CN105061769A - Polysiloxane diol and preparation method thereof - Google Patents
Polysiloxane diol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polysiloxane diol and a preparation method thereof. According to the invention, polysiloxane diol is prepared by means of trimethylation reaction, hydrosilylation reaction, alcoholysis reaction and ring-opening reaction. The polysiloxane diol has the characteristics that: (1) the hydroxyl of the polysiloxane diol is primary hydroxyl with equal activity, and hydroxyl is connected to a siloxane chain segment through alkyl; (2) the polysiloxane diol has the structural characteristics of double siloxane branched chains; and (3) the ring-opening reaction adopts different monomers and the amount ratio of different substances among the monomers to adjust the molecular weight and fluorine content of polysiloxane diol.
Description
Technical field
The invention belongs to the Application Areas of functional organosilicane monomer, organo-silicone rubber and modified poly ester thereof, be specifically related to a kind of silicone glycol and preparation method thereof.
Background technology
Organopolysiloxane (abbreviation polysiloxane) is with the characteristic of organic polymer and inorganic materials, show good thermostability, simultaneously polysiloxane also have that second-order transition temperature is low, ventilation property is high, dielectricity is excellent, with advantage and the special surface property such as good biocompatibility.Because the reactive force between polysiloxane molecule is more weak, when making it use as a kind of exotic materials, mechanical performance compare is poor, therefore limits its range of application to a certain extent.In order to improve the application of organosilicon in polyester material field, then need introduce active reactive group, as-NH at siloxanes segment
2,-OH, C=C etc.The silicone-modified petchem of hydroxyl alkyl belongs to half inorganic, the macromolecular compound of half organic structure, have the performance of inorganic materials and organic materials concurrently, its dielectric properties keep stable in larger temperature, humidity, range of frequency, also there is excellent resistance to oxidation, chemicals-resistant, electrical isolation, radiation hardness, weather-proof, hydrophobic, fire-retardant, salt spray resistance, the characteristic such as mould proof, be widely used in the industry such as electric, industry light industry textile industry, building, medical treatment.
Because hydroxyl alkyl can react with multiple organic group, as ester, carbamate etc. can be generated with radical reactions such as-COOH ,-NCO, therefore in polysiloxane segment, introducing hydroxyl alkyl, is make it to become one of the effective means with reactive behavior carbon functional group polysiloxane.By polycondensation, the groups such as the hydroxyl on the end of organopolysiloxane main chain or side chain and-COOH ,-NCO are linked, form block, grafting or interpenetrating network copolymer, by the method that chemical bond makes the larger polymer scale of these two kinds of polarity spectrum be combined, thus prepare satisfactory high performance material.
The two hydroxyl alkyl polysiloxane of end that the people such as Motegi have used the hydrogen-containing siloxane of 2-methylene radical-1,3-PD and long-chain-segment to react to generate wall scroll siloxane branches at patent US5059707.In case study on implementation, under the catalysis of Platinic chloride, carry out addition reaction of silicon with hydrogen with the single-ended hydrogeneous siloxy of long-chain-segment with 2-methylene radical-1,3-(trimethylsiloxane group) propane; Under obtaining methanol eddy effect subsequently, slough the protection of trimethylsiloxane group, release hydroxyl, generates the dihydroxyl-terminated siloxanes of band long-chain branch.There is shortcomings in this synthetic method: the more difficult purchase of reactant 2-methylene radical-1,3-PD, and raw materials cost is high; The product generated is only containing a siloxane branches, and silicone content is lower.The people such as KevinAnthonyO ' Lenick carry out Si―H addition reaction at patent US20100016501 vinyl carbinol and both-end hydrogen-containing siloxane, have synthesized both-end hydroxyl alkyl polysiloxane polymer.The hydroxyl of the polysiloxane polymer generated at the two ends of siloxanes segment, therefore generates Block copolymer when reacting with-COOH ,-NCO.In block structure, in order to reach good surface property, usually need to add relatively large siloxanes, but siloxanes and polyester poor compatibility, and there is serious microphase-separated by causing the polyester of modification in this, affects its mechanical property.And its siloxanes segment degree of freedom of the silicone-modified polyester of Grafting Structure is comparatively large, therefore less siloxanes add-on, polyester just can reach desirable surface modification effect.
Two hydroxyl alkyl polysiloxane prepared by these schemes all have its shortcoming, but the present invention's synthesis is two branched structures, simultaneously can be different with ratio with the consumption of fluorine-containing annular siloxane according to annular siloxane, prepare branch lengths adjustable, (fluorine-containing) silicone glycol that Oil repellent is variable, obtain more obvious with the surface of polyester improved performance of this glycol synthesis gained, application prospect is more wide.
Silicone glycol is the polymkeric substance that a class contains organic segment and combines with inorganic segment, be main chain with hydrocarbon segment in structure, containing two primary hydroxyls, the activity of hydroxyl is substantially identical, and be easy to and the group such as-NCO ,-COOH, epoxy generation copolyreaction, be grafted in polyester; And by same synthetic route by changing the ratio of the reactant of final step, different (fluorine-containing) silicone glycol different with siloxane branches length of Oil repellent can be prepared; Simultaneously containing two fluorinated polysiloxane side chains, when forming polyester copolymer with other materials, because the surface energy of element silicon and fluorine element is little, siloxanes segment can to surface extension, thus make polyester have excellent surface property, in view of the advantage of its Structure and Properties, the present invention is directed to the weak point of hydroxy silicon oil structure, propose new synthetic method, exemplified reaction formula is as follows:
Summary of the invention
All there is a lot of shortcoming in the two hydroxyl alkyl polysiloxane for preparation at present, the present invention has synthesized a kind of pair of branched structure, simultaneously can be different with ratio with the consumption of fluorine-containing annular siloxane according to annular siloxane, prepare branch lengths adjustable, (fluorine-containing) silicone glycol that Oil repellent is variable, obtain more obvious with the surface of polyester improved performance of this glycol synthesis gained, application prospect is more wide.
A kind of silicone glycol, the structural formula of this silicone glycol is as follows:
In formula, R is methyl, ethyl or phenyl; X+m+n+y's and be the natural number of 0-1000.
The synthetic route of described silicone glycol is as follows:
The synthesis step of described silicone glycol is as follows:
(1) tri-methylated reaction: add TriMethylolPropane(TMP) mono allyl ether in a reservoir, raised temperature is to 80-100 DEG C, slow dropping hexamethyldisilazane is in reaction system, after dropwising, be warming up to 80-100 DEG C, insulation 4h, after completion of the reaction, removes unnecessary hexamethyldisilazane;
(2) hydrosilation reaction: add heptamethyltrisiloxane in step (1) products therefrom, system is warming up to 90-120 DEG C, adds Pt-alkene complex catalyzer, is warming up to 80-100 DEG C of insulation 6h, removes unnecessary heptamethyltrisiloxane;
(3) alcoholysis reaction: add methyl alcohol in step (2) products therefrom, add a small amount of Glacial acetic acid, back flow reaction at 65 DEG C, insulation 6h, after completion of the reaction, removes unnecessary methyl alcohol, filters;
(4) ring-opening polymerization: get the solution that step (3) obtains and add in annular siloxane and fluorine-containing annular siloxane mixed solution, add catalyzer, react at being warming up to 50-60 DEG C, insulation 4h, unnecessary acid is removed with sodium carbonate, filter, remove unnecessary low-boiling-point substance, a kind of silicone glycol can be synthesized.
Further, the hydroxyl of described silicone glycol is the primary hydroxyl of isoreactivity, and hydroxyl is connected with siloxanes segment by alkyl; This silicone glycol has the constitutional features of two siloxane branches; Molecular weight and the Oil repellent of the adjustable silicone glycol of ratio of amount of substances different between different monomers and different monomers is adopted in ring-opening reaction.
Further, in described silicone glycol structural formula, if m=n=0, be the glycol of not fluorine-containing polysiloxane, structural formula is as follows:
In formula, R is methyl, ethyl or phenyl; X+y's and be the natural number of 0-1000.
Further, in described silicone glycol structural formula, if x=y=0, then when silicone glycol molecular weight one timing, fluorine content in this silicone glycol is the highest, and structural formula is as follows:
In formula, R is methyl, ethyl or phenyl; M+n's and be the natural number of 0-1000.
In described silicone glycol structural formula, if m=n=x=y=0, then this silicone glycol is the small molecules dibasic alcohol of silicone-containing, and structural formula is as follows:
In formula, R is methyl, ethyl or phenyl.
Further optimally, the preparation method of (fluorine-containing) silicone glycol comprises four-step reaction, and synthesis step is as follows:
In step (1), the molar ratio of TriMethylolPropane(TMP) mono allyl ether and hydroxy-protecting agent is 1:1.2-1:3.
Further optimally, in step (2), step (1) products therefrom and heptamethyltrisiloxane mol ratio are 1:2-1:3, system is warming up to 90-120 DEG C, add Pt-alkene complex catalyzer, the consumption of catalyzer is monomer total mass 6-9ppm, is warming up to 80-100 DEG C of insulation 6h, removes unnecessary heptamethyltrisiloxane;
Further optimally, in step (3), methyl alcohol is added in step (2) products therefrom, the mol ratio of step (2) products therefrom and methyl alcohol is 1:2-1:3, and the Glacial acetic acid consumption added is the 1%-5% of monomer total mass, back flow reaction at 65 DEG C, insulation 6h, after completion of the reaction, by methyl alcohol unnecessary for liquid removal, filter.
Further optimally, the solution that step (4) taken amount step (3) obtains adds in annular siloxane and fluorine-containing annular siloxane mixed solution, and mol ratio is determined according to the molecular weight of synthesized hydroxy silicon oil, adds catalyzer, react at being warming up to 50-60 DEG C, insulation 4h.
Compared with prior art, tool of the present invention has the following advantages and technique effect:
What the present invention synthesized is two branched structures, simultaneously can be different with ratio with the consumption of fluorine-containing annular siloxane according to annular siloxane, prepare branch lengths adjustable, (fluorine-containing) silicone glycol that Oil repellent is variable, obtain more obvious with the surface of polyester improved performance of this glycol synthesis gained, application prospect is more wide.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism figure of compound (IV).
Fig. 2 is the nuclear-magnetism figure of embodiment 2 product silicone glycol.
Fig. 3 is the nuclear-magnetism figure of embodiment 3 product fluorinated polysiloxane glycol.
Embodiment
Below in conjunction with accompanying drawing and example, specific embodiment of the invention is described further, but enforcement of the present invention and protection are not limited thereto.
Embodiment 1
Get 174g TriMethylolPropane(TMP) mono allyl ether in the four-hole boiling flask that whipping appts and thermometer are housed, slowly instillation 300g hexamethyldisilazane, at about 90 DEG C insulation 4h after dropwising.There is a large amount of ammonia to generate in reaction process, absorb with the dilute sulphuric acid that massfraction is 30%, after completion of the reaction, vacuumize the hexamethyldisilazane that removing is excessive.Obtaining clarified colorless liquid, is compd A, and productive rate is 97%.
Get 159g compd A and 200g heptamethyltrisiloxane in the there-necked flask with whipping appts, condensing reflux pipe and thermometer, raised temperature to 80 DEG C-100 DEG C, adds about 0.60gPt-alkene complex catalyzer, insulation reaction 6 hours.Generate compd B.After completion of the reaction, the excessive heptamethyltrisiloxane of removing is vacuumized.Obtaining clear, pale yellowish liquid, is compd B, and productive rate is 93%.
Get 135g compd B, 4.0g Glacial acetic acid and 30g methyl alcohol in the there-necked flask with whipping appts, condensing reflux pipe and thermometer, be warming up to 65 DEG C, insulation backflow.After completion of the reaction, the excessive methyl alcohol of removing and Glacial acetic acid is vacuumized.Having reacted and obtained clear, pale yellowish liquid, is Compound C, and productive rate is 95%.
Get 63g Compound C and 96gD
4in the there-necked flask with whipping appts, condensing reflux pipe and thermometer, be warming up to 55 DEG C, add 2.5ml concentrated sulfuric acid catalyst, insulation 4h.After completion of the reaction, add sodium carbonate and remove excessive acid, filter, suction removes the unnecessary low-boiling-point substance of organic pull-up, namely obtains the glycol containing double focusing siloxane branches.Having reacted and obtained clarified colorless liquid, is Compound D, and productive rate is 80%.The average molecular mass recording hydroxyl alkyl siloxanes according to GB120083-2009 is 1156.
Embodiment 2
Preparation Compound C step is identical with embodiment 1.
Get 63g Compound C and 96gD
4in the there-necked flask with whipping appts, condensing reflux pipe and thermometer, be warming up to 55 DEG C, add about 2.5ml concentrated sulfuric acid catalyst, insulation 4h.After completion of the reaction, add sodium carbonate and remove excessive acid, filter, vacuumize and remove unnecessary low-boiling-point substance, namely obtain the glycol containing double focusing siloxane branches.Having reacted and obtained clarified colorless liquid, is compd E, and productive rate is 79%.The average molecular mass recording hydroxyl alkyl siloxanes according to GB120083-2009 is 1173.
Embodiment 3
Preparation Compound C step is identical with embodiment 1.
Get 59.4g Compound C and 90.6gD
3 fin the there-necked flask with whipping appts, condensing reflux pipe and thermometer, be warming up to 55 DEG C, add about 2.5ml concentrated sulfuric acid catalyst, insulation 4h.After completion of the reaction, add sodium carbonate and remove excessive acid, filter, vacuumize and organic layer is removed unnecessary low-boiling-point substance, namely obtain the glycol containing double focusing siloxane branches.Having reacted and obtained clarified colorless liquid, is compound F 17-hydroxy-corticosterone, and productive rate is 83%.The average molecular mass recording hydroxyl alkyl siloxanes according to GB120083-2009 is 1146.
Claims (7)
1. a silicone glycol, is characterized in that, the structural formula of silicone glycol is as follows:
In formula, R is methyl, ethyl or phenyl; X+m+n+y's and be the natural number of 0-1000.
2. prepare the method for a kind of silicone glycol according to claim 1, it is characterized in that, the synthetic route of this silicone glycol is as follows:
3. the preparation method of a kind of silicone glycol according to claim 2, is characterized in that, the synthesis step of this silicone glycol is as follows:
(1) tri-methylated reaction: add TriMethylolPropane(TMP) mono allyl ether in a reservoir, raised temperature is to 80-100 DEG C, slow dropping hexamethyldisilazane is in reaction system, after dropwising, be warming up to 80-100 DEG C, insulation 4h-8h, after completion of the reaction, vacuumizes the hexamethyldisilazane that removing is excessive;
(2) hydrosilation reaction: add heptamethyltrisiloxane in step (1) products therefrom, system is warming up to 90-120 DEG C, add Pt-alkene complex catalyzer, be warming up to 80-100 DEG C of insulation 2h-4h, vacuumize the heptamethyltrisiloxane that removing is excessive;
(3) alcoholysis reaction: add methyl alcohol and Glacial acetic acid in step (2) products therefrom, back flow reaction at 60-65 DEG C, insulation 4-10h, after completion of the reaction, by liquid under certain vacuum degree and temperature, vacuumize the excessive methyl alcohol of removing and Glacial acetic acid, filter;
(4) ring-opening polymerization: get the solution that step (3) obtains and add in annular siloxane and fluorine-containing annular siloxane mixed solution, add concentrated sulfuric acid catalyst, react at being warming up to 50-60 DEG C, insulation 4h-7h, unnecessary acid is removed with sodium carbonate, filter, vacuumize and remove unnecessary low-boiling-point substance, a kind of silicone glycol can be synthesized.
4. a kind of silicone glycol according to claim 1, is characterized in that, the hydroxyl of this silicone glycol is the primary hydroxyl of isoreactivity, and hydroxyl is connected with siloxanes segment by alkyl; This silicone glycol has the constitutional features of two siloxane branches.
5. a kind of silicone glycol according to claim 1, if it is characterized in that m=n=0, silicone glycol is not fluorine-containing silicone glycol, and structural formula is as follows:
In formula, R is methyl, ethyl or phenyl; X+y's and be the natural number of 0-1000.
6. a kind of silicone glycol according to claim 1, is characterized in that, if x=y=0, then when silicone glycol molecular weight one timing, fluorine content in this silicone glycol is the highest, and structural formula is as follows:
In formula, R is methyl, ethyl or phenyl; M+n's and be the natural number of 0-1000.
7. a kind of silicone glycol according to claim 1, if it is characterized in that m=n=x=y=0, then this silicone glycol is the small molecules dibasic alcohol of silicone-containing, and structural formula is as follows:
In formula, R is methyl, ethyl or phenyl.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI672331B (en) * | 2017-01-30 | 2019-09-21 | 日商信越化學工業股份有限公司 | Stretchable film and method for forming the stretchable film |
| TWI687430B (en) * | 2017-10-10 | 2020-03-11 | 日商信越化學工業股份有限公司 | Silicon-containing compound, urethane resin, stretchable film, and method for forming the same |
| CN111718488A (en) * | 2020-08-06 | 2020-09-29 | 广州市斯洛柯高分子聚合物有限公司 | Single-ended dihydroxy alkyl silicone oil for polyurethane modification and preparation method thereof |
| CN113603858A (en) * | 2021-08-20 | 2021-11-05 | 上海涂固安高科技有限公司 | Water-based polymer inorganic composite nano-particles and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| JPH09316085A (en) * | 1996-05-23 | 1997-12-09 | Nippon Unicar Co Ltd | Reactive siloxane |
-
2015
- 2015-07-29 CN CN201510461145.6A patent/CN105061769A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| JPH09316085A (en) * | 1996-05-23 | 1997-12-09 | Nippon Unicar Co Ltd | Reactive siloxane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI672331B (en) * | 2017-01-30 | 2019-09-21 | 日商信越化學工業股份有限公司 | Stretchable film and method for forming the stretchable film |
| TWI687430B (en) * | 2017-10-10 | 2020-03-11 | 日商信越化學工業股份有限公司 | Silicon-containing compound, urethane resin, stretchable film, and method for forming the same |
| CN111718488A (en) * | 2020-08-06 | 2020-09-29 | 广州市斯洛柯高分子聚合物有限公司 | Single-ended dihydroxy alkyl silicone oil for polyurethane modification and preparation method thereof |
| CN113603858A (en) * | 2021-08-20 | 2021-11-05 | 上海涂固安高科技有限公司 | Water-based polymer inorganic composite nano-particles and application thereof |
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