CN101381462B - Polysiloxane binary alcohol with polyether block and preparation method thereof - Google Patents
Polysiloxane binary alcohol with polyether block and preparation method thereof Download PDFInfo
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- CN101381462B CN101381462B CN2008101965336A CN200810196533A CN101381462B CN 101381462 B CN101381462 B CN 101381462B CN 2008101965336 A CN2008101965336 A CN 2008101965336A CN 200810196533 A CN200810196533 A CN 200810196533A CN 101381462 B CN101381462 B CN 101381462B
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Abstract
The invention discloses polyether block polysiloxane diol and a method for preparing the same. The method is characterized by comprising the following steps: performing ring-opening polymerization through cyclic siloxane and dihydro terminated disiloxane first to obtain dihydro terminated polysiloxane, and then performing hydrosilylation reaction with mono-vinyl terminated polyether oligomer to form the polyether block polysiloxane diol the structural formula of which is shown in the graph, wherein R1 and R2 are CH3 and CH2CH3 and/or CH2CH2CH3 respectively, R3 is H or CH3, n is an integer between 1 and 1, 000, and p and q are integers between 1 and 100. The polyether block polysiloxane diol prepared by the method has the advantages of better hydrolysis resistance and storage stability, and high reactivity; in addition, the polyether block polysiloxane diol improves the problem of the unsatisfactory mechanical property of the prior siloxane diol in modifying copolymers.
Description
Technical field
The invention belongs to macromolecular material intermediate polysiloxane binary alcohol and preparation method thereof technical field, particularly polysiloxane binary alcohol of polyether oligomers block and preparation method thereof.
Background technology
Because there is terminal hydroxy group in polysiloxane binary alcohol, therefore often be used as multiple coating such as intermediate preparation urethane, polyester, superpolymer thermoplastic elastomer, foamed thermoplastic body etc.With polysiloxane binary alcohol as the material of intermediate preparation owing to have good water tolerance, resistance to deterioration and surface property and better biocompatibility etc., be used widely in a lot of fields.
Chinese patent CN90105777.0 has introduced a kind of lower molecular weight α that produces, the method for ω siloxane glycol, and secondary hydrolyzable alkoxy TMOS under an acidic catalyst effect makes the siloxanes two ends have hydroxy functional group.Since with the hydroxyl instability that siloxanes directly links to each other, the not too suitable intermediate of making materials such as preparation urethane, polyester.
Day disclosure special permission communique spy opens flat 5-97868 and has proposed the method that a kind of preparation one end contains the polysiloxane binary alcohol of two hydroxyls, is made by the polysiloxane addition reaction of silicon with hydrogen of the dibasic alcohol that contains vinyl and single si-h bond.Prepared silicone glycols needing solvent even mixed solvent often with the reaction of polar comonomer, therefore is unfavorable for save energy and environment protection because its polarity is lower.
U.S.'s " polymer science magazine " (Journal of Polymer Science, Part A:Polymer Chemistry, nineteen ninety-five, 1773 pages of 33 volumes) introduced and utilized α, the hydrolysis and obtain a kind of preparation method of polysiloxane binary alcohol of hydroxyl butyl end-capping under the acid catalyst effect of ω-dihydroxy butyl tetramethyl disiloxane and dimethoxy dimethylsilane.But thereby the end capped polysiloxane binary alcohol of this hydroxyalkyl makes polysiloxane binary alcohol hydroxyl meeting attack siloxane bond under comparatively high temps (as 70 ℃) of product stability reduction and hydroxyl butyl end-capping form shortcomings such as ring compound owing to easily generating end-vinyl after can't avoiding terminal hydroxy group to dewater, so the end capped polysiloxane binary alcohol of the type hydroxyalkyl has been subjected to more restriction as the intermediate preparation macromolecular material time.
Summary of the invention
The invention provides polysiloxane binary alcohol of a kind of polyether block and preparation method thereof, to overcome existing polysiloxane binary alcohol hydrolysis and package stability is poor, reactive behavior is low problem, the mechanical property when improving silicone-modified multipolymer simultaneously.
The preparation method of the polysiloxane binary alcohol of polyether block of the present invention is characterized in that: earlier annular siloxane and two hydrogen end-blocking sily oxide with the acid catalyst of press reactant total mass 0.5～2% at 40～60 ℃ are reacted 48～72hs in molar ratio at 20～2: 1; Post reaction mixture through deionized water wash-out catalyzer, distill out unreacted completely behind the annular siloxane, obtain two hydrogen terminated polysiloxanes; Again two hydrogen terminated polysiloxanes and mono-vinyl terminated polyether oligopolymer are pressed every gram reactant 10～35 μ g platinum metal catalyst 70～80 ℃ of addings, at 80～120 ℃ of reaction 4～8h; Reaction product is removed catalyzer and unreacted mono-vinyl terminated polyether oligopolymer completely through wash-out, underpressure distillation, promptly obtains the polysiloxane binary alcohol of polyether block.
The structural formula of described annular siloxane is:
R in the formula
1With R
2Be CH
3, CH
2CH
3Or CH
2CH
2CH
3M=3～6;
The structural formula of described pair of hydrogen end-blocking sily oxide is:
R in the formula
1With R
2Be CH
3, CH
2CH
3And/or CH
2CH
2CH
3
Described acid catalyst is sulfuric acid or trifluoroacetic acid;
The molecular formula of described pair of hydrogen terminated polysiloxane is:
R in the formula
1And R
2Be respectively CH
3, CH
2CH
3And/or CH
2CH
2CH
3N is 1～1000 integer; The molecular weight of this pair hydrogen terminated polysiloxane is to control by the ratio of annular siloxane and two hydrogen end-blocking sily oxide, and the ratio of annular siloxane and two hydrogen end-blocking sily oxide is high more, and molecular weight is big more.
Described mono-vinyl terminated polyether structural formula is:
R in the formula
3Be H or CH
3P and q are 1～100 integer.
Described platinum metal catalyst is the Virahol alcoholic solution or the silene complexing platinum catalyst of Platinic chloride.
The polysiloxane binary alcohol of the polyether block by method for preparing of the present invention is characterized in that structural formula is:
R in the formula
1And R
2Be respectively CH
3, CH
2CH
3And/or CH
2CH
2CH
3R
3Be H or CH
3N is 1～1000 integer; P and q are 1～100 integer.
Compare with existing polysiloxane binary alcohol,, have package stability preferably on molecular chain structure because the polysiloxane binary alcohol of polyether block of the present invention is not easy to dewater or the group of Cheng Huan; Owing to introduced the polarity polyether segment at polysiloxane segment two ends, increased the polarity of polysiloxane binary alcohol, improved when multiple materials such as preparation urethane, polyester and the consistency of other component, thereby improved the lower shortcoming of existing polysiloxane binary alcohol reactive behavior, can issue the ammonifying esterification in a small amount of even solvent-free condition, be very suitable for the preparation and the modification of aqueous, environmental protective coating, tackiness agent etc.
Preparation method of the present invention is owing to the length and the kind of polyether block in the polysiloxane binary alcohol of polyether block can change according to different needs, and the scope of application enlarges; Can control the molecular weight of polysiloxane block by the ratio of regulating annular siloxane and two hydrogen end-blocking sily oxide, thereby can prepare the polysiloxane binary alcohol of the polyether block of different polyether blocks, different molecular weight according to actual needs.
More than in molecular chain structure design and the advantage on the preparation method, make that the present invention is being to have higher using value and wide Application Areas in the macromolecular material design of intermediate and the preparation with the polysiloxane binary alcohol.
Description of drawings
Fig. 1 is for the polysiloxane binary alcohol of the polyether block of the inventive method preparation
1The H nmr spectrum.
Fig. 2 is the Fourier transform infrared spectroscopy figure of the polysiloxane binary alcohol of the polyether block of the inventive method preparation.
Embodiment
Embodiment 1:
With 149.0g octamethylcyclotetrasiloxane (D
4) and the 13.4g tetramethyl disiloxane add an exsiccant and be furnished with in the 500mL there-necked flask of thermometer, prolong and stirring, add the 1.62g vitriol oil again, at 45 ℃ of reaction 48h; With deionized water product is washed, underpressure distillation obtains the two end capped polysiloxane of hydrogen (HPDMS) of 146g line style.
Add above-mentioned 146g HPDMS in the 500mL there-necked flask, (MAPEO Mn=350), adds platinum acid chloride solution 0.65mL when being warming up to 80 ℃, continue to be warmed up to 100 ℃ and at 100 ℃ of reaction 5h to add the end capped polyoxyethylene of 80.5g monoene propyl group again.Behind unreacted MAPEO of deionized water flush away and catalyzer,, obtain the polysiloxane binary alcohol 216g of polyether block through underpressure distillation.
Accompanying drawing 1 has provided the present embodiment final product
1The H nmr spectrum, the upper left corner is the enlarged view of chemical shift (δ) in 0.3～3.5 interval among the figure.The triplet that δ is positioned at 0.49ppm is the proton absorption peak that is connected the methylene radical on the Siliciumatom, has proved the generation of silicon H-H reaction, and the polyoxyethylene oligopolymer successfully is connected on the two ends of polysiloxane.Silicon methyl (Si-CH
3) and oxyethylene group (O-CH
2-CH
2-δ O) is respectively 0.02～0.09 and 3.57～3.68ppm, and the ownership at other peak is respectively δ=1.58 (m, C-CH
2-C), δ=2.58 (OH), δ=3.39 (t, C-C-CH
2).
Accompanying drawing 2 has provided the Fourier transform infrared spectroscopy figure of present embodiment final product.As shown in Figure 2, in the product except the charateristic avsorption band that has linear polysiloxanes (1028,1093cm
-1) and the charateristic avsorption band of silicon methyl (1260,801cm
-1) outside, the methylene radical absorption peak in the polyoxyethylene (2935,2871,1410cm
-1) and hydroxyl (3475cm
-1) charateristic avsorption band also occur, illustrate that the polyoxyethylene oligopolymer successfully inserts polysiloxane.
Analytical results by above-mentioned nmr spectrum and infrared spectrogram proves that products therefrom is the polysiloxane binary alcohol of polyether block.
Embodiment 2:
With 238.4gD
4Add an exsiccant with the 13.4g tetramethyl disiloxane and be furnished with in the 500mL there-necked flask of thermometer, prolong and stirring, add the 1.26g trifluoroacetic acid again, at 45 ℃ of reaction 72h; With deionized water product is washed, underpressure distillation obtains 213g HPDMS.
In the 500mL there-necked flask, add above-mentioned 213g HPDMS, add 80.5g MAPEO (Mn=350) again, add platinum acid chloride solution 0.89mL when being warming up to 80 ℃, continue to be warmed up to 100 ℃ and at 100 ℃ of reaction 5h.Behind unreacted MAPEO of deionized water flush away and catalyzer,, obtain the polysiloxane binary alcohol 281g of polyether block through underpressure distillation.
The infrared spectrogram of gained final product is with accompanying drawing 2.
Embodiment 3:
With 112g hexamethyl cyclotrisiloxane (D
3) and the 13.4g tetramethyl disiloxane add an exsiccant and be furnished with in the 500mL there-necked flask of thermometer, prolong and stirring, add the 1.3g vitriol oil again, at 45 ℃ of reaction 48h; With deionized water product is washed, underpressure distillation obtains 118gHPDMS.
In the 500mL there-necked flask, add above-mentioned 118g HPDMS, add 80.5gMAPEO (M again
n=350), add platinum acid chloride solution 0.65mL when being warming up to 80 ℃, continue to be warmed up to 100 ℃ and at 100 ℃ of reaction 5h.Behind unreacted MAPEO of deionized water flush away and catalyzer,, obtain the polysiloxane binary alcohol 195g of polyether block through underpressure distillation.
The infrared spectrogram of gained final product is with accompanying drawing 2.
Embodiment 4:
With 149.0gD
4Add an exsiccant with the 13.4g tetramethyl disiloxane and be furnished with in the 500mL there-necked flask of thermometer, prolong and stirring, add the 1.62g vitriol oil again, at 45 ℃ of reaction 48h; With deionized water product is washed, underpressure distillation obtains 146g HPDMS.In the 500mL there-necked flask, add above-mentioned 146g HPDMS, add the end capped polyoxytrimethylene of 87.4g monoene propyl group (MAPPO, M again
n=380), add platinum acid chloride solution 0.65mL when being warming up to 80 ℃, continue to be warmed up to 100 ℃ and at 100 ℃ of reaction 5h.Remove unreacted MAPPO and,, obtain the polysiloxane binary alcohol 220g of polyether block with n-butyl acetate extraction through underpressure distillation with behind the deionized water flush away catalyzer.
The infrared spectrogram of the polysiloxane binary alcohol of this polyether block is with accompanying drawing 2.
Reactive behavior is embodiment relatively:
Use polysiloxane binary alcohol (A, the M of the polyether block of embodiment 1 preparation
n=2100), and with commercially available hydroxyl butyl end-capping polydimethylsiloxane (B, M
n=2000) be reference, compare that its result is as shown in table 1 by the reactive behavior of ammonia esterification to both.
Table 1
As shown in Table 1, when temperature of reaction was 60 ℃, the reaction rate constant of the polysiloxane binary alcohol of polyether block and isophorone diisocyanate (IPDI) was 3 times of hydroxyl butyl end-capping polydimethylsiloxane; And temperature of reaction is when being 80 ℃, and the reaction rate constant of the polysiloxane binary alcohol of polyether block and tolylene diisocyanate (TDI) then is 3.5 times of hydroxyl butyl end-capping polydimethylsiloxane.The polysiloxane binary alcohol that polyether block is described has high reaction activity and high.Its reason mainly is that being introduced in of polyether segment strengthens the polysiloxane binary alcohol polar simultaneously, has also improved the consistency of polysiloxane binary alcohol and other polar material, thereby has improved mutual reactive behavior.
Package stability embodiment:
Hydroxyl is as most important functional group in the polysiloxane binary alcohol, and its variation has directly reflected the stability of polysiloxane binary alcohol, changes by the hydroxyl value of measuring polysiloxane binary alcohol under varying environment, can carry out qualitative analysis to its stability.
Table 2 has provided the hydroxyl value mutation analysis result of the polysiloxane binary alcohol of polyether block prepared in the foregoing description 1,2,3,4.
Table 2
As shown in Table 2, at room temperature placed three months and 70 ℃ through 12 hours, the polysiloxane binary alcohol hydroxyl value of polyether block does not change; Even placed 8 hours down at 100 ℃, hydroxyl value does not change substantially yet.Dehydration and annulation do not take place in the polysiloxane binary alcohol that polyether block is described, have stability preferably.The introducing of polyether block has improved the package stability of polysiloxane binary alcohol.
Claims (7)
1. the preparation method of the polysiloxane binary alcohol of a polyether block is characterized in that: earlier annular siloxane and two hydrogen end-blocking sily oxide with the acid catalyst of press reactant total mass 0.5～2% at 40～60 ℃ are reacted 48～72hs in molar ratio at 20～2: 1; Post reaction mixture through deionized water wash-out catalyzer, distill out unreacted completely behind the annular siloxane, obtain two hydrogen terminated polysiloxanes; Again two hydrogen terminated polysiloxanes and mono-vinyl terminated polyether oligopolymer are pressed every gram reactant 10～35 μ g platinum metal catalyst 70～80 ℃ of addings, at 80～120 ℃ of reaction 4～8h; Reaction product is removed catalyzer and unreacted mono-vinyl terminated polyether oligopolymer completely through wash-out, underpressure distillation, promptly obtains the polysiloxane binary alcohol of polyether block; Described mono-vinyl terminated polyether structural formula is:
R in the formula
3Be H or CH
3P and q are 1～100 integer.
2. the preparation method of the polysiloxane binary alcohol of polyether block according to claim 1 is characterised in that the structural formula of described annular siloxane is:
R in the formula
1With R
2Be CH
3, CH
2CH
3Or CH
2CH
2CH
3M=3～6.
3. the preparation method of the polysiloxane binary alcohol of polyether block according to claim 1 is characterised in that the structural formula of described pair of hydrogen end-blocking sily oxide is:
R in the formula
1With R
2Be CH
3, CH
2CH
3And/or CH
2CH
2CH
3
4. the preparation method of the polysiloxane binary alcohol of polyether block according to claim 1 is characterised in that described acid catalyst is sulfuric acid or trifluoroacetic acid.
5. the preparation method of the polysiloxane binary alcohol of polyether block according to claim 1 is characterised in that the molecular formula of described pair of hydrogen terminated polysiloxane is:
R in the formula
1And R
2Be respectively CH
3, CH
2CH
3And/or CH
2CH
2CH
3N is 1～1000 integer.
6. the preparation method of the polysiloxane binary alcohol of polyether block according to claim 1 is characterised in that described platinum metal catalyst is the Virahol alcoholic solution or the silene complexing platinum catalyst of Platinic chloride.
7. polysiloxane binary alcohol by the polyether block of the described method of claim 1 preparation is characterized in that structural formula is:
R in the formula
1And R
2Be respectively CH
3, CH
2CH
3And/or CH
2CH
2CH
3R
3Be H or CH
3N is 1～1000 integer; P and q are 1～100 integer.
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| EP3336129B1 (en) * | 2016-12-16 | 2021-03-17 | Henkel AG & Co. KGaA | Process for the preparation of hydroxyl-functionalized polysiloxanes |
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| CN114026153B (en) * | 2019-06-24 | 2022-06-07 | 美国陶氏有机硅公司 | Organic silicon polyether foam control agent |
| CN116041651B (en) * | 2022-12-15 | 2024-07-19 | 中国石油大学(北京) | Organosilicon polymer for thickening carbon dioxide, preparation method and application thereof |
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| CN1946770A (en) * | 2004-04-20 | 2007-04-11 | 陶氏康宁公司 | Aqueous dispersions of silicone polyether block copolymers |
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Address after: 230026 Jinzhai Road, Anhui, China, No. 96, No. Co-patentee after: Hefei Scisky Technology Co., Ltd. Patentee after: University of Science and Technology of China Address before: 230026 Jinzhai Road, Anhui, China, No. 96, No. Co-patentee before: Hefei Ketian Chemical Co., Ltd. Patentee before: University of Science and Technology of China |
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Application publication date: 20090311 Assignee: Lanzhou Keshi Sicily Health Technology Co.,Ltd. Assignor: LANZHOU SCISKY TECHNOLOGY CO.,LTD. Contract record no.: X2021620000016 Denomination of invention: Polyether block polysiloxane diol and preparation method thereof Granted publication date: 20110119 License type: Exclusive License Record date: 20211116 |