CN104892944B - A kind of preparation method of (methyl) acryloyloxymethyl terminated polysiloxane - Google Patents
A kind of preparation method of (methyl) acryloyloxymethyl terminated polysiloxane Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of (methyl) acryloyloxymethyl terminated polysiloxane, comprise the following steps that (1) mixes (methyl) acryloyloxymethyl (methyl) acryloxy silane and hydroxyl polysiloxane, it is added or is added without organic solvent, it is uniformly mixed, obtains mixed material；(2) under inert gas protection by mixed material obtained by step (1), it is stirred to react in 15~60 DEG C 5~15 hours；(3) after completion of the reaction, cooled to room temperature removes organic solvent, and with methanol extraction, extract liquor is dry, remove methanol to get.The method of the present invention raw material is easy to get, without harsh reaction condition, easy to operate, reaction efficiently and post-processing is simple；It avoids being raw material using expensive platinum catalyst, and reaction can effectively control the polymerization of double bond, reaction hydroxyl high conversion rate, yield is high, side reaction is few.
Description
Technical field
The present invention relates to the preparation methods of (methyl) acryloyloxymethyl terminated polysiloxane, belong to organosilicon macromolecule
Synthesis technical field.
Background technique
The polysiloxanes of (methyl) acryloxyalkyl sealing end is a kind of organo-silicon compound having compared with high reaction activity,
It can be used as active organosilicon polymer to have a wide range of applications in organosilicon macromolecule synthesis field.Double bond and acyloxy impart
The new reactivity of this polysiloxanes, make this polysiloxanes can be used as crosslinking agent be widely used in silicone resin, silicon rubber,
The fields such as organosilicon coating.
In existing technology, the preparation method of polysiloxanes in relation to (methyl) acryloxyalkyl sealing end is mainly
Hydrosilation method.The polysiloxanes and diolefin carboxylate blocked by silicon hydrogen carries out addition under platinum compounds catalysts conditions,
This method expensive catalyst and reaction condition require stringent, the easy inactivation of catalyst, complicated for operation.And (methyl) propylene is made in this method
More than two carbon atoms are connected in silicon atom and acyloxy in the polysiloxanes of acyloxyallcyl sealing end, acyloxy cannot be made only
Pass through the polysiloxanes for (methyl) the acryloyloxymethyl sealing end that a methylene is connected with polysiloxanes silicon atom.
The characteristics of prior art determine the cost of material of preparation (methyl) acryloxyalkyl terminated polysiloxane compared with
Height, preparation method is harsh, and (methyl) acryloxyalkyl terminated polysiloxane because obtained from is expensive, hinders such
The use of compound.It there is no a kind of (methyl) acryloyloxymethyl envelope easy to operate, reaction is efficient, rapid and cheap at present
Hold the preparation method of polysiloxanes.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides simple one kind, safety, economy, high income, purity is high and side reaction
The preparation method of few (methyl) acryloyloxymethyl terminated polysiloxane.
Technical scheme is as follows:
A kind of preparation method of (methyl) acryloyloxymethyl terminated polysiloxane, described (methyl) acryloxy
Shown in the structural formula of methyl blocking polysiloxanes such as formula (I),
It comprises the following steps that
(1) (methyl) acryloyloxymethyl (methyl) acryloxy silane and hydroxyl polysiloxane are mixed, is added
Or it is added without organic solvent, it is uniformly mixed, obtains mixed material；
Shown in the structural formula such as formula (II) of described (methyl) acryloyloxymethyl (methyl) acryloxy silane,
Shown in the structural formula of the hydroxyl polysiloxane such as formula (III),
Formula (I), (II), in (III), R1For hydrogen atom or methyl, R2And R3For methyl or ethyl, R4And R5For hydrogen atom,
Methyl, ethyl or vinyl, n=10~8105, m=n+2；
(2) under inert gas protection by mixed material obtained by step (1), it is stirred to react in 15~60 DEG C 5~15 hours；
(3) after completion of the reaction, cooled to room temperature removes organic solvent, and with methanol extraction, extract liquor is dry, removes
Methanol to get.
, according to the invention it is preferred to, (methyl) acryloyloxymethyl (methyl) acryloxy described in step (1)
The molar ratio of hydroxyl is (1~1.5) in silane and hydroxyl polysiloxane: 1；
Preferably, the molecular weight of the hydroxyl polysiloxane is 1000~600000g/mol.
, according to the invention it is preferred to, in step (1) when adding organic solvent, the organic solvent is toluene or two
Toluene；
Preferably, the mass ratio of organic solvent and hydroxyl polysiloxane is (1~6): 1.
, according to the invention it is preferred to, the reaction temperature in step (2) is 30~60 DEG C, and the reaction time is 8~15 hours.
According to the present invention, described (methyl) acryloyloxymethyl (methyl) acryloxy silane is commercially available, can also
Self-control, is preferably prepared as follows to obtain:
(i) acrylic acid or acrylates or methacrylic acid or methacrylate, polymerization inhibitor, phase transfer catalyst are added
Enter into organic solvent, is uniformly mixed, obtains mixed material；
The polymerization inhibitor is 2,6 di tert butyl 4 methyl phenol, p-tert-Butylcatechol, 4-4- di-2-ethylhexylphosphine oxide
One of (2,6 di t butyl phenol)；The dosage of polymerization inhibitor is acrylic acid or acrylates or methacrylic acid or methyl-prop
The 0.1~2% of olefin(e) acid salt mole dosage；
The phase transfer catalyst is one of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutyl phosphonium bromide phosphine；Phase
The dosage of transfer catalyst be acrylic acid or acrylates or methacrylic acid or methacrylate mole dosage 0.2~
5%；
The organic solvent is toluene or dimethylbenzene；
(ii) chloromethyl chlorosilane is added dropwise into mixed material obtained by step (i), under inert gas protection, in 70~
100 DEG C are stirred to react 8~15 hours；
(iii) after completion of the reaction, cooled to room temperature is filtered under diminished pressure, and filtrate removes organic solvent, is evaporated under reduced pressure, i.e.,
?.Products therefrom is colourless transparent liquid.
, according to the invention it is preferred to, acrylic acid described in step (i) or acrylates or methacrylic acid or methyl-prop
The molar ratio of olefin(e) acid salt and chloromethyl chlorosilane described in step (ii) is (1~3): 1, further preferred (2~2.5): 1.
Hydroxyl polysiloxane used in the present invention is commercially available, can also be prepared by this field routine techniques.
According to the present invention, above-mentioned reaction can be in three equipped with constant pressure funnel, drier, magneton and T-type stop,threeway
It is carried out in mouth round-bottomed flask.
The principle of the present invention:
Reaction equation of the invention is as follows:
Si-O-CO- belongs to reactive group, and reacting with Si-OH can take off under the temperate condition existing for no catalyst
Carboxylic acid, reaction belong to necleophilic reaction, and condition is simple, and the extent of reaction is high.
Beneficial effects of the present invention:
The method of the present invention raw material is easy to get, without harsh reaction condition, easy to operate, reaction efficiently and post-processing is simple.
It avoids using expensive platinum catalyst being raw material, and reaction can effectively control the polymerization of double bond, react hydroxyl conversion ratio
High, yield height, side reaction are few, avoid high-temperature high-voltage reaction, are conducive to (methyl) acryloyloxymethyl terminated polysiloxane
Laboratory preparation and industrialized production.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 1 reactant hydroxyl dimethyl silicone polymer of the embodiment of the present invention.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of 1 reactant hydroxyl dimethyl silicone polymer of the embodiment of the present invention.
Fig. 3 is the infrared spectrum of 1 products therefrom of the embodiment of the present invention.
Fig. 4 is the nucleus magnetic hydrogen spectrum spectrogram of 1 products therefrom of the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, following embodiments be it is illustrative, be not restrictive,
It cannot be limited the scope of protection of the present invention with following embodiments.
(methyl) acryloyloxymethyl (methyl) acryloxy silane raw materials used in embodiment is made as follows
It is standby to obtain:
(i) sodium acrylate or Sodium methacrylate, polymerization inhibitor, phase transfer catalyst are added in organic solvent, are mixed
Uniformly, mixed material is obtained；
The polymerization inhibitor is p-tert-Butylcatechol；The dosage of polymerization inhibitor is that sodium acrylate or Sodium methacrylate rub
The 1% of that dosage；
The phase transfer catalyst is tetrabutylammonium chloride；The dosage of phase transfer catalyst is sodium acrylate or methyl-prop
The 3% of olefin(e) acid sodium mole dosage；
The organic solvent is toluene；
(ii) chloromethyl chlorosilane is added dropwise into mixed material obtained by step (i) to stir in 90 DEG C under inert gas protection
Mix reaction 10 hours；Chloromethyl chlorosilane used in embodiment is commercial products；
(iii) after completion of the reaction, cooled to room temperature is filtered under diminished pressure, and filtrate removes organic solvent, is evaporated under reduced pressure, i.e.,
?.
Hydroxyl polysiloxane used is commercial products in embodiment.
The preparation of embodiment 1, acryloyloxymethyl sealing end dimethyl silicone polymer
Acryloyloxymethyl blocks shown in the structural formula such as formula (IV) of dimethyl silicone polymer,
It comprises the following steps that
In the three neck round bottom flask equipped with constant pressure funnel, drier, magneton and T-type stop,threeway, it is put into
20.03g molecular weight is the hydroxyl dimethyl silicone polymer of 5000g/mol, by 1.78g acryloyloxymethyl acryloxy two
Methyl-monosilane, which is slowly dropped to, to be added in reaction flask, and is slowly stirred, 20 DEG C insulation reaction 5 hours, end of reaction after being added dropwise to complete
Afterwards, with methanol extraction, extract liquor is dry, removes methanol and obtains product, is i.e. acryloyloxymethyl blocks dimethyl silicone polymer.
Yield 84.29%.
Infrared, the nucleus magnetic hydrogen spectrum characterization such as Fig. 1, figure of the present embodiment reactant hydroxyl dimethyl silicone polymer and products therefrom
2, Fig. 3, Fig. 4.
The preparation of embodiment 2, methacryloxymethyl sealing end polymethyl hydrogen siloxane
Methacryloxymethyl blocks shown in the structural formula such as formula (V) of polymethyl hydrogen siloxane,
It comprises the following steps that
In the three neck round bottom flask equipped with constant pressure funnel, drier, magneton and T-type stop,threeway, it is put into 9.82g
Molecular weight is the hydroxyl polymethyl hydrogen siloxane of 10000g/mol, by 0.43g methacryloxymethyl methacryloxypropyl
Base dimethylsilane, which is slowly dropped to, to be added in reaction flask, and is slowly stirred, 30 DEG C insulation reaction 6 hours after being added dropwise to complete, reaction
After, cooled to room temperature, with methanol extraction, extract liquor is dry, removes methanol and obtains product, i.e. methacryloxy
Methyl blocking polymethyl hydrogen siloxane.Yield 83.16%.
The preparation of embodiment 3, acryloyloxymethyl sealing end Polymethyl methacrylate
Acryloyloxymethyl blocks shown in the structural formula such as formula (VI) of Polymethyl methacrylate,
It comprises the following steps that
In the three neck round bottom flask equipped with constant pressure funnel, drier, magneton and T-type stop,threeway, it is put into
50.02g molecular weight is hydroxyl Polymethyl methacrylate, the 100.05g toluene of 200000g/mol, will after stirring and dissolving
0.12g acryloyloxymethyl acryloxy dimethylsilane, which is dissolved in organic solvent being slowly dropped to, to be added in reaction flask, drop
40 DEG C insulation reaction 10 hours after the completion of adding, after completion of the reaction, cooled to room temperature is extracted after removing organic solvent with methanol
It takes, extract liquor is dry, removes methanol and obtains product, is i.e. acryloyloxymethyl blocks Polymethyl methacrylate.Yield
89.25%.
The preparation of embodiment 4, acryloyloxymethyl sealing end dimethyl silicone polymer
Acryloyloxymethyl blocks shown in the structural formula such as formula (VII) of dimethyl silicone polymer,
It comprises the following steps that
In the three neck round bottom flask equipped with constant pressure funnel, drier, magneton and T-type stop,threeway, it is put into
100.06g molecular weight is hydroxyl dimethyl silicone polymer, the 400.18g dimethylbenzene of 600000g/mol, will after stirring and dissolving
0.09g acryloyloxymethyl acryloxy dimethylsilane, which is dissolved in organic solvent being slowly dropped to, to be added in reaction flask, drop
40 DEG C insulation reaction 12 hours after the completion of adding, after completion of the reaction, cooled to room temperature is extracted after removing organic solvent with methanol
It takes, extract liquor is dry, removes methanol and obtains product, is i.e. acryloyloxymethyl blocks dimethyl silicone polymer.Yield
92.47%.
Claims (8)
1. a kind of preparation method of (methyl) acryloyloxymethyl terminated polysiloxane, described (methyl) the acryloxy first
The structural formula of base terminated polysiloxane is as shown in the formula (I),
(I),
It comprises the following steps that
(1) (methyl) acryloyloxymethyl (methyl) acryloxy silane and hydroxyl polysiloxane are mixed, is added or not
Organic solvent is added, is uniformly mixed, obtains mixed material；
Mole of hydroxyl in (methyl) acryloyloxymethyl (methyl) acryloxy silane and hydroxyl polysiloxane
Than for (1 ~ 1.5): 1；
The structural formula of described (methyl) acryloyloxymethyl (methyl) acryloxy silane is as shown in the formula (II),
(II),
The structural formula of the hydroxyl polysiloxane is as shown in the formula (III),
(III),
Formula (I), (II), in (III), R1For hydrogen atom or methyl, R2And R3For methyl or ethyl, R4And R5For hydrogen atom, methyl,
Ethyl or vinyl, n=10 ~ 8105, m=n+2；
(2) under inert gas protection by mixed material obtained by step (1), it is stirred to react in 30 ~ 60 DEG C 8 ~ 15 hours；
(3) after completion of the reaction, cooled to room temperature removes organic solvent, and with methanol extraction, extract liquor is dry, removes methanol,
To obtain the final product.
2. preparation method according to claim 1, which is characterized in that point of hydroxyl polysiloxane as described in step (1)
Son amount is 1000 ~ 600000g/mol.
3. preparation method according to claim 1, which is characterized in that described in step (1) when adding organic solvent
Organic solvent is toluene or dimethylbenzene.
4. preparation method according to claim 1, which is characterized in that in step (1) when adding organic solvent, You Jirong
The mass ratio of agent and hydroxyl polysiloxane is (1 ~ 6): 1.
5. preparation method according to claim 1, which is characterized in that (methyl) acryloxy as described in step (1)
Methyl (methyl) acryloxy silane is prepared as follows to obtain:
(i) acrylic acid or acrylates or methacrylic acid or methacrylate, polymerization inhibitor, phase transfer catalyst are added to
In organic solvent, it is uniformly mixed, obtains mixed material；
The polymerization inhibitor is 2,6 di tert butyl 4 methyl phenol, p-tert-Butylcatechol, 4-4- di-2-ethylhexylphosphine oxide (2,6-
One of DI-tert-butylphenol compounds)；
The phase transfer catalyst is one of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutyl phosphonium bromide phosphine；
The organic solvent is toluene or dimethylbenzene；
(ii) chloromethyl chlorosilane is added dropwise into step (i) gained mixed material to stir in 70 ~ 100 DEG C under inert gas protection
Mix reaction 8 ~ 15 hours；
(iii) after completion of the reaction, cooled to room temperature is filtered under diminished pressure, filtrate remove organic solvent, vacuum distillation to get.
6. preparation method according to claim 5, which is characterized in that the dosage of polymerization inhibitor described in step (i) is third
The 0.1 ~ 2% of olefin(e) acid or acrylates or methacrylic acid or methacrylate mole dosage.
7. preparation method according to claim 5, which is characterized in that the use of phase transfer catalyst described in step (i)
Amount is the 0.2 ~ 5% of acrylic acid or acrylates or methacrylic acid or methacrylate mole dosage.
8. preparation method according to claim 5, which is characterized in that acrylic acid described in step (i) or acrylates
Or the molar ratio of chloromethyl chlorosilane described in methacrylic acid or methacrylate and step (ii) is (1 ~ 3): 1.
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| EP3956383A4 (en) * | 2019-04-16 | 2023-02-22 | Saint-Gobain Performance Plastics Corporation | Dual cure compositions |
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| CN108219141B (en) * | 2017-12-20 | 2020-06-23 | 山东交通学院 | Ester-based functionalized polysiloxane, and preparation method and application thereof |
| KR20230009907A (en) * | 2020-05-07 | 2023-01-17 | 다우 실리콘즈 코포레이션 | (Meth)acrylate Functional Silicones and Methods of Making and Using The Same |
| CN113214310A (en) * | 2021-05-21 | 2021-08-06 | 安徽沸点新材料有限公司 | Preparation process of acryloxy silane oligomer |
| CN115678015A (en) * | 2021-07-29 | 2023-02-03 | 华为技术有限公司 | Modified organic silicon resin, conductive adhesive and preparation method thereof |
| CN113620987B (en) * | 2021-08-19 | 2022-05-06 | 山东大学 | Preparation method of functional silane |
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| US5182315A (en) * | 1990-11-19 | 1993-01-26 | Loctite Corporation | Photocurable silicone gel composition, and method of making the same |
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