CN102277722A - Modified nanometer oxide, preparation method and use method of self-emulsified dispersive liquid thereof - Google Patents
Modified nanometer oxide, preparation method and use method of self-emulsified dispersive liquid thereof Download PDFInfo
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Abstract
The invention discloses a modified nanometer oxide, which is a product with the structural formula as sown in the specification, wherein A represents a nanometer oxide which is one of nanometer titanium dioxide, nanometer zinc oxide, silver doped nanometer titanium dioxide, silver doped nanometer zinc oxide and nanometer silicon oxide, or a compound formed by two of the oxides; R1 having two isocyanatoes represents diisocyanate, including TD1, MD1, HD1, ND1 and IPD1; Y represents an end sealing agent, including ethanol, sodium hydrogensulfite, caprolactam and phenol; and n is a number within 10-135. The invention further discloses a preparation method and use method of a self-emulsified dispersive liquid of the modified nanometer oxide. The self-emulsified dispersive liquid of the modified nanometer oxide prepared by the technical scheme can be used for neatening the functions of soft goods, so that the natural fiber soft goods can have uvioresistant performance, infrared absorption resistance and antibacterial performance after the function neatening.
Description
Technical field
The invention belongs to the technical field of after-finishing of textile products auxiliary agent, specifically, the present invention relates to modified nano oxide compound.In addition, the invention still further relates to the preparation method and the using method thereof of the self-emulsifying dispersion liquid of described modified nano oxide compound.
Background technology
Nano titanium oxide, nano zine oxide are a kind of performance function inorganic material, have strong photocatalysis, antibiotic and ultraviolet screener performance, are widely used aspect textile material.Because nano titanium oxide, the nano zine oxide particle diameter is little, specific surface is big, surface energy is high, nano particle is easy to reunite, simultaneously nano titanium oxide, nano zine oxide and textile material particularly natural fabric combine durability not insufficient, apply thereby limited it.
For the dispersion that improves nano titanium oxide, nano zine oxide reaches and the natural fabric combination degree, be a kind of efficient ways to its surface modification.Be divided into inorganic modified and organically-modified by surface modifier.
Commonly used is inorganic modified for after adopting silica that titanium dioxide is carried out surface modification, implements silane coupler modifiedly again, and the nanoparticle surface after the modification is a hydrophobicity, is not suitable for disperseing in water, is very limited at field of textiles.
Organically-modified is main method of modifying.Mainly comprise surfactant method, coupling agent method and polymer overmold method.
Chinese patent literature (CN1389520)---" multifunctional nano zinc oxide suspension and preparation method thereof ", following technical scheme is disclosed: this multifunctional suspending liquid by the nano zine oxide of modification as the solid phase, be equipped with different surfactants and polymer mutually, adopt special process to make it to be suspended in different organic solvents, the water equal solvent liquid phase and be prepared from as stably dispersing.The multifunctional suspending liquid that utilizes this preparation method to make, it is dispersed stable, the uniformity unanimity, and functional strong, can be widely used in industry or fields such as coating, pottery, weaving.
Chinese patent literature (CN1511889)---" nano zine oxide aqueous dispersion of surface modification and its production and use ", following technical scheme is disclosed: described aqueous dispersion, in system weight percentage, comprising: 0.1～10% nano zine oxide; 0.06～10% hydration SiO
2, 0.12～20% hydration Al
2O
3Or 0.05～10% hydration Fe
2O
30.1～10% silane coupler; 0.2～9% water-soluble polymer; All the other are water.By hydration SiO
2, hydration Al
2O
3Or hydration Fe
2O
3Deposit to the surface of nano zine oxide, then evenly mix, make aqueous dispersion of the present invention with silane coupler, water-soluble polymer and water.Being uniformly dispersed of nano zine oxide, stable prevented the reunion between the nano granular of zinc oxide effectively in aqueous dispersion of the present invention.Aqueous dispersion of the present invention can be used for preparing uvioresistant textiles.
The modification of above-mentioned nano-oxide mainly is to carry out in the preparation, has improved the dispersiveness of nano particle, has avoided reunion, but does not solve nano particle combines durable shortcoming with natural fabric problem.
Chinese patent literature (CN1635033)---" modified nano oxide compound, preparation method and its usage " discloses following technical scheme: adopt chemical method, nano-oxide is carried out surface modification, make the modified nano oxide compound with reactive group.This nano-oxide produces the chemical bond combination by the hydroxyl on suitable crosslinking agent and the natural fabric, carboxyl, amino isoreactivity group, has improved nano particle and natural fabric combination degree.But this method resource consumption is many, and the cost height has certain pollution to environment.
Summary of the invention
The present invention at first provides a kind of modified nano oxide compound, its objective is that making the self-emulsifying dispersion liquid by it is used for finishing functions of textile fabrics, and the natural fabric textiles has uvioresistant, INFRARED ABSORPTION and anti-microbial property after putting in order through it.
To achieve these goals, the technical scheme taked of the present invention is:
Modified nano oxide compound provided by the present invention is the product with following structural formula:
Wherein:
A is a nano-oxide; Described nano-oxide is a kind of in nano titanium oxide, nano zine oxide, Ag doped with nano TiO 2, Ag doped with nano zinc oxide, the nano silicon oxide, or the compound of two kinds of formations wherein;
The R1 that has two isocyanos is a vulcabond, comprises TDI, MDI, HDI, NDI, IPDI;
Y is an end-capping reagent, comprises ethanol, sodium hydrogensulfite, caprolactam, phenol;
N is 10～135.
Perhaps, described compound is nano titanium oxide-zinc oxide composites, or Ag doped with nano TiO 2-zinc oxide composites, or nano titanium oxide-silica compound, or Ag doped with nano TiO 2-silica compound.
In order to realize the purpose identical with technique scheme, the present invention also provides the self-emulsifying dispersion liquid preparation method of above-mentioned modified nano oxide compound, and its technical scheme is:
1), the preparation of precast body:
Under nitrogen protection, be that 105 ℃, vacuum are under the condition of 100～150mmHg with polyethylene glycol in temperature, dehydration 1～2h; Be cooled to 55～50 ℃, slowly add vulcabond and dibutyl tin laurate again, be warming up to 80 ℃, reaction 2.5h obtains described performed polymer B;
The mol ratio of polyethylene glycol, vulcabond, dibutyl tin laurate is 2.05: 1: 0.0001;
2), modified process:
Performed polymer B is warming up to 95～100 ℃, adds the nano-oxide reaction 2～6h that accounts for gross weight 5～25%, be cooled to 20～25 ℃, add absolute ethyl alcohol, slowly add the sodium hydrogensulfite saturated solution then, reaction 2～4h obtains modified nano oxide compound;
3), dispersion step:
In above-mentioned modified nano oxide compound, add entry, make the water that is added account for 75%～95% of gross weight, disperse by high speed dispersor or ultrasonic disperser, described modified nano oxide compound is dispersed in the water, obtain the self-emulsifying dispersion liquid of modified nano oxide compound.
Also promptly: modified nano oxide compound is 5～25% at the percentage by weight of the self-emulsifying dispersion liquid of described modified nano oxide compound;
Described polyethylene glycol mean molecule quantity 400～6000.
The present invention also provides the using method of the self-emulsifying dispersion liquid of above-described modified nano oxide compound, and its technical scheme is:
The self-emulsifying dispersion liquid of described modified nano oxide compound is used as the textiles multifunction finishing agent; Its using method is:
1), washing procedure:
Natural fabric with washing in the alkaline soap lye, to remove surface impurity, is dried then;
2), dipping operation:
Is to soak 60min in 1～10g/L nano-oxide dressing liquid with textile impregnation in concentration;
(3), treatment process:
A baking one roasting technology is rolled in employing, and the fabric that dipping is good is handled, and obtains the function fabric of nano material arrangement after soaping;
Roll in a baking one roasting technology described, 110 ℃ of preliminary drying 3min, 150 ℃ bake 2min.
The present invention adopts technique scheme, by nano-oxide being adopted end-capping reagent protection isocyano, by treatment process, makes the modified Nano particle be dispersed in fabric surface under the penetrating agent JFC effect again; At last by selecting appropriate condition, promptly by selecting suitable temperature, impel sealer to take off envelope regeneration, impel isocyano to dissociate out, only with the fiber-reactive that has hydroxyl, amide groups, " expose " in fabric surface thereby make nano-oxide particles, each other the nano-function textile of covalent bonds.Both can give full play to the skin effect of nano particle, make it to have excellent ultraviolet shielded, INFRARED ABSORPTION, anti-microbial property, and can overcome again that common nano particle is easy to run off, the life-span is short, reclaim shortcoming such as difficulty.Compared with prior art, the present invention not only preparation technology is simple, good dispersion, and can conveniently be used as finishing functions of textile fabrics; To comprise natural fabrics such as COTTON FABRIC, ramie fabric, sodolin, silk fabric, wool fabric can adopt roll, dry by the fire, roasting technology carries out multi-functional arrangement.COTTON FABRIC after the arrangement has stronger and lasting ultraviolet shielded effect, and uvioresistant index (UPF) is 67.6, still can keep good ultraviolet protection washable 50 times.
Description of drawings
Below the expressed content of each width of cloth accompanying drawing of this specification is briefly explained:
Fig. 1 is the graph of a relation of modified nano-titanium dioxide finishing agent consumption and fabric UPF;
Fig. 2 is the graph of a relation of modified nano zinc oxide variable concentrations and fabric UPF;
Fig. 3 is the graph of a relation of modified nano-titanium dioxide finishing agent dip time and fabric UPF;
Fig. 4 is the graph of a relation of modified nano-titanium dioxide finishing agent dip time stoving temperature and fabric UPF.
The specific embodiment
Contrast accompanying drawing below, the description by to embodiment is described in further detail the specific embodiment of the present invention, to help those skilled in the art inventive concept of the present invention, technical scheme is had more complete, accurate and deep understanding.
The present invention is in conjunction with China's industry and resources characteristic and development level, and in order to make full use of existing weaponry and equipment and existing technology, by nano titanium oxide, nano zine oxide are carried out chemical modification, preparation stably dispersing, surface have the nano particle of isocyano; Adopt specific auxiliary agent protection isocyano then, the mode by dyeing and finishing processing makes the modified Nano particle be dispersed in fabric surface; At last by selecting appropriate condition, impel isocyano only to dissociate out and the fiber-reactive that has hydroxyl, amide groups, " expose " at fiber surface the nano-function textile of mutual covalent bonds thereby make nano particle.
Diisocyanate content of the present invention is greater than 99%; Described polyethylene glycol (PEG), dibutyl tin laurate are chemical pure;
Free isocyanate Determination on content among the described performed polymer B: adopt acetone-di-n-butylamine titration.
The mensuration of end-blocking rate: adopt I
2The solution titration.
The mensuration of described uvioresistant index: adopt UV textiles uvioresistant analyzer, the UPF index of fabric before and after the test arrangement.
Washing fastness is measured: on washfastness tester, carry out the washability test with reference to AATCC61 one 2001 standards.
Embodiment one:
1, the preparation of precast body:
Under nitrogen protection, be under the situation of 100～150mmHg with polyethylene glycol 105 ℃ of following vacuums, dehydration 1.5h; Be cooled to 55～50 ℃, slow again vulcabond and the dibutyl tin laurate that adds, the 80 ℃ of reactions that heat up promptly obtained performed polymer B in 2.5 hours.The mol ratio of polyethylene glycol, vulcabond, dibutyl tin laurate 2.05: 1: 0.0001;
2, modified process:
Performed polymer B is warming up to 95 ℃, adds nano zine oxide reaction 6 hours, be cooled to 20～25 ℃, add absolute ethyl alcohol, slowly add the sodium hydrogensulfite saturated solution then, reacted 2 hours, get final product;
3, dispersion step:
The gained modified nano zinc oxide is dispersed in the dispersion liquid that promptly gets the modified nano oxide compound self-emulsifying in the water through high speed dispersor or ultrasonic disperser.The percentage by weight of modified nano oxide compound self-emulsifying dispersion liquid is 15%.Dispersion stabilization is good, and is not stratified in 1 year.
Embodiment two:
(NCO) (mol ratio OH) is 1.4～2.2: 1, all the other are identical with embodiment one with polyethylene glycol for isocyanate group in MDI.Its result is as shown in table 1:
Table 1:
| N(NCO)∶n(OH) | Solution property |
| 1.4∶1 | Faint yellow translucent |
| 1.6∶1 | Yellow translucent |
| 1.8∶1 | Yellow transparent |
| 2.05∶1 | Yellow transparent |
| 2.2∶1 | Flocculent deposit |
By shown in the table 1:
(NCO) (mol ratio OH) seriously affects and contains isocyanate terminated base (polyurethane-modified dose character NCO), and then influence the quality of nano titanium oxide dressing liquid isocyanate group among the MDI with polyethylene glycol.When NCO with-mol ratio of OH is more near 1, the viscosity of later stage system is big more, react difficult more control, easy gel, preferable mol ratio n (NCO): n (OH) is 2.05: 1, can obtain the stabilizing solution of yellow transparent at this moment.
Embodiment three:
Except that the temperature of performed polymer B, the reaction time, all the other are identical with embodiment one.Its result is by shown in the table 2:
Table 2: pre-polymerization temperature, the influence of time to reacting
| 30min | 60min | 90min | 120min | 150min | 180min | |
| 60 ℃ M | 1.55 | 1.46 | 1.28 | 1.25 | 1.18 | 1.12 |
| 80 ℃ M | 1.21 | 1.17 | 1.13 | 1.06 | 1.03 | 1.02 |
| 100 ℃ M | 1.16 | 1.12 | 1.10 | 0.90 | 0.82 | 0.81 |
By table 2 as seen, (in polyurethane-modified dose of preparation NCO), temperature is crossed low then isocyanates does not have complete reaction, and residual have free isocyanate-monomer and a polyalcohol, causes reaction not exclusively to contain isocyanate terminated base.Increase in temperature, the reaction rate of isocyanates and all kinds of active hydrogen compoundss increases.Temperature is too high, end group-NCO easily with polyurethane on-that NH-or urea key form multiple spot is crosslinked, forms relative molecular mass and sharply increases, degree of branching increase causes gel.React more near terminal point, the approaching more theory of-NCO percentage-NCO percentage, promptly M is more near 1.As can be drawn from Table 2,80 ℃ is preferable prepolymerization reaction temperature, and the time is 2.5 hours.
Embodiment four:
The self-emulsifying dispersion liquid of modified nano oxide compound of the present invention is as the textiles multifunction finishing agent; Its using method is:
A, washing procedure: natural fabric with washing in the alkaline soap lye, to remove surface impurity, is dried then;
B, dipping operation: will soak 60 minutes in the nano titanium oxide dressing liquid that textile impregnation is 1,3,5 in concentration, 7g/L embodiment one is made;
C, treatment process: adopt and to roll a baking one roasting technology and will flood good fabric and handle, promptly get the function fabric that nano material is put in order after soaping;
In rolling a baking one roasting technology, adopt 110 ℃ * 3min of preliminary drying, bake 150 ℃ * 2min, dipping 60min process conditions are handled COTTON FABRIC.
The result of embodiment four is as shown in Figure 1:
As can be seen from Figure 1, the nano titanium oxide after the modification has tangible ultraviolet protection effect, and increases with its content, and UV screening property of cotton strengthens gradually.When titanium dioxide concentration reached 3g/L in the dressing liquid, the ultraviolet protection grade of COTTON FABRIC had reached splendid.Therefore, in conjunction with cost, the nano titanium oxide consumption is advisable with 3g/L.
Embodiment five:
Except " b, dipping operation " among the embodiment four changed into: is in the made nano titanium oxide dressing liquid of 3g/L embodiment one the soak time difference with textile impregnation in concentration, and all the other are identical with embodiment four.
The result is as shown in Figure 3:
Along with dip time prolongs, the content of titanium dioxide on the fabric obviously increases.This is because within a certain period of time, and along with dip time prolongs, nano particle combines manyly by OH a large amount of in hydrogen bond, Van der Waals force and the cotton fiber; When the time reached 30min, the distribution of titanium dioxide on fabric was even substantially; Prolong dip time again, nano particle increases not obvious.
Embodiment six:
The baking temperature in " c, treatment process ", all the other are identical with embodiment four.
Its result is as shown in Figure 4:
Along with baking temperature raises, the washability of fabric uvioresistant performance increases.About 170 ℃, the yellowing phenomenon appears in fabric, and brute force descends to some extent.When temperature was 100 ℃, the UPF index of fabric was lower, and this is because temperature is too low, some isocyano deblocking, and the washability of arrangement back fabric is poor.So baking temperature is advisable with 150 ℃.
Below in conjunction with the accompanying drawings the present invention has been carried out exemplary description; obviously specific implementation of the present invention is not subjected to the restriction of aforesaid way; as long as adopted the improvement of the various unsubstantialities that method of the present invention design and technical scheme carry out; or design of the present invention and technical scheme are directly applied to other occasion without improving, all within protection scope of the present invention.
Claims (5)
1. modified nano oxide compound is characterized in that having the product of following structural formula:
Wherein:
A is a nano-oxide; Described nano-oxide is a kind of in nano titanium oxide, nano zine oxide, Ag doped with nano TiO 2, Ag doped with nano zinc oxide, the nano silicon oxide, or the compound of two kinds of formations wherein;
The R1 that has two isocyanos is a vulcabond, comprises TDI, MDI, HDI, NDI, IPDI;
Y is an end-capping reagent, comprises ethanol, sodium hydrogensulfite, caprolactam, phenol;
N is 10～135.
2. according to the described modified nano oxide compound of claim 1, it is characterized in that: described compound is nano titanium oxide-zinc oxide composites, or Ag doped with nano TiO 2-zinc oxide composites, or nano titanium oxide-silica compound, or Ag doped with nano TiO 2-silica compound.
3. according to the self-emulsifying dispersion liquid preparation method of claim 1 or 2 described modified nano oxide compounds, it is characterized in that this preparation method comprises:
1), the preparation of precast body:
Under nitrogen protection, be that 105 ℃, vacuum are under the condition of 100～150mmHg with polyethylene glycol in temperature, dehydration 1～2h; Be cooled to 55～50 ℃, slowly add vulcabond and dibutyl tin laurate again, be warming up to 80 ℃, reaction 2.5h obtains performed polymer B;
The mol ratio of polyethylene glycol, vulcabond, dibutyl tin laurate is 2.05: 1: 0.0001;
2), modified process:
Described performed polymer B is warming up to 95～100 ℃, adds the nano-oxide reaction 2～6h that accounts for gross weight 5～25%, be cooled to 20～25 ℃, add absolute ethyl alcohol, slowly add the sodium hydrogensulfite saturated solution then, reaction 2～4h obtains modified nano oxide compound;
3), dispersion step:
In above-mentioned modified nano oxide compound, add entry, make the water that is added account for 75%～95% of gross weight, disperse by high speed dispersor or ultrasonic disperser, described modified nano oxide compound is dispersed in the water, obtain the self-emulsifying dispersion liquid of modified nano oxide compound.
4. according to the described modified nano oxide compound self-emulsifying of claim 3 dispersion liquid preparation method, it is characterized in that: described polyethylene glycol mean molecule quantity 400～6000.
5. according to the using method of the self-emulsifying dispersion liquid of the described modified nano oxide compound of claim 3, it is characterized in that: with the self-emulsifying dispersion liquid of described modified nano oxide compound as the textiles multifunction finishing agent; Its using method is:
1), washing procedure:
Natural fabric with washing in the alkaline soap lye, to remove surface impurity, is dried then;
2), dipping operation:
Is to soak 60min in 1～10g/L nano-oxide dressing liquid with textile impregnation in concentration;
3), treatment process:
A baking one roasting technology is rolled in employing, and the fabric that dipping is good is handled, and obtains the function fabric of nano material arrangement after soaping;
Roll in a baking one roasting technology described, 110 ℃ of preliminary drying 3min, 150 ℃ bake 2min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790202A (en) * | 2015-04-22 | 2015-07-22 | 广州大学 | Fluorine-free durable super-hydrophobic cotton fabric finishing agent and cotton fabric finishing method thereof |
| CN105420901A (en) * | 2015-12-30 | 2016-03-23 | 无锡红豆居家服饰有限公司 | Hodo fleece fabric with far infrared heating function |
| CN107280986A (en) * | 2017-06-06 | 2017-10-24 | 常州大学 | A kind of rutin modifying titanium dioxide compound and preparation method thereof |
| CN110157043A (en) * | 2019-05-09 | 2019-08-23 | 江苏理工学院 | A kind of composite assistant and preparation method thereof with improvement polymer ageing-resistant performance |
| CN110317459A (en) * | 2019-07-04 | 2019-10-11 | 安徽星鑫化工科技有限公司 | A kind of chlorinated paraffin ultraviolet absorbing agent |
| CN111939673A (en) * | 2020-08-27 | 2020-11-17 | 海信（山东）空调有限公司 | Filter screen and air conditioner |
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|---|---|---|---|---|
| CN1635033A (en) * | 2004-10-22 | 2005-07-06 | 上海工程技术大学 | Modified nano oxide compound, its application and use thereof |
-
2011
- 2011-05-12 CN CN 201110122412 patent/CN102277722A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635033A (en) * | 2004-10-22 | 2005-07-06 | 上海工程技术大学 | Modified nano oxide compound, its application and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《印染》 20090615 刘新华等 聚氨酯改性纳米二氧化钛整理剂的制备和应用 32-34 1-5 , 第12期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790202A (en) * | 2015-04-22 | 2015-07-22 | 广州大学 | Fluorine-free durable super-hydrophobic cotton fabric finishing agent and cotton fabric finishing method thereof |
| CN105420901A (en) * | 2015-12-30 | 2016-03-23 | 无锡红豆居家服饰有限公司 | Hodo fleece fabric with far infrared heating function |
| CN107280986A (en) * | 2017-06-06 | 2017-10-24 | 常州大学 | A kind of rutin modifying titanium dioxide compound and preparation method thereof |
| CN107280986B (en) * | 2017-06-06 | 2020-06-16 | 常州大学 | Rutin modified titanium dioxide compound and preparation method thereof |
| CN110157043A (en) * | 2019-05-09 | 2019-08-23 | 江苏理工学院 | A kind of composite assistant and preparation method thereof with improvement polymer ageing-resistant performance |
| CN110317459A (en) * | 2019-07-04 | 2019-10-11 | 安徽星鑫化工科技有限公司 | A kind of chlorinated paraffin ultraviolet absorbing agent |
| CN110317459B (en) * | 2019-07-04 | 2021-09-21 | 安徽星鑫化工科技有限公司 | Chlorinated paraffin ultraviolet absorbent |
| CN111939673A (en) * | 2020-08-27 | 2020-11-17 | 海信（山东）空调有限公司 | Filter screen and air conditioner |
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Application publication date: 20111214 |