CN102504261A - Alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane, synthetic method and midbody thereof - Google Patents
Alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane, synthetic method and midbody thereof Download PDFInfo
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Abstract
The invention discloses alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane, a synthetic method and a midbody thereof. The structure of the alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane is shown in the formula (I) described in the specification. A synthetic route is as follows: a target compound, namely the alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane, is obtained through hydroxyl protection, alkylation, hydrosilylation, alcoholysis and equilibrium polymerization by taking diethanol amine, hexamethyldisilazane, allyl bromide (or allyl chloride or allyl iodide), tetramethyldisiloxane and D4 as starting materials. Because two molecular ends of the alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane respectively have two hydroxyalkyl groups, the alpha,omega-(dihydroxyethyl) aminopropyl terminated polysiloxane can be reacted with other substances to obtain a polysiloxane modified material.
Description
Technical field
The present invention relates to a kind of α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, compound method and midbody thereof.
Background technology
Because the active hydroxyl alkyl functional group's of chemical property existence is arranged; Increasing hydroxyl alkyl ZGK 5 is used to react with NCO or carboxyl, thereby some synthetic resins (like urethane, polyester) is carried out the various performances that modification improves material.Compare with the hydroxyl on being directly connected to Siliciumatom, the introducing of hydroxyl alkyl makes multipolymer such as polyurethane-silicone increase the stability of hydrolysis, alcoholysis.In addition, the hydroxyl alkyl siloxanes also has following meliority: the one, and the kind of alkyl and character have bigger influence to the character of oligopolymer, and formulating of recipe leeway is big; The 2nd, the shortcoming that the solubility parameters of selecting suitable alkyl can improve soft or hard section in the multiphase copolymer objects system differs greatly.At present, the preparation of the two hydroxyl alkyl siloxanes of both-end mainly is to obtain through following two kinds of approach: the one, through the hydrolysis acquisition of bis-epoxy end-blocking siloxanes; The 2nd, obtain through two hydroxyl unsaturated compounds and the addition of Si-H key.
For approach one, U.S. Pat 4,689,383 disclose a kind of compound method of four hydroxyl alkyl terminated polysiloxanes.Basic step is: at first glycidyl allyl ether and tetramethyl disiloxane are carried out addition reaction of silicon with hydrogen and obtain bis-epoxy end-blocking siloxanes, make catalyzer with strong acid then, in the mixed system that water and acetone are formed, be hydrolyzed.In the building-up process in above-mentioned two steps, the reaction times reaches 3～4 days; In addition, the Si-O-Si key also is prone in hydrolytic process, rupture.
For approach two, in U.S. Pat 4,839,443 with U.S. Pat 5,059,707 in, used 2-allyloxy-1 respectively, ammediol and 2-methylene radical-1, ammediol is as the unsaturated compound that contains pair hydroxyl alkyls.Yet the 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
The objective of the invention is to design a kind of α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, and provide that a kind of synthesis technique is simple, reaction conditions is gentle, prepare the method for many hydroxyl alkyls ZGK 5 easily.
Technical characterictic of the present invention is: suc as formula the ZGK 5 shown in (I), and called after α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane.
In the formula, n is＞0 integer.
The key intermediate of compound shown in the synthesis type (I), its structural formula are respectively suc as formula shown in (II), (III), and difference called after 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide and 1 of 3-, 3-double hydroxyethyl amine propyl group end-blocking sily oxide.
The present invention also provides the compound method of this compound: with diethylolamine and hexamethyldisilazane is that raw material obtains two (trimethylsiloxy group) ethylamines through the hydroxyl protection reaction; With two (trimethylsiloxy group) ethylamines and allyl bromide 98 (or chlorallylene, allyl iodide) be raw material through alkylated reaction, obtain N, two (trimethylsiloxy group) allyl ethyl amine of N-; With N, two (trimethylsiloxy group) allyl ethyl amine of N-and tetramethyl disiloxane are that raw material obtains 1 through the addition of silicon hydrogen, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide (II) of 3-; 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-obtain 1 through alcoholysis reaction, 3-double hydroxyethyl amine propyl group end-blocking sily oxide (III) again; With 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide and D
4(octamethylcyclotetrasiloxane) obtains target compound α for raw material through equilibrium polymerization, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane.
Reaction formula of the present invention is following:
In the above-mentioned reaction formula, Compound C H
2=CHCH
2X be in these three kinds of compounds of chlorallylene, allyl bromide 98 or allyl iodide any one; N is＞0 integer in the formula.
The hydroxyl protection reaction is at room temperature; Earlier hexamethyldisilazane is added drop-wise in the diethylolamine, after dropwising reaction system is warming up to 90～120 ℃, and under this temperature, continue reaction 4～8 hours; Stopped reaction; Normal pressure is collected 218～220 ℃ cut, obtains two (trimethylsiloxy group) ethylamines, and molar ratio is in the said hydroxyl protection reaction process: diethylolamine: hexamethyldisilazane=1: 1.2～1: 1.5.
Alkylated reaction is meant in ice-water bath; Allyl bromide 98 (or chlorallylene, allyl iodide) is added drop-wise in the dichloromethane solution that contains two (trimethylsiloxy group) ethylamines and acid binding agent triethylamine; After dropwising reaction system is warming up to room temperature automatically, and under this temperature, continues reaction 1～2 hour, stopped reaction; After removing by filter triethylamine bromate (or triethylamine hydrochloride, triethylamine iodate); Methylene dichloride and excessive triethylamine are removed in underpressure distillation, and collect the cut of 117～120 ℃ (0.67kPa), obtain N; Two (trimethylsiloxy group) allyl ethyl amine of N-, molar ratio is in the described alkylation process: allyl bromide 98 (or chlorallylene, allyl iodide): two (trimethylsiloxy group) ethylamine: triethylamine=1.2: 1: 1.5～2: 1: 3.
Addition reaction of silicon with hydrogen is meant with the Platinic chloride to be catalyzer, tetramethyl disiloxane is added drop-wise to is dissolved with N, in the toluene solution of two (trimethylsiloxy group) allyl ethyl amine of N-; Protect with nitrogen in the reaction process, temperature of reaction is: 80～110 ℃, the reaction times is: 8～12h; Toluene and excessive N are removed in decompression; Two (trimethylsiloxy group) allyl ethyl amine of N-obtain 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-; Said addition reaction of silicon with hydrogen molar ratio is: N, two (trimethylsiloxy group) allyl ethyl amine of N-: tetramethyl disiloxane: Platinic chloride=2: 1: 3.1 * 10
-4～2.6: 1: 3.1 * 10
-4
It is catalyzer that alcoholysis reaction is meant with acetic acid, and with 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-join in the methyl alcohol; Temperature of reaction is: 65 ℃, and reaction 6～12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation; Obtain 1; 3-double hydroxyethyl amine propyl group end-blocking sily oxide, said alcoholysis reaction molar ratio is: 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-: methyl alcohol: acetic acid=1: 150: 0.8～1: 250: 1.3.
Balanced reaction is to be catalyzer with the trifluoromethane sulfonic acid, with 1, and two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-and D
4(octamethylcyclotetrasiloxane carries out polyreaction, protects with nitrogen in the reaction process, and temperature of reaction is: 65-75 ℃, the reaction times is: 20-48h obtains α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane; Said 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-and D
4Mol ratio be 1: n/4, n are＞0 integer; The add-on of said trifluoromethane sulfonic acid is 0.1%～0.5% of end-capping reagent and a monomer total mass.
The molar ratio of above-mentioned two kinds of reactants is looked the size of final product molecular weight and is decided in the said balanced reaction.According to above-mentioned reaction formula, molecular weight design formula (with 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide is an end-capping reagent, and consumption is that 1mol is an example) as follows, molecular weight (the 424)+D of the design molecular weight=end-capping reagent of ZGK 5
4Molecular weight (296) * D
4Amount of substance (x=n/4), i.e. the design molecular weight=74n+424 of ZGK 5, if the design molecular weight is 1600, n is 16 in the above-mentioned reaction formula, then x is about 4, promptly prepares molecular weight and be 1600 ZGK 5, needs the end-capping reagent of 1mol and the D of 4mol approximately
4
Beneficial effect of the present invention is:
1, the invention provides a kind of compound method of synthetic many hydroxyl alkyls ZGK 5 newly, the support that provides the necessary technical is provided for developing new product, this method reactions step is easy, and raw material is easy to get, and product yield and purity are high, are beneficial to industrial applications;
2, because the molecule two ends respectively have two hydroxyl alkyls, can be used for reacting with other materials, obtain polysiloxane-modified material.For example: utilize many hydroxyl alkyls terminated polysiloxane to replace traditional hydroxy silicon oil for rubber, through reacting with vulcabond, prepare new type silicone rubber, this will open up new way for exploitation Zylox product innovation provide new approaches.
Description of drawings
Accompanying drawing 1 is respectively 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide and 1 of 3-, 3-double hydroxyethyl amine propyl group end-blocking sily oxide
1The HNMR spectrogram.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified,
1In the ownership of H, corresponding H representes with underscore among the H NMR.
Embodiment 1
Hydroxyl protection reaction (mol ratio diethylolamine: hexamethyldisilazane=1: 1.5)
In the 250mL there-necked flask, add under the diethylolamine 52.50g room temperature, slowly drip hexamethyldisilazane 12110g, after dropwising, reaction system is warming up to 100 ℃, and under this temperature, continues reaction 8 hours, stopped reaction.The air distillation reaction solution is collected 218-220 ℃ cut, obtains two (trimethylsiloxy group) ethylamines of 120.70g, yield 97%.This compound correspondence
1H NMR (CDCl
3, ppm) analytical data is following: 0.03～0.22 (m, 18H, Si-C
H 3), 1.83 (s, 1H, N
H), 2.73～2.75 (t, 4H, N-C
H 2), 3.69～3.71 (t, 4H, O-C
H 2).
(mol ratio is alkylated reaction: allyl bromide 98: two (trimethylsiloxy group) ethylamine: triethylamine=1.2: 1: 1.5)
In the 250mL there-necked flask, add two (trimethylsiloxy group) ethylamines of 99.60g, 60.60g triethylamine and 100mL methylene dichloride successively.There-necked flask is positioned in the ice-water bath, and slow Dropwise 5 8.08g allyl bromide 98 is warming up to room temperature with reaction system after dropwising automatically under this temperature; And under this temperature, continue reaction 1.5 hours, stopped reaction, remove by filter the triethylamine bromate after; Methylene dichloride and excessive triethylamine are removed in underpressure distillation, and collect the cut of 117～120 ℃ (0.67kPa), obtain 102.88g N; Two (trimethylsiloxy group) allyl ethyl amine of N-, yield 89%.This compound correspondence
1H NMR (CDCl
3, ppm) analytical data is following: 0.07～0.22 (m, 18H, Si-C
H 3), 2.65～2.69 (t, 4H, N-C
H 2-CH
2), 3.19～3.22 (t, 2H, N-C
H 2-CH), 3.63～3.65 (t, 4H, Si-O-C
H 2-), 5.12～5.19 (m, 2H, C
H 2=CH-), 5.82～5.89 (m, 1H ,-C
H=CH
2).
Addition reaction of silicon with hydrogen (mol ratio N, two (trimethylsiloxy group) allyl ethyl amine of N-: tetramethyl disiloxane: Platinic chloride=2: 1: 3.1 * 10
-4)
In the 250ml four-hole bottle, add N successively, two (trimethylsiloxy group) allyl ethyl amine 57.81g of N-, 20mL toluene and 40 μ L contain Platinic chloride 3.1 * 10
-5The aqueous isopropanol of mol behind the feeding nitrogen 20min, is warming up to 100 ℃ with reaction system, under this temperature, drips the 13.41g tetramethyl disiloxane, termination reaction behind the reaction 8h.Toluene is removed in decompression, obtains 61.95g 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-, yield 87%.This compound correspondence
1H NMR (CDCl
3, ppm) analytical data is following: 0.00～0.25 (m, 48H, Si-C
H 3), 0.41～0.70 (t, 4H, Si-C
H 2), 1.25～1.60 (m, 4H, Si-CH
2-C
H 2), 1.90～2.20 (t, 4H, N-C
H 2-CH
2-CH
2), 2.25～2.50 (m, 8H, N-C
H 2-CH
2-O-Si), 3.40～3.82 (t, 8H, C
H 2-O-Si).
Alcoholysis reaction (mol ratio 1, two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-: methyl alcohol: acetic acid=1: 150: 0.8)
In the 250mL there-necked flask, add 35.60g 1 successively, the acetic acid of two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-, 240g methyl alcohol and 2.4g.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 20.78g1,3-double hydroxyethyl amine propyl group end-blocking sily oxide, yield 98%.This compound correspondence
1H NMR (CDCl
3, ppm) analytical data is following: 0.00～0.4 (m, 12H, Si-C
H 3), 0.50～0.82 (t, 4H, Si-C
H 2), 1.20～1.60 (m, 4H, Si-CH
2-C
H 2), 2.08 (s, 4H ,-O
H), 2.18～2.40 (t, 4H, N-C
H 2-CH
2-CH
2), 2.50～2.82 (m, 8H, N-C
H 2-CH
2-OH), 3.40～3.80 (t, 8H, C
H 2-OH).
Balanced reaction (mol ratio 1, two (trimethylsiloxy group) propyl group sily oxide: the D of 3-
4=1: 7)
In the 100ml three-necked bottle, add 4.24g 1 successively, 3-double hydroxyethyl amine propyl group end-blocking sily oxide and 20.72g D
4After feeding nitrogen 20min; Reaction system is warming up to 65 ℃ and add 30 μ L trifluoromethane sulfonic acids; Under this temperature, react 20h, the Pottasium Hydroxide-methanol solution with 0.50mL 1mol/L neutralizes then, and excessive Pottasium Hydroxide neutralizes with hydrochloric acid-methanol solution of 0.20mL1mol/L again.Low-boiling-point substance is removed in underpressure distillation, obtains 21.96g α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, yield 88%.This compound correspondence
1H NMR (CDCl
3, ppm) analytical data is following :-0.30～0.20 (m, 186H, Si-C
H 3), 0.30～0.50 (m, 4H, Si-C
H 2), 1.10～1.35 (m, 4H, Si-CH
2-C
H 2), 1.40～1.69 (s, 4H, O
H), 2.10～2.37 (t, 4H, N-C
H 2-CH
2-CH
2), 2.60～2.82 (m, 8H, N-C
H 2-CH
2-OH), 3.54～3.60 (m, 8H, C
H 2-OH).
In hydroxyl alkyl terminated polysiloxane molecule; Wasserstoffatoms that is connected on certain carbon atom on the hydroxyl alkyl and the Wasserstoffatoms on the silicon methyl are two kinds of diverse Wasserstoffatomss; Peak area through with two kinds of Wasserstoffatomss carries out integration; Then the ratio of peak area equals the number ratio of Wasserstoffatoms, is calculated in the polymkeric substance by the nuclear-magnetism method that the Wasserstoffatoms number is 186 on the silicon methyl.According to the structural formula of polymkeric substance, can calculate the value of repeating unit n in the structural formula, i.e. 6n+12=186, n=29 (theoretical value n=28).The n value is updated in the structural formula, and the molecular-weight average of the polymkeric substance that calculates through the nuclear-magnetism method is 2570; Molecular weight and theoretical value that its nuclear-magnetism method is calculated are very approaching, can prove to have obtained title product.
Utilizing molecular-weight average among the embodiment 1 is that many hydroxyl alkyls terminated polysiloxane of 2500 replaces traditional hydroxy silicon oil to be rubber, and employings tolylene diisocyanate is a linking agent, and aerosil (uses preceding through D
4With the hexamethyldisilazane hydrophobic treatment) be filler, dibutyl tin dilaurate is that crosslinking catalyst prepares Zylox, formulating of recipe is (in mass) as follows:
Rubber and filler is even according to prescription refining on mixing roll, thin logical 10～12 times, make it to keep good mobility.Add linking agent then and stir, add catalyzer after stirring again, pour mould into and discharge bubble, natural levelling leaves standstill and self cure.The correlated performance index of Zylox: tensile strength 2.5MPa, shore hardness 42, elongation at break 193%.
Embodiment 2
The ratio of diethylolamine and hexamethyldisilazane amount of substance in the reaction of embodiment 1 hydroxyl protection is become 1: 1.2; Temperature of reaction becomes 110 ℃, and the reaction times becomes 6h, described in other reaction conditionss such as the embodiment 1; Obtain two (trimethylsiloxy group) ethylamines, yield is 93%.
Embodiment 3
Allyl bromide 98 in embodiment 1 alkylated reaction is become chlorallylene; The ratio of the amount of substance of chlorallylene, two (trimethylsiloxy group) ethylamine and triethylamine becomes 2: 1: 3; Described in other reaction conditionss such as the embodiment 1; N, two (trimethylsiloxy group) allyl ethyl amine of N-, yield is 82%.
Embodiment 4
With in embodiment 1 balanced reaction 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide and D
4The ratio of amount of substance become 1: 5.5; Reaction times becomes 32h, and described in other reaction conditionss such as the embodiment 1, the molecular-weight average that obtains being different from embodiment 1 is 2000 target compound α; ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, yield 90%.
Embodiment 5
With in embodiment 1 balanced reaction 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide and D
4The ratio of amount of substance become 1: 6, the reaction times becomes 35h, described in other reaction conditionss such as the embodiment 1, the molecular-weight average that obtains being different from embodiment 1 is 2200 target compound α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, yield 93%.
Embodiment 6
With in embodiment 1 balanced reaction 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide and D
4The ratio of amount of substance become 1: 2, the reaction times becomes 20h, described in other reaction conditionss such as the embodiment 1, the molecular-weight average that obtains being different from embodiment 1 is 1000 target compound α, ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, yield 95%.
Embodiment 7
The ratio of diethylolamine and hexamethyldisilazane amount of substance in the reaction of embodiment 1 hydroxyl protection is become 1: 11; Allyl bromide 98 becomes allyl iodide in the alkylated reaction, and the ratio of the amount of substance of chlorallylene, two (trimethylsiloxy group) ethylamine and triethylamine becomes 1.5: 1: 2; N in the addition reaction of silicon with hydrogen, the ratio of two (trimethylsiloxy group) allyl ethyl amine of N-and tetramethyl disiloxane amount of substance becomes 2.2: 1; In the alcoholysis reaction, the ratio of the amount of substance of two (trimethylsiloxy group) ethylamine propyl group end-blocking sily oxide of 3-, methyl alcohol and acetic acid becomes 1: 250: 1.3; In the balanced reaction 1,3-double hydroxyethyl amine propyl group end-blocking sily oxide and D
4The ratio of amount of substance become 1: 15.5; Reaction times becomes 40h, and described in other reaction conditionss such as the embodiment 1, the molecular-weight average that obtains being different from embodiment 1 is 5000 target compound α; ω-(double hydroxyethyl) amine propyl group terminated polysiloxane, yield 85%.
Claims (9)
1. the ZGK 5 of representing by formula (I):
Wherein, n is＞0 integer.
2. the compound method of the ZGK 5 of formula (I) expression is characterized in that, is that raw material obtains two (trimethylsiloxy group) ethylamines through the hydroxyl protection reaction with diethylolamine and hexamethyldisilazane; With allyl bromide 98, chlorallylene or allyl iodide and two (trimethylsiloxy group) ethylamine be raw material through alkylated reaction, obtain N, two (trimethylsiloxy group) allyl ethyl amine of N-; With N, to be raw material obtain the compound of formula (II) through addition reaction of silicon with hydrogen for two (trimethylsiloxy group) allyl ethyl amine of N-and tetramethyl disiloxane,
The compound of formula (II) obtains the compound of formula (III) again through alcoholysis reaction;
Compound and octamethylcyclotetrasiloxane with formula (III) is raw material obtains formula (I) through equilibrium polymerization ZGK 5 again.
3. compound method as claimed in claim 2; It is characterized in that; Said alkylated reaction is meant in ice-water bath, and allyl bromide 98, chlorallylene or allyl iodide are added drop-wise in the dichloromethane solution that contains two (trimethylsiloxy group) ethylamines and acid binding agent triethylamine, after dropwising reaction system is warming up to room temperature automatically; And under this temperature, continue to react 1～2 hour; Stopped reaction, remove by filter triethylamine bromate, triethylamine hydrochloride or triethylamine iodate after, methylene dichloride and excessive triethylamine are removed in underpressure distillation; And collect 117～120 ℃ cut; Obtain N, two (trimethylsiloxy group) allyl ethyl amine of N-, molar ratio is in the described alkylation process: allyl bromide 98, chlorallylene or allyl iodide: two (trimethylsiloxy group) ethylamine: triethylamine=1.2: 1: 1.5～2: 1: 3.
4. compound method as claimed in claim 2 is characterized in that, said addition reaction of silicon with hydrogen is meant with the Platinic chloride to be catalyzer; Tetramethyl disiloxane is added drop-wise to is dissolved with N, in the toluene solution of two (trimethylsiloxy group) allyl ethyl amine of N-, protect with nitrogen in the reaction process; Temperature of reaction is: 80～110 ℃, the reaction times is: 8～12h, and toluene and excessive N are removed in decompression; Two (trimethylsiloxy group) allyl ethyl amine of N-obtain formula (II) compound; Said addition reaction of silicon with hydrogen molar ratio is: N, two (trimethylsiloxy group) allyl ethyl amine of N-: tetramethyl disiloxane: Platinic chloride=2: 1: 3.1 * 10
-4～2.6: 1: 3.1 * 10
-4
5. compound method as claimed in claim 2 is characterized in that, said alcoholysis reaction is meant with acetic acid to be catalyzer; Formula (II) compound is joined in the methyl alcohol; Temperature of reaction is: 65 ℃, and reaction 6～12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation; Obtain the compound of formula (III), said alcoholysis reaction molar ratio is: formula (II) compound: methyl alcohol: acetic acid=1: 150-0.8～1: 250: 1.3.
6. compound method as claimed in claim 2; It is characterized in that; Said balanced reaction is to be catalyzer with the trifluoromethane sulfonic acid, and the compound and the octamethylcyclotetrasiloxane of formula (III) carried out polyreaction, protects with nitrogen in the reaction process; Temperature of reaction is: 65-75 ℃, the reaction times is: 20-48h; The compound of said formula (III) and octamethylcyclotetrasiloxane mol ratio be 1: n/4, n are＞0 integer; The add-on of said trifluoromethane sulfonic acid be formula (III) compound and octamethylcyclotetrasiloxane total mass 0.1%～0.5%.
7. like any described compound method among the claim 2-6; It is characterized in that said hydroxyl protection reaction is at room temperature, earlier hexamethyldisilazane is added drop-wise in the diethylolamine; After dropwising reaction system is warming up to 90～120 ℃; And under this temperature, continue reaction 4～8 hours, and stopped reaction, normal pressure is collected 218～220 ℃ cut; Obtain two (trimethylsiloxy group) ethylamines, molar ratio is in the said hydroxyl protection reaction process: diethylolamine: hexamethyldisilazane=1: 1.2～1: 1.5.
8. the compound of representing by formula (III).
9. by the preparation method of the compound of formula (III) expression, it is characterized in that, is that raw material obtains pair (trimethylsiloxy group) ethylamines through the hydroxyl protection reaction with diethylolamine and hexamethyldisilazane; With allyl bromide 98, chlorallylene or allyl iodide and two (trimethylsiloxy group) ethylamine be raw material through alkylated reaction, obtain N, two (trimethylsiloxy group) allyl ethyl amine of N-; With N, to be raw material add the compound of an accepted way of doing sth (II) through silicon hydrogen for two (trimethylsiloxy group) allyl ethyl amine of N-and tetramethyl disiloxane, and the compound of formula (II) obtains the compound of formula (III) again through alcoholysis reaction.
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-
2011
- 2011-11-07 CN CN2011103474379A patent/CN102504261A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 于一涛: "双羟烃基聚硅氧烷的合成及其对水性聚氨酯改性的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| US20150164763A1 (en) * | 2013-12-12 | 2015-06-18 | Shin-Etsu Chemical Co., Ltd. | Cosmetic composition |
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| CN104706547B (en) * | 2013-12-12 | 2019-06-11 | 信越化学工业株式会社 | Cosmetic composition |
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| CN110759938A (en) * | 2019-11-08 | 2020-02-07 | 山东大学 | Hydroxyalkyl disiloxane containing hetero atoms, preparation method and application thereof |
| KR20230089821A (en) * | 2021-12-14 | 2023-06-21 | 소니드 주식회사 | Multifunctional silicone-modified urethane adhesive having minimal carbide with minimal change in optical properties and high-functional protective film for OLED and optical materials using the same |
| KR102651984B1 (en) | 2021-12-14 | 2024-03-29 | 주식회사 비엔엘테크 | Multifunctional silicone-modified urethane adhesive having minimal carbide with minimal change in optical properties and high-functional protective film for OLED and optical materials using the same |
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