CN1238333A - Process for preparing dihydroxyl silicate monomer and its polymers - Google Patents
Process for preparing dihydroxyl silicate monomer and its polymers Download PDFInfo
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- CN1238333A CN1238333A CN 99116232 CN99116232A CN1238333A CN 1238333 A CN1238333 A CN 1238333A CN 99116232 CN99116232 CN 99116232 CN 99116232 A CN99116232 A CN 99116232A CN 1238333 A CN1238333 A CN 1238333A
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Abstract
A process for preparing dihydroxyl silicate monomer and its polymer features use of cheaper and easily available SiO2 in the form of natural or industrial dregs as initial raw material and includes such technological steps as non-carbon thermal reduction to obtain 5-ligand active silicate, preparing dihydroxyl silicate monomer with high hydrolytic stability and easy purification, and polycondensating reaction with bifunctional active monomer or oligomer to obtain silicate polymer which has high molecular weight and hydrolytic stability, and is easily purified and processed for formation. Its advantages are low energy consumption, low requirement to equipment, low cost and no environmental pollution.
Description
The present invention relates to the preparation method of a kind of dihydroxyl silicate monomer and polymkeric substance thereof, refer to that specifically a kind of non-carbothermic reduction is directly prepared the method for dihydroxyl silicate monomer and polymkeric substance thereof by silicon-dioxide.
Most existing organosilicon raw material all is to be got by steps such as reaction (having strong pollution and the corrodibility) preparation of the carbothermic reduction step of highly energy-consuming (temperature is higher than 1200 ℃) and silicon and halohydrocarbon; therefore the development utilization cheap raw material directly obtains the organosilicon raw material through " non-carbothermic reduction " step; energy efficient, protection environment, reduction are had great importance to the requirement of equipment, become a problem that receives much attention.People [Zeldin N. such as Zeldin in 1987, ACS Symposium Series, 1987, Vol.360:238-241] find mineral silicate, hydrogenchloride, ethanol component distillation water outlet in toluene, can obtain the tetraethoxy of four-coordination, but productive rate is lower, and tetraethoxy to be continued the activity of substitution reaction not high.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 that has silicon-dioxide under catalyst action, directly to synthesize the silicon-containing compound of pentacoordinate or hexa-coordinate, 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 reaction of the particularly two halohydrocarbon of halohydrocarbon, hydroxy halogeno hydrocarbon, two (chloracetate) or two (chlor(o)acetamides) etc.People's such as these several years Laine research work mainly concentrates on other polyvalent alcohol and replaces the cracking of ethylene glycol and product thereof to prepare high-performance ceramic; Or carry out polycondensation with polyvalent alcohol oligopolymer and pentacoordinate or hexa-coordinate silicon-containing compound 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, owing to still contain alkaline metal ion in the polymkeric substance, so be easy to suction, 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 the stability to hydrolysis of the ionic conductive polymer of this method gained is not good enough, also restive product is crosslinked, the precision architecture of restive product, so product is difficult to purification, structural characterization and forming process.And the main chain of the polymkeric substance that obtains of people's such as Laine method only is confined to polyether structure, because of having alkaline atoms metal on the silicon, be difficult to make main chain polymkeric substance as polyester or polyurethane structural except polyether structure, bring great limitation for the range of application of product.
The objective of the invention is to overcome the defective of above-mentioned 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 (temperature is not higher than 200 ℃) preparation activated silica acid esters, by the activated silica acid esters further prepare stability to hydrolysis high, purify to be easy to dihydroxyl silicate monomer, again by with active bifunctional monomer or oligopolymer carry out polycondensation obtain molecular weight high, purification and machine-shaping is easy to, stability to hydrolysis the is good dihydroxyl silicate monomer and the preparation method of polymkeric substance thereof.
The objective of the invention is to reach by following technical solution:
The preparation method of a kind of dihydroxyl 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 dihydroxyl silicate monomer
As follows by the activated silica acid esters with the chemical equation of two halohydrocarbon or dichloro acetic acid ester or dichloro acetamide or the synthetic dihydroxyl silicate of hydroxy halogeno hydrocarbon:
In formula (2), (3):
R
2The alkyl that do not replace or that replace of=C2～C18,
The aryl that do not replace or that replace of C6～C18,
-CH
2COO-R
3-OOCCH
2-、
Or-CH
2CONH-R
3-NHOCCH
2-(wherein, R
3=C2～C12
Alkyl that not replace or that replace),
R
4The alkyl that do not replace or that replace of=C2～C12,
X=Cl、Br、I；
According to chemical equation (2), (3), 1mol activated silica acid esters with the step 1 gained, in methanol solution, directly reacted 0.5～8 hour down at 25～65 ℃ with the two halohydrocarbon of 0.5mol or 0.5mol dichloro acetic acid ester or 0.5mol dichloro acetamide or 1mol hydroxy halogeno hydrocarbon, filtration, distilling off solvent obtain 0.95～1mol dihydroxyl silicate monomer;
Used couple of α that halohydrocarbon can be C2～C12 in this step, ω-two halogenated alkanes, santochlor, to toluene dichloride, wherein a kind of to dichloro ethylbenzene etc.;
The dichloro acetic acid ester can be the wherein a kind of of dichloro acetic acid C2～C12 binary aliphatic alcohol ester, dichloro acetic acid Resorcinol ester, dichloro acetic acid resorcinol, dichloro acetic acid pyrocatechol ester, dichloro acetic acid bisphenol-A ester etc.;
Dichloro acetamide can be that two chloracetyls C2～C12 binary aliphatic amide, dichloro acetyl-p-phenylenediamine, two chloracetyl mphenylenediamines, two chloracetyl O-Phenylene Diamines, two chloracetyls are wherein a kind of to diphenylmethane diamine etc. to phenyl ether diamines, two chloracetyls;
The hydroxy halogeno hydrocarbon can be the wherein a kind of of chloroethanol, propylene chlorohydrin, halo C4～C12 alcohol etc.;
Step 3: the preparation of main chain silicon ester polymkeric substance
The chemical equation of dihydroxyl silicate monomer and vulcabond or the polycondensation of binary acyl chlorides is as follows:
In the formula (4):
Y=-COCl、NCO,
During Y=-COCl ,-R
5Alkyl or the C6～C18 that do not replace or that replace of-=C2～C12
Aryl that not replace or that replace,
During Y=-NCO ,-R
5Alkyl or the C6～C18 that do not replace or that replace of-=C2～C12
Aryl that not replace or that replace, or molecular weight is 500
～5000 both-end hydroxyl prepolymer (can be poly-second two
Alcohol, polypropylene glycol, polytetrahydrofuran, poly-C4～C12 two
Wherein one of the lipid acid C2 of unit～C12 binary aliphatic alcohol ester etc.
Kind);
Shown in chemical equation (4), be dissolved in the 1mol dihydroxyl silicate monomer in polar aprotic solvent or the non-polar solvent or under the solvent-free state, with 1～0.8mol vulcabond or diisocyanate terminated molecular weight be 500～5000 both-end hydroxyl prepolymer, 0～0.2mol chainextender or with 1mol binary acyl chlorides, 2mol chlorine hydride absorbent in 0～80 ℃ of polycondensation 10 minutes～8 hours through distilling off solvent or through the precipitation agent precipitation, obtain main chain silicon ester polymkeric substance.
Used polar aprotic solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethyl acetate, butylacetate etc. in this step,
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.,
Vulcabond can be tolylene diisocyanate, 4,4 '-diisocyanate based ditane, hexamethylene-diisocyanate etc. wherein a kind of,
Diisocyanate terminated molecular weight is that 500～5000 both-end hydroxyl prepolymer can be the wherein a kind of of polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran, poly-C4～C12 binary lipid acid C4～C12 binary aliphatic alcohol ester etc.,
Chainextender can be the wherein a kind of of the aliphatic diamine of aliphatic dihydroxy alcohol, C2～C12 of C2～C12 or aromatic diamine etc.,
The binary acyl chlorides can be the wherein a kind of of the aliphatics of C2～C12 or aromatic dicarboxylic acyl chlorides,
Chlorine hydride absorbent can be the wherein a kind of of triethylamine, Tributylamine, pyridine etc.,
Precipitation agent can be the wherein a kind of of methyl alcohol, ethanol, 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 waste residue natural or industry 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 temperature of reaction low (25～80 ℃) of activated silica acid esters with two halohydrocarbon, hydroxy halogeno hydrocarbon, two (chloracetate) and two (chlor(o)acetamides) etc. of silicon-dioxide preparation.Than traditional organosilicon preparation method less energy consumption, low, the environmentally safe of equipment requirements, the cost of the silicon ester polymkeric substance of gained is low.
(3) by the activated silica acid esters of silicon-dioxide preparation can be not earlier through separate just purify can with above-mentioned pair of halogenated compound or hydroxy halogeno hydrocarbon reaction, avoided the hydrolysis of activated silica acid esters in the separation purification process; The dihydroxyl silicate monomer of gained can be purified; The backbone structure of the polycondensate of polymerization gained is not limited to polyethers, can also be polyester, polymeric amide and urethane etc.; The main chain silicon ester polymkeric substance of gained can not take place crosslinked, and structure can accurately be controlled, and because of the metal ion of alkali-free in the polymkeric substance, so suction stability improves greatly, can carry out melt-processed or solution casting moulding easily.Therefore can be applied at aspects such as the copolymerizing modifier of novel material, polyester or urethane, novel organosilicon coupling agent, polymeric crosslinker, organic/inorganic hybrid materials.
The invention will be further described below by embodiment: embodiment 1
Potassium type activated silica acid esters and chloroethanol reaction
Preparation dihydroxyl 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, all steam excessive ethylene glycol immediately, 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 40.5 gram chloroethanols while stirring under the room temperature, be warming up to 60 ℃ of reactions 2 hours, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 125 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned dihydroxyl silicate monomer of 12.7 grams is dissolved in 200 milliliters of butylacetates, stir polypropylene glycol 105 grams that add down with the end capped molecular weight 2000 of tolylene diisocyanate, 60 ℃ of following stirring reactions 4 hours, with getting main chain silicon ester polymkeric substance white solid 117 grams behind 1000 milliliters of petroleum ether precipitations, it is 70000 that GPC records number-average molecular weight.Embodiment 2
Sodium type activated silica acid esters and propylene chlorohydrin reaction
Preparation dihydroxyl silicate monomer and polymkeric substance thereof
In the 1500ml 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 immediately and 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, drip 94.5 gram propylene chlorohydrins while stirring under the room temperature, be warming up to 65 ℃ of reactions 8 hours, metering ground generates white sodium-chlor and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 265 grams of solid state in 50 ℃ of following vacuum.
In the 1000ml flask, the above-mentioned dihydroxyl silicate monomer of 26.5 grams is dissolved in 500 milliliters of ethyl acetate, stir add down with 4,4 '-polypropylene glycol 210 of the end capped molecular weight 2000 of diisocyanate based ditane restrains, 80 ℃ of following stirring reactions 2 hours, with getting main chain silicon ester polymkeric substance white solid 236 grams behind 2000 milliliters of ether sedimentations, it is 75000 that GPC records number-average molecular weight.Embodiment 3
Ammonium type activated silica acid esters and chloroethanol reaction
Preparation dihydroxyl 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, heat up and all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 400 ml methanol dissolvings gained crystallization get colorless cleared solution, in solution, drip 40.5 gram chloroethanols while stirring under the room temperature, be warming up to 60 ℃ of reactions 1 hour, metering ground generates white Tributylamine hydrochloride and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 126 grams of solid state in 50 ℃ of following vacuum.
In the 1000ml flask, the above-mentioned dihydroxyl silicate monomer of 25.4 grams is dissolved in 500 milliliters of dimethyl formamides, stir and to add 18.3 restrain oneself diacid chloride and 21 gram chlorine hydride absorbent triethylamines down, 0 ℃ of stirring reaction 10 minutes, remove by filter triethylamine hydrochloride, filtrate gets main chain silicon ester polymkeric substance white solid 36 grams with 2000 ml methanol post precipitations, and it is 90000 that GPC records number-average molecular weight.Embodiment 4
Potassium type activated silica acid esters and ethylene dichloride reaction
Preparation dihydroxyl 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 ℃ and steam the water of generation and excessive ethylene glycol, silicon-dioxide all dissolves after about 3 hours, heat up immediately and all steam excessive ethylene glycol, 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 25 gram ethylene dichloride while stirring in solution under the room temperature, is warming up to 55 ℃ of reactions 4 hours, and metering ground generates white Repone K precipitation.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 111 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned dihydroxyl silicate monomer of 22.2 grams is dissolved in 200 milliliters of toluene, add poly-hexanodioic acid second diester 106 grams with the end capped molecular weight 2000 of tolylene diisocyanate, 25 ℃ of stirring reactions 8 hours, with getting main chain silicon ester polymkeric substance white solid 128 grams behind 1000 milliliters of petroleum ether precipitations, it is 70000 that GPC records number-average molecular weight.Embodiment 5
Sodium type activated silica acid esters with toluene dichloride is reacted
Preparation dihydroxyl 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 46.5 grams while stirring under the room temperature to toluene dichloride, 25 ℃ of reactions 0.5 hour, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 130 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, above-mentioned dihydroxyl silicate monomer of 26.1 grams and poly-hexanodioic acid second diester 108 with the end capped molecular weight 2000 of tolylene diisocyanate restrained and mix, 60 ℃ of stirring reactions 4 hours, get main chain silicon ester polymkeric substance white solid 134 grams, it is 75000 that GPC records number-average molecular weight.Embodiment 6
Potassium type activated silica acid esters and the reaction of dichloro acetic acid hexylene glycol ester
Preparation dihydroxyl 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 immediately, 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 68 gram dichloro acetic acid hexylene glycol esters while stirring under the room temperature, be warming up to 50 ℃ of reactions 1 hour, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 145 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask with the above-mentioned dihydroxyl silicate monomer of 23.5 grams, mix with polypropylene glycol 105 grams and the 1.2 gram chainextender quadrols of tolylene diisocyanate end capped molecular weight 2000,60 ℃ of stirring reactions 4 hours, get main chain silicon ester polymkeric substance white solid 134 grams, it is 70000 that GPC records number-average molecular weight.Embodiment 7
Sodium type activated silica acid esters and the reaction of two chloracetyl hexanediamines
Preparation dihydroxyl 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, all steam excessive ethylene glycol, 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 135 grams, two chloracetyl hexanediamines while stirring under the room temperature, be warming up to 50 ℃ of reactions 2 hours, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 290 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned dihydroxyl silicate monomer of 29.1 grams is dissolved in 200 milliliters of tetrahydrofuran (THF)s, adding 30 grams 4,4 under stirring '-diisocyanate based ditane and 1.8 gram chainextender butyleneglycols, 25 ℃ of stirring reactions 4 hours, with getting main chain silicon ester polymkeric substance white solid 60 grams behind 1000 milliliters of ethanol sedimentations, it is 70000 that GPC records number-average molecular weight.Embodiment 8
Sodium type activated silica acid esters and the reaction of two chloracetyl hexanediamines
Preparation dihydroxyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 20 gram sodium 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, steam all excessive ethylene glycol immediately, 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 67 grams, two chloracetyl hexanediamines while stirring under the room temperature, be warming up to 50 ℃ of reactions 2 hours, metering ground generates white sodium-chlor and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 145 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned dihydroxyl silicate monomer of 29.1 grams is dissolved in 200 milliliters of butylacetates, adding 30 grams 4,4 under stirring '-diisocyanate based ditane and 2.3 gram chainextender hexanediamines, 40 ℃ of stirring reactions 6 hours, with getting main chain silicon ester polymkeric substance white solid 61 grams behind 1000 milliliters of ether sedimentations, it is 100000 that GPC records number-average molecular weight.Embodiment 9
Ammonium type activated silica acid esters and the reaction of dichloro acetyl-p-phenylenediamine
Preparation dihydroxyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 92.5 gram Tributylamine and 420 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, all steam excessive ethylene glycol, stop to heat postcooling to room temperature and obtain activated silica acid esters white crystals.With 200 ml methanol dissolvings gained crystallization get colorless cleared solution, in solution, add 65.5 gram dichloro acetyl-p-phenylenediamines while stirring under the room temperature, be warming up to 60 ℃ of reactions 4 hours, metering ground generates white Tributylamine hydrochloride and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 141 grams of solid state in 50 ℃ of following vacuum.
In the 500ml flask, the above-mentioned dihydroxyl silicate monomer of 28.3 grams is dissolved in 200 milliliters of dimethyl formamides, stir and add 20.3 gram p-phthaloyl chlorides and 21 gram chlorine hydride absorbent triethylamines down, 40 ℃ of stirring reactions 0.5 hour, remove by filter triethylamine hydrochloride, with getting main chain silicon ester polymkeric substance white solid 48.5 grams behind 1000 milliliters of ethanol sedimentations, it is 80000 that GPC records number-average molecular weight.Embodiment 10
Potassium type activated silica acid esters and the reaction of dichloro acetic acid dihydroxyphenyl propane ester
Preparation dihydroxyl silicate monomer and polymkeric substance thereof
In the 500ml there-necked flask, add 30 gram silicon-dioxide, 28 gram potassium hydroxide and 540 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, all steam excessive ethylene glycol immediately, 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 96 gram dichloro acetic acid dihydroxyphenyl propane esters while stirring under the room temperature, be warming up to 50 ℃ of reactions 6 hours, metering ground generates white Repone K and precipitates.Filter the back and steam methyl alcohol, obtain white dihydroxyl silicate monomer 401 grams of solid state in 50 ℃ of following vacuum.
In the 1000ml flask, the above-mentioned dihydroxyl silicate monomer of 80.6 grams is dissolved in 500 milliliters of dimethyl formamides, stir and add 40.3 gram p-phthaloyl chlorides and 74 gram chlorine hydride absorbent Tributylamines down, 60 ℃ of stirring reactions 20 minutes, with getting main chain silicon ester polymkeric substance white solid 121 grams behind 2000 milliliters of ethanol sedimentations, it is 90000 that GPC records number-average molecular weight.Embodiment 11
Sodium type activated silica acid esters and the reaction of dichloro acetic acid dihydroxyphenyl propane ester
Preparation dihydroxyl silicate monomer and polymkeric substance thereof
In the 1000ml there-necked flask, add 30 gram silicon-dioxide, 20 gram sodium hydroxide and 600 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, all steam excessive ethylene glycol immediately, 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 96 gram dichloro acetic acid dihydroxyphenyl propane esters while stirring under the room temperature, be warming up to 50 ℃ of reactions 6 hours, metering ground generates white sodium-chlor and precipitates.Filter back decompression under 50 ℃ and steam methyl alcohol, obtain white dihydroxyl silicate monomer 403 grams of solid state.
In the 5000ml flask, the above-mentioned dihydroxyl silicate monomer of 80.6 grams is dissolved in 2000 milliliters of benzene, stirring adds 464 grams down and uses the poly-hexanodioic acid second diester and 35.4 of the end capped molecular weight 2000 of hexamethylene-diisocyanate to restrain chainextenders 2,5-dichloro Ursol D, 30 ℃ of stirring reactions 8 hours, get main chain silicon ester polymkeric substance white solid 584 grams with 4000 ml methanol post precipitations, it is 80000 that GPC records number-average molecular weight.
Claims (4)
1. the preparation method of dihydroxyl 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 oxygen oxide compound or boiling point are higher than the wherein a kind of of tertiary amine of 180 ℃ etc.;
Step 2: the preparation of dihydroxyl silicate monomer
As follows by the activated silica acid esters with the chemical equation of two halohydrocarbon or dichloro acetic acid ester or dichloro acetamide or the synthetic dihydroxyl silicate of hydroxy halogeno hydrocarbon:
In formula (2), (3):
R
2The aryl that do not replace or that replace that alkyl that do not replace or replacement, C6～C18 of=C2～C18 ,-CH
2COO-R
3-OOCCH
2-or-CH
2CONH-R
3-NHOCCH
2-(wherein, R
3The alkyl that do not replace or that replace of=C2～C12),
R
4The alkyl that do not replace or that replace of=C2～C12,
X=Cl、Br、I；
According to chemical equation (2), (3), 1mol activated silica acid esters with the step 1 gained, in methanol solution, directly react down O.5～8 hour at 25～65 ℃ with the two halohydrocarbon of 0.5mol or 0.5mol dichloro acetic acid ester or 0.5mol dichloro acetamide or 1mol hydroxy halogeno hydrocarbon, filtration, distilling off solvent obtain 0.95～1mol dihydroxyl silicate monomer;
Step 3: the preparation of main chain silicon ester polymkeric substance
The chemical equation of dihydroxyl silicate monomer and vulcabond or the polycondensation of binary acyl chlorides is as follows:
In the formula (4):
Y=-COCl、NCO,
During Y=-COCl ,-R
5The aryl that does not replace or replace that alkyl that do not replace or replacement or C6～C18 of-=C2～C12,
During Y=-NCO ,-R
5The alkyl that not replace or that replace of-=C2～C12 or C6～C18 an aryl that does not replace or replace, or molecular weight is that 500～5000 both-end hydroxyl prepolymer (can be the wherein a kind of of polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran, poly-C4～C12 binary lipid acid C2～C12 binary aliphatic alcohol ester etc.;
Shown in chemical equation (4), be dissolved in the 1mol dihydroxyl silicate monomer in polar aprotic solvent or the non-polar solvent or under the solvent-free state, with 1～0.8mol vulcabond or diisocyanate terminated molecular weight be 500～5000 both-end hydroxyl prepolymer, 0～0.2mol chainextender or with 1mol binary acyl chlorides, 2mol chlorine hydride absorbent in 0～80 ℃ of polycondensation 10 minutes～8 hours through distilling off solvent or through the precipitation agent precipitation, obtain main chain silicon ester polymkeric substance.
2. the preparation method of a kind of dihydroxyl silicate monomer according to claim 1 and polymkeric substance thereof is characterized in that the step 1 catalyst system therefor is potassium hydroxide and sodium hydroxide in this method, and temperature of reaction is 180-200 ℃.
3. the preparation method of a kind of dihydroxyl silicate monomer according to claim 1 and polymkeric substance thereof, it is characterized in that used couple of α that halohydrocarbon can be C2～C12 in this method, ω-two halogenated alkanes, santochlor, to toluene dichloride, wherein a kind of to dichloro ethylbenzene etc.;
The dichloro acetic acid ester can be the wherein a kind of of dichloro acetic acid C2～C12 binary aliphatic alcohol ester, dichloro acetic acid Resorcinol ester, dichloro acetic acid resorcinol, dichloro acetic acid pyrocatechol ester, dichloro acetic acid bisphenol-A ester etc.;
Dichloro acetamide can be that two chloracetyls C2～C12 binary aliphatic amide, dichloro acetyl-p-phenylenediamine, two chloracetyl mphenylenediamines, two chloracetyl O-Phenylene Diamines, two chloracetyls are wherein a kind of to diphenylmethane diamine etc. to phenyl ether diamines, two chloracetyls;
The hydroxy halogeno hydrocarbon can be the wherein a kind of of chloroethanol, propylene chlorohydrin, halo C4～C12 alcohol etc.;
Polar aprotic solvent can be the wherein a kind of of dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane, ethyl acetate, butylacetate etc.;
Non-polar solvent can be the wherein a kind of of benzene,toluene,xylene etc.;
Vulcabond can be tolylene diisocyanate, 4,4 '-diisocyanate based ditane, hexamethylene-diisocyanate etc. wherein a kind of;
Diisocyanate terminated molecular weight is that 500～5000 both-end hydroxyl prepolymer can be the wherein a kind of of polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran, poly-C4～C12 binary lipid acid C4～C12 binary aliphatic alcohol ester etc.;
Chainextender can be the wherein a kind of of the aliphatic diamine of aliphatic dihydroxy alcohol, C2～C12 of C2～C12 or aromatic diamine etc.;
The binary acyl chlorides can be the wherein a kind of of the aliphatics of C2～C12 or aromatic dicarboxylic acyl chlorides;
Chlorine hydride absorbent can be the wherein a kind of of triethylamine, Tributylamine, pyridine etc.;
Precipitation agent can be the wherein a kind of of methyl alcohol, ethanol, ether, sherwood oil, hexane, hexanaphthene etc.
4. according to the preparation method of claim 1,2,3 described a kind of dihydroxyl silicate monomers and polymkeric substance thereof, it is characterized in that two halohydrocarbon used in this method are ethylene dichloride, to toluene dichloride;
The dichloro acetic acid ester is dichloro acetic acid glycol ester, dichloro acetic acid hexylene glycol ester, dichloro acetic acid Resorcinol ester, dichloro acetic acid bisphenol-A ester;
The hydroxy halogeno hydrocarbon is a chloroethanol;
Polar aprotic solvent is dimethyl formamide, tetrahydrofuran (THF), ethyl acetate, butylacetate;
Chainextender is butyleneglycol, quadrol, hexanediamine, 2,5-dichloro Ursol D;
The binary acyl chlorides is p-phthaloyl chloride, hexanedioyl chlorine;
Precipitation agent is methyl alcohol, ethanol, sherwood oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116232A CN1075814C (en) | 1999-06-11 | 1999-06-11 | Process for preparing dihydroxyl silicate monomer and its polymers |
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| CN99116232A CN1075814C (en) | 1999-06-11 | 1999-06-11 | Process for preparing dihydroxyl silicate monomer and its polymers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140994B (en) * | 2006-09-04 | 2012-01-18 | 三星Sdi株式会社 | Organic electrolyte solution including silane compound and lithium battery employing the same |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766189A (en) * | 1987-08-13 | 1988-08-23 | Fused Kontacts Of Chicago, Inc. | Compositions for making improved gas permeable contact lenses |
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1999
- 1999-06-11 CN CN99116232A patent/CN1075814C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140994B (en) * | 2006-09-04 | 2012-01-18 | 三星Sdi株式会社 | Organic electrolyte solution including silane compound and lithium battery employing the same |
| US8968920B2 (en) | 2006-09-04 | 2015-03-03 | Samsung Sdi Co., Ltd. | Organic electrolyte solution including silane compound and lithium battery employing the same |
| 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 |
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| Publication number | Publication date |
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| CN1075814C (en) | 2001-12-05 |
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