CN1238332A - Low-temp synthesis process for vinyl silicate monomer and its polymers - Google Patents
Low-temp synthesis process for vinyl silicate monomer and its polymers Download PDFInfo
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- CN1238332A CN1238332A CN 99116231 CN99116231A CN1238332A CN 1238332 A CN1238332 A CN 1238332A CN 99116231 CN99116231 CN 99116231 CN 99116231 A CN99116231 A CN 99116231A CN 1238332 A CN1238332 A CN 1238332A
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Abstract
A low-temp. process for synthesizing vinylsilicate monomer and its polymer features use of SiO2 in the form of natural or industrial dregs as initial raw material which is cheaper and easily available, and includes the steps of low-temp. non-carbon thermal reduction to synthesize active silicate, reaction on halogen-contained vinyl monomer to synthesize vinylsilicate monomer, and free-radical homopolymerization or copolymerization to obtain high-molecular substance containing silicate radical at side chain. Its advantages are low energy consumption, low requirement to equipment and no environmental pollution.
Description
The present invention relates to the low-temperature synthetic method of a kind of vinyl silicate monomer and polymkeric substance thereof, specifically refer to the method for a kind of non-carbothermic reduction by direct synthesis of vinyl silicate monomer of silicon-dioxide and polymkeric substance thereof.
Silicoorganic compound play an important role in the development of new chemical reagent, polymkeric substance, advanced glass and pottery, yet the required starting raw material-silicon of organosilicon almost all depends on the carbothermic reduction (temperature is higher than 1200 ℃) of silicon-dioxide, the approach that silicon is converted into silicoorganic compound again mainly contains two: (1) obtains silicon tetrachloride and trichlorosilane alkane by silicon and hcl reaction, and silicon tetrachloride obtains organosilicon with organometallics reactions such as refined reagent of Green or organolithiums again; (2) in the presence of copper/tin catalyst in 200-350 ℃ with halohydrocarbons reactions such as silicon and methyl chloride, can be converted into the organosilicon raw material to silicon.All there is the high energy consumption of carbothermic reduction in these two kinds of methods and inevitably to the high request of the anti-hydrogen-chloride etching of equipment, and exist serious environmental to pollute, and make organosilyl production cost very high.Therefore the development utilization cheap raw material directly obtains the organosilicon raw material through " non-carbothermic reduction " step becomes a problem that receives much attention.People [Zeldin N. such as Zeldin in 1987, ACS Symposium Series, 1987,360:238-241] find mineral silicate, hydrogenchloride and ethanol in toluene through the component distillation water outlet, can obtain the tetraethoxy of four-coordination, but productive rate is lower, and tetraethoxy to be continued the activity of substitution reaction not high, also be difficult to make vinyl silicate monomer and polymkeric substance with this method.The people such as Laine of the U.S. in 1991 [R.M.Laine, K.Y.Blohowiak, T.R.Robinson, M.L.Hoppe, P.Nardi, J.Kampf, J.Uhm, Nature, 1991, Vol.353:642] reported a kind of method of under catalyst action, directly synthesizing the silicon-containing compound of pentacoordinate or hexa-coordinate by silicon-dioxide, the pentacoordinate silicon ester of gained is very active, not expensive, provide a new way for synthesizing silicon-containing compound and polymkeric substance.USP5099052 and USP5216155 disclose a kind of preparation of pentacoordinate silicon ester and follow-up reaction thereof, as with the reaction of exsiccant hydrogenchloride, diacetyl oxide, ethylene glycol oligopolymer etc., but do not relate to and the particularly monomeric reaction of vinyl Halogen of halohydrocarbon.People's such as these several years Laine research work mainly concentrates on other polyvalent alcohol and replaces the cracking of ethylene glycol activated silica acid esters and product thereof to prepare high-performance ceramic; Or carry out polycondensation with polyvalent alcohol oligopolymer and pentacoordinate or hexa-coordinate silicon ester and prepare polymkeric substance as ionophore etc.USP5418298 wherein, 1995 disclose a kind of poly-metal oxygen alkane of single or blended that is prepared neutrality or anionic by silicon-dioxide or other metal oxide or oxyhydroxide and polyol reaction, but the molecular weight of the polymkeric substance that this approach obtains is lower, difficult the purification, and have the crosslinked problem of product inevitably; USP5440011,1995 disclose the method that a kind of pentacoordinate that is directly made by silicon-dioxide low temperature or hexa-coordinate silicon ester and polyether glycol obtain ionic conductive polymer, but this method can not obtain the polymkeric substance that side chain contains coordination silicon ester group, and the stability to hydrolysis of the ionic conductive polymer of gained is not good enough, also restive product is crosslinked, so product is difficult to purify and forming process.
The objective of the invention is to overcome the defective of above prior art, providing a kind of is starting raw material with silicon-dioxide cheap, the forms such as natural or industrial residue that are easy to get, through non-carbothermic reduction and under catalyst action with organism prepared in reaction molecular weight height, purification and machine-shaping is easy, stability to hydrolysis the is high vinyl silicate monomer and the low-temperature synthetic method of polymkeric substance thereof.The vinyl silicate monomer and the polymkeric substance of gained of the present invention have industrial application value, can be used as novel material, novel organosilicon coupling agent, polymeric crosslinker, organic/inorganic hybrid materials etc.
The objective of the invention is to reach by following technical solution:
The low-temperature synthetic method of a kind of vinyl silicate monomer and polymkeric substance thereof may further comprise the steps and processing condition:
Step 1: the preparation of activated silica acid esters
Chemical equation by silicon-dioxide low temperature composite reactive silicon ester is as follows:
In the formula (1), n=5-20,
m=0、1、2,
R
1The alkyl that do not replace or that replace of=C2～C12,
M (OH)
m=alkalimetal oxide or oxyhydroxide or boiling point are higher than 180 ℃ tertiary amine etc.;
Shown in chemical equation (1), add dibasic alcohol and the 1mol catalyzer of 1mol silicon-dioxide, 5～25molC2～C12 in the reactor in the lump, under whipped state, 150～200 ℃ of following low-temp reactions 1～4 hour, after distilling out the water of unnecessary dibasic alcohol and by-product, get the activated silica acid esters of 0.95～1mol;
This step catalyst system therefor can be that alkalimetal oxide or oxyhydroxide or boiling point are higher than the wherein a kind of of tertiary amine of 180 ℃ etc.;
Step 2: the preparation of vinyl silicate monomer
Chemical equation by activated silica acid esters and Halogen vinyl monomer reaction synthesis of vinyl silicate monomer is as follows:
In formula (2), (3):
R
2The alkyl that do not replace or that replace of=H, C1～C18,
R
3The aryl that do not replace or that replace of=C7～C19,
The alkyl that do not replace or that replace of C1～C18,
-COOR
4-(wherein-R
4The alkane that do not replace or that replace of-=C1～C18
Base),
R5, R6, the alkyl that do not replace or that replace of R7=C1～C18,
X
-=Cl
-、Br
-、I
-、NO
3 -、CH
2SO
3 -；
According to chemical equation (2), (3), 1mol activated silica acid esters with the step 1 gained, in methyl alcohol or under the solvent-free state directly with 0.5 or 1mol vinyl Halogen monomer 25～80 ℃ of reactions 0.5～6 hour down, remove by filter the salt of generation, distilling off solvent obtains 0.95～1mol vinyl silicate monomer;
The used vinyl Halogen of this step monomer can be a methacrylic acid chloroethene alcohol ester, vinylformic acid chloroethene alcohol ester, propenyl chloride, vinylchlorid, vinyl chloroacetate, Mono Chloro Acetic Acid propylene ester, p-chloromethyl styrene, toxilic acid dichlroroethanol ester, toxilic acid list C1～C18 alcohol ester chloroethene alcohol ester, methylacryoyloxyethyl-three (C1～C18 alkyl) ammonium halide, acrylyl oxy-ethyl-three (C1～C18 alkyl) ammonium halide, ethenylphenyl-three (C1～C18 alkyl) ammonium halide, allyl group-three (C1～C18 alkyl) ammonium halide etc. wherein a kind of;
Step 3: the homopolymerization of vinyl silicate monomer
The homopolymerization chemical equation of vinyl silicate monomer is as follows:
In formula (4), (5):
n＞5
Shown in chemical equation (4), (5), the 1mol vinyl silicate monomer is dissolved in polar solvent or the non-polar solvent, or under solvent-free state, the radical initiator that adds 0.01～0.5% (weight), 60～85 ℃ of following polymerizations 2～12 hours, through distilling off solvent or add precipitation agent precipitation, obtain the polyamino polymer of the siliceous acid esters group of side chain;
This step is used:
Polar solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethanol, ethyl acetate, butylacetate etc.,
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.,
Radical initiator can be the wherein a kind of of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dilauroyl peroxide etc.,
Precipitation agent can be the wherein a kind of of methyl alcohol, ether, sherwood oil, hexane, hexanaphthene etc.,
In addition, also can obtain the copolymerized macromolecule of the siliceous acid esters group of side chain by the copolyreaction of vinyl silicate monomer and other vinyl monomer, its chemical equation is as follows:
In formula (6), (7):
n,m＞5,
n:m=0.01～100,
R
2The alkyl that do not replace or that replace of=H, C1～C18,
R
8=-C
6H
6、-Cl、-OCOCH
3、-COOR
12(C1～C18
Alkyl that not replace or that replace) ,-CN;
Shown in chemical equation (6), (7), be dissolved in the 1mol vinyl silicate monomer in polarity or the non-polar solvent or under the solvent-free state, the radical initiator that adds the vinyl monomer and 0.01～0.5% (weight) of 0.01～100mol, 60～85 ℃ of following polymerizations 2～12 hours, distilling off solvent or adding precipitation agent precipitate, and obtain the copolymerized macromolecule of the siliceous acid esters group of side chain;
This step is used:
Polar solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethanol, ethyl acetate, butylacetate etc.;
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.;
Radical initiator can be the wherein a kind of of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dilauroyl peroxide etc.;
Vinyl monomer can be the wherein a kind of of vinylbenzene, vinylchlorid, vinylidene chloride, vinyl acetate, vinylformic acid (C1～C18 alkyl) ester, methacrylic acid (C1～C18 alkyl) ester, toxilic acid two (C1～C18 alkyl) ester, vinyl cyanide etc.;
Precipitation agent can be the wherein a kind of of methyl alcohol, ether, sherwood oil, hexane, hexanaphthene etc.
The present invention compared with prior art has following advantage:
(1) source of silicon-dioxide is not limited to pure silicon-dioxide, the waste residue (silicon powder) of cheapness, the natural or industrial waste residue that is easy to get such as natural amorphous silica, diatomite, rice husk ash, aluminium metallurgy white residue, ferro-silicon factory etc. can be utilized, preparation cost can be directly reduced.
(2) the required starting raw material of organosilicon in the prior art---silicon almost all depends on the carbothermic reduction of silicon-dioxide, and its temperature all is higher than 1200 ℃.The invention belongs to " non-carbothermic reduction ", by the activated silica acid esters of silicon-dioxide preparation and the monomeric temperature of reaction of vinyl Halogen low (normal temperature～80 ℃).Therefore, this law has avoided the conventional carbon hot reducing method to prepare the shortcomings such as highly energy-consuming, deep-etching and pollution that organosilicon material exists, and the vinyl silicate monomer of gained and the cost of polymkeric substance thereof are cheaper than traditional organosilicon material.
(3) by the activated silica acid esters of silicon-dioxide preparation can be earlier through separate just purify can with vinyl Halogen monomer reaction, avoided the organosilyl hydrolysis of pentacoordinate in the separation purification process, the vinyl silicate monomer of gained can be purified, thereby obtains pure polymkeric substance.
(4) polymkeric substance by the further polymerization gained of the vinyl silicate monomer of gained can not take place crosslinked, therefore can adopt the processing molding method of general polymerization thing to carry out forming process, the vinyl silicate monomer of gained and polymkeric substance thereof can be used as aspects such as novel material, novel organosilicon coupling agent, polymeric crosslinker, organic/inorganic hybrid materials and are applied.
Below will the invention will be further described by embodiment: embodiment 1
Potassium type activated silica acid esters and the reaction of methacrylic acid chloroethene alcohol ester
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 28 gram potassium hydroxide and 300 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 1 hour, and excessive ethylene glycol was all steamed in about 3 hours.Stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.Crystallization with 200 milliliters of anhydrous methanol dissolving gained gets colorless cleared solution, drips 74.5 gram methacrylic acid chloroethene alcohol esters while stirring in solution under the room temperature, is warming up to 50 ℃ of reactions 1 hour, and metering ground generates white Repone K precipitation.Filter the back and steam methyl alcohol, obtain thick colourless vinyl silicate monomer 161 grams in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned vinyl silicate monomer of 161 grams is dissolved in 200 milliliters of butylacetates, the Diisopropyl azodicarboxylate that adds 0.4 gram, the inflated with nitrogen sealing of vibration dissolving back, 65 ℃ of following constant temperature polymerizations 8 hours, with homopolymer white solid 158 grams that get the siliceous acid esters group of side chain behind 1000 milliliters of petroleum ether precipitations, it is 120000 that GPC records number-average molecular weight.
In the 250ml flask, 16.1 above-mentioned vinyl silicate monomers of gram and 50 gram methyl methacrylates are mixed, the Diisopropyl azodicarboxylate that adds 0.3 gram, the inflated with nitrogen sealing of vibration dissolving back, 65 ℃ of following constant temperature polymerizations 8 hours, obtain multipolymer white solid 65 grams of the siliceous acid esters group of side chain after the cooling, it is 150000 that GPC records number-average molecular weight.Embodiment 2
Sodium type activated silica acid esters and the reaction of vinylformic acid chloroethene alcohol ester
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 1000ml there-necked flask, add 60 gram silicon-dioxide, 40 gram sodium hydroxide and 600 milliliters of ethylene glycol, under agitation be warming up to 150 ℃ of water that steam generation, silicon-dioxide all dissolves after about 4 hours, heat up again and all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.Directly drip 134.5 gram vinylformic acid chloroethene alcohol esters under the room temperature, be warming up to 80 ℃ of stirring reactions 0.5 hour, metering ground generates white sodium-chlor precipitation.Directly obtain thick colourless vinyl silicate monomer 307 grams after the filtration down at 80 ℃.
The Diisopropyl azodicarboxylate that in the 50ml polymerization bottle, adds 31 above-mentioned vinyl silicate monomers of gram and 0.1 gram, the inflated with nitrogen sealing of vibration dissolving back, 60 ℃ of following constant temperature polymerizations 12 hours, get polymkeric substance white solid 31 grams of the siliceous acid esters group of side chain, it is 150000 that GPC records number-average molecular weight.
In the 2500ml flask, 3.1 above-mentioned vinyl silicate monomers of gram and 104 gram vinylbenzene are mixed, the Diisopropyl azodicarboxylate that adds 0.2 gram, the inflated with nitrogen sealing of vibration dissolving back, 60 ℃ of following constant temperature polymerizations 12 hours, obtain multipolymer white solid 105 grams of the siliceous acid esters group of side chain after the cooling, it is 180000 that GPC records number-average molecular weight.Embodiment 3
Potassium type activated silica acid esters and p-chloromethyl styrene reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 1000ml there-necked flask, add 30 gram silicon-dioxide, 23.5 gram potassium oxide and 600 milliliters of ethylene glycol, under agitation be warming up to 170 ℃ of water that steam generation, silicon-dioxide all dissolves after about 3 hours, continuing to heat up all steams excessive ethylene glycol, stops to heat postcooling to room temperature and obtains activated silica acid esters white crystals.With 200 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, drip 76.5 gram p-chloromethyl styrenes while stirring under the room temperature, 25 ℃ of reactions 0.5 hour down, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain thick colourless vinyl silicate monomer 162 grams in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned vinyl silicate monomer of 32.6 grams is dissolved in 200 milliliters of toluene, the dibenzoyl peroxide that adds the 0.0l gram, the inflated with nitrogen sealing of vibration dissolving back, 80 ℃ of following constant temperature polymerizations 10 hours, the homopolymer white solid 32 that gets the siliceous acid esters group of side chain with 1000 milliliters of hexanaphthene post precipitations restrains, and it is 140000 that GPC records number-average molecular weight.
In the 2500ml flask, the above-mentioned vinyl silicate monomer of 163 grams, 10.4 gram vinylbenzene are dissolved in the 1500ml benzene, the Diisopropyl azodicarboxylate that adds 0.9 gram, the inflated with nitrogen sealing of vibration dissolving back, 65 ℃ of following constant temperature polymerizations 6 hours, with ether sedimentation, filtration, oven dry, obtain multipolymer white solid 172 grams of the siliceous acid esters group of side chain, it is 180000 that GPC records number-average molecular weight.Embodiment 4
Sodium type activated silica acid esters and the reaction of toxilic acid dichlroroethanol ester
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 15.5 gram sodium oxide and 150 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 2 hours, all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 200 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, add 60.5 gram toxilic acid dichlroroethanol esters while stirring under the room temperature, be warming up to 60 ℃ of reactions 6 hours, metering ground generates white sodium-chlor and precipitates.Filter the back and steam methyl alcohol, obtain white vinyl silicate monomer 147 grams of solid state in 50 ℃ of following vacuum.
In the l00ml polymerization bottle, 58.8 above-mentioned vinyl silicate monomers of gram and 8.6 gram vinyl acetates are mixed, the 2,2'-Azobis(2,4-dimethylvaleronitrile) that adds 0.1 gram, the inflated with nitrogen sealing of vibration dissolving back, 75 ℃ of following constant temperature polymerizations 8 hours, obtain multipolymer white solid 67 grams of the siliceous acid esters group of side chain after the cooling, it is 200000 that GPC records number-average molecular weight.Embodiment 5
Potassium type activated silica acid esters and methylacryoyloxyethyl-benzyl dimethyl ammonium chloride reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 28 gram potassium hydroxide and 240 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 1 hour, all steam excessive ethylene glycol then, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 200 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, drip 100 milliliters of methanol solutions that contain 142 gram methylacryoyloxyethyl-benzyl dimethyl ammonium chlorides while stirring under 25 ℃, reacted 0.5 hour, metering ground generates white Repone K precipitation.Filter the back and steam methyl alcohol, obtain crystal 2 27 grams of white vinyl silicate monomer in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned vinyl silicate monomer of 45.7 grams is dissolved in 200 milliliters of tetrahydrofuran (THF)s, the tertbutyl peroxide that adds 0.005 gram, the inflated with nitrogen sealing of vibration dissolving back, 65 ℃ of following constant temperature polymerizations 10 hours, with homopolymer white solid 44.5 grams that get the siliceous acid esters group of side chain behind 1000 milliliters of petroleum ether precipitations, it is 120000 that GPC records number-average molecular weight.
In the 250ml flask, the above-mentioned vinyl silicate monomer of 4.57 grams is dissolved in the 100 gram methyl methacrylates, the dilauroyl peroxide that adds 0.4 gram, the inflated with nitrogen sealing of vibration dissolving back, 80 ℃ of following constant temperature polymerizations 6 hours, obtain multipolymer white solid 104.5 grams of the siliceous acid esters group of side chain after the cooling, it is 180000 that GPC records number-average molecular weight.Embodiment 6
Potassium type activated silica acid esters and vinyl chloroacetate reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 1000ml there-necked flask, add 30 gram silicon-dioxide, 28 gram potassium hydroxide and 450 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 1 hour, all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.Directly drip 61 gram vinyl chloroacetates under the room temperature while stirring, be warming up to 50 ℃ of reactions 1 hour, metering ground generates white Repone K precipitation.50 ℃ of direct filtration obtain thick colourless vinyl silicate monomer 145 grams.
The 2,2'-Azobis(2,4-dimethylvaleronitrile) that in the 50ml polymerization bottle, adds 29.4 above-mentioned vinyl silicate monomers of gram and 0.15 gram, the inflated with nitrogen sealing of 2,2'-Azobis(2,4-dimethylvaleronitrile) dissolving back is treated in vibration, 75 ℃ of following constant temperature polymerizations 4 hours, get homopolymer white solid 29 grams of the siliceous acid esters group of side chain, it is 130000 that GPC records number-average molecular weight.
In the 1500ml flask, add in 1000ml tetrahydrofuran (THF), the 14.7 above-mentioned vinyl silicate monomers of gram and the 128 gram butyl acrylates, the Diisopropyl azodicarboxylate that adds 0.08 gram, the inflated with nitrogen sealing of vibration dissolving back, 65 ℃ of following constant temperature polymerizations 10 hours, obtain multipolymer white solid 142 grams of the siliceous acid esters group of side chain after the cooling, it is 160000 that GPC records number-average molecular weight.Embodiment 7
Sodium type activated silica acid esters and p-chloromethyl styrene reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 2000ml there-necked flask, add 60 gram silicon-dioxide, 40 gram sodium hydroxide and 720 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 2 hours, steam excessive ethylene glycol immediately, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 800 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, drip 152.5 gram p-chloromethyl styrenes while stirring under the room temperature, 25 ℃ of reactions 1.5 hours down, metering ground generates white sodium-chlor and precipitates.Filter the back and steam methyl alcohol, obtain thick colourless vinyl silicate monomer 325 grams in 50 ℃ of following vacuum.
In the 50ml polymerization bottle, the above-mentioned vinyl silicate monomer of 3.3 grams is dissolved in 20 milliliters of dimethyl formamides, the dibenzoyl peroxide that adds 0.001 gram, the inflated with nitrogen sealing of vibration dissolving back, 85 ℃ of following constant temperature polymerizations 2 hours, with homopolymer white solid 3.2 grams that get the siliceous acid esters group of side chain after 100 ml methanol precipitation, the drying, it is 80000 that GPC records number-average molecular weight.
In the 250ml flask, 163 above-mentioned vinyl silicate monomers of gram and 0.5 gram methyl methacrylate are mixed, the dibenzoyl peroxide that adds 0.018 gram, vibration makes the inflated with nitrogen sealing of dibenzoyl peroxide dissolving back, 85 ℃ of following constant temperature polymerizations 2 hours, obtain multipolymer white solid 163 grams of the siliceous acid esters group of side chain after the cooling, it is 90000 that GPC records number-average molecular weight.Embodiment 8
Ammonium type activated silica acid esters and the reaction of methacrylic acid chloroethene alcohol ester
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 1000ml there-necked flask, add 30 gram silicon-dioxide, 92.5 gram Tributylamine and 450 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 4 hours, steam excessive ethylene glycol immediately, stop to heat postcooling to room temperature and obtain white crystals.With 300 ml methanol dissolvings gained crystallization get colorless cleared solution, in solution, drip 74.5 gram methacrylic acid chloroethene alcohol esters while stirring under the room temperature, 50 ℃ of reactions 4 hours down, metering ground generates white Tributylamine hydrochloride and precipitates.Filter the back and steam methyl alcohol, obtain thick colourless vinyl silicate monomer 160 grams in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned vinyl silicate monomer of 32.6 grams is dissolved in 200 milliliters of toluene, the dicumyl peroxide that adds 0.1 gram, the inflated with nitrogen sealing of vibration dissolving back, 85 ℃ of following constant temperature polymerizations 12 hours, with homopolymer white solid 31 grams that get the siliceous acid esters group of side chain behind 1000 milliliters of petroleum ether precipitations, it is 130000 that GPC records number-average molecular weight.
In the 1500ml flask, 163 above-mentioned vinyl silicate monomers of gram and 20.8 gram vinylbenzene are dissolved in the 1000ml butylacetate, the 2,2'-Azobis(2,4-dimethylvaleronitrile) that adds 0.55 gram, vibration makes the inflated with nitrogen sealing of 2,2'-Azobis(2,4-dimethylvaleronitrile) dissolving back, 65 ℃ of following constant temperature polymerizations 8 hours, with multipolymer white solid 182 grams that obtain the siliceous acid esters group of side chain after hexanaphthene precipitation, the filtration, it is 190000 that GPC records number-average molecular weight.Embodiment 9
Potassium type activated silica acid esters and propenyl chloride reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 2000ml there-necked flask, add 60 gram silicon-dioxide, 56 gram potassium hydroxide and 840 milliliters of ethylene glycol, under agitation be warming up to 180 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 2 hours, all steam excessive ethylene glycol immediately, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 500 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, drip 76.5 gram propenyl chlorides while stirring under the room temperature, 35 ℃ of reactions 2.5 hours down, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain thick colourless vinyl silicate monomer 248 grams in 50 ℃ of following vacuum.
In the 500ml flask, 25.0 above-mentioned vinyl silicate monomers of gram and 28.8 gram dimethyl maleates are dissolved in 300 milliliters of toluene, the dibenzoyl peroxide that adds 0.22 gram, the inflated with nitrogen sealing of vibration dissolving back, 85 ℃ of following constant temperature polymerizations 6 hours, with multipolymer white solid 53.5 grams that get the siliceous acid esters group of side chain behind 1000 milliliters of petroleum ether precipitations, it is 160000 that GPC records number-average molecular weight.Embodiment 10
Potassium type activated silica acid esters and vinylchlorid reaction
Preparation vinyl silicate monomer and polymkeric substance thereof
In the 2500ml stainless steel cauldron, add 60 gram silicon-dioxide, 40 gram potassium hydroxide and 1080 milliliters of ethylene glycol, under agitation be warming up to 200 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 1 hour, heat up and all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain white crystals.With 1000 milliliters of anhydrous methanols dissolving gained crystallization get colorless cleared solution, in solution, feed 62.5 gram vinylchlorid gases while stirring under the room temperature, airtight back is in 60 ℃ of reactions 6 hours down, metering ground generates white Repone K and precipitates.Cooling, filtration back steam methyl alcohol in 50 ℃ of following vacuum, obtain thick colourless vinyl silicate monomer 235 grams.
In the 500ml flask, 23.5 above-mentioned vinyl silicate monomers of gram and 21.2 gram vinyl cyanide are dissolved in 200 milliliters of dimethyl formamides, the dibenzoyl peroxide that adds 0.014 gram, the inflated with nitrogen sealing of vibration dissolving back, 80 ℃ of following constant temperature polymerizations 10 hours, with multipolymer white solid 44 grams that get the siliceous acid esters group of side chain behind 1000 milliliters of ether sedimentations, it is 180000 that GPC records number-average molecular weight.
Claims (7)
1. the low-temperature synthetic method of vinyl silicate monomer and polymkeric substance thereof is characterized in that this method may further comprise the steps and processing condition:
Step 1: the preparation of activated silica acid esters
Chemical equation by silicon-dioxide low temperature composite reactive silicon ester is as follows:
In the formula (1), n=5-20,
m=0、1、2,
R
1The alkyl that do not replace or that replace of=C2～C12,
M (OH)
m=alkalimetal oxide or oxyhydroxide or boiling point are higher than 180 ℃ tertiary amine etc.;
Shown in chemical equation (1), add dibasic alcohol and the 1mol catalyzer of 1mol silicon-dioxide, 5～25molC2～C12 in the reactor in the lump, under whipped state, 150～200 ℃ of following low-temp reactions 1～4 hour, after distilling out the water of unnecessary dibasic alcohol and by-product, get the activated silica acid esters of 0.95～1mol;
This step catalyst system therefor can be that alkalimetal oxide or oxyhydroxide or boiling point are higher than the wherein a kind of of tertiary amine of 180 ℃ etc.;
Step 2: the preparation of vinyl silicate monomer
Chemical equation by activated silica acid esters and Halogen vinyl monomer reaction synthesis of vinyl silicate monomer is as follows:
In formula (2), (3):
R
2The alkyl that do not replace or that replace of=H, C1～C18,
R
3The aryl that do not replace or that replace of=C7～C19,
The alkyl that do not replace or that replace of C1～C18,
-COOR
4-(wherein-R
4The alkane that do not replace or that replace of-=C1～C18
Base),
R5, R6, the alkyl that do not replace or that replace of R7=C1～C18;
X
-=Cl
-、Br
-、I
-、NO
3 -、CH
2SO
3 -；
According to chemical equation (2), (3), 1mol activated silica acid esters with the step 1 gained, in methyl alcohol or under the solvent-free state directly with 0.5 or 1mol vinyl Halogen monomer 25～80 ℃ of reactions 0.5～6 hour down, remove by filter the salt of generation, distilling off solvent obtains 0.95～1mol vinyl silicate monomer;
Step 3: the homopolymerization of vinyl silicate monomer
The homopolymerization chemical equation of vinyl silicate monomer is as follows:
In formula (4), (5):
n＞5
Shown in chemical equation (4), (5), the 1mol vinyl silicate monomer is dissolved in polar solvent or the non-polar solvent, or under solvent-free state, the radical initiator that adds 0.01～0.5% (weight), 60～85 ℃ of following polymerizations 2～12 hours, through distilling off solvent or add precipitation agent precipitation, obtain the polyamino polymer of the siliceous acid esters group of side chain;
2. the low-temperature synthetic method of a kind of vinyl silicate monomer according to claim 1 and polymkeric substance thereof is characterized in that in this method:
The step 1 catalyst system therefor is potassium hydroxide and sodium hydroxide, and temperature of reaction is 180～200 ℃;
The radical initiator consumption of step 3 is 0.1～0.4% (weight).
3. the low-temperature synthetic method of a kind of vinyl silicate monomer according to claim 1 and polymkeric substance thereof is characterized in that in this method:
Used vinyl Halogen monomer can be a methacrylic acid chloroethene alcohol ester, vinylformic acid chloroethene alcohol ester, propenyl chloride, vinylchlorid, vinyl chloroacetate, Mono Chloro Acetic Acid propylene ester, p-chloromethyl styrene, toxilic acid dichlroroethanol ester, toxilic acid list C1～C18 alcohol ester chloroethene alcohol ester, methylacryoyloxyethyl-three (C1～C18 alkyl) ammonium halide, acrylyl oxy-ethyl-three (C1～C18 alkyl) ammonium halide, ethenylphenyl-three (C1～C18 alkyl) ammonium halide, propenyl-three (C1～C18 alkyl) ammonium halide etc. wherein a kind of;
Polar solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethanol, ethyl acetate, butylacetate etc.,
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.,
Radical initiator can be the wherein a kind of of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dilauroyl peroxide etc.,
Precipitation agent can be the wherein a kind of of methyl alcohol, ether, sherwood oil, hexane, hexanaphthene etc.
4. the low-temperature synthetic method of a kind of vinyl silicate monomer according to claim 1 and polymkeric substance thereof is characterized in that in this method:
Vinyl Halogen monomer is methacrylic acid chloroethene alcohol ester, vinylformic acid chloroethene alcohol ester, vinyl chloroacetate, p-chloromethyl styrene, toxilic acid dichlroroethanol ester, methylacryoyloxyethyl-trimethyl ammonium chloride, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, ethenylphenyl-triethyl ammonium
Polar solvent is dimethyl formamide, tetrahydrofuran (THF), ethanol, ethyl acetate, butylacetate,
Radical initiator is Diisopropyl azodicarboxylate, dicumyl peroxide, dibenzoyl peroxide,
Precipitation agent is ether, sherwood oil.
5. the low-temperature synthetic method of vinyl silicate monomer and polymkeric substance thereof, it is characterized in that this method can obtain the copolymerized macromolecule of the siliceous acid esters group of side chain by the copolyreaction of vinyl silicate monomer and other vinyl monomer, its chemical equation is as follows:
In formula (6), (7):
n,m＞5,
n:m=0.01～100,
R
2The alkyl that do not replace or that replace of=H, C1～C18,
R
8=-C
6H
6,-Cl ,-OCOCH
3,-COOR
12(C1～C18's
The alkyl that does not replace or replace) ,-CN;
Shown in chemical equation (6), (7), be dissolved in the 1mol vinyl silicate monomer in polarity or the non-polar solvent or under the solvent-free state, the radical initiator that adds the vinyl monomer and 0.01～0.5% (weight) of 0.01～100mol, 60～85 ℃ of following polymerizations 2～12 hours, through distilling off solvent or add precipitation agent precipitation, obtain the copolymerized macromolecule of the siliceous acid esters group of side chain;
6. the low-temperature synthetic method of a kind of vinyl silicate monomer according to claim 5 and polymkeric substance thereof is characterized in that used:
Polar solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethanol, ethyl acetate, butylacetate etc.;
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.;
Radical initiator can be the wherein a kind of of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dilauroyl peroxide etc.;
Vinyl monomer can be the wherein a kind of of vinylbenzene, vinylchlorid, vinylidene chloride, vinyl acetate, vinylformic acid (C1～C18 alkyl) ester, methacrylic acid (C1～C18 alkyl) ester, toxilic acid two (C1～C18 alkyl) ester, vinyl cyanide etc.;
Precipitation agent can be the wherein a kind of of methyl alcohol, ether, sherwood oil, hexane, hexanaphthene etc.
7. according to the low-temperature synthetic method of claims 5,6 described a kind of vinyl silicate monomers and polymkeric substance thereof, it is characterized in that in this method:
Vinyl monomer is vinylbenzene, vinyl acetate, butyl acrylate, methyl methacrylate, vinyl cyanide,
The radical initiator consumption is 0.1～0.4% (weight),
Polar solvent is tetrahydrofuran (THF), ethyl acetate, butylacetate,
Radical initiator is Diisopropyl azodicarboxylate, dicumyl peroxide, dibenzoyl peroxide,
Precipitation agent is methyl alcohol, sherwood oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116231 CN1075813C (en) | 1999-06-11 | 1999-06-11 | Low-temp synthesis process for vinyl silicate monomer and its polymers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116231 CN1075813C (en) | 1999-06-11 | 1999-06-11 | Low-temp synthesis process for vinyl silicate monomer and its polymers |
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| CN1075813C CN1075813C (en) | 2001-12-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312254C (en) * | 2005-04-26 | 2007-04-25 | 华南理工大学 | Phosphosilicate containing fire retardant and its prepn process |
| CN110218447A (en) * | 2019-07-03 | 2019-09-10 | 唐海球 | A kind of high-temperature resistant antibacterial plastics and preparation method thereof |
| CN111100155A (en) * | 2019-06-03 | 2020-05-05 | 杭州师范大学 | Is made of SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
-
1999
- 1999-06-11 CN CN 99116231 patent/CN1075813C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312254C (en) * | 2005-04-26 | 2007-04-25 | 华南理工大学 | Phosphosilicate containing fire retardant and its prepn process |
| CN111100155A (en) * | 2019-06-03 | 2020-05-05 | 杭州师范大学 | Is made of SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
| CN111100155B (en) * | 2019-06-03 | 2022-11-01 | 杭州师范大学 | Is prepared from SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
| CN110218447A (en) * | 2019-07-03 | 2019-09-10 | 唐海球 | A kind of high-temperature resistant antibacterial plastics and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1075813C (en) | 2001-12-05 |
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