CN101096450A - Polyurethane additive and preparation method and application thereof - Google Patents
Polyurethane additive and preparation method and application thereof Download PDFInfo
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- CN101096450A CN101096450A CNA2006100901592A CN200610090159A CN101096450A CN 101096450 A CN101096450 A CN 101096450A CN A2006100901592 A CNA2006100901592 A CN A2006100901592A CN 200610090159 A CN200610090159 A CN 200610090159A CN 101096450 A CN101096450 A CN 101096450A
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Abstract
The invention discloses a multifunctional polyurethane additive, which contains modified cellulose with isocyanate and polyol as optimum, wherein the additive can be reacted by cellulose and the material with isocyanate, which has good dispersibility to be dissolved in the polyurethane paint directly. The invention saves manufacturing cost, which simplifies the applying method.
Description
Technical field
The present invention relates to additive agent field, relate in particular to polyurethane additive, functional type polyurethane additive especially, and its production and application.
Background technology
Urethane claims polyurethane(s) again, is the general name of being reacted the macromolecular compound that forms by polyisocyanates and polyvalent alcohol (or multi-hydroxy compound), contains the amino ester group of multiple on its main chain.Urethane has good viscosity and binding property, is good coating, for example is used as the water-proof coating of fabric, plastics or leather.
The polyurethane coating fabric generally possesses functions such as windproof preferably, rainproof, warming, and appearance style softness, moderate cost, gets consumer reception.Yet because the constructional feature of urethane material itself makes it have a lot of shortcomings, for example the polyurethane coating water vapour permeability is poor, because the existence of free ammonia ester bond makes the polyurethane coating facile hydrolysis aging, adhesive is strong.But, much use the waterproof fabric of polyurethane coating, for example raincoat cloth, cloth of tent etc. require formed polyurethane coating to have performances such as favorable waterproof property, water vapour permeability, antiblocking performance, bacteriostasis property, anti ageing property and eliminate optical property.Therefore need improve polyurethane coating, make that the coating that forms has above-mentioned fine quality.
Term in the literary composition " water resistance " is meant the water permeable ability of polyurethane coating, presses as its measurement index with the water purification of coating.The water purification of polyurethane coating is pressed big more, and then the water resistance of coating is high more, and moisture is not easy to see through coating; Otherwise littler if the water purification of polyurethane coating is pressed, then the water resistance of coating is low more, and moisture sees through coating easily.
Term in the literary composition " water vapour permeability " is meant the ability of steam permeable coating, with the vapor transfer rate of coating as index.The vapor transfer rate of coating is big more, and then water vapour is easy of more coating, and water vapour permeability is good more; Otherwise if the vapor transfer rate of coating is more little, then water vapour is difficult more by coating, and water vapour permeability is poor more.
Water resistance and water vapour permeability are a pair of contradiction, and well then water vapour permeability is poor for general water resistance, and well then water resistance is poor for water vapour permeability.
In order to make polyurethane coating reach above-mentioned desirable quality, need in polyurethane coating, add additive.Up to the present, in the prior art, additive generally is a single performance, and promptly every kind of additive can only improve certain character.Substantially also do not find the additive of composite performance, especially can improve the composite additive of coating water resistance and water vapour permeability simultaneously.
In order to make polyurethane coating have above-mentioned multiple good character, need in polyurethane coating, add multiple additives.For example in order to increase water vapour permeability, can add wet additive (saturating humectant), inorganic powder or ether of cellulose such as for example inferior nano-silica powder end or inferior nano zirconium dioxide, but because consistency is very poor between these inorganic powder grains and the organic materials urethane, cause the coated membrane structure to be evacuated, filmogen is not in conjunction with tight, and slowly migration of inorganic particulate, so the non-constant of the water resistance of gained coating; When adding the cellulose ethers material, but ether of cellulose is met water generation swelling, causes the poor adhesion between polyurethane coating and the fabric, and peeling force reduces, thereby significantly reduces its work-ing life, and the easy moldy metamorphism of coating, promotes the biological degradation of urethane.Though more than two kinds of methods can improve the water vapour permeability of polyurethane coating, all non-constant of the water resistance of coating.
In this case, to improve the coating water resistance be very difficult by adding other additives, because the consistency between additive that is added and urethane and the wet thoroughly additive can be poorer, this moment can be by improving the water-repellancy that urethane molecular chain length of the present invention improves coated membrane, but cost and costliness thereof, and effect is not very good yet.
When in polyurethane coating, adding various additive, for example saturating humectant, water-resisting agent, protective agent, matting agent etc., in view of various additives in urethane dispersion and with urethane compatibility problem each other, the quality of gained coated membrane is unsatisfactory, and manufacturing procedure is complicated.
Summary of the invention
The object of the present invention is to provide a kind of multifunctional polyurethane paint additive, this additive has good dispersing property, after adding to it in polyurethane coating, the coating that forms has good performance, as water resistance, water vapour permeability, anti ageing property, anti performance, eliminate optical property etc.
Another object of the present invention is to provide the preparation method of above-mentioned multifunctional polyurethane paint additive.
The present invention also aims to provide the application of above-mentioned multifunctional polyurethane paint additive.
Basic design of the present invention is as follows: the Mierocrystalline cellulose of isocyano modification is added in the polyurethane coating as additive, because complicated physics chemical action makes both that complicated physics chemical action take place between the Mierocrystalline cellulose of isocyano modification and the urethane, therefore formed coated membrane has performances such as excellent waterproof, saturating wet, anti-aging, anti and delustring.
According to an aspect of the present invention, provide a kind of multifunctional polyurethane paint additive, wherein comprised Mierocrystalline cellulose by the material institute modification that contains isocyano.
Preferably, also contain polyvalent alcohol in this additive.
According to another aspect of the present invention, a kind of method for preparing above-mentioned multifunctional polyurethane paint additive is provided, this method comprises: Mierocrystalline cellulose is carried out modification with the material that contains isocyano handle, preferably also comprise in the modification products therefrom adding polyvalent alcohol.
Below describe the present invention.
The Mierocrystalline cellulose (Mierocrystalline cellulose of isocyano modification) that contains the material root modification of isocyanic acid can react by Mierocrystalline cellulose and the material that contains isocyano and obtains.
Used contain isocyano (that is, the material of isocyanato-R=C=O) can be any material that contains isocyano, not special the qualification.It can be isocyanic ester, for example monobasic or binary or multicomponent isocyanate, the monobasic isocyanic ester is the chloro-phenyl-isocyanic ester for example, cyclohexyl isocyanate, phenylcarbimide, isopropyl isocyanate, Sulfuryl chloride isocyanate, the tolysulfonyl isocyanic ester, the trimethylphenylmethane isocyanic ester, benzene isocyanic ester and octadecylisocyanate etc., vulcabond is tolylene diisocyanate (TDI) for example, '-diphenylmethane diisocyanate (MDI), terephthalylidene vulcabond (XD1), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H
12MDI), naphthalene diisocyanate (NDI), polyisocyanates is thiophosphoric acid triphenyl triisocyanate, triphenylmethane triisocyanate and dimethyl triphenyl methane tetraisocyanate etc. for example.These materials can use arbitrarily, promptly can use separately, also can arbitrary combination use.
When carrying out above-mentioned modified-reaction, because Mierocrystalline cellulose itself is a solid particulate matter, when the used material that contains isocyano is liquid state, both speed of response are higher, when the used material that contains isocyano is colloid or increases speed of response for the contact area that increases both when solid-state, can add an amount of organic solvent, certainly still can add solvent with further raising speed of response when the used material that contains isocyano is liquid state, organic solvent can be for example benzene or its homologue or dimethyl formamide etc.
The possible action principle of additive of the present invention is as described below:
About water resistance: Mierocrystalline cellulose is natural polymer substance, its molecular chain is very long, wherein contain great amount of hydroxy group, when a large amount of Mierocrystalline celluloses contact with the material that contains isocyano on a small quantity, hydroxyl can react with isocyano, generate fibrination functional polyurethane performed polymer, it is the Mierocrystalline cellulose of isocyano modification, wherein still exist a large amount of not by the hydroxyl of isocyano modification, when joining it in urethane and urethane macromolecular crosslinking reaction takes place, the polyurethane coating of Xing Chenging is tightr thus, so water-repellancy strengthens; And Mierocrystalline cellulose itself has the micropore result, also has corresponding microvoid structure by Mierocrystalline cellulose and the performed polymer that the substance reaction that contains isocyano obtains, and when this performed polymer mixed with urethane, can produce stronger physical bond power, coated membrane intensity increases, and this has also strengthened the water resistance of coating.In other words, because additive (is the Mierocrystalline cellulose of isocyano modification, perhaps be called fibrination functional polyurethane performed polymer) and urethane between complicated physics chemical action make that formed coated membrane is finer and close, intensity is higher, make the water resistance of coating significantly improve.
About water vapour permeability:, make formed coating have stronger water vapour and see through ability that the vapor transfer rate of coating significantly improves owing to contain a large amount of hydrophilic radical such as hydroxyl in the additive.
About anti-aging, anti performance: thus the hydroxyl in the additive can with free ammonia ester group reaction in the urethane with its elimination, thereby avoided its hydrolysising aging, improved the anti performance.
About delustring: because the microvoid structure of additive makes formed coatingsurface produce very strong refraction to light, thereby reached delustring or inferior actinic effect.
Directly do not use as additive if Mierocrystalline cellulose has modification, because the consistency of Mierocrystalline cellulose and urethane is poor, it is not tight to cause formed coated membrane to connect, and water resistance is poor.
Thereby Mierocrystalline cellulose is carried out in the process of modification reacting with the material that contains isocyano by Mierocrystalline cellulose, used Mierocrystalline cellulose is preferably 100: 3 with the ratio of the substance weight that contains isocyano～and 20, more preferably 100: 4～12, more preferably 100: 8～10.If the ratio of Mierocrystalline cellulose and the substance weight that contains isocyano was less than 100: 3, then modification is incomplete, after the gained additive is used for polyurethane coating after the modification, and the water resistance variation of the coating that forms; If the ratio of Mierocrystalline cellulose and the substance weight that contains isocyano was greater than 100: 20, then the urethano mass contg in the gained additive is too high after the modification, self can condense the generation mound, bad dispersibility, need to handle again and could use, and can cause final formed polyurethane coating water resistance variation.
Preferably, also contain polyvalent alcohol in the additive, its can with not with the substance reaction that contains isocyano of fibrin reaction, thereby this part isocyano is eliminated, thereby eliminate the peculiar taste of isocyano, and make that fibrination functional polyurethane performed polymer is more stable.Used polyvalent alcohol can be conventional dibasic alcohol or polyvalent alcohol, and is not particularly limited.The amount of polyvalent alcohol is preferably 1～10wt% of used cellulose amount, is preferably 1～5wt%, more preferably 2～3wt%.
In order further to increase the bacteriostasis property of additive, can in advance Mierocrystalline cellulose be handled with fungistat, used fungistat for example is the wk fungistat.
Additive of the present invention can be used for any polyurethane coating, all can use as urethane dry method solvent based coating, water-soluble type coating and wet method coating, and effect is all fine, in particular for the dry method solvent based coating.
When additive of the present invention was used for polyurethane coating, the amount of additive can be regulated according to used coating type and purposes.For example, when this additive was used for the dry method solvent based coating, as bottom urethane bed material solution, the amount of the additive that is added can be 5～20% of urethane solid content in the coating, for example 10%; As surface layer urethane bed material solution, the amount of the additive that is added can be 60～80% of urethane solid content in the coating, for example 70%, and can make the gained fabric have very excellent water vapour permeability and water resistance like this.
Additive of the present invention has good dispersing property, can directly be dissolved in the polyurethane coating and without any need for extra operation, the coating process of coating and technology are without any need for variation, production unit and processing condition need not made any adjustment and change, application method is simple, compares with adding multiple other additives, has greatly simplified operation, reduce energy consumption, saved cost.
Under the identical situation of coated membrane thickness, do not compare with using additive polyurethane coating of the present invention, use the formed coated membrane of polyurethane coating of additive of the present invention, its water purification is pressed and is doubled, and vapor transfer rate improves more than 50%; Press when identical at water purification, the coated membrane thickness that uses additive of the present invention than and do not use the coated membrane thickness of additive of the present invention reduce by three/one or more.
And the polyurethane coating adhesion of use additive of the present invention is very good, combine closely with fabric to be difficult to peel off, and after washing, its vapor transfer rate changes little.
In addition, the price of additive of the present invention only is 1/3rd of the saturating humectant of silicon class, has significantly reduced production cost.
Embodiment
Further describe the present invention below in conjunction with embodiment, characteristics of the present invention and effect will be illustrated more fully.
Cellulosic pre-treatment
Grind: cellulosic fibre is ground to more than 400 orders;
Bleaching: cellulose powder is put into stainless steel cauldron, add clear water again, water temperature is heated to 80 ℃, and under this temperature, soaked 6 hours, add quality again and be 27% hydrogen peroxide solution of Mierocrystalline cellulose quality 80%, stirring reaction filtered cellulose powder, dry after 24 hours, put into reactor again, carry out the bleaching second time by above-mentioned steps;
Antibacterial processing: cellulose powder after will bleaching filters, and dries, and adding weight be its clear water of 5 times, heats water to 90 degree, and adding weight is the wk fungistat of cellulose 5%, keeps temperature 2 hours, during stirring in per 30 minutes once;
Oven dry: the cellulose powder after the antibacterial processing is filtered, dry, through the hotblast stove oven dry, hot-blast furnace temperature is controlled in 140 degree, and the Mierocrystalline cellulose moisture content is controlled in 0.5%.
Embodiment 1
The cellulose powder 1000g of above-mentioned pre-treatment gained is joined in the stainless steel cauldron, be dissolved in the solution of gained in the 100g benzene to wherein adding 8g MDI again, stirred 20 minutes, add 2g glycerine again, stirred 20 minutes, obtain additive, it is an oyster white powder, and average particle size is about 30 microns.
Embodiment 2
The cellulose powder 1000g of above-mentioned pre-treatment gained is joined in the stainless steel cauldron, to wherein adding the 4g isopropyl isocyanate, stirred 15 minutes again, add 5g ethylene glycol again, stirred 20 minutes, obtain additive, it is an oyster white powder, and average particle size is about 30 microns.
Embodiment 3
The cellulose powder 1000g of above-mentioned pre-treatment gained is joined in the stainless steel cauldron, to wherein adding 10g HDI and 120gDMF, stirred 30 minutes again, add the 10g hexylene glycol again, stirred 15 minutes, obtain additive, it is an oyster white powder, and average particle size is about 30 microns.
Embodiment 4
The cellulose powder 1000g of above-mentioned pre-treatment gained is joined in the stainless steel cauldron, to wherein adding 20g rubigan isocyanic ester and 200g benzene, stirred 30 minutes again, add the 1g butyleneglycol again, stirred 10 minutes, it is an oyster white powder, and average particle size is about 30 microns.
Embodiment 5
The cellulose powder 1000g of above-mentioned pre-treatment gained is joined in the stainless steel cauldron, to wherein adding 3g triphenyl triisocyanate, stirred 20 minutes again, add the 1g butyleneglycol again, stirred 10 minutes, obtain additive, it is an oyster white powder, and average particle size is about 30 microns.
The test example
The additive of embodiment 1～5 gained is joined respectively among dry method solvent borne polyurethane coating FS5880, FS5811, FS816, FS800 and the FS5711, wherein add-on is the 10wt% of urethane solid content in priming paint, add-on is the 70wt% of urethane solid content in the investment precoat, on identical base cloth, use ordinary method to obtain 5 kinds of fabrics that are coated with polyurethane coating, be called fabric 1～5, it is carried out vapor transfer rate and the check of water purification pressure, the results are shown in the following table 1.
Use the method identical with aforesaid method to make respectively and the corresponding 5 kinds of fabrics (becoming comparison fabric 1～5) that are coated with polyurethane coating of above-mentioned 5 kinds of fabrics, its difference only is not use the additive of embodiment 1～5 gained.It is carried out vapor transfer rate and water purification press check, the result also is listed in the table below in 1.
Testing tool:
DH-40N; Shelley water purification pressure tester; ISO-4920
Testing method:
GB/T 12704-1991；FZ/T 01004-1991；GB/T 4745-1997
The vapor transfer rate of table 1 coating and water purification are pressed observed value
| Project | Vapor transfer rate g/m 2·d | Water purification is pressed KPa | ||
| Initially | After washing 15 times | Initially | After washing 15 times | |
| Fabric 1 | 2310 | 2980 | ＞200 | ＞200 |
| Comparison fabric 1 | 1420 | 3470 | 78.6 | 0.7 |
| Fabric 2 | 2070 | 3870 | ＞200 | 123.7 |
| Comparison fabric 2 | 1290 | 3900 | 81.2 | 5.6 |
| Fabric 3 | 2580 | 2870 | ＞200 | ＞200 |
| Comparison fabric 3 | 1300 | 2800 | 69.7 | 0.7 |
| Fabric 4 | 2010 | 3540 | ＞200 | ＞200 |
| Comparison fabric 4 | 1120 | 2400 | 113.0 | 1.2 |
| Fabric 5 | 2130 | 3200 | ＞200 | 69.7 |
| Comparison fabric 5 | 1130 | 2350 | 79.4 | 0.6 |
From last table content as can be seen, compare with comparison fabric 1～5, for fabric 1～5, its water purification is depressed into and has fewly improved 2 times, and vapor transfer rate has improved over half at least.
Claims (8)
1. a polyurethane additive is characterized in that, comprises the Mierocrystalline cellulose by the material institute modification that contains isocyano in this additive.
2. polyurethane additive according to claim 1 is characterized in that, also contains polyvalent alcohol in this additive.
3. the method for preparing the described polyurethane additive of claim 1, this method comprises: Mierocrystalline cellulose is carried out modification with the substance reaction that contains isocyano to Mierocrystalline cellulose handle.
4. method according to claim 3 is characterized in that, this method also comprises in the modification products therefrom and adds polyvalent alcohol.
5. according to claim 3 or 4 described methods, it is characterized in that described Mierocrystalline cellulose obtains through pre-treatment, preprocessing process comprises antibacterial processing.
6. method according to claim 4 is characterized in that, Mierocrystalline cellulose is preferably 100: 3 with the ratio of the substance weight that contains isocyano～and 20, more preferably 100: 4～12, more preferably 100: 8～10.
7. method according to claim 4 is characterized in that the amount of polyvalent alcohol is 1～10wt% of cellulose amount, is preferably 1～5wt%, more preferably 2～3wt%.
8. claim 1 or 2 the application of polyurethane additive in polyurethane coating.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2006100901592A CN101096450A (en) | 2006-06-29 | 2006-06-29 | Polyurethane additive and preparation method and application thereof |
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| CNA2006100901592A CN101096450A (en) | 2006-06-29 | 2006-06-29 | Polyurethane additive and preparation method and application thereof |
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| CN101096450A true CN101096450A (en) | 2008-01-02 |
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| CNA2006100901592A Pending CN101096450A (en) | 2006-06-29 | 2006-06-29 | Polyurethane additive and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073267A (en) * | 2019-12-13 | 2020-04-28 | 南通市裕如工程材料有限责任公司 | High-molecular elastic plugging agent |
| CN111303379A (en) * | 2020-03-19 | 2020-06-19 | 江苏新视客光电科技有限公司 | PC lens without bisphenol A and preparation method thereof |
-
2006
- 2006-06-29 CN CNA2006100901592A patent/CN101096450A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073267A (en) * | 2019-12-13 | 2020-04-28 | 南通市裕如工程材料有限责任公司 | High-molecular elastic plugging agent |
| CN111303379A (en) * | 2020-03-19 | 2020-06-19 | 江苏新视客光电科技有限公司 | PC lens without bisphenol A and preparation method thereof |
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