CN103804690A - Method for preparing double amino-terminated linear polydimethylsiloxane - Google Patents
Method for preparing double amino-terminated linear polydimethylsiloxane Download PDFInfo
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- CN103804690A CN103804690A CN201410096655.3A CN201410096655A CN103804690A CN 103804690 A CN103804690 A CN 103804690A CN 201410096655 A CN201410096655 A CN 201410096655A CN 103804690 A CN103804690 A CN 103804690A
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- polydimethylsiloxane
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- terminated linear
- linear polydimethylsiloxane
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Abstract
The invention discloses a method for preparing double amino-terminated linear polydimethylsiloxane. The method comprises the following steps: 1, dewatering polydimethylsiloxane; 2 adding a silane coupling agent to a product in the step 1 and agitating, then adding a basic catalyst to a reactor, and carrying out balanced reaction at the temperature of 70-120 DEG C under protection of nitrogen; and 3, dewatering a mixture obtained by reaction in the step 2 and removing a low-boiling-point substance. The double amino-terminated linear polydimethylsiloxane reacts through hydroxyl-terminated polydimethylsiloxane and the silane coupling agent under the condition of a catalyst, so as to obtain the double amino-terminated linear polydimethylsiloxane. Active terminal hydroxyls are formed at two ends of the hydroxyl-terminated polydimethylsiloxane, and the double amino-terminated linear polydimethylsiloxane has the characteristics of being low in reaction temperature, high in transformation rate, high in molecular weight, good in stability and the like. A high reaction speed can be obtained just by adding a little of catalyst in synthesis, the reaction time is greatly shortened, the molecular weight of the final product is more even, and the final product obtained by reaction is better in effect when being used as a conditioner in a hair care composition.
Description
[technical field]
The present invention relates to a kind of preparation method of two amino-terminated linear polydimethylsiloxane-s.
[background technology]
At present two amino-terminated linear polydimethylsiloxane-s generally adopt two step method preparation, the first step: basic cpd reacts with cyclosiloxane prepares silicon alkoxide catalyzer; Second step: adopting cyclosiloxane is that hexamethyl cyclotrisiloxane D3, octamethylcyclotetrasiloxane (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic ring six siloxanes (D6) or dimethyl siloxane mixed methylcyclosiloxane (DMC) react under hot conditions with 1,3 two (aminopropyl) tetramethyl disiloxane and silicon alkoxide catalyzer.In this preparation process, first, cyclosiloxane: hexamethyl cyclotrisiloxane D3, octamethylcyclotetrasiloxane (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic ring six siloxanes (D6) or dimethyl siloxane mixed methylcyclosiloxane (DMC) etc. belong to ring texture, must react with coupling agent again through high temperature open loop, starting temperature is 120 ~ 150 ℃, long reaction time, temperature of reaction is high; Its two, cyclosiloxane purity is lower, contains more volatile matter, in building-up process, molecular weight is difficult to control, reaction conversion ratio imbalance, its transformation efficiency of 3h in reaction early stage can reach 45%, but later stage transformation efficiency is obviously much lower; Its three, synthesis temperature height easily causes product appearance to occur obvious xanthochromia, product colour-change is large, molecular weight and effect are unstable, fluctuation is large.
[summary of the invention]
The object of this invention is to provide a kind of reaction times short, temperature of reaction is low, stable reaction, the preparation method of two amino-terminated linear polydimethylsiloxane-s that transformation efficiency is high.
In order to achieve the above object, preparation method that the present invention adopts, comprises step:
1. the early-stage preparations of polydimethylsiloxane: polydimethylsiloxane is added in reactor, be warmed up to 100 ~ 120 ℃, carry out dehydration reaction 0.5 ~ 1h under 0.01 ~-0.07mPa decompression bar; Raw material through processed, can be got rid of the interference of moisture to coupling agent polymerization before reaction, improves reaction efficiency.Described polydimethylsiloxane is hydroxyl endblocked polydimethylsiloxane.
2. silane coupling agent is added the product of step 1 to stir 20min, then basic catalyst is added in reactor, at nitrogen protection, 70 ~ 120 ℃ of temperature, carry out balanced reaction 2 ~ 4h.The mass ratio of silane coupling agent and polydimethylsiloxane is 1:3 ~ 700, and the add-on of basic catalyst is 0.01 ~ 1% of reactant total mass;
3. the mixture obtaining after step 2 being reacted, removes water, low-boiling-point substance under carrying out under 120 ~ 150 ℃, 0.01 ~-0.07mPa decompression bar, obtains described two amino-terminated linear polydimethylsiloxane-.After building-up reactions, can produce by product as the low-boiling-point substance such as methyl alcohol and moisture, the product after high temperature removal water and low-boiling-point substance has the features such as amino-terminated rate is high, good stability.
The present invention is by linear polydimethylsiloxane-and silane coupling agent, reacts having under catalyzer condition, draws two amino-terminated linear polydimethylsiloxane-s.Adopt conventional formulation, after reaction 10h, remove low-boiling-point substance, decomposition catalyst, products therefrom yield is 80%, does not reach yet the theoretical yield of balanced reaction; Detect by amino content, the amino-terminated rate of product is 87%.Place 1 month under 48 ℃ of constant temperatures after, there is the phenomenons such as outward appearance flavescence, viscosity increase, molecular weight increase in products therefrom.Reaction times of the present invention obviously shortens, and product yield reaches more than 90%, has also avoided the generation of product Yellowing simultaneously, can obtain water white product.Products therefrom is placed 1 month under 48 ℃ of constant temperatures, and outward appearance, xanthochromia, viscosity have no significant change.Its end group of linear polydimethylsiloxane-has activity, especially hydroxyl endblocked polydimethylsiloxane two ends are active terminal hydroxy group, there is the features such as temperature of reaction is low, transformation efficiency is high, final product molecular weight is high, good stability, when synthetic, only need add a small amount of catalyzer and can obtain higher speed of response, reaction times also can shorten greatly, the molecular weight of final product also can be average, and the effect that reaction gained final product uses as amendment in hair care composition is also better.
[embodiment]
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
The step of the two amino-terminated linear polydimethylsiloxane-s of preparation is:
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1000g hydroxyl endblocked polydimethylsiloxane, under 100 ℃ and 0.01mPa decompression bar, remove reaction of moisture 0.5h.
(2) then add 1 of 2.5g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane stirs 20min; Then add 0.1g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 70 ℃ of conditions, carry out balanced reaction 2h.
(3) by the mixture obtaining after step (2) reaction, under 150 ℃ ,-0.07mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 4000mPa.s, productive rate are 95%.
Embodiment 2
The step of the two amino-terminated linear polydimethylsiloxane-s of preparation is:
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1000g hydroxyl endblocked polydimethylsiloxane, under 120 ℃ ,-0.07mPa decompression bar, remove reaction of moisture 1h.
(2) then add 1 of 26g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane stirs 20min, then adds 1g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 120 ℃ of conditions, carries out balanced reaction 2h.
(3) by the mixture obtaining after step (2) reaction, under 120 ℃, 0.01mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 1520mPa.s, productive rate are 97%.
Embodiment 3
The step of the two amino-terminated linear polydimethylsiloxane-s of preparation is:
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1000g hydroxyl endblocked polydimethylsiloxane, under 110 ℃ ,-0.07mPa decompression bar, remove reaction of moisture 1h.
(2) then add 1 of 5g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane carries out balanced reaction 20min; Then add 0.15g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 110 ℃ of conditions, carry out balanced reaction 2.5h.
(3) by the mixture obtaining after step (2) reaction, under 120 ℃ ,-0.05mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 2000mPa.s, productive rate are 98.2%.
Embodiment 4
A kind of liquid rosin resin, adopts following methods preparation;
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1000g hydroxyl endblocked polydimethylsiloxane, under 100 ℃ ,-0.07mPa decompression bar, remove reaction of moisture 1h.
(2) add 1 of 5g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane, then add 0.15g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 110 ℃ of conditions, carry out balanced reaction 3h.
(3) by the mixture obtaining after step (2) reaction, under 150 ℃ ,-0.05mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 5000mPa.s, productive rate are 99.5%.
Embodiment 5
A kind of liquid rosin resin, adopts following methods preparation;
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1000g hydroxyl endblocked polydimethylsiloxane, under 100 ℃, 0.01mPa decompression bar, remove reaction of moisture 0.5h.
(2) then add 1 of 23g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane carries out balanced reaction 20min; Then add 0.15g sodium hydroxide, under nitrogen protection, 110 ℃ of conditions, carry out balanced reaction 2h.
(3) by the mixture obtaining after step (2) reaction, under 140 ℃ ,-0.05mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 7000mPa.s, productive rate are 95.6%.
Embodiment 6
A kind of liquid rosin resin, adopts following methods preparation;
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1200g hydroxyl endblocked polydimethylsiloxane, under 110 ℃ ,-0.07mPa decompression bar, remove reaction of moisture 0.9h.
(2) then add 1 of 11.5g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane carries out balanced reaction 20min; Then add 0.2g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 110 ℃ of conditions, carry out balanced reaction 2h.
(3) by the mixture obtaining after step (2) reaction, under 140 ℃ ,-0.07mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 8000mPa.s, productive rate are 98.6%.
Embodiment 7
A kind of liquid rosin resin, adopts following methods preparation;
(1) in the reactor that agitator and logical nitrogen tube are housed, add 1750g hydroxyl endblocked polydimethylsiloxane, under 110 ℃ ,-0.07mPa decompression bar, remove reaction of moisture 0.5h;
(2) then add 1 of 5g, 3-pair-(2-aminoethylamino methyl) tetramethyl-disilane carries out balanced reaction 20min; Then add 0.2g Tetramethylammonium hydroxide catalyzer, under nitrogen protection, 110 ℃ of conditions, carry out balanced reaction 2.5h;
(3) by the mixture obtaining after step (2) reaction, under 150 ℃, 0.01mPa decompression bar, carry out lower dehydration, low-boiling-point substance, obtain the present embodiment water white transparency, viscosity is the two amino-terminated linear polydimethylsiloxane-that 5000mPa.s, productive rate are 97.8%.
Polydimethylsiloxane in above embodiment meets FAO/WHO-1990 quality standard.
Below the present invention is described in detail, the above, be only the present invention's preferred embodiment, do not limit the scope of the present invention, allly does impartial variation and modification according to the application's scope, all should still belong in covering scope of the present invention.
Claims (6)
1. the preparation method of pair amino-terminated linear polydimethylsiloxane-, comprises step:
(1) early-stage preparations of polydimethylsiloxane: polydimethylsiloxane is added in reactor, be warmed up to 100 ~ 120 ℃, carry out dehydration reaction 0.5 ~ 1h under 0.01 ~-0.07mPa decompression bar;
(2) silane coupling agent is added the product of step 1 stir 20min, then basic catalyst is added in reactor, at nitrogen protection, 70 ~ 120 ℃ of temperature, carry out balanced reaction 2 ~ 4h;
(3) mixture obtaining after step 2 is reacted removes water, low-boiling-point substance under 120 ~ 150 ℃, 0.01 ~-0.07mPa decompression bar, obtains described two amino-terminated linear polydimethylsiloxane-.
2. the preparation method of two amino-terminated linear polydimethylsiloxane-s as claimed in claim 1, is characterized in that, the mass ratio of polydimethylsiloxane and silane coupling agent is 3 ~ 700:1.
3. the preparation method of described two amino-terminated linear polydimethylsiloxane-s as claimed in claim 1, is characterized in that, the add-on of basic catalyst is 0.01% ~ 1% of reactant total mass.
4. the preparation method of two amino-terminated linear polydimethylsiloxane-s as claimed in claim 1, is characterized in that, described basic catalyst is sodium hydroxide or Tetramethylammonium hydroxide catalyzer.
5. the preparation method of two amino-terminated linear polydimethylsiloxane-s as claimed in claim 1, is characterized in that, described polydimethylsiloxane is linear polydimethylsiloxane-.
6. the preparation method of the two amino-terminated linear polydimethylsiloxane-s as described in claim 1 or 5, is characterized in that, described polydimethylsiloxane is hydroxyl endblocked polydimethylsiloxane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280041A (en) * | 2020-11-23 | 2021-01-29 | 江西蓝星星火有机硅有限公司 | Preparation method of amino silicone oil with low organosilicon ring body content |
| CN112646189A (en) * | 2020-12-22 | 2021-04-13 | 太仓宝霓实业有限公司 | Synthesis method of amino modified organic silicon polymer |
| CN112915046A (en) * | 2021-01-28 | 2021-06-08 | 广州市仲沅其新型材料有限公司 | Organic silicon elastomer gel and preparation method and application thereof |
| CN113512199A (en) * | 2021-08-16 | 2021-10-19 | 广东传化富联精细化工有限公司 | High-purity epoxy-terminated silicone oil and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280041A (en) * | 2020-11-23 | 2021-01-29 | 江西蓝星星火有机硅有限公司 | Preparation method of amino silicone oil with low organosilicon ring body content |
| CN112280041B (en) * | 2020-11-23 | 2022-05-27 | 江西蓝星星火有机硅有限公司 | Preparation method of amino silicone oil with low organosilicon ring body content |
| CN112646189A (en) * | 2020-12-22 | 2021-04-13 | 太仓宝霓实业有限公司 | Synthesis method of amino modified organic silicon polymer |
| CN112915046A (en) * | 2021-01-28 | 2021-06-08 | 广州市仲沅其新型材料有限公司 | Organic silicon elastomer gel and preparation method and application thereof |
| CN112915046B (en) * | 2021-01-28 | 2021-10-22 | 广州市仲沅其新型材料有限公司 | Organic silicon elastomer gel and preparation method and application thereof |
| CN113512199A (en) * | 2021-08-16 | 2021-10-19 | 广东传化富联精细化工有限公司 | High-purity epoxy-terminated silicone oil and preparation method thereof |
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