CN101508778A - Synthesis of polysiloxane containing bishydroxymethyl at single end - Google Patents
Synthesis of polysiloxane containing bishydroxymethyl at single end Download PDFInfo
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- CN101508778A CN101508778A CNA2009100145739A CN200910014573A CN101508778A CN 101508778 A CN101508778 A CN 101508778A CN A2009100145739 A CNA2009100145739 A CN A2009100145739A CN 200910014573 A CN200910014573 A CN 200910014573A CN 101508778 A CN101508778 A CN 101508778A
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Abstract
The invention discloses a method for synthesizing polysiloxane which contains bis-hydroxyl alkyl at one end. In the preparation method, allyl bromide, 2, 2-dimethylol propionic acid, hexamethyldisilazane and D3 (hexamethylcyclotrisiloxane) are used as initial raw materials on which esterification reaction, hydroxyl group protection, anionic ring opening polymerization, hydrosilylation and alcoholysis reaction are carried out to obtain a target compound of the polysiloxane which contains bis-hydroxyl alkyl at one end, and the purity of the product is higher than 98 percent. The invention has the advantages of mild reaction condition, available raw materials, high yield and purity of the product, etc.
Description
Technical field
The present invention relates to a kind of single-ended synthetic method that contains the polysiloxane of two hydroxyl alkyls.
Background technology
Because the active hydroxyl alkyl functional group's of chemical property existence is arranged, and the hydroxyl alkyl polysiloxane can utilize hydroxyl alkyl and isocyanate group or carboxyl to react, thereby some synthetic resins (as urethane, polyester) is carried out the surface property that modification improves resin.Dihydroxyl-terminated polysiloxane is as a member in the hydroxyl alkyl polysiloxane family, become a kind of intermediate of important organosilicon grafted and modified high molecular polymer.
1989, U.S. Pat 4,839,443 disclose a kind of 2-of utilization allyloxy-1, and ammediol and the single-ended polysiloxane that contains silicon hydrogen group prepare the method for dihydroxyl-terminated polysiloxane.
1991, U.S. Pat 5,059,707 disclose a kind of 2-of utilization methylene radical-1, and ammediol and the single-ended polysiloxane that contains silicon hydrogen group prepare the method for dihydroxyl-terminated polysiloxane.
There is a common shortcoming in synthetic method that above-mentioned two pieces of patents are reported, and promptly in the process of synthesising target compound, the employed unsaturated compound that contains two hydroxyl alkyls is difficult to obtain, and it is very harsh to prepare the reaction conditions of this unsaturated compound.For example: 2-allyloxy-1, in the building-up process of ammediol, need use the active sodium hydride of character under condition of ice bath; And 2-methylene radical-1 in the building-up process of ammediol, needs to use 520 ℃ high temperature.
Summary of the invention
In order to overcome the above-mentioned shortcoming that prior art exists, the invention provides that a kind of synthesis technique is simple, reaction conditions is gentle, use the unsaturated compound that contains two hydroxyl alkyls that obtains easily to prepare the method for dihydroxyl-terminated polysiloxane.
Technical characterictic of the present invention is: with allyl bromide 98,2; 2-dimethylol propionic acid, hexamethyldisilazane and D3 (hexamethyl cyclotrisiloxane) are starting raw material, obtain the single-ended polysiloxane that contains two methylols of target compound through esterification, hydroxyl protection, anionic ring-opening polymerization, the addition of silicon hydrogen and alcoholysis reaction.
Reaction formula of the present invention is as follows:
In the above-mentioned reaction formula, the used alkali (Base) of esterification is any one in salt of wormwood, sodium hydroxide, potassium hydroxide, yellow soda ash and the sodium bicarbonate; D
3The used initiator (RLi) of anionic ring-opening polymerization reaction be in n-Butyl Lithium, s-butyl lithium, the trimethylsiloxy group lithium any one; The used solvent (Solvent) of polyreaction is any one in benzene, toluene, normal hexane, the hexanaphthene; The used promotor (Promoter) of polyreaction is any one in tetrahydrofuran (THF), methyl-sulphoxide, the hexamethylphosphoramide; N represents the integer of 12-39 in the formula.
The principal reaction of synthetic method of the present invention is as follows:
Esterification: earlier with 2, the 2-dimethylol propionic acid is dissolved in N, in the dinethylformamide (DMF), add alkali again and make 2, the 2-dimethylol propionic acid changes into carboxylate salt, and reaction system is warming up to 60～80 ℃, stir and slowly drip allyl bromide 98 down to containing 2, the N of 2-dimethylol propionic acid salt in the dinethylformamide solution, dropwises the back and continues reaction 6～10h, stopped reaction, the cut of 148～150 ℃/1.33KPa is collected in underpressure distillation, obtains 2,2-dimethylol propionic acid allyl alcohol ester.Molar ratio is in the above-mentioned esterification reaction interval: 2,2-dimethylol propionic acid: allyl bromide 98: alkali=1:1:0.5～1:1.5:1.2, the alkali in the anticaustic process of above-mentioned esterification is meant any one in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood and the sodium bicarbonate.
Hydroxyl protection: under the room temperature; hexamethyldisilazane is added drop-wise to 2; in the 2-dimethylol propionic acid allyl alcohol ester; reaction system is warming up to 90～120 ℃; and this temperature continuation reaction 4～8h hour, stopped reaction, normal pressure is collected 250～252 ℃ cut; obtain 2,2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester.Molar ratio is in the hydroxyl protection reaction process: 2, and 2-dimethylol propionic acid allyl alcohol ester: hexamethyldisilazane=1:1.2～1:1.5.
D
3Anionic ring-opening polymerization reaction: with D
3Prepare the single-ended polysiloxane that contains silicon hydrogen group with initiator ring-opening polymerization in organic solvent, the design molecular weight of polysiloxane is by adjusting D
3And recently obtaining of the amount of substance between the initiator.According to above-mentioned reaction formula, molecular weight design formula (with the n-Butyl Lithium is initiator, and consumption is that 1mol is an example) is as follows, the design molecular weight=CH of polysiloxane
3CH
2CH
2CH
2-molecular weight (57)+(CH
3)
2The molecular weight of SiH-(59)+D
3Molecular weight (222.46) * D
3Amount of substance (x=n/3), i.e. the design molecular weight=222.46x+116 of polysiloxane, if the design molecular weight is 1000, then x is about 4, designs that n is 12 in the above-mentioned reaction formula, promptly prepares molecular weight and be 1000 polysiloxane, needs the D of 4mol
3
Feeding mode is earlier with D
3Be dissolved in the non-polar organic solvent, join in the reaction flask after anhydrous and oxygen-free is handled, inject initiator and promotor, temperature of reaction: 0～30 ℃, reaction times: 4～12h injects dimethyl hydrogen one chlorosilane termination reaction with syringe at last.Reaction soln is filtered, and low-boiling-point substance is removed in underpressure distillation, obtains the single-ended polysiloxane that contains silicon hydrogen group.Above-mentioned non-polar organic solvent is meant any one in benzene, toluene, normal hexane, the hexanaphthene, initiator is meant any one in n-Butyl Lithium, s-butyl lithium, the trimethylsiloxy group lithium, promotor is meant any one in tetrahydrofuran (THF), methyl-sulphoxide, the hexamethylphosphoramide, D
3Anionic ring-opening polymerization reaction in molar ratio be D
3: initiator: dimethyl hydrogen one chlorosilane=4:1:2～13:1:2.
Addition reaction of silicon with hydrogen: with the Platinic chloride is catalyzer; the single-ended polysiloxane that contains silicon hydrogen group is added drop-wise to 2; in the toluene solution of 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester; protect with nitrogen in the reaction process; temperature of reaction is: 80～110 ℃; reaction times is: 8～12h obtains the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl.Above-mentioned addition reaction of silicon with hydrogen, molar ratio is: the single-ended polysiloxane that contains silicon hydrogen group: 2,2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester: Platinic chloride=1:1.2:3.1 * 10
-4～1:1.5:3.1 * 10
-4
Alcoholysis reaction: with acetic acid is catalyzer, the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl is joined in the methanol solution, and temperature of reaction is: 65 ℃, and reaction 6～12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation, promptly obtain the single-ended polysiloxane that contains two methylols of target compound.The alcoholysis reaction molar ratio is: the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl: methyl alcohol: acetic acid=1:150:0.8～1:250:1.3.
Beneficial effect of the present invention is:
1. synthesized the unsaturated compound that contains two methylols by esterification.This esterification mild condition neither needs to use the active sodium hydride of character in the reaction process, also do not need 520 ℃ reaction high temperature.
2. each the step reaction in the synthetic route does not have by product to produce, the yield height, and respectively go on foot reactor product and be easy to separate and purify.
3. used raw material is easy to get in the synthetic route of the present invention, and for example: allyl bromide 98 and 2, the 2-dimethylol propionic acid is industrialization all.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified.
Embodiment 1
Esterification (mol ratio 2,2-dimethylol propionic acid: allyl bromide 98: salt of wormwood=1:1.2:0.5)
In the 250mL three-necked bottle, add 13.37g2,2-dimethylol propionic acid, 7.00g salt of wormwood and 100mLN, dinethylformamide.Reaction system is warming up to 60 ℃, stirs slowly to drip the 14.42g allyl bromide 98 down, dropwises the back and continues reaction 6h, stopped reaction.Low-boiling-point substance and solvent are removed in underpressure distillation, collect the cut of 148-150 ℃ (1.33Kpa), obtain colourless transparent liquid 2,2-dimethylol propionic acid allyl alcohol ester 15.22g, yield 87.7%
The hydroxyl protection reaction (mol ratio 2,2-dimethylol propionic acid allyl alcohol ester: hexamethyldisilazane=1:1.5)
In the 100mL three-necked bottle, add 2,2-dimethylol propionic acid allyl alcohol ester 10.03g.Under the room temperature, slowly drip hexamethyldisilazane 14.25g, after dropwising, reaction system is warming up to 100 ℃, and on this temperature, continue reaction 8 hours, stopped reaction.The air distillation reaction solution is collected 250-252 ℃ cut, obtains weak yellow liquid 2,2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester 15.34g, yield 84.2%.
Anionic ring-opening polymerization reaction (mol ratio D
3: n-Butyl Lithium: dimethyl hydrogen one chlorosilane=4:1:2)
In the 250ml reaction flask after handling through anhydrous and oxygen-free, the n-Butyl Lithium, the 30mL that add 0.02mol with syringe successively contain 17.90g D
3Benzole soln and 40ml tetrahydrofuran (THF), behind 25 ℃ of following stirring reaction 8h, add the dimethyl hydrogen one chlorosilane termination reaction of 0.04mol with syringe.Reacting liquid filtering is removed the lithium chloride of generation, after low-boiling-point substance is removed in underpressure distillation, get the single-ended polysiloxane (Mn=1000) that contains silicon hydrogen group of 19.76g colourless transparent liquid, yield 97.7%.
Addition reaction of silicon with hydrogen (the mol ratio polysiloxane: 2,2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester: Platinic chloride=1:1.2:3.1 * 10
-4)
In the 100ml four-necked bottle, add 2 successively, 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester 3.86g, 10mL toluene and 40 μ L contain Platinic chloride 3.1 * 10
-6The aqueous isopropanol of mol, feed nitrogen 20min after, reaction system is warming up to 100 ℃, under this temperature, drip the polysiloxane that contains silicon hydrogen group (10.12g, Mn=1000), termination reaction behind the reaction 8h.Low-boiling-point substance is removed in underpressure distillation, obtains the single-ended polysiloxane (12.54g) that contains two (trimethylsiloxy group) methyl of glassy yellow transparent liquid, yield 94%.
Alcoholysis reaction (the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl of mol ratio: methyl alcohol: acetic acid=1:150:0.83)
In the 250mL three-necked bottle, add the single-ended acetic acid that contains polysiloxane, 30g methyl alcohol and the 0.3g of two (trimethylsiloxy group) methyl of 8.00g successively.Under the reflux condition, temperature of reaction is: 65 ℃, react stopped reaction after 8 hours.Acetic acid, excessive methyl alcohol and low-boiling-point substance are removed in underpressure distillation, obtain the single-ended polysiloxane that contains two methylols of 6.85g glassy yellow transparent liquid, yield 96%.
Embodiment 2
With in embodiment 1 esterification 2, the ratio of the amount of substance of 2-dimethylol propionic acid and allyl bromide 98 becomes 1:1.5, salt of wormwood changes yellow soda ash into, temperature of reaction becomes 80 ℃, reaction times becomes 10h, and other reaction conditionss get 2 as described in example 1 above, 2-dimethylol propionic acid allyl alcohol ester, yield is 84%.
Embodiment 3
With in embodiment 1 esterification 2, the ratio of the amount of substance of 2-dimethylol propionic acid and allyl bromide 98 becomes 1:1, other reaction conditionss as described in example 1 above, 2,2-dimethylol propionic acid allyl alcohol ester, yield is 80%.
Embodiment 4
With in the embodiment 1 hydroxyl protection reaction 2; the ratio of the amount of substance of 2-dimethylol propionic acid allyl alcohol ester and hexamethyldisilazane becomes 1:1.2, and other reaction conditionss get 2 as described in example 1 above; 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester, yield is 81.3%.
Embodiment 5
With D in the reaction of embodiment 1 anionic ring-opening polymerization
3Add-on becomes 13.92g, n-Butyl Lithium 0.01mol, and the dimethyl hydrogen one chlorosilane termination reaction of 0.02mol, other reaction conditionss get the single-ended polysiloxane 14.50g (Mn=1500) that contains silicon hydrogen group, yield 96.2% as described in example 1 above.The condition of addition reaction of silicon with hydrogen and alcoholysis reaction gets the single-ended polysiloxane that contains two methylols of target compound that molecular weight is different from embodiment 1, yield 93% as described in example 1 above.
Embodiment 6
With D in the reaction of embodiment 1 anionic ring-opening polymerization
3Add-on becomes 19.60g, initiator becomes s-butyl lithium 0.01mol, promotor becomes methyl-sulphoxide, 0.02mol dimethyl hydrogen one chlorosilane termination reaction, reaction times becomes 5h, other reaction conditionss get the single-ended polysiloxane 19.56g (Mn=2000) that contains silicon hydrogen group, yield 94.2% as described in example 1 above.The condition of addition reaction of silicon with hydrogen and alcoholysis reaction gets the single-ended polysiloxane that contains two methylols of target compound that molecular weight is different from embodiment 1, yield 93.4% as described in example 1 above.
Embodiment 7
With D in the reaction of embodiment 1 anionic ring-opening polymerization
3Add-on becomes 24.02g, n-Butyl Lithium 0.01mol, and the dimethyl hydrogen one chlorosilane termination reaction of 0.02mol, other reaction conditionss get the single-ended polysiloxane 22.86g (Mn=2500) that contains silicon hydrogen group, yield 90.8% as described in example 1 above.In the addition reaction of silicon with hydrogen 2,2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester and the single-ended polysiloxane that contains silicon hydrogen group become 1:1.5; The ratio of the amount of substance of single-ended polysiloxane that contains two (trimethylsiloxy group) methyl and methyl alcohol becomes 1:250 in the alcoholysis reaction, other reaction conditionss as described in example 1 above, get the single-ended polysiloxane that contains two methylols of target compound that molecular weight is different from embodiment 1, yield 95%.
Claims (6)
1, a kind of single-ended synthetic method that contains the polysiloxane of two methylols is characterized in that: with allyl bromide 98,2, and 2-dimethylol propionic acid, hexamethyldisilazane and D
3Be starting raw material, obtain the single-ended polysiloxane that contains two methylols through esterification, hydroxyl protection, anionic ring-opening polymerization, the addition of silicon hydrogen and alcoholysis reaction.
2, a kind of single-ended synthetic method that contains the polysiloxane of two methylols according to claim 1, it is characterized in that: described esterification is earlier with 2, the 2-dimethylol propionic acid is dissolved in N, in the dinethylformamide, add alkali again and make 2, the 2-dimethylol propionic acid changes into carboxylate salt, reaction system is warming up to 60～80 ℃, stir and slowly drip allyl bromide 98 down to containing 2, the N of 2-dimethylol propionic acid salt, in the dinethylformamide solution, dropwise the back and continue reaction 6～10h, stopped reaction, 148～150 ℃ cut obtains 2 under the underpressure distillation collection 1.33KPa, 2-dimethylol propionic acid allyl alcohol ester, molar ratio is in the described esterification reaction interval: 2, and 2-dimethylol propionic acid: allyl bromide 98: alkali=1:1:0.5～1:1.5:1.2, the alkali in the anticaustic process of described esterification is meant sodium hydroxide, potassium hydroxide, yellow soda ash, in salt of wormwood and the sodium bicarbonate any one.
3; a kind of single-ended synthetic method that contains the polysiloxane of two methylols according to claim 1; it is characterized in that: described hydroxyl protection reaction is under the room temperature; earlier hexamethyldisilazane is added drop-wise to 2; in the 2-dimethylol propionic acid allyl alcohol ester; reaction system is warming up to 90～120 ℃; and this temperature continuation reaction 4～8h hour; stopped reaction; normal pressure is collected 250～252 ℃ cut; obtain 2; 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester, molar ratio is in the described hydroxyl protection reaction process: 2,2-dimethylol propionic acid allyl alcohol ester: hexamethyldisilazane=1:1.2～1:1.5.
4, according to the described a kind of single-ended polysiloxane that contains two methylols of claim 1 synthetic method, it is characterized in that: described anionic ring-opening polymerization reaction for earlier with D
3Be dissolved in the non-polar organic solvent, join in the reaction flask after anhydrous and oxygen-free is handled, inject initiator and promotor, temperature of reaction: 0～30 ℃, reaction times: 4～12h injects dimethyl hydrogen one chlorosilane termination reaction with syringe at last, reaction soln is filtered, low-boiling-point substance is removed in underpressure distillation, obtains the single-ended polysiloxane that contains silicon hydrogen group, and molar ratio is D in the described anionic ring-opening polymerization reaction
3: initiator: dimethyl hydrogen one chlorosilane=4:1:2～13:1:2, described non-polar organic solvent is meant any one in benzene, toluene, normal hexane, the hexanaphthene, initiator is meant any one in n-Butyl Lithium, s-butyl lithium, the trimethylsiloxy group lithium, and promotor is meant any one in tetrahydrofuran (THF), methyl-sulphoxide, the hexamethylphosphoramide.
5; a kind of single-ended synthetic method that contains the polysiloxane of two methylols according to claim 1; it is characterized in that: described addition reaction of silicon with hydrogen is to be catalyzer with the Platinic chloride; the single-ended polysiloxane that contains silicon hydrogen group is added drop-wise to 2; in the toluene solution of 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester; protect with nitrogen in the reaction process; temperature of reaction is: 80～110 ℃; reaction times is: 8～12h; obtain the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl; described addition reaction of silicon with hydrogen molar ratio is: the single-ended polysiloxane that contains silicon hydrogen group: 2, and 2-two (trimethylsiloxy group) methylpropanoic acid vinyl carbinol ester: Platinic chloride=1:1.2:3.1 * 10
-4～1:1.5:3.1 * 10
-4
6, a kind of single-ended synthetic method that contains the polysiloxane of two methylols according to claim 1, it is characterized in that: described alcoholysis reaction is to be catalyzer with acetic acid, the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl is joined in the methanol solution, temperature of reaction is: 65 ℃, reaction 6～12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation, promptly obtain the single-ended polysiloxane that contains two methylols of target compound, described alcoholysis reaction molar ratio is: the single-ended polysiloxane that contains two (trimethylsiloxy group) methyl: methyl alcohol: acetic acid=1:150:0.8～1:250:1.3.
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