NL2031434B1

NL2031434B1 - Modified vinyl silane and preparation method and application thereof

Info

Publication number: NL2031434B1
Application number: NL2031434A
Authority: NL
Inventors: Li Pengtao; Kong Fanzhen; Qu Yuan; Yang Tiantian; Li Hanghang; Qi Shilin; Lu Haifeng; Kong Linggang
Original assignee: Shandong Guike New Mat Co Ltd
Priority date: 2022-01-07
Filing date: 2022-03-29
Publication date: 2023-07-13
Also published as: CN114805426B; ZA202213851B; WO2023130551A1; CN114805426A

Abstract

The present disclosure provides modified vinyl silane and a preparation method and an application thereof, and belongs to the technical field of organic silicon materials. According to the present disclosure, an oily group (a silicone oil group or a ring opening group of a dimethyl siloxane cyclics) is grafted to vinyl silane, the obtained modified vinyl silane has increased oiliness, low viscosity and enhanced dispersibility, when the modified Vinyl silane is used as a coupling agent for organic and/or inorganic powder, the modified powder has good dispersibility and can be uniformly and stably grafted to the organic and/or inorganic powder, and the stability of the modified material is improved.

Description

MODIFIED VINYL SILANE AND PREPARATION METHOD AND APPLICATION

THEREOF

TECHNICAL FIELD

The present disclosure relates to the technical field of or- ganic silicon materials, and particularly relates to modified vi- nyl silane and a preparation method and an application thereof.

BACKGROUND ART

Vinyl silane coupling agent is relatively simple in struc- ture, with the structural formula of R-Si-0X. It is characterized by amphoteric ability, which can organically link organic materi- als (for example, polyethylene or polyvinyl chloride) and inorgan- ic materials (for example, magnesium hydroxide, calcium carbonate, titanium dioxide or silica) together. However, the silane coupling agents have obvious shortcomings, such as insufficient oiliness.

When they are applied to organic-inorganic hybrid materials, the modified powder will have weak dispersibility and unstable perfor- mance, thereby reducing some physical properties of the material, such as dielectric constant, toughness and elasticity.

SUMMARY

The object of the present disclosure is to provide modified vinyl silane and a preparation method and an application thereof.

The modified vinyl silane contains oily groups, and after organic and inorganic hybrid materials are modified, the obtained modified materials are good in dispersibility and high in stability.

In order to achieve the above object, the present disclosure provides the following technical solutions:

The present disclosure provides modified vinyl silane which has the structure shown in the formula I:

OR:

AN

4

Formula I;

OR;

Ll ol dT {4 ON —_—

OR,

Wherein, R includes or ra

F § ° | nh oa >

TL

OR,

R; includes methyl, ethyl, propyl or isopropyl, x = 2-8, and y = 1-50.

Preferably, the viscosity of the modified vinyl silane is 2- 50 mPa/s.

The present disclosure provides to a method for preparing the modified vinyl silane in the above technical solution. The method comprises the following steps:

Mixing vinyl silane, a modifying agent, a catalyst and water, and performing modifying reaction to obtain the modified vinyl silane.

The vinyl silane comprises vinyl trialkoxysilane; the vinyl trialkoxysilane comprises vinyl trimethoxy silane, vinyl triethox- ysilane, vinyl triproxysilane or vinyl triisopropoxysilane.

The modifying agent comprises silicone oil or dimethyl silox- ane cyclics.

The silicone oil has the structure shown in the formula II: ~d B lL ~~ So om

Formula II, m=1~50.

The dimethyl siloxane cyclics has the structure shown in the formula III.

Ra in

Formula III, n=2-8.

Preferably, the mass ratio of vinyl silane to the modifying agent is 1: (0.3-1.2).

Preferably, the catalyst comprises caustic alkali or concen- trated sulfuric acid.

Preferably, the mass of the catalyst accounts for 0.01-0.03% of the total mass of vinyl silane and the modifying agent.

Preferably, the mass of water accounts for 5-20% of the mass of vinyl silane.

Preferably, the temperature of the modifying reaction is 50- 100°C, and the time is 1-12 h.

Preferably, the mixing process of vinyl silane, the modifying agent, the catalyst and water comprises the steps of: mixing vinyl silane and the modifying agent, heating to 50-100°C, adding water and the catalyst into the obtained mixture at the same time, wherein the time of adding water and the catalyst is 0.5-2 h.

The present disclosure provides an application of the modi- fied vinyl silane in the technical solution or the modified vinyl silane prepared by the preparation method in synthesis of organic and inorganic hybrid materials.

The present disclosure provides the modified vinyl silane.

The modified vinyl silane is grafted with an oily group (a sili- cone oil group or a ring-opening group of dimethyl siloxane cy- clics) so that the oiliness of the obtained modified vinyl silane can be increased, the viscosity is reduced, and the dispersibility is enhanced; and when the obtained modified vinyl silane is used as a coupling agent for organic and/or inorganic powder, the modi- fied powder is high in dispersibility and can be uniformly and stably grafted to the organic and/or inorganic powder, and the stability of the modified material is improved.

The present disclosure provides the method for preparing the modified vinyl silane. According to the preparation method, the vinyl silane and the modifying agent are subjected to a rearrange- ment reaction under the effect of the catalyst, the modifying agent is high in oiliness and dispersibility, the dispersibility of the modified vinyl silane can be enhanced, the grafting capaci- ty of the modified vinyl silane in organic and/or inorganic powder is improved, and the binding force of the modified vinyl silane and the organic and/or inorganic powder when the modified vinyl silane serves as the coupling agent to be applied is enhanced.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG.1 shows the NMR spectrum of the modified vinyl silane prepared by Example 1;

FIG.2 shows the infrared spectrum of the modified vinyl silane prepared by Example 1;

FIG.3 shows the NMR spectrum of the modified vinyl silane prepared by Example 2;

FIG.4 shows the infrared spectrum of the modified vinyl silane prepared by Example 2;

FIG.5 shows the NMR spectrum of the modified vinyl silane prepared by Example 3;

FIG.6 shows the infrared spectrum of the modified vinyl silane prepared by Example 3;

FIG.7 shows the NMR spectrum of the modified vinyl silane prepared by Example 4;

FIG.8 shows the infrared spectrum of the modified vinyl silane prepared by Example 4.

DETAILED DESCRIPTION OF THE EMBODIMENTS

OR:

ZN | Og i Y formula I;

OR, {4 Si Xu ’

Wherein, R includes OR; or ra >

LLL ne dT

LM Si Si

TL

OR,

R; includes methyl, ethyl, propyl or isopropyl, x = 2-8, and 5 y = 1-50.

In the present disclosure, the viscosity of the modified vi- nyl silane is preferably 2-50 mPa/s, more preferably 5-22 mPa/s, further more preferably 18-20 mPa/s.

In the present disclosure, the structural formula of the modified vinyl silane is preferably:

OCH:CHs OCH:CHs; [oy | o\] 7 re

ZN Si a Xx nen

GCH:CHs OCH:CH: ‚ X=2;

O CH:CH: ~~ OCH:CHs = Ng Si DN nent

OCH:CHs OCH:CH; ‚ x=4;

OCHsCH; = {| 0 0

Fg NT NT NT

TU EE

OCH:CH: OCH:CH4 - r YS=3 or

OCH; OCH

A eo

AN 4, NN

CT

OCH; OCH; x=4.

The present disclosure provides to a method for preparing the modified vinyl silane in the above technical solution. The method comprises the following steps: mixing vinyl silane, a modifying agent, a catalyst and water, and performing modifying reaction to obtain the modified vinyl silane; the vinyl silane comprises vinyl trialkoxysilane; the vinyl trialkoxysilane comprises vinyl trimethoxy silane, vinyl triethox- ysilane, vinyl triproxysilane or vinyl triisopropoxysilane; the modifying agent comprises silicone oil or dimethyl silox- ane cyclic; the silicone oil has the structure shown in the formula II: / _ A 4”

SIS Nod

Formula II, m=1~50;

The dimethyl siloxane cyclics has the structure shown in the formula III:

Ra in

Ee Formula III, n=2~8.

In the present disclosure, unless otherwise specified, the required raw materials are all commercially available products well known to those skilled in the art.

In the present disclosure, vinyl silane, modifying agent, catalyst and water are mixed. In the present disclosure, the vinyl silane comprises vinyl trialkoxysilane; the vinyl trialkoxysilane comprises vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triproxysilane or vinyl triisopropoxysilane.

In the present disclosure, the modifying agent comprises sil- icone oil or dimethyl siloxane cyclic (DMC).

The silicone oil has the structure shown in the formula II:

ON]

NY Si ~~

At

Formula II, m=1~50, more prefer- ably 3;

The dimethyl siloxane cyclics has the structure shown in the formula III:

HH

‚Nn

ST Formula III, n=2~8, more preferably 3-4.

In the present disclosure, the mass ratio of vinyl silane to the modifying agent is preferably 1: (0.3-1.2), more preferably 1: (0.5=-1.0), further more preferably 1: (0.6-0.8).

In the present disclosure, the catalyst preferably comprises caustic alkali or concentrated sulfuric acid; the mass concentra- tion of the concentrated sulfuric acid is preferably 98%. In the present disclosure, the mass of the catalyst preferably accounts for 0.01-0.03%, more preferably 0.015-0.02% of the total mass of vinyl silane and the modifying agent.

In the present disclosure, the mass of water preferably ac- counts for 5-20%, more preferably 8-155, and further more prefera- bly 12-13% of the mass of vinyl silane. By adding the water phase, the present disclosure increases the ratio of vinyl functional groups in vinyl silane, increases the content of vinyl in modified vinyl silane, and then improves the coupling properties of modi-

fied vinyl silane.

In the present disclosure, the mixing process of vinyl silane, the modifying agent, the catalyst and water preferably comprises the steps of: mixing vinyl silane and the modifying agent, heating to 50-100°C, adding water and the catalyst into the obtained mixture at the same time; the heating process is not par- ticularly limited in the present disclosure, the heating can be conducted according to the process well known in the art. Accord- ing to the present disclosure, after water and the catalyst are mixed preferably, and the resulting catalyst solution is added dropwise into a mixture of the vinyl silane and the modifying agent. In the present disclosure, the time of adding the water and the catalyst is preferably 0.5-2 h, more preferably 1.0-1.5 h.

After mixing is completed, the modifying reaction is prefer- ably conducted; the temperature of the modifying reaction is pref- erably 50-100°C, more preferably 60-80°C, and further more prefera- bly 65-70°C; the time is preferably 1-12 h, more preferably 1.5-3 h.

In the present disclosure, when the content of vinyl silane in a product obtained through the modifying reaction is lower than 10%, it is judged that the modifying reaction is completed, and dealcoholization is conducted on the obtained product. The specif- ic method for detecting the content of vinyl silane in the product is not particularly limited in the present disclosure, and detec- tion can be conducted according to a method well known in the art.

In the present disclosure, the temperature of dealcoholization is preferably 60-100°C, and more preferably 70-90°C; after dealcoholi- zation is completed, ethyl alcohol is extracted, the obtained product is cooled and filtered, and the modified vinyl silane is obtained. The processes of extracting ethyl alcohol, cooling and filtering, and detection are not particularly limited in the pre- sent disclosure, and can be conducted according to the process well known in the art.

In the present disclosure, when the odifying reagent is dime- thyl siloxane cyclics (DMC), the reaction formula of the modifying reaction is:

OR,

VS am i Catalyst ee fod pce Magy = © ĳ - ensen ee er en / 3 of - > spe HY ein 3 ¥ EN ~ i i Ei: i i

SUS

OR

Vinyl alkoxy silane

IB HR

Ry . | \ CR 1 oh

SN ] Ad A | en, a “ =>

EN | ~ oo A Se 3 $Y Ei

OR, | OR ’

When the modifying agent is silicone oil, the reaction formu- la of the modifying reaction is:

OR, , i x X ; B AY; el Lory N / ; 2 Catalyst § Sg % i § NN

OR, * > x

OR == . = pte eR TIRE eT TY eT ee RI == Bi Us FoR BT + RE

OR : OR

The present disclosure provides an application of the modi- fied vinyl silane in the technical solution or the modified vinyl silane prepared by the preparation method in the technical solu- tion in synthesis of organic materials and/or inorganic materials.

The application method is not particularly limited in the present disclosure, and the modified vinyl silane is used as the coupling agent for synthesizing the organic materials and/or inorganic ma- terials according to the method well known in the art.

The technical solution of the present disclosure will be de- scribed clearly and completely below in conjunction with the em- bodiments. Obviously, embodiments described are only a part of em- bodiments of the present disclosure, and are not all of embodi-

ments thereof. All other embodiments obtained by persons of ordi- nary skill in the art based on the embodiments of the present dis- closure without creative efforts shall fall within the protection scope of the present disclosure.

Example 1

To a 500-L reactor, 100 kg of vinyl triethoxysilane was pumped; then 50 kg of DMC (dimethyl siloxane cyclics) was added, heated to 60°C, and a mized solution of 5 kg of water and 0.015 kg of potassium hydroxide was added dropwise to the resulting mixture simultaneously for 0.5h, keeping the temperature at 70 °C for re- acting for 3 h, then samples were taken for analysis; when the content of vinyl silane in the product was less than 10%, the mix- ture was heated to 80 °C, a total of 25 kg of ethanol was extract- ed, and the obtained product was cooled and filtered to obtain 130 kg of colorless and transparent modified vinyl silane product. The viscosity of the obtained product was 5mPa/s;

The modified vinyl silane prepared in this example had a structural formula as below:

OCH: Hs OCH:CH:

AAA A

AS» \ "Si AN

OO]

OCH:CHa ! QCHCHs , X=2.

Example 2

To a 500-L reactor, 100 kg of vinyl triethoxysilane was pumped; then 50 kg of DMC (dimethyl siloxane cyclics) was added, heated to 60°C, and a mixed solution of 10 kg of water and 0.03 kg of potassium hydroxide was added dropwise to the resulting mixture simultaneously for 1 h, keeping the temperature at 70 °C for react- ing for 3 h, then samples were taken for analysis; when the con- tent of vinyl silane in the product was less than 10%, the mixture was heated to 80 °C, a total of 50 kg of ethanol was extracted, and the obtained product was cooled and filtered to obtain 110 kg of finished product. The viscosity of the obtained product was 20 mPa/s;

OCH:CH: | OCH:CH:

DN ol Pa

ZZ Ng \ Si’ si” Xx

OO]

OCH:CE: ! OCHCH; ‚ X=4.

Example 3

To a 500-L reactor, 100 kg of vinyl triethoxysilane was pumped; then 50 kg of silicone oil (viscosity of 500 mPa/s) was added, heated to 60°C, and a mixed solution of 10 kg of water and 0.03 kg of potassium hydroxide was added dropwise to the resulting mixture simultaneously for 1 h, keeping the temperature at 70 °C for reacting for 3 h, then samples were taken for analysis; when the content of vinyl silane in the product was less than 10%, the mixture was heated to 80 °C, a total of 50 kg of ethanol was ex- tracted, and the cbtained product was cooled and filtered to ob- tain 110 kg of finished product. The viscosity of the obtained product was 18 mPa/s;

OCH:CH; | A

PN ol on]

AS Ng \ Si “Si ‘Si

CAT

QCHCH; OCH:CHs ‚ V=3.

Example 4

To a 500-L reactor, 100 kg of vinyl trimethoxysilane was pumped; then 50 kg of DMC (dimethyl siloxane cyclics) was added, heated to 60°C, and a mixed solution of 12 kg of water and 0.03 kg of concentrated sulfuric acid (mass concentration of 983) was add- ed dropwise to the resulting mixture simultaneously for 1 h, keep- ing the temperature at 70 °C for reacting for 3 h, then samples were taken for analysis; when the content of vinyl silane in the product was less than 10%, the mixture was heated to 80 °C, a total of 42 kg of methanol was extracted, and the obtained product was cooled and filtered to obtain 110 kg of finished product. The vis- cosity of the obtained product was 22 mPa/s.

OCH; OCH: on 0 OW | . = Si Si Si : ee

OCH; OCH; x=4.

Characterization and Performance Testing 1) The NMR and IR characterizations of the modified vinyl silane prepared by Example 1 to 4 were carried out, and the re- sults were shown in FIGS. 1 to 8; FIGS. 1, 3, 5 and 7 showed the

NMR spectra of the modified vinyl silane prepared by Examples 1 to 4. As shown in FIG.1, 5.80~5.93 represented CH=CH peak; 3.60~3.74 represented CH; peak of CH:CH;; 1.08~1.14 represented CH; peak of

CHsCH:; -0.1~0.06 represented CH; peak of CHsSi. As shown in FIG.3, 5.81~5.95 represented CH;=CH peal; 3.62~3.75 represented CH: peak of CH:CH;; 1.10~1.16 represented CH; peak of CH3CH;; -0.09~0.07 rep- resented CH: peak of CH3Si. As shown in FIG. 5, 5.84~6.02 repre- sented CH.=CH peak; 3.63~3.78 represented CH. peak of CH:CH:; 1.10~1.16 represented CH: peak of CH:CH;; -0.07~0.05 represented

CH; peak of CH:Si. As shown in FIG. 7, 5.791~5.94 represented

CH,=CH peak; 3.36~3.47 represented CH; peak of CH30 ; -0.11~0.05 represented CH; peak of CH;Si.

FIGS. 2, 4, 6 and 8 showed the IR spectra of modified vinyl silane prepared from Examples 1 to 4 respectively. In FIGS. 2, 4, 6 and 8, 2885cm™ and 2973cm represented C-H vibration peak, 1259cm: represented CH:Si peak, 1031/1037/1047/1051cm* represented

Si-0-Si peak, 955/961/963cmt represented CH:=CH peak, 788/795/796cm * represented CH: Si-CHs.

Verification of application effect

Verification principle: only a small part of unmodified high- purity magnesium hydroxide (blank sample) floated on the water surface, the activation rate was low, but the magnesium hydroxide modified by modified silane had the characteristics of part of or- ganic matter, the oiliness of magnesium hydroxide powder could be increased, the activation rate was increased, the magnesium hy- droxide powder floated on the water surface and could not precipi- tate, and most of the modified powder did not precipitate during liquid separation. 1) 50 g of ground magnesium hydroxide was added into 1.5 g of modified vinyl silane prepared in the Examples 1 to 4 respective- ly, and mechanically stirred, and reacted at the temperature of 85°C for 1 h to obtain modified silane modified magnesium hydroxide powder. 2) Verification of activation rate: 5 g of modified vinyl silane modified magnesium hydroxide powder prepared in the Exam- ples 1 to 4 were weighed respectively, the powder was added into a beaker, 300 g of distilled water was added, full stirring was car- ried out, then standing for separating liquid, the lower layer of liquid and a small amount of precipitate were discharged, the mod- ified magnesium hydroxide floated on the water surface, refined filtration was performed to obtain the floating solid, and drying was carried out to obtain the modified magnesium hydroxide sample;

At the same time, the magnesium hydroxide was modified with vinyl triethoxysilane, vinyl trimethoxysilane and 500-viscosity silicone oil by adopting the method in the step 1), to obtain the modified magnesium hydroxide powder; and then an activation rate verification experiment was carried out according to the method in the step 2).

The activation rates of the magnesium hydroxide modified by different modifying agents were respectively tested, wherein the activation rate = the total mass of the modified magnesium hydrox- ide sample/the weight (5 g) of the magnesium hydroxide sample * 100%, and a blank sample (unmodified magnesium hydroxide powder) was used as a comparison. The result was shown in the Table 1.

Table 1 Activation rates of the magnesium hydroxide modified by different modifying agents 47.01% ysilane pi” 54.24¢ ysilane 41.06% silicone oil

As shown in Table 1, the activation rate of the unmodified magnesium hydroxide (blank sample) was low, the magnesium hydrox- ide was basically precipitated in water, but the modified magnesi- um hydroxide had partial organic matter characteristics, and the activation rate was improved. Moreover, compared with the silane monomer, the performance of the magnesium hydroxide was greatly improved by the vinyl silane modified in the Examples 1 to 4.

The foregoing description merely describes the preferred em- bodiments of the present disclosure. It should be noted that for those of ordinary skill in the art, several improvements and modi- fications can be made without departing from the principle of the present disclosure, and these improvements and modifications shall also fall within the scope of protection of the present disclo- sure.

Claims

CONCLUSIONS

A modified vinyl silane having the structure as shown in Formula I: OR: I Formula I; OR; si STD OR, where, R is or = 2 a 0 - Jo Son FL SL { } 3 Si = OR, J ; where Ry; represents methyl, ethyl, propyl or isopropyl; where further x = 2 to 8, and y = 1 to 50.

The modified vinyl silane according to claim 1, wherein the viscosity of the modified vinyl silane is from 2 to 50 mPa/s.

A process for preparing the modified vinyl silane according to claim 1 or 2, comprising the steps of: mixing vinyl silane, a modifying agent, a catalyst and water, and conducting a modifying reaction to obtain the modified vinyl silane ; wherein the vinyl silane comprises vinyl trialkoxy silane; wherein the vinyltrialkoxysilane is vinyltrimethoxysilane, vinyltriethoxysilane,

vinyltriproxysilane or vinyltriisopropoxysilane; wherein the modifying agent comprises silicone oil or cyclic dimethylsiloxane; wherein the silicone oil has the structure as shown in Formula II: / J \ ~~ ~~ ot ~o tn ~~ Formula II, where m = 1 to 50; wherein the dimethylsiloxane cyclic compound has the structure shown in Formula III: Lo Ra \ | It A Formula IIT, where n = 2~8.

The method of claim 3 wherein the mass ratio of vinylsilane to modifier is 1: (0.3 to 1.2).

The method of claim 3, wherein the catalyst comprises caustic alkali or concentrated sulfuric acid.

The method of claim 3 or 5, wherein the mass of the catalyst is from 0.01 to 0.03% of the total mass of vinylsilane and modifier.

The method of claim 3, wherein the mass of water is from 5 to 20% of the mass of vinylsilane.

The method of claim 3, wherein the temperature of the modifying reaction is 50 to 100°C and the time is 1 to 12 hours.

The method of claim 3, wherein the mixing process of vinyl silane, modifier, catalyst and water comprises the following steps: mixing vinyl silane and modifier, heating to 50 to 100°C, adding at the same time of water and the catalyst to the resulting mixture, the time of adding water and the catalyst being 0.5 to 2 hours.

Use of the modified vinyl silane according to claim 1 or 2 or the modified vinyl silane prepared by the preparation method of any one of claims 3 to 9 in the synthesis of organic and inorganic hybrid materials.