阅读说明：本技术 一种十二烷基改性硅油的制备方法 (Preparation method of dodecyl modified silicone oil ) 是由 欧阳密 秦超 郑启波 张�诚 于 2020-12-03 设计创作，主要内容包括：一种十二烷基改性硅油的制备方法,配置质量百分比浓度为1～2％的Speier催化剂,然后取质量比为1：(0.014～0.042)的Speier催化剂和乙醇于烧杯中,然后加入硅胶,搅拌均匀后静置18～24h,在70～75℃下放置2～3h除去乙醇得到干燥的、浓度为0.0325～0.0975g/g的硅胶负载铂催化剂；将十二烯与硅胶负载铂催化剂投入反应釜中,搅拌下升温至60～70℃后,滴加含氢硅油,滴加时间控制在15～30min,滴加完毕后在90～130℃下反应4～8h。将所得产物进行真空抽滤,回收硅胶负载铂催化剂,再脱低得到十二烷基改性硅油。本发明工艺制备的十二烷基改性硅油具有过程简单、易操作、效率高、质量好等优点。(A preparation method of dodecyl modified silicone oil comprises the steps of preparing a Speier catalyst with the mass percentage concentration of 1-2%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: (0.014-0.042) adding a Speier catalyst and ethanol into a beaker, then adding silica gel, uniformly stirring, standing for 18-24 h, and standing for 2-3 h at 70-75 ℃ to remove ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.0325-0.0975 g/g; adding dodecene and a silica gel supported platinum catalyst into a reaction kettle, heating to 60-70 ℃ under stirring, dropwise adding hydrogen-containing silicone oil, controlling the dropwise adding time to be 15-30 min, and reacting for 4-8 h at 90-130 ℃ after dropwise adding. And carrying out vacuum filtration on the obtained product, recovering the silica gel supported platinum catalyst, and removing the catalyst to obtain the dodecyl modified silicone oil. The dodecyl modified silicone oil prepared by the process has the advantages of simple process, easy operation, high efficiency, good quality and the like.)

1. The preparation method of the dodecyl modified silicone oil is characterized by comprising the following steps:

step 1, preparing a Speier catalyst with the mass percentage concentration of 1-2%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: (0.014-0.042) putting a Speier catalyst and ethanol into a beaker, then adding silica gel with the mass ratio of 10.3-30.8 to the Speier catalyst, uniformly stirring, and standing for 18-24 h; placing the beaker in an oven, and placing the beaker at the temperature of 70-75 ℃ for 2-3 hours to remove the solvent ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.0325-0.0975 g/g;

step 2, putting dodecene and a silica gel-loaded platinum catalyst into a reaction kettle, heating to 60-70 ℃ under stirring, dropwise adding hydrogen-containing silicone oil, controlling the dropwise adding time to be 15-30 min, and reacting for 4-8 h at 90-130 ℃ after dropwise adding; and carrying out vacuum filtration on the obtained product, recovering the silica gel supported platinum catalyst, and then carrying out reduced pressure distillation on the product to remove low boiling point to obtain the long-chain alkyl modified hydrogen-containing silicone oil lubricating oil.

2. The method for preparing dodecyl modified silicone oil according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.4-1.6 wt%; the viscosity of the hydrogen-containing silicone oil is 60-80 mpa.s; the mol ratio of hydrogen-containing silicone oil to dodecene is 1: (1-1.3); the vacuum degree of the reduced pressure distillation is-0.0998 to-0.1 Mpa; the reduced pressure distillation temperature is 20-180 ℃; the Speier catalyst is a mixture of chloroplatinic acid and isopropanol; the mesh number of the silica gel is 100-200 meshes.

3. The method for preparing dodecyl modified silicone oil as claimed in claim 2, wherein the concentration of the platinum catalyst supported on silica gel is 0.0325-0.0975 g/g, and the amount of the platinum catalyst added is 4 g.

4. The method for preparing dodecyl modified silicone oil according to claim 2, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.5 wt%, the viscosity of the hydrogen-containing silicone oil is 70mpa.s, the molar ratio of the hydrogen-containing silicone oil to dodecene is 1:1.2, the vacuum degree of reduced pressure distillation is-0.1 Mpa, and the temperature of reduced pressure distillation is 150 ℃.

Technical Field

The invention relates to a preparation method of dodecyl modified silicone oil.

Background

The long-chain alkyl modified silicone oil represented by dodecyl modified silicone oil is modified silicone oil prepared by grafting dodecyl on a side chain of hydrogen-containing silicone oil through hydrosilylation reaction. The introduction of the long-chain alkyl optimizes the compatibility with organic matters and extreme pressure lubricity, has stronger oil film strength than dimethyl silicone oil, and is widely applied to lubrication of plastic parts or plastic parts and metal parts in household appliances, office machines and automobile internal parts.

The route of the prior art is as follows: 1. the method comprises the following steps of carrying out hydrosilylation on a monomethyl hydrosilane monomer or a methylhydrogen silane coupling agent and long-chain alpha-olefin under the action of a catalyst to synthesize methyl long-chain alkyl dichlorosilane or a silane coupling agent containing long-chain alkyl, then carrying out hydrolysis and dehydration condensation to obtain siloxane oligomer and siloxane ring bodies, and then carrying out catalytic equilibrium telomerization on the siloxane oligomer and the siloxane ring bodies with octamethylcyclotetrasiloxane, hexamethyldisiloxane and the like to obtain long-chain alkyl modified silicone oil; the drawbacks of this route are: in the reaction steps of hydrolysis and condensation, HCI gas is discharged, equipment is corroded, the process is complicated, and the requirement on the purity of the monomer is high. 2. Taking hydrogen-containing silicone oil and dodecene as raw materials, and preparing a product by a Speier catalyst through a silicon-hydrogen addition reaction; the drawbacks of this route are: the Speier catalyst is a homogeneous catalyst, has good catalytic effect, but has large using amount and high cost, is easy to cause olefin isomerization side reaction, silicon-hydrogen crosslinking and product color yellowing, and lacks competitiveness in application in high-end markets.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides the preparation method of the dodecyl modified silicone oil, which has the advantages of simple process, easy operation, high efficiency, good quality and the like.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of dodecyl modified silicone oil comprises the following steps:

step 1, preparing a Speier catalyst with the mass percentage concentration of 1-2%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: (0.014-0.042) putting a Speier catalyst and ethanol into a beaker, then adding silica gel with the mass ratio of 10.3-30.8 to the Speier catalyst, uniformly stirring, and standing for 18-24 h; placing the beaker in an oven, and placing the beaker at the temperature of 70-75 ℃ for 2-3 hours to remove the solvent ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.0325-0.0975 g/g;

step 2, putting dodecene and a silica gel-loaded platinum catalyst into a reaction kettle, heating to 60-70 ℃ under stirring, dropwise adding hydrogen-containing silicone oil, controlling the dropwise adding time to be 15-30 min, and reacting for 4-8 h at 90-130 ℃ after dropwise adding; and carrying out vacuum filtration on the obtained product, recovering the silica gel supported platinum catalyst, and then carrying out reduced pressure distillation on the product to remove low boiling point to obtain the long-chain alkyl modified hydrogen-containing silicone oil lubricating oil.

Further, the hydrogen content of the hydrogen-containing silicone oil is 0.4-1.6 wt%, and preferably 0.5 wt%.

Still further, the viscosity of the hydrogen-containing silicone oil is 60-80 mpa.s, and preferably 70 mpa.s.

Furthermore, the molar ratio of the hydrogen-containing silicone oil to the dodecene is 1: (1-1.3), preferably 1: 1.2.

Preferably, the vacuum degree of the reduced pressure distillation is-0.0998 to-0.1 MPa, and is preferably-0.1 MPa.

Preferably, the reduced pressure distillation temperature is 20-180 ℃, and preferably 150 ℃.

The Speier catalyst is a mixture of chloroplatinic acid and isopropanol.

The mesh number of the silica gel is 100-200 meshes.

The dodecyl modified silicone oil is characterized by nuclear magnetic resonance and infrared spectrum, and the result shows that the dodecyl modified silicone oil prepared by the preparation method of the dodecyl modified silicone oil has a single structure and higher purity.

Compared with the prior art, the invention has the beneficial effects that: the raw material cost is low; the silica gel supported platinum catalyst can be recycled, so that the platinum consumption is reduced, and the cost is reduced; strong acid and strong alkali are not needed, post-treatment such as water washing, neutralization and the like is not needed, and reaction steps and time are saved.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of modified silicone oil prepared by the method for preparing dodecyl modified silicone oil of example 1.

FIG. 2 is an infrared spectrum of a modified silicone oil prepared by the method for preparing a dodecyl-modified silicone oil of example 1.

Detailed Description

The invention is further described below with reference to the accompanying drawings.

Example 1

Referring to fig. 1 and 2, a preparation method of dodecyl modified silicone oil comprises the following steps:

step 1, preparing a Speier catalyst with the mass percentage concentration of 1.5%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: 0.028 of Speier catalyst and ethanol are put in a beaker, then silica gel with the mass ratio of 20.6 to the Speier catalyst is added, and the mixture is stirred uniformly and then is kept stand for 21 hours; placing the beaker in an oven, and placing the beaker at 73 ℃ for 2.5h to remove the solvent ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.05 g/g;

step 2, pouring 50.4g of dodecene and 4g of silica gel supported platinum catalyst with the concentration of 0.0975g/g into a 500ml three-hole flask at room temperature, stirring, heating to 70 ℃, dropwise adding 50g of hydrogen-containing silicone oil for 30min, and then maintaining at 130 ℃ for 8 h; and finally cooling to room temperature, vacuumizing to remove low boiling, wherein the vacuum degree is-0.0998 MPa, the highest temperature is 150 ℃, and the time is 1.5 hours, so that a qualified product is obtained.

The product index is as follows:

viscosity: 500 to 1200mpa.s

Refractive index: 1.4300-1.4370

Volatile components: 0.1 to 1 percent.

Example 2

A preparation method of dodecyl modified silicone oil comprises the following steps:

step 1, preparing a Speier catalyst with the mass percentage concentration of 2%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: 0.042 of Speier catalyst and ethanol are put in a beaker, then silica gel with the mass ratio of 30.8 to the Speier catalyst is added, and the mixture is stirred uniformly and then stands for 24 hours; placing the beaker in an oven, and placing the beaker at 75 ℃ for 3h to remove the solvent ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.0975 g/g;

step 2, pouring 46.2g of dodecene and 4g of silica gel-supported platinum catalyst with the concentration of 0.05g/g into a 50ml three-hole flask at room temperature, stirring, heating to 65 ℃, dropwise adding 50g of hydrogen-containing silicone oil for 20min, and then maintaining at 110 ℃ for 6 h; and finally cooling to room temperature, vacuumizing to remove low boiling, wherein the vacuum degree is-0.099 MPa, the highest temperature is 150 ℃, and the time is 1.5h, so that a qualified product is obtained.

The product index is as follows:

viscosity: 500 to 1200mpa.s

Refractive index: 1.4300-1.4370

Volatile components: 0.1 to 1 percent.

Example 3

A preparation method of dodecyl modified silicone oil comprises the following steps:

step 1, preparing a Speier catalyst with the mass percentage concentration of 1%, and then taking a mixture of the Speier catalyst and the Speier catalyst in a mass ratio of 1: 0.014 Speier catalyst and ethanol are put in a beaker, then silica gel with the mass ratio of 10.3 to the Speier catalyst is added, and the mixture is stirred uniformly and then stands for 18 hours; placing the beaker in an oven, and placing the beaker at 70 ℃ for 2h to remove the solvent ethanol to obtain a dry silica gel supported platinum catalyst with the concentration of 0.0325 g/g;

step 2, pouring 42g of dodecene and 4g of silica gel-supported platinum catalyst with the concentration of 0.0325g/g into a 500ml three-hole flask at room temperature, stirring, heating to 60 ℃, dropwise adding 50g of hydrogen-containing silicone oil for 15min, and maintaining at 90 ℃ for 4 h; and finally cooling to room temperature, vacuumizing to remove low boiling, wherein the vacuum degree is-0.1 MPa, the highest temperature is 150 ℃, and the time is 1.5 hours, so that a qualified product is obtained.

Comparative example 1

50g of hydrogen-containing silicone oil is poured into a 500ml three-hole flask at room temperature, stirred, heated to 70 ℃, and then 50.4g of dodecene and 0.1339g of Speier catalyst are dropwise added for 15min and then maintained at 100 ℃ for 6 h. And finally cooling to room temperature, vacuumizing to remove low boiling, wherein the vacuum degree is-0.099 MPa, the highest temperature is 150 ℃, and the time is 1.5h, so that a qualified product is obtained.

The product index is as follows:

viscosity: 500 to 1200mpa.s

Refractive index: 1.4300-1.4370

Volatile components: 0.1 to 1 percent.

Comparative example 2

Pouring 70g of hydrogen-containing silicone oil into a 500ml three-hole flask at room temperature, stirring, heating to 80 ℃, dropwise adding 70.6g of dodecene and 0.3g of Speier catalyst for 18min, and maintaining at 110 ℃ for 6 h. And finally cooling to room temperature, vacuumizing to remove low boiling, wherein the vacuum degree is-0.099 MPa, the highest temperature is 150 ℃, and the time is 1.5h, so that a qualified product is obtained.

The product index is as follows:

viscosity: 500 to 1200mpa.s

Refractive index: 1.4300-1.4370

Volatile components: 0.1 to 1 percent.

The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.