CN105331174B - A kind of cross-linking organosilicon slip agent and preparation method thereof - Google Patents
A kind of cross-linking organosilicon slip agent and preparation method thereof Download PDFInfo
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- CN105331174B CN105331174B CN201510891924.XA CN201510891924A CN105331174B CN 105331174 B CN105331174 B CN 105331174B CN 201510891924 A CN201510891924 A CN 201510891924A CN 105331174 B CN105331174 B CN 105331174B
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Abstract
The present invention relates to macromolecular material territory, a kind of cross-linking organosilicon slip agent and preparation method thereof.The present invention provides the structure of described modified ultra-high molecular mass polysiloxanes to beWherein, described x, z value is 30 50；Y value is 1 10；M value is 1 10, and n value is 0 10.This invention address that the raising slippery of paint film, wearability, and slight decrease surface tension, to solve that coating foam is excessively stable and the problem such as recoating performance reduction.
Description
Technical field
The present invention relates to polymeric material field, a kind of cross-linking organosilicon slip agent and preparation thereof
Method.
Technical background
Slip agent is a kind of coating additive improving film Lubricity, floats over coating surface, and the surface reducing coating is opened
Power, makes film reduce the coefficient of friction on second surface, makes paint film prevent plowing from, also can improve the industry of the serialization of coating
The workability of application.Conventional slip agent includes: (1) fat hydrocarbon such as liquid paraffin, vaseline, synthesis paraffin, Tissuemat E,
Polypropylene wax；(2) fatty acid acyl amine such as oleamide；(3) silicone such as polydimethylsiloxane, polyphenyl methyl silica
Alkane, polyether-modified polydimethylsiloxane.
Although woodwork coating, coatings for furniture, plastic paint or finishing varnish there are differences in terms of outward appearance and protectiveness, but objective
Family is intended to obtain the coating products being provided that Surface feel is good.Preparing such coating is the work that a difficulty is higher, because of
For while realizing excellent flatness and feel, it will usually occur that foam is excessively stable and recoats the problems such as performance reduction.
Therefore, it is necessary to a kind of slip agent of exploitation, the slippery of paint film, wearability, and slight decrease surface tension can be improved,
Excessively stablize with solution coating foam and recoat the problems such as performance reduction.
Summary of the invention
(1) to solve the technical problem that
The present invention, on the basis of having drawn forefathers' research experience, is devoted to improve the slippery of paint film, wearability, and slightly
Reduce surface tension, to solve that coating foam is excessively stable and the problem such as recoating performance reduction.
(2) technical scheme
A kind of modified ultra-high molecular mass polysiloxanes, its chemical structural formula is
Wherein, described x, z value is 30-50；Y value is 1-10；M value be 1-10, n value be 0-10.
Described modified ultra-high molecular mass polysiloxanes is used for cross-linking organosilicon slip agent.
The preparation method of described modified ultra-high molecular mass polysiloxanes is as follows:
Step 1) by polydimethylsiloxane and hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D4) reaction, obtain side chain hydrogeneous
Silicone oil, i.e. intermediate compound I；
Step 2) alkene C30H60React with side chain containing hydrogen silicone oil intermediate compound I, obtain intermediate II
Step 3) the allyl polyether intermediate III of intermediate II with band epoxy-functional is reacted, obtain claim 1
Described epoxy-capped polyether-modified super high molecular weight polysiloxanes
The invention have the benefit that the present invention improves the slippery of paint film, wearability, and slight decrease surface tension, add
Dosage seldom achieves that excellent feel, it is achieved excellent coating flatness and good levelability, and does not affect the weight of coating
Tu Xing.
Accompanying drawing explanation
Figure of description 1 is test example 2: prepared by scraping coating, measures the dynamic friction of 20 differences.Fig. 1: friction
Coefficient results (unit: μ), wherein:
Comparative example
Embodiment 1
Embodiment 2
Embodiment 3
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention of greater clarity, below in conjunction with detailed description of the invention, to this
Invention further describes.It should be understood that these describe the most exemplary, and it is not intended to limit the scope of the present invention.This
Outward, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily obscuring idea of the invention.
Embodiment 1
Step 1: by the polydimethylsiloxane 90g of viscosity about 20mcSt, hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D4)
68g and 300ml isobutanol, acetic acid 0.5g add in the three-neck flask being furnished with condenser and thermometer as catalyst, at nitrogen
Under, through 2 hours, they are heated to 85 DEG C, then under 85 DEG C and decompression (-101.325kPa), make reactant mixture degassing 4
Hour, after reaction terminates, by product is removed low molecular weight substance, thus prepare intermediate product I (A1).A1 is at 40 DEG C
Viscosity be 601356mPa s, molecular weight is about 263000, and the degree of polymerization is 3552.
According to infrared spectrogram:
1056.8cm-1Show containing Si-O；1010.3cm-1Show containing Si C；1257.5cm-1、785.8cm-1Show
Containing Si CH3、Si—(CH3)3Structure；2963cm-1Show containing methyl structural；3400～3600cm-1Place and 1600cm-1
Around all there is no absworption peak, show to there is not group Si OH.
According to nmr spectrum1H-NMR:
δ=0.07 is Si-CH3Middle H absworption peak；δ=0.62 is Si-CH2The absworption peak of-middle H；δ=1.33 be in-CH2-
The absworption peak of middle H (removes-CH being directly connected with Si2-)。
Step 2: be furnished with N2In the reaction bulb of conduit, thermometer and still head add 100g tetramethyl-ring tetrasiloxane,
0.12g Tetramethylammonium hydroxide and 122g A1, logical N2Being slowly heated, be warming up to 70 DEG C, maintain 0.5 hour, catalyst is the most molten
Solve follow-up temperature of continuing rising, react 6 hours at 80 DEG C, react complete, temperature is risen to about 150 DEG C, maintain 0.5 hour.Not
Disconnected stirring is lower adds 25g 0.01N aqueous hydrochloric acid solution, positive 30 alkene of 128g, makes mixture hydrolyze 2 hours at 65-75 DEG C；With
The allyl polyether of rear use 96g band epoxy-functional carries out polycondensation within the time of 3.5 hours, and abjection low-boiling-point substance i.e. obtains
134g modified ultra-high molecular mass polysiloxanes (B1).
According to infrared spectrogram:
1061.3cm-1Show containing Si-O；1013.1cm-1Show containing Si C；1253.2cm-1、773.1cm-1Show
Containing Si CH3、Si—(CH3)3Structure；3019cm-1Show containing methyl structural；913cm-1Show containing epoxy radicals structure；
3400～3600cm-1Place and 1600cm-1Around all there is no absworption peak, show to there is not group Si OH.
According to nmr spectrum1H-NMR:
δ=0.06 is Si-CH3Middle H absworption peak；δ=0.63 is Si-CH2The absworption peak of-middle H；δ=1.32 be in-CH2-
The absworption peak of middle H (removes-CH being directly connected with Si2-)。
Embodiment 2
Step 1: by the polydimethylsiloxane 109g of viscosity about 50mcSt, hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D4)
68g and 350ml isobutanol, the methanesulfonic acid 1.3g of 98% add the three-neck flask being furnished with condenser and thermometer as catalyst
In, under a nitrogen, through 2 hours, they are heated to 85 DEG C, then under 85 DEG C and decompression (-101.325kPa), make reaction mix
Compound deaerates 4 hours, after reaction terminates, by removing low molecular weight substance in product, thus prepares intermediate product I (A2).
A2 viscosity at 25 DEG C is 993700mPa s, and molecular weight is about 303414, and the degree of polymerization is 4098.
According to infrared spectrogram:
1053.2cm-1Show containing Si-O；1021.3cm-1Show containing Si C；1307.6cm-1、806.1cm-1Show
Containing Si CH3、Si—(CH3)3Structure；2889cm-1Show containing methyl structural；3400～3600cm-1Place and 1600cm-1
Around all there is no absworption peak, show to there is not group Si OH.
According to nmr spectrum1H-NMR:
δ=0.07 is Si-CH3Middle H absworption peak；δ=0.63 is Si-CH2The absworption peak of-middle H；δ=1.30 be in-CH2-
The absworption peak of middle H (removes-CH being directly connected with Si2-)。
Step 2: be furnished with N2In the reaction bulb of conduit, thermometer and still head add 93g tetramethyl-ring tetrasiloxane,
0.06g Tetramethylammonium hydroxide and 78g modified ultra-high molecular mass polysiloxanes (A2), logical N2It is slowly heated, is warming up to 75 DEG C, dimension
Holding 0.6 hour, catalyst all dissolves follow-up temperature of continuing rising, reacts 5.5 hours, react complete, temperature is risen to 160 at 85 DEG C
About DEG C, maintain 1.5 hours.It is being stirred continuously lower addition 21g 0.01N aqueous hydrochloric acid solution, positive 30 alkene of 168g, is making mixing
Thing hydrolyzes 1.5 hours at 65-75 DEG C；Use the allyl polyether of 106g band epoxy-functional subsequently within the time of 3.5 hours
Carrying out polycondensation, abjection low-boiling-point substance i.e. obtains 209g modified ultra-high molecular mass polysiloxanes (B2).
According to infrared spectrogram:
1066.1cm-1Show containing Si-O；1013.7cm-1Show containing Si C；1273.6cm-1、791.3cm-1Show
Containing Si CH3、Si—(CH3)3Structure；2963cm-1Show containing methyl structural；916cm-1Show containing epoxy radicals structure；
3400～3600cm-1Place and 1600cm-1Around all there is no absworption peak, show to there is not group Si OH.
According to nmr spectrum1H-NMR:
δ=0.07 is Si-CH3Middle H absworption peak；δ=0.58 is Si-CH2The absworption peak of-middle H；δ=1.43 be in-CH2-
The absworption peak of middle H (removes-CH being directly connected with Si2-)。
Embodiment 3
Step 2: be furnished with N2In the reaction bulb of conduit, thermometer and still head add 156g tetramethyl-ring tetrasiloxane,
0.9g Tetramethylammonium hydroxide and 273g modified ultra-high molecular mass polysiloxanes (A2), logical N2It is slowly heated, is warming up to 70 DEG C, dimension
Holding 1.8 hours, catalyst all dissolves follow-up temperature of continuing rising, reacts 7 hours, react complete, temperature rises to 165 DEG C at 80 DEG C
Left and right, maintains 2 hours.It is being stirred continuously lower addition 23g 0.01N aqueous hydrochloric acid solution, positive 30 alkene of 123g, is making mixture exist
65-75 DEG C hydrolyzes 2 hours；Use 87g terminal hydroxy group allyl polyether to carry out polycondensation within the time of 4.8 hours subsequently, deviate from low
Boiling thing i.e. obtains 187g modified ultra-high molecular mass polysiloxanes (B3).
According to infrared spectrogram:
1066.8cm-1Show containing Si-O；1023.2cm-1Show containing Si C；1411.3cm-1、766.1cm-1Show
Containing Si CH3、Si—(CH3)3Structure；2907cm-1Show containing methyl structural；921cm-1Show containing epoxy radicals structure；
3400～3600cm-1Place and 1600cm-1Around all there is no absworption peak, show to there is not group Si OH.
According to nmr spectrum1H-NMR:
δ=0.06 is Si-CH3Middle H absworption peak；δ=0.66 is Si-CH2The absworption peak of-middle H；δ=1.29 be in-CH2-
The absworption peak of middle H (removes-CH being directly connected with Si2-)。
Test example
Comparative example, according to WO03/033603 embodiment 1.
Dimethylbenzene (29.0g) is placed in reactor under nitrogen atmosphere and is heated to reflux (140 DEG C).Pre-composition is existed
In 3 hours, metering adds, and this pre-composition is by 53.33g n-butyl acrylate, 14.79g isobutyl methacrylate, 0.54g
Zonyl Ba-L-maleate, 1.37g di-tert-butyl peroxide form.After pre-composition adds, will react at 140 DEG C
Carry out 3 hours.By addition dimethylbenzene, solid content is adjusted to 70% and obtains colourless transparent liquid.
Zonyl BA-L: be line style fluorinated alcohols RfCH2CH2The mixture of OH, wherein Rf=C4F9< 4%, C6F13 50±
3%, C8F1729 ± 2%, C10F2111 ± 2% and >=C12F25Fluorinated compound less than 6%.The average M of this mixtureW
It is 443g/mol；This mixture is from DuPont.
Test example 1: anti-blockage holes performance test
Table 1: the formula of double pack PU
| Double pack PU system/double-component PU coating | Weight (g) | |
| 1 | Synthalat A150 (polyurethane, available from Synthapol) | 83.5 |
| 2 | Blue colorant | 1.4 |
| 3 | Butyl acetate | 10.4 |
| 4 | EFKA-2018 (defoamer) | 4.7 |
| Summation | 100.0 |
1-3 item is merged, and in skandex shaking machine, shakes 5min.After shake, add the 4th and stir with spatula
Mix mixing until obtaining uniform mixture.
Table 2: for testing the formula of slip agent
By the stirring mixing of 1-3 item spatula until obtaining uniform mixture.Prepare the scraping coating (75 μm) of sample 1-5.
Table 3: anti-blockage holes performance test results
Note: 1=is without cratering；The a large amount of cratering of 8=.
Test example 2: stability and coefficient of friction
Table 1: baking vanish formula
| Baking vanish | (g) | |
| 1 | Vialkyd AC451 | 70.5 |
| 2 | Maprenal MF650 | 19.0 |
| 3 | Butyl acetate | 10.5 |
| Summation | 100.0 |
By the stirring of 1-3 item until obtaining uniform mixture.
Table 2: for testing the formula of slip agent
| 1 | Baking vanish | 99.75g |
| 2 | Comparative example, the product of embodiment 13 | 0.25g |
1 and 2 mixed being incorporated in skandex shaking machine is shaken 30 minutes.
Table 3: formation of foam result
| 0.30% | Blank | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 0min | 8 | 8 | 8 | 8 | 8 |
| 5min | 7 | 6 | 6 | 7 | 7 |
| 10min | 5 | 5 | 5 | 7 | 6 |
| 15min | 4 | 3 | 3 | 5 | 5 |
| 20min | 2 | 1 | 1 | 4 | 3 |
| 25min | 1 | 1 | 1 | 3 | 2 |
| 30min | 1 | 1 | 1 | 2 | 2 |
| 35min | 1 | 1 | 1 | 1 | 1 |
Note: visualization foam, 1=non-foam, a large amount of foam of 8=
Prepared by scraping coating: after whole lather collapses, prepares the scraping coating of 75 μm on the plastic film.Scraping coating is blown
Wash 10 minutes.Baking time 30min, temperature 135 DEG C.Measure the dynamic friction of 20 differences.Result of the test: see explanation
Book accompanying drawing: Fig. 1: coefficient of friction result (unit: μ), wherein:
Comparative example
Embodiment 1
Embodiment 2
Embodiment 3
Table 4: average friction coefficient (C.O.F.)
| Kinetics COF | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| 1 | 0.25% additive | 0.57 | 0.39 | 0.32 | 0.27 |
Test example 3: surface tension is tested
Surface tension sessile drop method is measured.
Table 5: surface tension result
| Surface tension (mN/m) | |
| Comparative example | 28 |
| Embodiment 1 | 22 |
| Embodiment 2 | 20 |
| Embodiment 3 | 20 |
In sum, use according to the slip agent of the present invention show low-friction coefficient, excellent sliding, for substrate
Moistening completely.It contributes to preventing the formation of cratering and pin hole, and thus provide smooth, suitable levelling does not has Pericarpium Citri Reticulatae
The paint film of wrinkle, thus produces dry film U.S. decorations outward appearance of improvement.
Claims (3)
1. a modified polyorganosiloxane, it is characterised in that the structure of described modified polyorganosiloxane is
Wherein, described x, z value is 30-50；Y value is 1-10；M value be 1-10, n value be 0-10.
Modified polyorganosiloxane the most according to claim 1, it is characterised in that described modified polyorganosiloxane has for bridging property
Machine silicon slip agent.
Modified polyorganosiloxane the most according to claim 1, it is characterised in that the preparation method of described modified polyorganosiloxane is such as
Under:
Step 1) polydimethylsiloxane is reacted with hydrogeneous tetramethyl-ring tetrasiloxane, obtain intermediate compound I；
Step 2) C30H60React with containing hydrogen silicone oil intermediate compound I, obtain intermediate II
Step 3) the allyl polyether intermediate III of intermediate II with band epoxy-functional is reacted, obtain described modification and gather
Siloxanes
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