CN103804690B - Method for preparing double amino-terminated linear polydimethylsiloxane - Google Patents
Method for preparing double amino-terminated linear polydimethylsiloxane Download PDFInfo
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- CN103804690B CN103804690B CN201410096655.3A CN201410096655A CN103804690B CN 103804690 B CN103804690 B CN 103804690B CN 201410096655 A CN201410096655 A CN 201410096655A CN 103804690 B CN103804690 B CN 103804690B
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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 double amino-terminated linear polydimethylsiloxane-s.
【Background technology】
At present double amino-terminated linear polydimethylsiloxane-s are generally prepared using two step method, the first step：Alkali compoundss
Silanol salt catalyst is prepared with cyclosiloxane reaction；Second step:Cyclosiloxane is adopted for hexamethyl cyclotrisiloxane D3, eight first
Basic ring tetrasiloxane（D4）, decamethylcyclopentaandoxane（D5）, the siloxanes of ten diformazan basic ring six（D6）Or dimethyl siloxane is mixed
Cyclization body（DMC）With 1,3 2（Aminopropyl）Tetramethyl disiloxane and silanol salt catalyst are reacted under the high temperature conditions.
In this preparation process, first, cyclosiloxane：Hexamethyl cyclotrisiloxane D3, octamethylcy-clotetrasiloxane（D4）, ten first
Base D5（D5）, the siloxanes of ten diformazan basic ring six（D6）Or dimethyl siloxane mixed methylcyclosiloxane（DMC）Etc. belonging to ring-type
Structure, must react again through high temperature open loop with coupling agent, and started temperature is 120 ~ 150 DEG C, and the response time is long, and reaction temperature is high；
Second, cyclosiloxane purity is relatively low, containing more volatile matter, building-up process middle-molecular-weihydroxyethyl is difficult to control to, and reaction conversion ratio is not
Balance, 3h its conversion ratio for reacting early stage can reach 45%, but later transformation rate is substantially much lower；Third, synthesis temperature
Height is easily caused product appearance and obvious xanthochromia occurs, and coloured product changes greatly, and molecular weight and application effect are unstable, and fluctuation is big.
【The content of the invention】
It is an object of the invention to provide a kind of response time is short, reaction temperature is low, stable reaction, double amino of high conversion rate
The preparation method of endcapped linear polydimethylsiloxane.
In order to achieve the above object, the present invention adopts preparation method, including step：
1. the early-stage preparations of polydimethylsiloxane：Polydimethylsiloxane is added in reactor, it is warmed up to 100 ~
120 DEG C, under 0.01 ~ -0.07mPa decompression bars 0.5 ~ 1h of dehydration is carried out；Raw material Jing processed before the reaction, can arrange
The interference that moisture removal is polymerized to coupling agent, improves reaction efficiency.Described polydimethylsiloxane is hydroxy-end capped poly dimethyl
Siloxanes.
2. silane coupler is added into the product stirring 20min of step 1, then base catalyst is added in reactor,
Nitrogen protection, it is balanced 2 ~ 4h of reaction at a temperature of 70 ~ 120 DEG C.Silane coupler is with the mass ratio of polydimethylsiloxane
1:3 ~ 700, the addition of base catalyst is the 0.01 ~ 1% of reactant gross mass；
3. the mixture obtained after step 2 is reacted, under carrying out under 120 ~ 150 DEG C, 0.01 ~ -0.07mPa decompression bars
Removing water, low-boiling-point substance, obtain final product double amino-terminated linear polydimethylsiloxane-s.By-product can be produced after synthetic reaction
Such as methanol and moisture low-boiling-point substance, the product after high temperature removal water and low-boiling-point substance has that amino-terminated rate is high, good stability
The features such as.
The present invention is reacted by linear polydimethylsiloxane- and silane coupler in the case where there is catalysts conditions, is obtained
Go out double amino-terminated linear polydimethylsiloxane-s.Using conventional formulation, after reaction 10h low-boiling-point substance, decomposition catalyst, institute are removed
Product yield is 80%, the still not up to theoretical yield of balancing response；Detected by amino content, the amino-terminated rate of product is
87%.There is yellowish appearance, viscosity increase, molecular weight increase etc. in products therefrom after placing 1 month under 48 DEG C of constant temperatures existing
As.Response time of the invention substantially shortens, and product yield reaches more than 90%, while the generation of product Yellowing is it also avoid,
Water white product is obtained.Products therefrom is placed 1 month under 48 DEG C of constant temperatures, and outward appearance, xanthochromia, viscosity are without substantially
Change.Linear polydimethylsiloxane- its end group has activity, and especially hydroxyl endblocked polydimethylsiloxane two ends are living
Bold and vigorous terminal hydroxy group, with reaction temperature is low, high conversion rate, final product molecular weight are high, good stability the features such as, only need during synthesis
Adding a small amount of catalyst can obtain higher response speed, and the response time also can greatly shorten, the molecular weight of final product
Can be average, the effect that reaction gained final product is used in hair care composition as conditioner is also more preferable.
【Specific embodiment】
With reference to specific embodiment, the present invention is further detailed explanation.
Embodiment 1
The step of preparing double amino-terminated linear polydimethylsiloxane- be：
（1）1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
Carry out removing reaction of moisture 0.5h under 100 DEG C and 0.01mPa decompression bars.
（2）It is subsequently adding 1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane stirring 20min of 2.5g;So
0.1g Tetramethylammonium hydroxide catalyst is added afterwards, and reaction 2h is balanced under the conditions of nitrogen protection, 70 DEG C.
（3）By step（2）The mixture obtained after reaction, under 150 DEG C, -0.07mPa decompression bars lower dehydration, low is carried out
Boiling thing, obtains final product the present embodiment water white transparency, viscosity for 4000mPa.s, the double amino-terminated linear polydimethyl silicon that yield is 95%
Oxygen alkane.
Embodiment 2
The step of preparing double amino-terminated linear polydimethylsiloxane- be：
（1）1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
120 DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 1h.
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 26g is stirred 20min,
1g Tetramethylammonium hydroxide catalyst is added, reaction 2h is balanced under the conditions of nitrogen protection, 120 DEG C.
（3）By step（2）The mixture obtained after reaction, under 120 DEG C, 0.01mPa decompression bars lower dehydration, low boiling are carried out
Thing, obtains final product the present embodiment water white transparency, viscosity for 1520mPa.s, the double amino-terminated linear polydimethyl silica that yield is 97%
Alkane.
Embodiment 3
The step of preparing double amino-terminated linear polydimethylsiloxane- be：
（1）1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
110 DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 1h.
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 5g is balanced reaction
20min;0.15g Tetramethylammonium hydroxide catalyst is subsequently adding, under the conditions of nitrogen protection, 110 DEG C reaction is balanced
2.5h。
（3）By step（2）The mixture obtained after reaction, under 120 DEG C, -0.05mPa decompression bars lower dehydration, low is carried out
Boiling thing, obtains final product the present embodiment water white transparency, viscosity for 2000mPa.s, the double amino-terminated linear polydimethyl that yield is 98.2%
Siloxanes.
Embodiment 4
A kind of liquid rosin resin, is prepared using following methods；
（1）1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
100 DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 1h.
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane of 5g is added, 0.15g tetramethyls are subsequently adding
Base ammonium hydroxide catalyst, is balanced reaction 3h under the conditions of nitrogen protection, 110 DEG C.
（3）By step（2）The mixture obtained after reaction, under 150 DEG C, -0.05mPa decompression bars lower dehydration, low is carried out
Boiling thing, obtains final product the present embodiment water white transparency, viscosity for 5000mPa.s, the double amino-terminated linear polydimethyl that yield is 99.5%
Siloxanes.
Embodiment 5
A kind of liquid rosin resin, is prepared using following methods；
（1）1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
100 DEG C, 0.01mPa decompression bar under carry out remove reaction of moisture 0.5h.
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 23g is balanced reaction
20min;0.15g sodium hydroxide is subsequently adding, reaction 2h is balanced under the conditions of nitrogen protection, 110 DEG C.
（3）By step（2）The mixture obtained after reaction, under 140 DEG C, -0.05mPa decompression bars lower dehydration, low is carried out
Boiling thing, obtains final product the present embodiment water white transparency, viscosity for 7000mPa.s, the double amino-terminated linear polydimethyl that yield is 95.6%
Siloxanes.
Embodiment 6
A kind of liquid rosin resin, is prepared using following methods；
（1）1200g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
110 DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 0.9h.
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 11.5g is balanced reaction
20min;0.2g Tetramethylammonium hydroxide catalyst is subsequently adding, under the conditions of nitrogen protection, 110 DEG C reaction is balanced
2h。
（3）By step（2）The mixture obtained after reaction, under 140 DEG C, -0.07mPa decompression bars lower dehydration, low is carried out
Boiling thing, obtains final product the present embodiment water white transparency, viscosity for 8000mPa.s, the double amino-terminated linear polydimethyl that yield is 98.6%
Siloxanes.
Embodiment 7
A kind of liquid rosin resin, is prepared using following methods；
（1）1750g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube,
110 DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 0.5h；
（2）1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 5g is balanced reaction
20min;0.2g Tetramethylammonium hydroxide catalyst is subsequently adding, under the conditions of nitrogen protection, 110 DEG C reaction is balanced
2.5h;
（3）By step（2）The mixture obtained after reaction, under 150 DEG C, 0.01mPa decompression bars lower dehydration, low boiling are carried out
Thing, obtains final product the present embodiment water white transparency, viscosity for 5000mPa.s, the double amino-terminated linear polydimethyl silicon that yield is 97.8%
Oxygen alkane.
Polydimethylsiloxane in above example meets FAO/WHO-1990 quality standards.
Below the present invention has been described in detail, the above, only the preferred embodiments of the invention is not limited
The scope of the present invention processed, i.e., it is all to make impartial change and modification according to the application scope, all should still belong in covering scope of the present invention.
Claims (1)
1. the preparation method of pair amino-terminated linear polydimethylsiloxane-, including step：
(1) 1000g hydroxyl endblocked polydimethylsiloxanes are added in the reactor equipped with agitator and logical nitrogen tube, 110
DEG C, -0.07mPa decompression bar under carry out remove reaction of moisture 1h；
(2) 1,3- pair-(2- aminoethylaminomethyls) tetramethyl disilane for being subsequently adding 5g is balanced reaction 20min；
0.15g Tetramethylammonium hydroxide catalyst is subsequently adding, reaction 2.5h is balanced under the conditions of nitrogen protection, 110 DEG C；
(3) mixture that will be obtained after step (2) reaction, under 120 DEG C, -0.05mPa decompression bars lower dehydration, low-boiling-point substance are carried out,
Water white transparency, viscosity are obtained final product for 2000mPa.s, the double amino-terminated linear polydimethylsiloxane- that yield is 98.2%.
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| 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 |
| CN112646189B (en) * | 2020-12-22 | 2022-05-13 | 太仓宝霓实业有限公司 | Synthesis method of amino modified organic silicon polymer |
| 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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| JPS58104926A (en) * | 1981-12-18 | 1983-06-22 | Yukio Imanishi | Preparation of polydimethylsiloxane having amino groups at both ends |
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