CN105331174A - Crosslinking type organic silicon slipping agent and preparation method thereof - Google Patents
Crosslinking type organic silicon slipping agent and preparation method thereof Download PDFInfo
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- CN105331174A CN105331174A CN201510891924.XA CN201510891924A CN105331174A CN 105331174 A CN105331174 A CN 105331174A CN 201510891924 A CN201510891924 A CN 201510891924A CN 105331174 A CN105331174 A CN 105331174A
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Abstract
The invention relates to the field of high polymer materials, in particular to a crosslinking type organic silicon slipping agent and a preparation method thereof. The structure of the modified ultra-high molecular weight polysiloxane is shown in the specification, the values of x and z are 30-50, the value of y is 1-10, the value of m is 1-10, and the value of n is 0-10. According to the crosslinking type organic silicon slipping agent, the slipping degree and wear resistance of a film are improved, the surface tension is slightly lowered, and the problems that coating foams are excessively stable and the recoating performance is lowered are solved.
Description
Technical field
The present invention relates to polymeric material field, relate to a kind of cross-linking organosilicon slip(ping)agent and preparation method thereof in particular.
Technical background
Slip(ping)agent is a kind of coatings additive(s) improving film Lubricity, floats over coating surface, reduces the surface tension of coating, film is reduced second surperficial frictional coefficient, makes paint film avoid scratching, also can improve the workability of the industrial coating of the serialization of coating.Conventional slip(ping)agent comprises: (1) fat hydrocarbon is as whiteruss, Vaseline, synthesis paraffin, polyethylene wax, Poly Propylene Wax; (2) fatty acid acyl amine is as amine hydroxybenzene; (3) silicone based as polydimethylsiloxane, polyphenyl methyl siloxane, polyether-modified polydimethylsiloxane.
Although woodwork coating, coatings for furniture, plastic paint or finishing paint there are differences in outward appearance and protectiveness, client wishes to obtain can provide the coating products that Surface feel is good.Preparing such coating is the work that a difficulty is higher, because while realizing excellent smoothness and feel, usually there will be the problems such as the excessively stable and recoat performance reduction of foam.
Therefore, be necessary to develop a kind of slip(ping)agent, the slippery of paint film, wear resistance can be improved, and slightly reduce surface tension, to solve the problems such as the excessively stable and recoat performance reduction of coating foam.
Summary of the invention
(1) technical problem that will solve
The present invention, on the basis of having drawn forefathers' research experience, is devoted to improve slippery, the wear resistance of paint film, and slightly reduces surface tension, to solve the problems such as the excessively stable and recoat performance reduction of coating foam.
(2) technical scheme
A kind of modified ultra-high molecular mass polysiloxane, its chemical structural formula is
Wherein, described x, z value is 30-50; Y value is 1-10; M value is 1-10, n value is 0-10.
Described modified ultra-high molecular mass polysiloxane is used for cross-linking organosilicon slip(ping)agent.
The preparation method of described modified ultra-high molecular mass polysiloxane is as follows:
Step 1) by polydimethylsiloxane and hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D
4) reaction, obtain side chain containing hydrogen silicone oil, i.e. intermediate compound I;
Step 2) alkene C
30h
60react 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 epoxy-capped polyether-modified ultra-high molecular weight polysiloxane according to claim 1
Beneficial effect of the present invention is: the present invention improves slippery, the wear resistance of paint film, and slightly reduces surface tension, and addition seldom just can realize excellent feel, realizes excellent coating smoothness and good levelling property, and does not affect the recoatability of coating.
Accompanying drawing explanation
Figure of description 1 is test example 2: prepared by scraping coating, measures the dynamic friction of 20 differences.Fig. 1: frictional coefficient result (unit: μ), wherein:
comparative example
embodiment 1
embodiment 2
embodiment 3
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is described in more detail.Should be appreciated that, these describe just exemplary, and do not really want to limit the scope of the invention.In addition, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily obscuring concept of the present invention.
Embodiment 1
Step 1: viscosity is about the polydimethylsiloxane 90g of 20mcSt, hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D4) 68g and 300ml isopropylcarbinol, acetic acid 0.5g add in the three-necked flask being furnished with condenser and thermometer as catalyzer, under a nitrogen, through 2 hours, they are heated to 85 DEG C, then under 85 DEG C and decompression (-101.325kPa), make reaction mixture degassed 4 hours, after reaction terminates, low molecular weight substance is removed, thus obtained intermediate product I (A1) by reaction product.The viscosity of A1 at 40 DEG C is 601356mPas, and molecular weight is about 263000, and the polymerization degree 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-CH
3, Si-(CH
3)
3structure; 2963cm
-1show containing methyl structural; At 3400 ~ 3600cm
-1place and 1600cm
-1all there is no absorption peak around, show to there is not group Si-OH.
According to nmr spectrum
1h-NMR:
δ=0.07 is Si-CH
3middle H absorption peak; δ=0.62 is Si-CH
2the absorption peak of-middle H; δ=1.33 be in-CH
2the absorption peak (-CH that removing is directly connected with Si of-middle H
2-).
Step 2: be furnished with N
2100g tetramethyl-ring tetrasiloxane, 0.12g Tetramethylammonium hydroxide and 122gA1 is added, logical N in the reaction flask of conduit, thermometer and still head
2slow heating, is warming up to 70 DEG C, and maintain 0.5 hour, catalyzer all dissolves follow-up temperature of continuing rising, reacts 6 hours, react complete, temperature is risen to about 150 DEG C, maintain 0.5 hour at 80 DEG C.Under constantly stirring, add 25g0.01N aqueous hydrochloric acid, positive 30 alkene of 128g, make mixture 65-75 DEG C of hydrolysis 2 hours; Use 96g to be with the allyl polyether of epoxy-functional to carry out polycondensation within the time of 3.5 hours subsequently, deviate from low-boiling-point substance and namely obtain 134g modified ultra-high molecular mass polysiloxane (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-CH
3, Si-(CH
3)
3structure; 3019cm
-1show containing methyl structural; 913cm
-1show containing epoxy group(ing) structure; At 3400 ~ 3600cm
-1place and 1600cm
-1all there is no absorption peak around, show to there is not group Si-OH.
According to nmr spectrum
1h-NMR:
δ=0.06 is Si-CH
3middle H absorption peak; δ=0.63 is Si-CH
2the absorption peak of-middle H; δ=1.32 be in-CH
2the absorption peak (-CH that removing is directly connected with Si of-middle H
2-).
Embodiment 2
Step 1: viscosity is about the polydimethylsiloxane 109g of 50mcSt, hydrogeneous tetramethyl-ring tetrasiloxane (hydrogeneous D4) 68g and 350ml isopropylcarbinol, 98% methylsulfonic acid 1.3g add in the three-necked flask being furnished with condenser and thermometer as catalyzer, under a nitrogen, through 2 hours, they are heated to 85 DEG C, then under 85 DEG C and decompression (-101.325kPa), make reaction mixture degassed 4 hours, after reaction terminates, low molecular weight substance is removed, thus obtained intermediate product I (A2) by reaction product.The viscosity of A2 at 25 DEG C is 993700mPas, and molecular weight is about 303414, and the polymerization degree 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-CH
3, Si-(CH
3)
3structure; 2889cm
-1show containing methyl structural; At 3400 ~ 3600cm
-1place and 1600cm
-1all there is no absorption peak around, show to there is not group Si-OH.
According to nmr spectrum
1h-NMR:
δ=0.07 is Si-CH
3middle H absorption peak; δ=0.63 is Si-CH
2the absorption peak of-middle H; δ=1.30 be in-CH
2the absorption peak (-CH that removing is directly connected with Si of-middle H
2-).
Step 2: be furnished with N
293g tetramethyl-ring tetrasiloxane, 0.06g Tetramethylammonium hydroxide and 78g modified ultra-high molecular mass polysiloxane (A2) is added, logical N in the reaction flask of conduit, thermometer and still head
2slow heating, is warming up to 75 DEG C, and maintain 0.6 hour, catalyzer all dissolves follow-up temperature of continuing rising, reacts 5.5 hours, react complete, temperature is risen to about 160 DEG C, maintain 1.5 hours at 85 DEG C.Under constantly stirring, add 21g0.01N aqueous hydrochloric acid, positive 30 alkene of 168g, make mixture 65-75 DEG C of hydrolysis 1.5 hours; Use 106g to be with the allyl polyether of epoxy-functional to carry out polycondensation within the time of 3.5 hours subsequently, deviate from low-boiling-point substance and namely obtain 209g modified ultra-high molecular mass polysiloxane (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-CH
3, Si-(CH
3)
3structure; 2963cm
-1show containing methyl structural; 916cm
-1show containing epoxy group(ing) structure; At 3400 ~ 3600cm
-1place and 1600cm
-1all there is no absorption peak around, show to there is not group Si-OH.
According to nmr spectrum
1h-NMR:
δ=0.07 is Si-CH
3middle H absorption peak; δ=0.58 is Si-CH
2the absorption peak of-middle H; δ=1.43 be in-CH
2the absorption peak (-CH that removing is directly connected with Si of-middle H
2-).
Embodiment 3
Step 2: be furnished with N
2156g tetramethyl-ring tetrasiloxane, 0.9g Tetramethylammonium hydroxide and 273g modified ultra-high molecular mass polysiloxane (A2) is added, logical N in the reaction flask of conduit, thermometer and still head
2slow heating, is warming up to 70 DEG C, and maintain 1.8 hours, catalyzer all dissolves follow-up temperature of continuing rising, reacts 7 hours, react complete, temperature is risen to about 165 DEG C, maintain 2 hours at 80 DEG C.Under constantly stirring, add 23g0.01N aqueous hydrochloric acid, positive 30 alkene of 123g, make mixture 65-75 DEG C of hydrolysis 2 hours; Use 87g terminal hydroxy group allyl polyether to carry out polycondensation subsequently within the time of 4.8 hours, deviate from low-boiling-point substance and namely obtain 187g modified ultra-high molecular mass polysiloxane (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-CH
3, Si-(CH
3)
3structure; 2907cm
-1show containing methyl structural; 921cm
-1show containing epoxy group(ing) structure; At 3400 ~ 3600cm
-1place and 1600cm
-1all there is no absorption peak around, show to there is not group Si-OH.
According to nmr spectrum
1h-NMR:
δ=0.06 is Si-CH
3middle H absorption peak; δ=0.66 is Si-CH
2the absorption peak of-middle H; δ=1.29 be in-CH
2the absorption peak (-CH that removing is directly connected with Si of-middle H
2-).
Test example
Comparative example, according to WO03/033603 embodiment 1.
Dimethylbenzene (29.0g) to be placed in reactor under nitrogen atmosphere and to be heated to backflow (140 DEG C).Be metered in 3 hours by pre-composition, this pre-composition is made up of 53.33g n-butyl acrylate, 14.79g isobutyl methacrylate, 0.54gZonylBa-L-maleic acid ester, 1.37g ditertiary butyl peroxide.After pre-composition adds, reaction is carried out 3 hours at 140 DEG C.Solid content is adjusted to 70% obtains colourless transparent liquid by adding dimethylbenzene.
ZonylBA-L: be line style fluorinated alcohols R
fcH
2cH
2the mixture of OH, wherein Rf=C
4f
9<4%, C
6f
1350 ± 3%, C
8f
1729 ± 2%, C
10f
2111 ± 2% and>=C
12f
25fluorinated compound be less than 6%.The average M of this mixture
w443g/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/bis-component PU coating | Weight (g) | |
| 1 | Synthalat A150 (urethane, available from Synthapol) | 83.5 |
| 2 | Blue colorant | 1.4 |
| 3 | N-BUTYL ACETATE | 10.4 |
| 4 | EFKA-2018 (defoamer) | 4.7 |
| Summation | 100.0 |
1-3 item is merged, and shake 5min in skandex wobbler.After shake, add the 4th and be uniformly mixed with spatula until obtain uniform mixture.
Table 2: for testing the formula of slip(ping)agent
1-3 item spatula is uniformly mixed until obtain 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 frictional coefficient
Table 1: baking vanish formula
| Baking vanish | (g) | |
| 1 | Vialkyd AC451 | 70.5 |
| 2 | Maprenal MF650 | 19.0 |
| 3 | N-BUTYL ACETATE | 10.5 |
| Summation | 100.0 |
1-3 item is stirred until obtain uniform mixture.
Table 2: for testing the formula of slip(ping)agent
| 1 | Baking vanish | 99.75g |
| 2 | The product of comparative example, embodiment 1-3 | 0.25g |
1 and 2 mixed being incorporated in skandex wobbler 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: visual observation 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.By scraping coating purge 10 minutes.Baking time 30min, temperature 135 DEG C.Measure the dynamic friction of 20 differences.Test-results: see Figure of description: Fig. 1: frictional coefficient 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, slip(ping)agent according to the present invention is used to show low-friction coefficient, excellent sliding, soak completely for substrate.It contributes to the formation preventing cratering and pin hole, provides the paint film not having orange-peel of smooth, suitable levelling thus, produces dry film U.S. decorations outward appearance of improvement thus.
Claims (3)
1. a modified ultra-high molecular mass polysiloxane, is characterized in that, the structure of described modified ultra-high molecular mass polysiloxane is
Wherein, described x, z value is 30-50; Y value is 1-10; M value is 1-10, n value is 0-10.
2. modified ultra-high molecular mass polysiloxane according to claim 1, is characterized in that, described modified ultra-high molecular mass polysiloxane is used for bridging property organic silicon rigidity-increasing lubrication prescription.
3. modified ultra-high molecular mass polysiloxane according to claim 1, is characterized in that, the preparation method of described modified ultra-high molecular mass polysiloxane is as follows:
Step 1) polydimethylsiloxane and hydrogeneous tetramethyl-ring tetrasiloxane are reacted, obtain intermediate compound I;
Step 2) C
30h
60react 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 modified ultra-high molecular mass polysiloxane according to claim 1
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|---|---|---|---|
| CN201510891924.XA CN105331174B (en) | 2015-12-06 | 2015-12-06 | A kind of cross-linking organosilicon slip agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047452A (en) * | 2017-12-20 | 2018-05-18 | 山东东岳有机硅材料股份有限公司 | A kind of levelling agent super high molecular weight Siloxane-Oxyalkylene Copolymers and preparation method and application |
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| CN101153076A (en) * | 2006-09-29 | 2008-04-02 | 北京化工大学 | Polysiloxane resin with lateral group containing alkoxyl, producing method and use of the same |
| KR101546599B1 (en) * | 2011-03-30 | 2015-08-21 | 아사히 가세이 케미칼즈 가부시키가이샤 | Organopolysiloxane, method for producing same, and curable resin composition containing organopolysiloxane |
| CN104927366A (en) * | 2015-06-30 | 2015-09-23 | 广州市斯洛柯高分子聚合物有限公司 | Organic silicon anti-wear agent and preparation method thereof |
-
2015
- 2015-12-06 CN CN201510891924.XA patent/CN105331174B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153076A (en) * | 2006-09-29 | 2008-04-02 | 北京化工大学 | Polysiloxane resin with lateral group containing alkoxyl, producing method and use of the same |
| KR101546599B1 (en) * | 2011-03-30 | 2015-08-21 | 아사히 가세이 케미칼즈 가부시키가이샤 | Organopolysiloxane, method for producing same, and curable resin composition containing organopolysiloxane |
| CN104927366A (en) * | 2015-06-30 | 2015-09-23 | 广州市斯洛柯高分子聚合物有限公司 | Organic silicon anti-wear agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047452A (en) * | 2017-12-20 | 2018-05-18 | 山东东岳有机硅材料股份有限公司 | A kind of levelling agent super high molecular weight Siloxane-Oxyalkylene Copolymers and preparation method and application |
| CN108047452B (en) * | 2017-12-20 | 2021-02-26 | 山东东岳有机硅材料股份有限公司 | Ultrahigh molecular weight polyether modified polysiloxane for leveling agent and preparation method and application thereof |
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