CN102653592A - Dual-cured side active polysiloxane and preparation method thereof - Google Patents
Dual-cured side active polysiloxane and preparation method thereof Download PDFInfo
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- CN102653592A CN102653592A CN2012101042680A CN201210104268A CN102653592A CN 102653592 A CN102653592 A CN 102653592A CN 2012101042680 A CN2012101042680 A CN 2012101042680A CN 201210104268 A CN201210104268 A CN 201210104268A CN 102653592 A CN102653592 A CN 102653592A
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Abstract
The invention provides a dual-cured side active polysiloxane and a preparation method of the dual-cured side active polysiloxane, belongs to the field of high-molecular compounds, and particularly relates to a dual-cured side active polysiloxane and a preparation method of the dual-cured side active polysiloxane. The structural formula of the dual-cured side active polysiloxane and the preparation method of the dual-cured side active polysiloxane provided by the invention can be shown in Figure (I). The preparation method comprises the following steps of: (1) at the temperature of 0-150 DEG C, evenly mixing the side alkoxy polysiloxane with hydroxyl crylic acid (ester)-containing substances in a stirring way according to the condition that the molar ratio of the alkoxy to the hydroxyl is 1:(0.01-3), and adding a catalyst of which the weight is 0.1%-5% of that of the side active polysiloxane and a polymerization inhibitor of which the weight is 0.1-2% of that of the side active polysiloxane; and (2) at the reflow temperature of 0-150 DEG C, after reacting for 0.5-50 hours, rotatably evaporating small-molecule substances in a pressure reducing way, so as to obtain the liquid dual-cured side active polysiloxane. The preparation method provided by the invention has the advantages that a transesterification process is adopted, so that the operation is simple, the raw material cost is low, no solvent is required, and the prepared dual-cured side active polysiloxane can be cured by not only the moisture but also the ultraviolet light, and can be further taken as annexing agent to be used in a thermo-curing or ultraviolet light coating material, so that the prepared dual-cured side active polysiloxane is good in performance.
Description
Technical field
The invention belongs to the macromolecular compound field, particularly a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof.
Background technology
Organopolysiloxane is a kind of functional type resin with good thermotolerance, lower temperature resistance, weathering resistance, contamination resistance and outstanding adhesion, is widely used in fields such as coating, sizing agents.The reactive group alkoxyl group of PMOS only has less consistency with the organic constituent of coating, in its side chain, has introduced acryloxy, makes its not only moisture-curable but also uV curable, also can be used as additive and is used for thermofixation or ultraviolet-curing paint.Along with the rapid expansion of macromolecular material Application Areas, to gathering the increasing functionalization research of having of oxyalkylsiloxane resin.There is the investigator to make the part alkoxyl group of PMOS become acryl with silane coupling agent through hydrolysis-condensation reaction; But this method needs solubilizing agent, water, catalyzer; Because the alkoxyl group organopolysiloxane itself is exactly a coupling agent, meet water generation hydrolytic crosslinking, be prone to form gel or crosslinking curing.Though can through strictness control that amount of water, catalyzer, solvent, temperature and preparation technology come to product, have its complicated process of preparation, require very harshly, process is wayward, cost is high, and the easy contaminate environment of the solvent of production usefulness.There also have the investigator to utilize to be polysiloxane-grafted on the polyacrylic ester chain, but this method needs high temperature and have solvent to exist, and is inapplicable to UV-light coating.
The present invention makes catalyzer with high-efficiency activated material, and directly having synthesized with ester-interchange method can the active organopolysiloxane PAMOS of two solidified sides.Advantage of the present invention is that synthesized with ester-interchange method can the active organopolysiloxane PAMOS of two solidified sides; It is simple to operate, and raw materials cost is low, need not solvent; The not only moisture-curable but also uV curable that make; Also can be used as additive and be used for thermofixation or UV-light coating, excellent performance can be widely used.
Summary of the invention
The object of the present invention is to provide a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof.
Functional poly oxyalkylsiloxane PAMOS proposed by the invention, structural formula is as follows.
The method for preparing functional poly oxyalkylsiloxane PAMOS proposed by the invention comprises process synthetic and aftertreatment, it is characterized in that:
(1) in the four-hole boiling flask that prolong, TM, logical nitrogen are housed with mass ratio be 1: 0.2～1.2 gather oxyalkylsiloxane and the mixing of esters of acrylic acid material.
(2) control reaction temperature drips catalyzer and stopper at 0 ℃～120 ℃, and the organic tin catalyzer is 1～5: 1000 with the mass ratio that gathers oxyalkylsiloxane, and quinones substance is 1～10: 1000 with the mass ratio that gathers oxyalkylsiloxane.
(3) in logical nitrogen atmosphere, reaction 0.5～20h.
(4) after the reaction, vacuum rotary steam obtains the liquid of clear.
Wherein, the preferred mass ratio that gathers oxyalkylsiloxane and esters of acrylic acid material in the step (1) is 0.464.
Preferred temperature of reaction is at 70 ℃ in the step (2).
Preferred organic tin material is a di lauric dibutyl alkene in the step (2), and it is 2: 1000 with the mass ratio that gathers oxyalkylsiloxane.
Preferred quinones substance is a hydroquinone monomethyl ether in the step (2), and it is 5: 1000 with the mass ratio that gathers oxyalkylsiloxane.
The preferred reaction times is 12h in the step (3).
The prepared PAMOS of the present invention is the liquid state of clear, adopts infrared spectroscopy to characterize its structure, and infrared spectrum is as shown in Figure 1.
Description of drawings
Fig. 1 is the infrared spectrogram of the prepared PAMOS of the present invention.
By the infrared spectrum of product, we can find out that the pairing peak of each group is as shown in table 1.
The pairing group of each wave number on table 1 infrared spectrum
| Wave number (cm -1) | The peak position ownership |
| 2969 | -CH 2Antisymmetric stretching vibration |
| 2841 | -CH 2Symmetrical stretching vibration |
| 1729 | The stretching vibration of carbonyl in the acryl |
| 1637 | Unsaturated double-bond H in the acryl 2The stretching vibration of C=CH- |
| 1072 | Si-O-Si and Si-O-C stretching vibration absorption peak superpose |
| 808 | The flexural vibration of the Wasserstoffatoms that is connected with two keys in the acryl |
Embodiment
Embodiment 1
Preparing method of the present invention is added to mixing and stirring in the four-hole boiling flask with 40g polymethoxy siloxanes PMOS and 9.28g vinylformic acid-2-hydroxyl ethyl ester HEA; Take by weighing the 0.04g dibutyl tin laurate; 0.2g hydroquinone monomethyl ether is added drop-wise in the four-hole boiling flask; Oil bath is warming up to 70 ℃, reaction 10h under nitrogen protection.
After reaction was accomplished, vacuum rotary steam obtained liquid product.
Embodiment 2
Preparing method of the present invention is added to mixing and stirring in the four-hole boiling flask with 40g polymethoxy siloxanes PMOS and 18.56g vinylformic acid-2-hydroxyl ethyl ester HEA; Take by weighing the 0.04g dibutyl tin laurate; 0.2g hydroquinone monomethyl ether is added drop-wise in the four-hole boiling flask; Oil bath is warming up to 70 ℃, reaction 10h under nitrogen protection.
After reaction was accomplished, vacuum rotary steam obtained liquid product.
Embodiment 3
Preparing method of the present invention is added to mixing and stirring in the four-hole boiling flask with 40g polymethoxy siloxanes PMOS and 27.84g vinylformic acid-2-hydroxyl ethyl ester HEA; Take by weighing the 0.08g dibutyl tin laurate; 0.2g hydroquinone monomethyl ether is added drop-wise in the four-hole boiling flask; Oil bath is warming up to 70 ℃, reaction 12h under nitrogen protection.
After reaction was accomplished, vacuum rotary steam obtained liquid product.
Embodiment 4
Preparing method of the present invention is added to mixing and stirring in the four-hole boiling flask with 40g polymethoxy siloxanes PMOS and 37.12g vinylformic acid-2-hydroxyl ethyl ester HEA; Take by weighing the 0.08g dibutyl tin laurate; 0.4g hydroquinone monomethyl ether is added drop-wise in the four-hole boiling flask; Oil bath is warming up to 90 ℃, reaction 12h under nitrogen protection.
After reaction was accomplished, vacuum rotary steam obtained liquid product.
Embodiment 5
Preparing method of the present invention is added to mixing and stirring in the four-hole boiling flask with 40g polymethoxy siloxanes PMOS and 46.4g vinylformic acid-2-hydroxyl ethyl ester HEA; Take by weighing the 0.08g dibutyl tin laurate; 0.4g hydroquinone monomethyl ether is added drop-wise in the four-hole boiling flask; Oil bath is warming up to 90 ℃, reaction 12h under nitrogen protection.After reaction was accomplished, vacuum rotary steam obtained the clear liquid product.
Claims (8)
- One kind can the active organopolysiloxane of two solidified sides and preparation method thereof, it is characterized in that described can the active organopolysiloxane structural formulas of two solidified sides shown in (I):
The preparation method of this functional poly oxyalkylsiloxane PAMOS is: (1) mixes a side alkoxyl group organopolysiloxane and hydroxy acryl acid (ester) type material at 0 ℃～150 ℃ with alkoxyl group and hydroxyl mol ratio 1: 0.01～3.Add the active organopolysiloxane quality of side 0.1%～5% catalyzer, 0.1%～2% stopper.(2) under 0 ℃～150 ℃ of reflux temperatures, behind reaction 0.5～50h, vacuum rotary steam goes out small-molecule substance, and obtaining liquid state can the active organopolysiloxane of two solidified sides. - 2. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, it is characterized in that R in the described side alkoxyl group poly organo alkyl structure 1Be CH 3, C 6H 5, CH=CH 2, CH=CHCH 3,Deng, R 2Be CH 3, C 6H 5, OCH 3, OCH 2CH 3, OCH (CH 3) 2Deng, R 3Be OCH 3, OCH 2CH 3, OCH (CH 3) 2, O (CH 2) nCH 3Deng, R 4For
Deng, R 5Be H, OH, CH 3Deng.
- 3. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, it is characterized in that described hydroxy acryl acid (ester) type structure of matter is among
etc. one or more.
- 4. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, the mol ratio that it is characterized in that described side alkoxyl group and hydroxyl is 1: 0.01～3.
- 5. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof; It is characterized in that described catalyzer is metallic compounds such as stanniferous, titanium, zinc, one or more in preferred organotin, titanic acid ester, tin inner complex or the titanium chelate.
- 6. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, its characteristic step is that catalyst consumption is the active organopolysiloxane 0.1～5% of side.
- 7. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, it is characterized in that described stopper consumption is 0.01%～2% of a side alkoxyl group organopolysiloxane quality.
- 8. according to claim 1 a kind of can the active organopolysiloxane of two solidified sides and preparation method thereof, it is characterized in that said stopper is meant one or more in hydroquinone monomethyl ether (MEHQ), para benzoquinone (BQ), tetrachlorobenzoquinone, anthraquinone, the Resorcinol quinones stoppers such as (HQ).
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| CN2012101042680A CN102653592A (en) | 2012-04-10 | 2012-04-10 | Dual-cured side active polysiloxane and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403627A (en) * | 2014-11-12 | 2015-03-11 | 北京化工大学常州先进材料研究院 | High refractive index ultraviolet light /moisture double curing silicone adhesive |
| CN109929079A (en) * | 2019-02-27 | 2019-06-25 | 惠州市德佑威新材料有限公司 | A kind of UV/ moisture dual cure resin and preparation method thereof |
| CN112680103A (en) * | 2020-12-15 | 2021-04-20 | 北京化工大学常州先进材料研究院 | Ultrahigh-strength hydrophobic antifogging coating composition and application thereof |
| CN113388144A (en) * | 2020-03-13 | 2021-09-14 | 北京化工大学 | Ultraviolet light-induced surface amination method for polymer |
-
2012
- 2012-04-10 CN CN2012101042680A patent/CN102653592A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403627A (en) * | 2014-11-12 | 2015-03-11 | 北京化工大学常州先进材料研究院 | High refractive index ultraviolet light /moisture double curing silicone adhesive |
| CN109929079A (en) * | 2019-02-27 | 2019-06-25 | 惠州市德佑威新材料有限公司 | A kind of UV/ moisture dual cure resin and preparation method thereof |
| CN113388144A (en) * | 2020-03-13 | 2021-09-14 | 北京化工大学 | Ultraviolet light-induced surface amination method for polymer |
| CN113388144B (en) * | 2020-03-13 | 2022-05-27 | 北京化工大学 | Ultraviolet light-induced surface amination method for polymer |
| CN112680103A (en) * | 2020-12-15 | 2021-04-20 | 北京化工大学常州先进材料研究院 | Ultrahigh-strength hydrophobic antifogging coating composition and application thereof |
| CN112680103B (en) * | 2020-12-15 | 2022-03-18 | 北京化工大学常州先进材料研究院 | Ultrahigh-strength hydrophobic antifogging coating composition and application thereof |
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Application publication date: 20120905 |