CN101386682A - Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather - Google Patents
Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather Download PDFInfo
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- CN101386682A CN101386682A CNA2007100458414A CN200710045841A CN101386682A CN 101386682 A CN101386682 A CN 101386682A CN A2007100458414 A CNA2007100458414 A CN A2007100458414A CN 200710045841 A CN200710045841 A CN 200710045841A CN 101386682 A CN101386682 A CN 101386682A
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- hydroxyl alkyl
- polysiloxane
- terminated polysiloxane
- alkyl polysiloxane
- artificial leather
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Abstract
The invention discloses a terminal hydroxyl alkyl polysiloxane with the following structure and a preparation method thereof. The method for preparing the terminal hydroxyl alkyl polysiloxane comprises the following steps of: 1) preparing a terminal hydrogen group alkyl polysiloxane; and 2) preparing the terminal hydroxyl alkyl polysiloxane. Compared with the common siloxane compounds, the terminal hydroxyl alkyl polysiloxane overcomes the defect of the prior polyurethane leather addictive, and has better compatibility, levelability, waterproof and moisture proof effects and adhesive resistance.
Description
Technical field
The present invention relates to synthetic leather additive technology field, more specifically to hydroxyl alkyl-terminated polysiloxane and as the purposes of additive agent of polyurethane artificial leather.
Background technology
In order to improve the Synthetic Leather surface quality, be known method to wherein adding polysiloxane.The application of polysiloxane is diversified.For example lower molecular weight dimethyl polysiloxane and methyl phenyl silicone are added in the Synthetic Leather slurry,, improve smooth feeling, play antiseized effect to strengthen its flow leveling.Yet, under many circumstances, because consistency, add that polydimethylsiloxane causes in the slurry undesirable turbidity, pin hole, shrinkage cavity and bad phenomenon such as grow dim.If the polysiloxane molecule amount that adds is too high, then there is major defect, as serious bad phenomenon such as pit, flake on the synthetic leather surface.If common polyether modified silicon oil is substituted above-mentioned polysiloxane, though above-mentioned bad phenomenon can be eliminated, smooth feeling again can not be satisfactory.And after above-mentioned a few class additive adding, the water tolerance of synthetic leather all there is not help.
Summary of the invention
Purpose of the present invention is for providing a kind of hydroxyl alkyl-terminated polysiloxane.
Another object of the present invention is for providing the purposes of above-mentioned hydroxyl alkyl-terminated polysiloxane compound.
The structure of hydroxyl alkyl-terminated polysiloxane of the present invention is as follows:
Wherein, m=1-100; N=0-20;
R
1-OH is-C
aH
2a-OH, a=2-4;
Perhaps-(CH
2)
3-O-(C
2H
4O)
p(C
3H
6O)
qH, p=1-15, q=0-15;
R
2For-C
bH
2b+1, b=1-20;
Perhaps-(CH
2)
3-O-(C
2H
4O)
p(C
3H
6O)
qH, p=1-15, q=0-15;
R
1, R
2Can be identical, also can be inequality.
The preparation method of hydroxyl alkyl-terminated polysiloxane of the present invention is as follows:
(1) end hydrogen based polysiloxane preparation method
Can make both-end hydrogen based polysiloxane or both-end hydrogen base polymethyl hydrogen siloxane earlier, and then make the purpose product with the addition reaction of unsaturated terminal hydroxy group hydrocarbon.
(1) mixes organochlorosilane cohydrolysis condensation method cohydrolysis reaction
Balanced reaction
In the following formula, s+t=m, m=0-100.
In reactor, add toluene and water mixture earlier, at room temperature slowly add HMe by a certain percentage
2SiCl and Me
2SiCl
2Mixture carries out cohydrolysis, isolates the toluene solution of hydrolyzate then, make catalyzer with the vitriol oil again, heating divides oil-yielding stratum after the balance, use charcoal absorption impurity, wash with water then to neutrality, decompression adds thermal distillation and removes toluene, water and low-boiling-point substance, and the last centrifugal suspended substance of removing gets containing hydrogen silicone oil, this method manufacturing cost is lower, but technology is complicated.
(2) hybrid silicone null readings
In the following formula, m=0-100, n=0-20
In reactor, add mixture of siloxanes, under agitation add acidity of catalyst carclazyte (market is buied), and be heated to 40-70 ℃, balanced reaction 3-24h more after filtration, removes carclazyte, and low-boiling-point substance is removed in underpressure distillation then, gets transparent hydrogen end-blocking silicone oil.
Catalyzer also can be selected strongly acidic macroporous cation exchange resin, trifluoromethane sulfonic acid and sulfuric acid etc.
(2) hydroxyl alkyl-terminated polysiloxane preparation method
Second step was that addition polymerization in the presence of catalyzer forms by Si-H key and unsaturated hydrocarbons.
In the formula, R '=-OH, ,-C
nH
2nOH (wherein n=0-5),
-CH
2O-(C
2H
4O)
p(C
3H
6O)
q-R ＂ (p=0-25 wherein, q=0-25).
In reaction flask, add hydrogen end-blocking silicone oil and the unsaturated polyether or the alkene alcohol (market is buied) of the first step preparation in proportion, exist reacting by heating to make the hydroxyl alkyl-terminated polysiloxane compound at platinum catalyst.
Yet in above-mentioned addition reaction, with Si-H and-OH take off H
2Reaction must be added buffer reagent makes stable reaction.And more effective ways are that first hydroxyl with unsaturated alcohol protects with trimethyl silicon based, carry out addition reaction again, and then hydrolysis recovers hydroxyl:
Hydroxyl alkyl-terminated polysiloxane of the present invention is during as additive agent of polyurethane artificial leather, hydroxyl alkyl-terminated and NCO ionic bond, and easy fracture not, key is stronger, compares with common silicone compounds, and effect is better.
Beneficial effect of the present invention:
The hydroxyl alkyl-terminated polysiloxane compound that the present invention adopts two-step reaction to make is compared with common silicone compounds, overcome the shortcoming of conventional urethane synthetic leather additive, its consistency, levelling property, waterproof moisture-proof effect and non-stick property have all been obtained better effect.
Embodiment
The present invention is further elaborated below by specific embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
Synthesizing of both-end hydrogen based polysiloxane:
In the 500ml glass there-necked flask of electric mixer, reflux exchanger and thermometer is housed, add D earlier
4(prestox ring four oxosilanes) 347.8g starts and stirs and adding (HMe
2Si)
2O 14.2g adds acidic white earth 28g again, heat temperature raising, and keep 8h at 40-80 ℃, and be cooled to 50 ℃ then, remove by filter catalyzer.Reactor is made into water distilling apparatus, and low-boiling-point substance is removed in distillation under 100 ℃, 1.3KPa, clear, colorless both-end hydrogen based polysiloxane.Viscosity (25 ℃) 43mpa.s, reactive hydrogen massfraction 0.05%, its structural formula is as follows:
Embodiment 2
Synthesizing of the poly-methyl hydrogen radical siloxane of both-end hydrogen base
In reactor assembly (with embodiment 1), add D earlier
4(prestox ring four oxosilanes) 335g, D4H14.8g starts and stirs, and adds (HMe again
2Si)
2O11.5g adds H then slowly
2SO
418g, heat temperature raising and at 40-60 ℃ of balanced reaction 10h, after be cooled to 50 ℃, slowly add Na
2CO
325g, and then add deionized water and be washed till neutrality.Reactor is made into water distilling apparatus, steams at 110 ℃, 1.3KPa and dewater and low-boiling-point substance, the clear, colorless containing hydrogen silicone oil, viscosity (25 ℃) 55mpa.s, reactive hydrogen massfraction amount 0.105%, its structural formula is as follows:
Embodiment 3
The preparation of both-end hydroxyl alkyl polysiloxane
In being housed, the 1000ml glass there-necked flask of electronic stirring, condenser and thermometer adds the containing hydrogen silicone oil 150g that embodiment 2 makes, glycol monomethyl allyl ether 117g, sodium-acetate 5g (2% aqueous isopropanol), start and stir, evenly, at room temperature, (Pt content is 15 * 10 of reactant total mass to add platinum-divinyl tetramethyl disiloxane toluene solution 1.1g
-6), reactant generates heat immediately, slowly splashes into the containing hydrogen silicone oil 350g of surplus again, drips off material back and continues to stir 2h, analyzes through IR, confirm that the Si-H peak has disappeared after, again under 100 ℃, 133Pa through distilling out low-boiling-point substance, filter, colourless transparent liquid 550g.(IR analyzes, and hydroxyl quantitatively reaches GPC and measures) confirms the product molecular structure by analysis:
Embodiment 4
The preparation of both-end hydroxyl alkyl polysiloxane
In embodiment 3 same apparatus, add the both-end hydrogen based polysiloxane 150g that embodiment 1 makes, glycol monomethyl allyl ether 55g, Potassium ethanoate 5g (aqueous isopropanol of 2% massfraction), start to stir, (Pt content is 15 * 10 of reactant total mass at room temperature to add platinum-divinyl tetramethyl disiloxane toluene solution 1g after evenly
-6), reactant generates heat immediately, slowly splash into the containing hydrogen silicone oil 350g of surplus again, drip off the back and continue reaction 2h, analyze, after affirmation Si-H peak has disappeared through IR, resultant under 100 ℃, 133Pa through distilling out low-boiling-point substance, filter, get colourless transparent liquid 510g, through confirming that with embodiment 3 same analysis the product molecular structure is as follows:
Comparative example
The siloxanes that is used for comparison is the polysiloxane by the following structural of known method preparation:
Make use-case
With 0.5g from the product high speed dispersion stirring and dissolving of embodiment 3, example 4 and comparative example in the polyurethane slurry of 100g30% (solvent is a dimethyl formamide), after leaving standstill half an hour, at first estimate its consistency, use the scraper coating that sample is coated with 200 μ m thick film in being of a size of 100 * 250mm
2Sheet glass on, dry after-vision check levelling effect and waterproof moisture-proof effect.
An electronic stroke of film device that constant rate of advance is arranged is then used in the smoothness test, and by each resistance that this slide mass ran under the computer recording, simultaneously pure hand sense of touch test non-stick property, the result is as follows:
| Sample | Consistency | Levelling property | Waterproof moisture-proof effect | Non-stick property | Skid resistance (N) |
| Embodiment 3 | Transparent | Good | Best | Good | 3.1 |
| Embodiment 4 | Transparent | Best | Good | Best | 2.3 |
| Comparative example | Slightly muddy | Generally | Water spot is arranged | Generally | 4.5 |
Claims (4)
1. hydroxyl alkyl-terminated polysiloxane compound, structure is as follows:
Wherein, m=10-100; N=0-20;
R
1-OH is-C
aH
2a-OH, a=2-4;
Perhaps-(CH
2)
3-O-(C
2H
4O)
p(C
3H
6O)
qH, p=1-15, q=0-15;
R
2For-C
bH
2b+1, b=1-20;
Perhaps-(CH
2)
3-O-(C
2H
4O)
p(C
3H
6O)
qH, p=1-15, q=0-15;
R
1, R
2Can be identical, also can be inequality.
2. hydroxyl alkyl-terminated polysiloxane compound according to claim 1 is characterized in that, described R
2For-CH
2CH
2CH
2-O-CH
2CH
2OH or CH
3
3. hydroxyl alkyl-terminated polysiloxane compound according to claim 1 is characterized in that, described R
1For-CH
2CH
2CH
2-O-CH
2CH
2OH.
4. hydroxyl alkyl-terminated polysiloxane compound as claimed in claim 1, the application in the preparation additive agent of polyurethane artificial leather.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100458414A CN101386682A (en) | 2007-09-11 | 2007-09-11 | Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100458414A CN101386682A (en) | 2007-09-11 | 2007-09-11 | Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather |
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| Publication Number | Publication Date |
|---|---|
| CN101386682A true CN101386682A (en) | 2009-03-18 |
Family
ID=40476369
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926208A (en) * | 2012-10-16 | 2013-02-13 | 淮安凯悦科技开发有限公司 | Surface treating agent for skin-touch polyurethane resin artificial leather |
| CN105017535A (en) * | 2015-06-17 | 2015-11-04 | 建德市聚合新材料有限公司 | Preparation method and applications of hydroxyalkyl silicone oil |
| CN109705310A (en) * | 2018-12-18 | 2019-05-03 | 上海华峰超纤材料股份有限公司 | Water-proof air-permeable leather polyurethane resin and preparation method thereof |
| CN113818256A (en) * | 2021-09-26 | 2021-12-21 | 南通中豪超纤制品有限公司 | Preparation process of blending modified easy-to-clean leather |
-
2007
- 2007-09-11 CN CNA2007100458414A patent/CN101386682A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926208A (en) * | 2012-10-16 | 2013-02-13 | 淮安凯悦科技开发有限公司 | Surface treating agent for skin-touch polyurethane resin artificial leather |
| CN105017535A (en) * | 2015-06-17 | 2015-11-04 | 建德市聚合新材料有限公司 | Preparation method and applications of hydroxyalkyl silicone oil |
| CN109705310A (en) * | 2018-12-18 | 2019-05-03 | 上海华峰超纤材料股份有限公司 | Water-proof air-permeable leather polyurethane resin and preparation method thereof |
| CN109705310B (en) * | 2018-12-18 | 2021-09-10 | 上海华峰超纤科技股份有限公司 | Polyurethane resin for waterproof breathable leather and preparation method thereof |
| CN113818256A (en) * | 2021-09-26 | 2021-12-21 | 南通中豪超纤制品有限公司 | Preparation process of blending modified easy-to-clean leather |
| CN113818256B (en) * | 2021-09-26 | 2024-05-31 | 南通中豪超纤制品有限公司 | Process for preparing blending modified easy-to-decontaminate leather |
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Application publication date: 20090318 |