CN103289267A - Preparation method and application of hydrogen-containing polysiloxane and polyacrylate semi-interpenetrating network polymer - Google Patents
Preparation method and application of hydrogen-containing polysiloxane and polyacrylate semi-interpenetrating network polymer Download PDFInfo
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- CN103289267A CN103289267A CN201210519600XA CN201210519600A CN103289267A CN 103289267 A CN103289267 A CN 103289267A CN 201210519600X A CN201210519600X A CN 201210519600XA CN 201210519600 A CN201210519600 A CN 201210519600A CN 103289267 A CN103289267 A CN 103289267A
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Abstract
The invention relates to the field of high polymer materials and provides a preparation method of a hydrogen-containing polysiloxane and polyacrylate semi-interpenetrating network polymer for improving structural stability of blend of polysiloxane and polar polymer. The preparation method comprises the following steps of: blending acrylic ester with hydrogen-containing polysiloxane, adding lewis acid and protonic acid, stirring and reacting for more than one hour at the temperature ranging from room temperature to 100 DEG C, cooling to room temperature, adding water and quenching, then washing to be neutral, removing a solvent, and drying to obtain the hydrogen-containing polysiloxane and polyacrylate semi-interpenetrating network polymer. The preparation method is easy to operate, reaction conditions are mild, yield is high, and the obtained product has excellent structural stability. The invention also provides an application of the prepared hydrogen-containing polysiloxane and polyacrylate semi-interpenetrating network polymer in organic synthesis reaction.
Description
Technical field
The present invention relates to polymeric material field, relate in particular to preparation method and the application of the polymkeric substance with half interpenetrating network structure of a kind of hydrogen containing siloxane and polyacrylic ester formation.
Technical background
The organosilicon macromolecule compound is high heat resistance, high-weatherability, high-biocompatibility, low surface energy, the low base polymer that rubs, reaches the high performance material of high-low temperature resistant alternation, be one of macromolecular material that under extreme and particular surroundings, uses, to the design of this class material with synthesize significant to the demand that satisfies new and high technology.The organosilicon material that with the polysiloxane is base polymer is the earliest by cognitive and the widest organosilicon macromolecule compound of purposes, diversification of varieties, liquid (silicone oil), elastomerics (silicon rubber), resin, sizing agent, emulsion etc. are arranged, be widely used in each side such as aerospace, aviation, electric, electronics, light industry, machinery, chemical industry, medical science.But the consistency of polysiloxane, particularly polydimethylsiloxane and other polymkeric substance is relatively poor, has serious being separated during especially with polymer blending with polarity.Interpenetrating net polymer is the co-mixing system that is interted mutually, tangled and constitute by two or more polymeric constituent.When having only a kind of crosslinked polymer, its product is called semi-interpenetrating network polymer.Compare with traditional blend, the polymkeric substance with half interpenetrating network structure has consistency preferably, can improve the structural stability of blend.Therefore, utilize the structural performance of semi-interpenetrating network polymer, can develop a kind of easy, prepare the novel method of hydrogen containing siloxane and polar polymer (polyacrylic ester) blend efficiently, solve polysiloxane and the polar polymer consistency is poor, the problem of blend structure poor stability.Adopt hydrogen containing siloxane, this semi-interpenetrating network polymer be can be used as a kind ofly go back the deoxygenation that original reagent is used for alcohol, aldehyde and ketone and generate corresponding alkane.
Summary of the invention:
In order to improve the structural stability of polysiloxane and polar polymer blend, the invention provides the preparation method of a kind of hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer, this method is easy and simple to handle, reaction conditions is gentle, productive rate is high, and the product that obtains has good structural stability.
The invention provides the application of this hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer simultaneously, this polymkeric substance has its unique physicochemical property, can be applicable in the organic synthesis, metal had load preferably and package action, thereby make metal catalyst have better catalytic activity, and recyclable recycling.
The present invention is achieved by the following technical solutions: the preparation method of a kind of hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer, described preparation method is following steps: acrylate and hydrogen containing siloxane is mixed, add Lewis acid and protonic acid, ℃ following stirring reaction was cooled to room temperature more than 1 hour in room temperature~100, added shrend and went out, extraction then, be washed to neutrality, desolventizing namely obtains hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer after the drying.The form of the time of stirring according to product determines that product is white emulsion liquid when the reaction times is 1~7 h; Reaction times product for greater than 7 h the time is white solid.Described semi-interpenetrating network polymer is that linear polyacrylic ester is interspersed in the crosslinked hydrogen containing siloxane.Described preparation method's room temperature is commonly referred to as 25 ℃, and pressure is 101 kPas.
Described acrylate is selected from methyl acrylate, ethyl propenoate, isobutyl acrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, and is a kind of in methacrylic tert-butyl acrylate, the butyl acrylate.
Described hydrogen containing siloxane is selected from Methyl Hydrogen Polysiloxane Fluid, phenyl hydrogen-containing silicon oil, the methyl and phenyl hydrogen-containing silicon oil a kind of, and wherein the hydrogen containing siloxane hydrogen content is 0.1~1.6% for the quality percentage composition.
As preferably, in the acrylate in carbon carbon unsaturated double-bond and the hydrogen containing siloxane mol ratio of si-h bond be 1:0.5~10.
Described Lewis acid is selected from boron trifluoride, zinc chloride, iron(ic) chloride, aluminum chloride, iron bromide, zinc fluoride, columbium pentachloride, antimony pentafluoride, Indium-111 chloride, tin protochloride, palladium, neutralized verdigris, Cobaltous diacetate, nickel acetate, Xiao Suangu, copper trifluoromethanesulfcomposite, Bismuth triflate, silver trifluoromethanesulfonate, the trifluoromethanesulfonic acid zinc a kind of, and the mol ratio of Lewis acid and acrylate is 1:50~1000.
Described protonic acid is selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, trifluoroacetic acid, thionamic acid, tosic acid, the trifluoromethanesulfonic acid a kind of, and the mol ratio of si-h bond is 1:10~500 in protonic acid and the hydrogen containing siloxane.
The hydrogen containing siloxane that the preparation method of a kind of hydrogen containing siloxane of the present invention and polyacrylic ester semi-interpenetrating network polymer prepares and the application of polyacrylic ester semi-interpenetrating network polymer in organic synthesis.This polymkeric substance both can be used as a kind of carrier to load metal catalyzer as a kind of metal catalyst, simultaneously can also generate corresponding alkane as the deoxygenation that the metal catalyst of going back the collaborative loadization of original reagent is used for pure, aldehyde and ketone.Its reaction process is as follows:
,
,
,
Wherein, R is selected from
o-CH
3,
m-CH
3,
p-CH
3,
o-OCH
3,
m-OCH
3,
p-OCH
3,
o-OH,
m-OH,
p-OH,
o-CH
3OH,
m-CH
3OH,
p-CH
3OH ,-a kind of among the Ph, R
1Be selected from-H ,-CH
3,-CH
2CH
3In a kind of.
Compared with prior art, the invention has the beneficial effects as follows:
(1) preparation method of the present invention is easy and simple to handle, reaction conditions is gentle, productive rate is high, and the polymkeric substance that obtains has good structural stability.
(2) polymkeric substance of the present invention not only can be used as a kind of carrier to load metal catalyzer, also can be used as the deoxygenation that the metal catalyst of going back the collaborative loadization of original reagent is used for alcohol, aldehyde and ketone and generates corresponding alkane; Can also recycle and reuse simultaneously.
Description of drawings
Fig. 1 is the transmission electron microscope figure of the product of embodiment 1.
Embodiment
Be described in further detail below in conjunction with the present invention of embodiment, raw materials used all commercially available among the embodiment.
Embodiment 1:
Ethyl propenoate 10.9 mL (0.10 mol), Methyl Hydrogen Polysiloxane Fluid (hydrogen content quality percentage composition 1.55%) 19.4 g (Si-H:0.30 mol) are mixed, add iron(ic) chloride 0.324 g (2.0 mmol), acetic acid 0.036 g (0.60 mmol), behind 90 ℃ of stirring 7 h, be cooled to room temperature, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product methyl hydrogen containing siloxane and polyethyl acrylate semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 94%, product state: white emulsion liquid.
The physical and chemical index of embodiment 1 product:
1H NMR δ H (400 MHz, CDCl3): 4.708 (s, 3H), 4.109 (s, 2H), 2.293 (s, 1H), 1.910 (t, 2H), 1.243 (s, 3H), 0.191 (s, 10H); IR:3427.4,2963.9,2917.9,2880.9,2223.3,1412.4,1261.7,1026.2,960.2,850.9,799.7,757.6,688.5,530.9.
The transmission electron microscope figure of this product as shown in Figure 1.
Embodiment 2:
Ethyl propenoate 10.9 mL (0.10 mol), Methyl Hydrogen Polysiloxane Fluid (hydrogen content quality percentage composition 1.55%) 19.4 g (Si-H:0.30 mol) are mixed, add aluminum chloride 0.013 g (0.10 mmol), trifluoroacetic acid 0.171 g (1.50 mmol), after heating 60 ℃ of stirring 18 h, be cooled to room temperature, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product methyl hydrogen containing siloxane and polyethyl acrylate semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 93%, product state: white solid.
Embodiment 3:
Tert-butyl acrylate 14.5 mL (0.1 mol), Methyl Hydrogen Polysiloxane Fluid (hydrogen content quality percentage composition 1.55%) 65 g (Si-H:1.0 mol) are mixed, add neutralized verdigris 0.036 g (0.20 mmol), acetic acid 6..0 g (0.1 mol), behind 90 ℃ of stirring 18 h, be cooled to room temperature, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product methyl hydrogen containing siloxane and polyacrylic acid tert-butyl ester semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 97%, product state: white solid.
Embodiment 4:
Methyl acrylate 9.00 mL (0.1 mol), Methyl Hydrogen Polysiloxane Fluid (hydrogen content quality percentage composition 0.2%) 25.0 g (Si-H:0.05 mol) are mixed, add iron(ic) chloride 0.032 g (0.2 mmol), acetic acid 0.015 g (0.25 mmol), behind the stirring at room 18h, be cooled to room temperature again, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product methyl hydrogen containing siloxane and polymethyl acrylate semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 92%, product state: white solid.
Embodiment 5:
With methyl methacrylate 10.6 mL (0.1 mol), aminomethyl phenyl hydrogen containing siloxane (hydrogeneous quality percentage composition 0.5%) 20 g (Si-H:0.1 mol) mix, silver trifluoromethanesulfonate 0.064 g (0.25 mmol), phosphoric acid 0.098 g (1.0 mmol), after heating 100 ℃ of stirring 24 h, be cooled to room temperature, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product aminomethyl phenyl hydrogen containing siloxane and polymethylmethacrylate semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 97%, product state: white solid.
Embodiment 6:
Ethyl propenoate 10.9mL (0.1 mol), aminomethyl phenyl hydrogen containing siloxane (hydrogen content quality percentage composition 0.5 %) 20 g (Si-H:0.1 mol) are mixed, add iron(ic) chloride 0.032 g (0.2 mmol), thionamic acid 0.024 g (0.25 mmol), behind 30 ℃ of stirring 24 h, be cooled to room temperature again, add shrend and go out, use CHCl
3Extraction is washed to neutrality, and steaming desolventizes, and gets product aminomethyl phenyl hydrogen containing siloxane and polyethyl acrylate semi-interpenetrating network polymer after the vacuum-drying.Productive rate: 95%, product state: white solid.
Application examples 1:
With product methyl hydrogen containing siloxane and the polyethyl acrylate semi-interpenetrating network polymer load P d that embodiment 2 obtains, be used for the reduction reaction of alcohol:
Under the noble gas atmosphere, 1.58 g 2-are methyl alcohol, PdCl how
2(5 moL%), 3 g PEA, 20 mL methyl alcohol join in the dry flask in 40 ℃ of heated and stirred 24 h, leave standstill the Pd of lower floor loaded article deposition after the reaction, upper organic phase adds n-hexane extraction, and drying is revolved and desolventized, obtain product, GC productive rate by the thin-layer chromatography separation〉99%
The PEA/PdCl of lower floor
2By atomic absorption, IR its physico-chemical property is characterized, Pd content is 1.87%; IR:2966.8,2163.8,1729.9,1446.9,1380.5,1259.6,1032.5,838.6,803.7,760.3.
The physical and chemical index of reduzate:
1H-NMR (400 MHz, CDCl
3): δ=7.855(d, J=7.6Hz, 1H); 7.806(q, 2H); 7.552(t, 1H); 7.670 (s, 1H); 7.481(m, 2H); 7.375(d, J=8.4Hz, 1H); 2.574(s, 3H).
Application examples 2:
With product (PEA/SiH) the load P d that embodiment 2 obtains, be used for the reduction reaction of ketone:
Under the noble gas atmosphere, 1.502 g o-methoxyacetophenones, PdCl
2(10moL%), 6 g PEA/SiH, 20 mL methyl alcohol join in the dry flask in 40 ℃ of heated and stirred 24 h, leave standstill the Pd of lower floor loaded article deposition after the reaction, upper organic phase adds n-hexane extraction, and drying is revolved and desolventized, obtain product, GC productive rate by the thin-layer chromatography separation〉99%.
The PEA/PdCl of lower floor
2By atomic absorption, IR its physico-chemical property is characterized, Pd content is 1.87%; IR:2966.8,2163.8,1729.9,1446.9,1380.5,1259.6,1032.5,838.6,803.7,760.3.
The physical and chemical index of reduzate:
1H-NMR (400 MHz, CDCl
3): δ=7.179(m, 2H); 6.886(m, 2H); 3.837(s, 3H); 2.655(q, 2H); 1.207(t, J=7.6Hz, 3H).
Above-described embodiment will help to understand the present invention, but not limit content of the present invention.
Claims (8)
1. the preparation method of a hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, described preparation method is following steps: acrylate and hydrogen containing siloxane is mixed, add Lewis acid and protonic acid, and ℃ following stirring reaction is more than 1 hour in room temperature~100, be cooled to room temperature, add shrend and go out, extraction is washed to neutrality then, desolventizing namely obtains hydrogen containing siloxane and polyacrylic ester semi-interpenetrating network polymer after the drying.
2. the preparation method of a kind of hydrogen containing siloxane according to claim 1 and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, described acrylate is selected from methyl acrylate, ethyl propenoate, isobutyl acrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, and is a kind of in methacrylic tert-butyl acrylate, the butyl acrylate.
3. the preparation method of a kind of hydrogen containing siloxane according to claim 1 and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, described hydrogen containing siloxane is selected from Methyl Hydrogen Polysiloxane Fluid, phenyl hydrogen-containing silicon oil, the methyl and phenyl hydrogen-containing silicon oil a kind of, and wherein the hydrogen containing siloxane hydrogen content is 0.1~1.6% for the quality percentage composition.
4. according to the preparation method of claim 1 or 2 or 3 described a kind of hydrogen containing siloxanes and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, in the acrylate in carbon carbon unsaturated double-bond and the hydrogen containing siloxane mol ratio of si-h bond be 1:0.5~10.
5. the preparation method of a kind of hydrogen containing siloxane according to claim 1 and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, described Lewis acid is selected from boron trifluoride, zinc chloride, iron(ic) chloride, aluminum chloride, iron bromide, zinc fluoride, columbium pentachloride, antimony pentafluoride, Indium-111 chloride, tin protochloride, palladium, neutralized verdigris, Cobaltous diacetate, nickel acetate, Xiao Suangu, copper trifluoromethanesulfcomposite, Bismuth triflate, silver trifluoromethanesulfonate, the trifluoromethanesulfonic acid zinc a kind of, and the mol ratio of Lewis acid and acrylate is 1:50~1000.
6. the preparation method of a kind of hydrogen containing siloxane according to claim 1 and polyacrylic ester semi-interpenetrating network polymer, it is characterized in that, described protonic acid is selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, trifluoroacetic acid, thionamic acid, tosic acid, the trifluoromethanesulfonic acid a kind of, and the mol ratio of si-h bond is 1:10~500 in protonic acid and the hydrogen containing siloxane.
7. hydrogen containing siloxane and the application of polyacrylic ester semi-interpenetrating network polymer in organic synthesis of preparing according to the preparation method of a kind of hydrogen containing siloxane as claimed in claim 1 and polyacrylic ester semi-interpenetrating network polymer.
8. the application of a kind of hydrogen containing siloxane according to claim 7 and polyacrylic ester semi-interpenetrating network polymer is characterized in that, this polymkeric substance is as a kind of metal catalyst.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105647381A (en) * | 2016-01-13 | 2016-06-08 | 上海应用技术学院 | 3D stereoscopic magnetic pearlescent light-sensitive adhesive and preparation method thereof |
CN107793580A (en) * | 2017-11-14 | 2018-03-13 | 合肥工业大学 | One kind can self-healing gel rubber material and preparation method thereof |
CN113260640A (en) * | 2019-01-07 | 2021-08-13 | 信越化学工业株式会社 | Interpenetrating network polymer comprising organopolysiloxane cross-linked product and (meth) acrylic polymer, and method for producing same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153641A (en) * | 1977-07-25 | 1979-05-08 | Bausch & Lomb Incorporated | Polysiloxane composition and contact lens |
-
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---|---|---|---|---|
US4153641A (en) * | 1977-07-25 | 1979-05-08 | Bausch & Lomb Incorporated | Polysiloxane composition and contact lens |
Non-Patent Citations (1)
Title |
---|
程栋材,黄志雄,秦岩: "聚硅氧烷/聚丙烯酸甲酯IPNs的阻尼性能研究", 《武汉理工大学学报》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105647381A (en) * | 2016-01-13 | 2016-06-08 | 上海应用技术学院 | 3D stereoscopic magnetic pearlescent light-sensitive adhesive and preparation method thereof |
CN105647381B (en) * | 2016-01-13 | 2019-01-18 | 上海应用技术学院 | 3D solid magnetic pearlescent light-sensitive emulsion and preparation method thereof |
CN107793580A (en) * | 2017-11-14 | 2018-03-13 | 合肥工业大学 | One kind can self-healing gel rubber material and preparation method thereof |
CN107793580B (en) * | 2017-11-14 | 2020-04-21 | 合肥工业大学 | Self-healing gel material and preparation method thereof |
CN113260640A (en) * | 2019-01-07 | 2021-08-13 | 信越化学工业株式会社 | Interpenetrating network polymer comprising organopolysiloxane cross-linked product and (meth) acrylic polymer, and method for producing same |
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