions, observes D until gas chromatographic analysis
3Near transforming fully.Use alkyl dimethiconol negatively charged ion (alkylpolydimethylsiloxonalate anion) endization of excessive Chlorodimethyl silane to generating.
The reaction product that generates of purifying by the following method: filter LiCl; Evaporate excessive Chlorodimethyl silane; With buck (sodium bicarbonate of dilution) wash residual thing to remove residual HCl, with after washing; And dry (anhydrous sodium sulphate) and distillation (using falling-film evaporator or wiped film evaporator or other distillating methods well known by persons skilled in the art) are anhydrated and any residual D to remove
3Or senior ring compound.It is alkyl-mPDMS-H that～413 narrow MW distributes that aforesaid method generates average MW, described MW distribution can passing through gel permeation chromatography, NMR (
1H and
29Si) and mass spectrum (MALDI-TOF) analyze determine.Can under controlled temperature and vacuum condition, use fractionating method well known by persons skilled in the art to be further purified the narrow dispersion product that is generated, to generate single normal-butyl-mPDMS-H derivative or sec-butyl-mPDMS-H derivative of disperseing.Flow process 1B has described the synthetic schemes of relevant MW for the alkyl-hydroxyl-mPDMS synthetics of～613g/ mole.
Flow process 1B:MW is～single alkyl-hydroxyl-mPDMS-method 1 of disperseing of 613g/ mole.
Step 2: be combined to and purification of hydroxy-mPDMS by hydrosilanes
The product that purified narrow dispersion that obtains from step 1 (method A or method B) or monodispersed end are hydride reacts with the methacrylic acid allyloxy hydroxypropyl ester (AHM) or the vinylformic acid allyloxy hydroxypropyl ester (AHA) of molar excess in the presence of hydrosilylation catalysts.Suitable catalyzer comprise based on rhodium catalyzer (for example Wilkinson ' s catalyzer) and based on the catalyzer of platinum (for example Karstedt catalyzer, Pt (O) tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, Platinic chloride, Pt/C and PtO
2).Be reflected under the atmosphere of dried compressed air, nitrogen or argon gas, about 5 ℃ to about 40 ℃ temperature, carry out, and continue to and detect (analyzing) initial mPDMS-H and almost completely consume by FTIR.When reaction finishes, use diethyl ethylenediamine in a small amount (be generally active Pt catalyzer mole number about 10 times to about 100 times) deactivation mixture.Spent glycol washs " so synthetic " reaction product several times then, to remove unreacted AHM or AHA (residual A HM or AHA＜0.1% in product usually).For removing the residual unreacted mPDMS-H and the by product of any high molecular weight/polymeric, product can be in ethylene glycol washing back with methyl alcohol dilution (volume ratio of 1:3 to 1:5).The turbid solution that obtains after the sedimentation has two-phase.Can repeat this process, until detecting less than mPDMS-H at FTIR in the product of washing.Can use batch centrifugal separator (batchcentrifugal separator), continuous contactor equipment or other separating devices well known by persons skilled in the art to quicken above-mentioned washing/leaching process.Suppress liquid-liquid by MEHQ or BHT (being generally～50ppm to 100ppm) and extract the product that the back obtains, use falling-film evaporator or wiped film evaporator distillation (until removing almost all ethylene glycol) subsequently, generated highly purified hydroxyl-mPDMS derivative.
Therefore, can use AHM and suitable alkyl-mPDMS-H to obtain to have single alkyl-hydroxyl-mPDMS derivative that disperses of different MW, it is the product example of 391g/ mole and 613g/ mole that flow process 1A and flow process 1B have listed MW respectively.Can adopt similarly to synthesize to prepare trimethyl silyl-hydroxyl-mPDMS derivative, use the lithium salts or the 4-butyl ammonium of trimethyl silyl alcohol, described in flow process 2 with purification process.This general hydrosilanes is combined to the alkyl-hydroxyl-mPDMS analogue that can be used for synthetic higher MW with purge process, uses more high-molecular weight alkyl-mPDMS-hydride starting raw material.More than disclosed general synthetic and purification process can be used for preparing the alkyl-hydroxyl-mPDMS synthetics of different molecular weight with polydispersion molecular weight distribution, use suitable polydispersion alkyl-PDMS-H starting raw material.
Flow process 2: trimethyl silyl-hydroxyl-mPDMS-method 1.
Method 2:
Second method that is used for synthetic alkyl-hydroxyl of the present invention-mPDMS comprises three step successive processess.Flow process 3 has been listed the strategy of this method, and final product MW is～the 613g/ mole.
Flow process 3:MW is single alkyl-hydroxyl-mPDMS-method 2 of disperseing of 613g/ mole.
Step 1: the synthetic and purifying of alkyl-mPDMS-H derivative
First synthesis step in the method 2 is followed the identical negatively charged ion open loop experiment design of describing in the step 1 (method B) of method 1.
Step 2: be combined to/purification of alkyl-epoxy-mPDMS derivative by hydrosilanes
Can the commercial allyl glycidyl ether that obtains with step 1 in the narrow dispersion that obtains or the hydrosilylation reactions of single alkyl-mPDMS-H of dispersion, generate the intermediate alkyl-epoxy-mPDMS derivative of hope with good yield.Can use falling-film evaporator or wiped film evaporator high vacuum and in/distill the alkyl-epoxy-mPDMS derivative that is generated under the high-temperature, to generate very highly purified epoxy derivative.
Step 3: synthesize/purification of alkyl-hydroxyl-mPDMS by the oxyethane ring-opening reaction
Ring-opening reaction
After purge process well known by persons skilled in the art, use methacrylate or acrylate to make purified alkyl-epoxy-mPDMS open loop, generate the corresponding alkyl-hydroxyl-mPDMS derivative of good purity.
Method 3:
Flow process 4 has been described two-stage process.
Flow process 4: single alkyl-hydroxyl-mPDMS-method 3 of disperseing.
Step 1: be combined to " end-capping reagent " by hydrosilanes
First step be AHM or AHA and can the commercial Chlorodimethyl silane that obtains between hydrosilylation reactions.Under inert/dry conditions and the product that uses distillation technique purifying well known by persons skilled in the art to generate, highly purified product is provided, it is effective chain terminator or " end-capping reagent " that is used for next reactions steps.
Step 2: pass through D
3
Ring opening synthesis alkyl-hydroxyl-mPDMS
Second step is to hexamethyl cyclotrisiloxane (D by the process described in the step 1 of method 1
3) open loop controllably, use " end-capping reagent " termination silica alkanol negatively charged ion subsequently.By extracting and distillating method purifying " so synthetic " reaction product, generate highly purified alkyl-hydroxyl-mPDMS.
Disclosed method contains the new synthetic and purification process of hydroxyl disclosed herein-simple function PDMS propyl group glycerine (methyl) acrylate derivative (have different molecular weight and have from singly being dispersed to the narrow differing molecular that is dispersed to the polydispersion product and distribute).
New single the dispersion and narrow dispersion mPDMS propyl methyl acid esters synthetics
Two embodiment of the new methacrylic ester-monofunctional polydimethylsiloxane derivative preparation method with single dispersion and narrow MW distribution are described below:
Method 1:
The reaction process that is used for the synthetic new single mPDMS of dispersion derivative has been described in the flow process 5.In nonpolar and/or polar proton inert solvent, under the anionoid polymerization of control, carry out D
3Ring-opening reaction, generated in-situ subsequently silica alkanol negatively charged ion and the methacrylic acid Chlorodimethyl silyl propyl diester reaction that can commercially obtain can generate narrow dispersion and monodispersed mPDMS derivative, and it has the terminal methyl group acrylate-functional groups.
Flow process 5: methacrylate functionalized mPDMS derivative synthetic.
Method 2:
The design of this compound experiment adopt single disperse or narrow dispersive alkyl-PDMS-H and can the commercial allyl methacrylate(AMA) that obtains when synthesis of alkyl hydroxyl-mPDMS the hydrosilylation reactions under the described condition.Described in the flow process 6 and to have obtained MW for～982g/ mole and have the synthesis step of the final product of narrow polymolecularity.
Flow process 6:MW is～the methacrylate functionalized mPDMS derivative-method 2 of narrow dispersion of 982g/ mole.
Claims (34)
1. one kind is used to prepare single the dispersion or the method for narrow dispersive monofunctional polydimethylsiloxane synthetics, and this method comprises the steps:
With the alkyl lithium compounds reaction of hexamethyl cyclotrisiloxane and formula RLi, wherein R is the alkyl of 1 to 8 carbon atom.
2. be used to prepare the method for the claim 1 of singly dispersion or narrow dispersive hydroxyl-alkyl-simple function dimethyl siloxane synthetics, this method comprises the steps:
The alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and molar excess is reacted in non-polar solvent to generate the silanol negatively charged ion, and wherein R is the alkyl of 1 to 8 carbon atom;
With the Chlorodimethyl silane reaction of described silanol negatively charged ion and molar excess, has single alkyl simple function dimethyl siloxane that disperses of SiH end group with generation; With
With described alkyl-simple function dimethyl siloxane with SiH end group in the presence of platinum or rhodium catalyst with (methyl) vinylformic acid allyloxy hydroxy-propyl ester reaction of molar excess, have the polydimethylsiloxane of the monodispersed alkyl end of (methyl) vinylformic acid hydroxy-propyl ester ether end group with generation.
3. be used to prepare the method for the claim 1 of singly dispersion or narrow dispersive hydroxyl-functional polydimethylsiloxanes synthetics, this method comprises the steps:
Reaction is to generate alkyl tetramethyl--tetrasiloxane alcohol negatively charged ion in nonpolar and polar proton inert solvent with the alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and calculated amount, and wherein R is the alkyl of 1 to 8 carbon atom;
With the Chlorodimethyl silane reaction of described alkyl tetramethyl--tetrasiloxane alcohol negatively charged ion and molar excess, has the terminal polydimethylsiloxane of narrow dispersion alkyl of SiH end group with generation;
The described terminal polydimethylsiloxane of narrow dispersion alkyl with SiH end group of fractionation has the single of SiH end group with generation and disperses or the terminal polydimethylsiloxane of narrow dispersion alkyl; With
Described single dispersion or the terminal polydimethylsiloxane of narrow dispersion alkyl with SiH end group reacted with the allyl glycidyl ether of molar excess in the presence of platinum or rhodium catalyst, to generate single the dispersion or narrow dispersive alkyl-epoxy-mPDMS derivative; With
With described alkyl-epoxy-mPDMS derivative and the reaction of (methyl) acrylate, have the single of (methyl) vinylformic acid hydroxy-propyl ester ether end group with generation and disperse or the terminal polydimethylsiloxane of narrow dispersion alkyl.
4. be used to prepare that have a terminal methyl group acrylate-functional groups single disperses or the method for the claim 1 of narrow dispersion polydimethylsiloxane, this method comprises the steps:
The alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and calculated amount is reacted in non-polar solvent to generate the silanol negatively charged ion, and wherein R is the alkyl of 1 to 8 carbon atom; With
With the methacrylic acid Chlorodimethyl silyl propyl diester reaction of described silanol negatively charged ion and molar excess, has the terminal polydimethylsiloxane of narrow dispersion alkyl of methacryloxypropyl end group with generation;
The described terminal polydimethylsiloxane of narrow dispersion alkyl with methacryloxypropyl end group of fractionation, the list that has the methacryloxypropyl end group with generation disperses the terminal polydimethylsiloxane of alkyl.
5. be used to prepare single the dispersion or the method for the claim 1 of the polydimethylsiloxane synthetics of narrow dispersive hydroxyl-functional, this method comprises the steps:
With (methyl) vinylformic acid allyl group oxygen base hydroxypropyl acrylate in the presence of platinum or rhodium catalyst with the Chlorodimethyl silane reaction, have (methyl) Propylene glycol monoacrylate of chloromethane silylation chain termination end group with generation; With
The alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and calculated amount and described (methyl) Propylene glycol monoacrylate with chloromethane silylation chain termination end group reacted in nonpolar and/or polar proton inert solvent have the single of (methyl) Propylene glycol monoacrylate ether end group with generation and disperse or the terminal polydimethylsiloxane of narrow dispersion alkyl, wherein R is the alkyl of 1 to 8 carbon atom.
6. one kind is used to prepare single the dispersion or the method for narrow dispersive monofunctional polydimethylsiloxane synthetics, and this method comprises the steps:
The alkyl lithium compounds of hexamethyl cyclotrisiloxane and formula RLi is reacted to generate the silanol negatively charged ion, and wherein R is the alkyl of 1 to 8 carbon atom; With
Chlorodimethyl silane reaction with described silanol negatively charged ion and molar excess.
7. be used to prepare that have a terminal methyl group acrylate-functional groups single disperses or the method for the claim 6 of narrow dispersion polydimethylsiloxane, this method comprises the steps:
Reaction is to generate the silanol negatively charged ion in nonpolar and polar proton inert solvent with the alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and calculated amount, and wherein R is the alkyl of 1 to 8 carbon atom;
With the Chlorodimethyl silane reaction of described silanol negatively charged ion and molar excess, has the terminal polydimethylsiloxane of narrow dispersion alkyl of SiH end group with generation;
The described terminal polydimethylsiloxane of narrow dispersion alkyl of fractionation with SiH end group, the list that has the SiH end group with generation disperses the terminal polydimethylsiloxane of alkyl; With
With the terminal polydimethylsiloxane of the narrow dispersion alkyl of the described SiH of having end group or have a SiH end group single disperse the terminal polydimethylsiloxane of alkyl in the presence of platinum or rhodium catalyst with (methyl) allyl acrylate reaction of molar excess, have narrow dispersion or single alkyl end polydimethylsiloxane that disperses of methacryloxypropyl end group with generation.
8. be used to prepare the method for the claim 6 of the narrower dispersion of high molecular or single polydimethylsiloxane synthetics that disperses hydroxyl-functional, this method comprises the steps:
Reaction is to generate silica alkanol negatively charged ion in the mixture of nonpolar and polar solvent with the alkyl lithium compounds of the formula RLi of hexamethyl cyclotrisiloxane and calculated amount, and wherein R is the alkyl of 1 to 8 carbon atom;
With the Chlorodimethyl silane reaction of described silica alkanol negatively charged ion and molar excess, has the terminal polydimethylsiloxane of narrow dispersion alkyl of SiH end group with generation;
The described terminal polydimethylsiloxane of narrow dispersion alkyl of fractionation with SiH end group, the list that has the SiH end group with generation disperses the terminal polydimethylsiloxane of alkyl; With
With the terminal polydimethylsiloxane of described alkyl with SiH end group in the presence of platinum or rhodium catalyst with (methyl) vinylformic acid allyloxy hydroxypropyl ester reaction of molar excess, have narrow dispersion or single alkyl end polydimethylsiloxane that disperses of (methyl) vinylformic acid hydroxypropyl ester ether end group with generation.
9. one kind is used to prepare single the dispersion or the method for narrow dispersive monofunctional polydimethylsiloxane synthetics, and this method comprises the steps:
With hexamethyl cyclotrisiloxane and trialkyl silanol reactant salt.
10. be used to prepare single the dispersion or the method for the claim 9 of the polydimethylsiloxane synthetics of narrow dispersion hydroxyl-functional, this method comprises the steps:
The trimethyl silyl alkoxide of hexamethyl cyclotrisiloxane and calculated amount and the Chlorodimethyl silane of molar excess are reacted the terminal polydimethylsiloxane of trimethyl silyl that has the SiH end group with generation in non-polar solvent and/or polar proton inert solvent, the positively charged ion of wherein said trimethyl silyl alkoxide is lithium ion or formula R
4N
+Quaternary ammonium ion, wherein R is the alkyl of 1 to 8 carbon atom; With
With the terminal polydimethylsiloxane of described trimethyl silyl with SiH end group in the presence of platinum or rhodium catalyst with (methyl) vinylformic acid allyl group oxygen base hydroxypropyl ester reaction of molar excess, have the alkyl end polydimethylsiloxane of (methyl) vinylformic acid hydroxypropyl ester ether end group with generation.
List with terminal methyl group acrylate-functional groups disperses or the method for the claim 9 of narrow dispersion polydimethylsiloxane 11. be used to prepare, and this method comprises the steps:
The lithium salts or the 4-butyl ammonium of the trimethyl silyl alcohol of hexamethyl cyclotrisiloxane and calculated amount are reacted in nonpolar and/or polar proton inert solvent to generate silica alkanol negatively charged ion; With
The methacrylic acid Chlorodimethyl silyl propyl diester of described silica alkanol negatively charged ion and molar excess is reacted in the presence of hydrosilylation catalysts, have the single of methacryloxypropyl end group with generation and disperse or the terminal polydimethylsiloxane of narrow dispersion trimethyl silyl.
12. a method, this method comprises:
(a) the trialkyl silicomethane alkoxide of hexamethyl cyclotrisiloxane and molar excess or functionalized or not functionalized organometallic compound are reacted at least a non-polar solvent, to generate the silanol negatively charged ion;
(b) with the chlorosilane cpd of the formula I of described silanol negatively charged ion and molar excess:
Cl-Si-(CH
3)
2-R
1
Reaction, wherein R
1Be selected from C1 to the C8 alkyl of H, C1 to C8 alkyl or replacement, wherein said substituting group comprises the proton inertia substituting group, for example Bao Hu hydroxyl, free radical reaction group and combination thereof.
13. the method for claim 12, wherein said non-polar solvent are selected from pentane, hexanaphthene, hexane, heptane, benzene, toluene, high-grade non-polar hydrocarbons and composition thereof more.
14. the method for claim 12, wherein said non-polar solvent are selected from pentane, hexanaphthene, hexane, its mixture etc.
15. the method for claim 12, wherein said non-polar solvent comprises hexanaphthene.
16. the method for claim 12, wherein said reactions steps (a) was carried out about 1 hour to 4 hours to about 60 ℃ temperature at about 5 ℃.
17. the method for claim 12, wherein R
1Be C1 to the C8 alkyl of the replacement that comprises the free radical reaction group, described free radical reaction group is selected from (methyl) acrylate group, styryl, vinyl, vinyl ether group, vinylformic acid C
1-6Alkyl group, acrylamide group, C
1-6Alkyl acrylamide group, N-vinyl lactam group, N-vinylamide group, C
2-12Alkenyl, C
2-12Alkenyl phenyl, C
2-12Alkenyl naphthyl or C
2-6Alkenyl phenyl C
1-6Alkyl.
18. the method for claim 17, wherein said free radical reaction group are selected from (methyl) acrylate group, acryloxy and (methyl) acrylamide group.
19. the method for claim 12, wherein R
1Be H, reactions steps (b) generates the polydimethylsiloxane of silane end, and described method further comprises the steps:
(c) polydimethylsiloxane of described silane end and (methyl) allyl acrylate of molar excess or the epoxide of replacement are reacted in the presence of at least a hydrosilylation catalysts.
20. the method for claim 19, wherein said hydrosilylation catalysts are Pt
2{ [(CH2=CH) Me
2Si]
2O}
3Or Ashby ' s catalyzer.
21. the method for claim 20, wherein said hydrosilylation catalysts exists to the amount of about 500ppm with about 5ppm, and described being reflected under the condition that comprises about 0 ℃ of extremely about 100 ℃ temperature reaches about 24 hours.
22. the method for claim 21, wherein reactions steps (c) is carried out under condition of no solvent.
23. the method for claim 19, terminal polydimethylsiloxane of wherein said silane and the reaction of (methyl) allyl acrylate.
24. the method for claim 23, wherein said (methyl) allyl acrylate are selected from (methyl) allyl acrylate, methacrylic acid allyl group oxygen base hydroxy-propyl ester and vinylformic acid allyl group oxygen base hydroxy-propyl ester.
25. the method for claim 23, wherein said (methyl) allyl acrylate are methacrylic acid allyl group oxygen base hydroxy-propyl ester or vinylformic acid allyl group oxygen base hydroxy-propyl ester.
26. the method for claim 19, the epoxide reaction of the replacement of terminal polydimethylsiloxane of wherein said silane and formula III epoxide:
Wherein B is the group that can form hydrogen bond with another group or carboxylic acid derivative.
27. the method for claim 29, wherein B is selected from heteroatoms, carbonyl, has alkylidene group, amine, acid amides, ether, ester, aldehyde, ketone, aromatic group, alkyl and the combination thereof of 1 to 6 carbon atom, and described alkylidene group can be unsubstituted or be replaced by hydroxyl.
28. the method for claim 29, wherein B is the alkyl that O or the hydroxyl with 1 to 4 carbon atom replace.
29. the method for claim 29, the epoxide of wherein said replacement are allyl glycidyl ether.
30. the method for claim 19, this method further are included in reactions steps (c) step of the terminal polydimethylsiloxane of the described silane of purifying before.
31. the method for claim 30, wherein said purification step comprises: evaporation uses buck to carry out water extraction at the remaining chlorosilane in step (b) back subsequently, and distillation.
32. the method for claim 12, wherein said organometallic compound are the alkyl lithium compounds of formula RLi, wherein R is the alkyl of 1 to 8 carbon atom.
33. the method for claim 30, wherein said purification step comprise that the terminal polydimethylsiloxane of the described silane of fractionation is to generate single the dispersion or the terminal polydimethylsiloxane of narrow dispersive silane.
The method of claim 23, wherein the product of reactions steps (c) is a free radical reaction, replace or the polydimethylsiloxane of substituted alkyl end not, and described method further comprises step (d): the described free radical reaction of fractionation, replace or not the polydimethylsiloxane of substituted alkyl end replace or the polydimethylsiloxane of substituted alkyl end not to generate single the dispersion or narrow dispersive free radical reaction.
34. the process of claim 1 wherein that described reactions steps carries out in non-polar solvent.
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|---|---|---|---|
| US66255605P | 2005-03-17 | 2005-03-17 | |
| US60/662,556 | 2005-03-17 | ||
| US60/682,410 | 2005-05-19 |
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| CN109071575A (en) * | 2016-04-27 | 2018-12-21 | 信越化学工业株式会社 | Hydrolytic resistance silicone compounds and its manufacturing method |
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| CN114716680B (en) * | 2021-06-23 | 2023-08-25 | 浙江赢科新材料股份有限公司 | Preparation method of single-end gamma-methacryloxypropyl functional group-terminated polydimethylsiloxane |
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