CN103437187B - Method for preparing hollow silicon dioxide/waterborne polyurethane composite slurry used for synthetic leather - Google Patents
Method for preparing hollow silicon dioxide/waterborne polyurethane composite slurry used for synthetic leather Download PDFInfo
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Abstract
The invention discloses a method for preparing hollow silicon dioxide/waterborne polyurethane composite slurry used for synthetic leather. The method comprises the following steps: adding an cationic surfactant into a mixture liquid A formed by mixing ethanol and water, uniformly stirring, subsequently adding a silicon source and stronger ammonia water, reacting at the room temperature, centrifuging, washing and subsequently drying after the reaction so as to obtain hollow silicon dioxide nano particles; adding the hollow silicon dioxide nano particles into a mixture liquid B formed by mixing ethanol and water, and uniformly dispersing in an ultrasonic mode so as to obtain a hollow silicon dioxide nano particles suspension; adding the hollow silicon dioxide nano particles suspension into waterborne polyurethane, and uniformly stirring at 75 DEG C so as to obtain the hollow silicon dioxide/waterborne polyurethane composite slurry. Compared with pure water polyurethane, the composite slurry prepared by using the method has the advantages that the moisture permeability is improved by 49.57%, the water resistance is improved by 18.31%, and the elongation at break and the tensile strength are respectively improved by 17.45% and 24.51%.
Description
Technical field
The present invention relates to a kind of preparation method of composite mortar, particularly a kind of preparation method of use for synthetic leather hollow silica/aqueous polyurethane composite mortar.
Technical background
Synthetic leather because of its physical and mechanical properties excellent, there is the advantages such as wear-resisting, ageing-resistant, cold-resistant, become and replace the ideal artificial material of natural leather.But the polyurethane coating that synthetic leather surface applies is dense, causes its gas permeability, water vapor permeability poor, makes the sanitation performance of product be subject to extreme influence.In order to improve the sanitation performance of synthetic leather, improve the vapor pervious performance of polyurethane coating, domestic and international researcher has carried out a large amount of research work.On the whole, two aspects are mainly concentrated on: one is improve the ratio of in polyurethane molecular chain soft section; Two is in polyurethane, introduce hydroaropic substance (as collagenous fibres, cyclodextrin etc.).(Talakesh M M, Sadeghi M, Chenar M P, et al.Gas separation properties of poly (ethylene glycol)/poly (tetramethylene glycol) based polyurethane membranes [J] .Journal of Membrane Science, 2012, 415:469-477.Levine F, Escarsega J, LaScala J.Effect of isocyanate to hydroxyl index on the properties of clearpolyurethane films [J] .Progress in Organic Coatings, 2012, 74 (3): 572-581. Ma Xingyuan, Lv Lingyun, Jiang Kun, Deng. collagenous fibres/polyurethane wet solidifies micro-structure and property research [J] of composite membrane. leather science and engineering, 2011, 4:005.).Although above-mentioned research can improve the transfer rate of vapour molecule, improve the water vapor permeability of coating, the resistance to water of coating and mechanical property but can be subject to negative effect.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of use for synthetic leather hollow silica/aqueous polyurethane composite mortar, the method technique is simple, be easy to operation, after the hollow silica/aqueous polyurethane composite mortar film forming of preparation, not only there is good vapor pervious performance, and there is excellent resistance to water and mechanical property.
For achieving the above object, the technical solution used in the present invention comprises the following steps:
1) preparation of hollow silica nano particle:
Cationic surface active agent is joined in the mixed liquor A mixed by second alcohol and water, add silicon source and concentrated ammonia liquor after stirring, under room temperature, react 0.5h ~ 6h, through centrifugal, washing after reaction terminates, then dry, obtain hollow silica nano particle; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is (3 ~ 7): 10; The cationic surface active agent of every 0.06g ~ 0.10g needs the concentrated ammonia liquor adding 0.3mL ~ 0.7mL silicon source and 0.4mL ~ 0.6mL;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by hollow silica nano particle in the mixed liquid B mixed by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; It is in the aqueous polyurethane of 30% that hollow silica nano particle turbid liquid is joined solid content, then stirs at 75 DEG C, obtains hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1; Hollow silica nano particle accounts for 0.5% ~ 2% of aqueous polyurethane quality.
Described step 1) cationic surfactant is the mixture of one or more arbitrary proportions in Dodecyl trimethyl ammonium chloride (DTAC), tetradecyl trimethyl ammonium chloride (TTAC), hexadecyltrimethylammonium chloride (CTAC), octadecyl trimethyl ammonium chloride (OTAC), softex kw (CTAB).
The cationic surface active agent of 0.06g ~ 0.10g is added in every 45mL mixed liquor A in described step 1).
Silicon source in described step 1) is the mixture of one or more arbitrary proportions in ethyl orthosilicate (TEOS), tetramethoxy-silicane (TMOS), 3-aminopropyl triethoxysilane (APTES), vinyltriethoxysilane (A-151).
Drying in described step 1) is carried out in an oven, and baking temperature is 60 DEG C.
Described step 2) in every 15mL mixed liquid B in add the hollow silica nano particle of 0.15g ~ 0.6g.
Described step 2) in mixing speed be 350rpm.
Compared with prior art, beneficial effect of the present invention is as follows:
1) hollow silica have that density is little, the feature such as specific area is large, good stability, its boring structure can encapsulate gas or small-molecule substance, can be used as the inorganic filler etc. in the carrier of medicament slow release and building coating.And the present invention utilizes hollow silica nano particle to carry out modification to aqueous polyurethane, hollow structure due to hollow silica provide in polyurethane coating vapour molecule through passage, therefore, the vapor pervious performance of the coating that hollow silica/aqueous polyurethane composite mortar that the present invention obtains is formed is significantly improved; In addition, the present invention has also played the stability of silica inorganic nano particle excellence and activeness and quietness effect in order to improve resistance to water and the mechanical property of coating.Overcome traditional method of modifying to reduce the defect that water-resistance property of coating and mechanical property are cost.Prove through test, the film performance of the hollow silica that the present invention obtains/aqueous polyurethane composite mortar is compared with water-based polyurethane, its water vapor permeability improves 49.57%, and resistance to water improves 18.31%, and elongation at break and tensile strength improve 17.45% and 24.51% respectively.
2) the present invention prepares hollow silica nano particle with soft template method, physical blending process carries out modification to aqueous polyurethane, due to the relative hard template method of soft template method, it is prepared hollow silica nano particle and has the advantages such as technique is simple, template removal is easy, therefore, present invention process is simple, is easy to operation.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the hollow silica nano particle that the present invention obtains;
Fig. 2 is the enlarged drawing of Fig. 1.
Detailed description of the invention
Embodiment 1:
1) preparation of hollow silica nano particle:
The softex kw (CTAB) of 0.08g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the ethyl orthosilicate (TEOS) of 0.5mL and 0.5mL mass concentration are 26% ~ 28% is added after stirring, 6h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 5:10;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.3g in the mixed liquid B mixed by 15mL second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 2:
1) preparation of hollow silica nano particle:
The hexadecyltrimethylammonium chloride (CTAC) of 0.06g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the tetramethoxy-silicane (TMOS) of 0.6mL and 0.4mL mass concentration are 26% ~ 28% is added after stirring, 3h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 7:10;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.15g in the mixed liquid B mixed by 15mL second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 3:
1) preparation of hollow silica nano particle:
The tetradecyl trimethyl ammonium chloride (TTAC) of 0.10g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the 3-aminopropyl triethoxysilane (APTES) of 0.7mL and 0.6mL mass concentration are 26% ~ 28% is added after stirring, 2h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 6:10.
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.6g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 4:
1) preparation of hollow silica nano particle:
The octadecyl trimethyl ammonium chloride (OTAC) of 0.07g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the vinyltriethoxysilane (A-151) of 0.3mL and 0.45mL mass concentration are 26% ~ 28% is added after stirring, 4h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 4:10.
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.45g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 5:
1) preparation of hollow silica nano particle:
The Dodecyl trimethyl ammonium chloride (DTAC) of 0.08g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the ethyl orthosilicate (TEOS) of 0.4mL and 0.55mL mass concentration are 26% ~ 28% is added after stirring, 5h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 3:10;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.3g in the mixed liquid B mixed by 15mL second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 6:
1) preparation of hollow silica nano particle:
The softex kw (CTAB) of 0.09g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the 3-aminopropyl triethoxysilane (APTES) of 0.4mL and 0.6mL mass concentration are 26% ~ 28% is added after stirring, 1h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 5:10;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.15g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 7:
1) preparation of hollow silica nano particle:
The hexadecyltrimethylammonium chloride (CTAC) of 0.08g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that 0.5mL ethyl orthosilicate (TEOS) and 0.55mL mass concentration are 26% ~ 28% is added after stirring, 0.5h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 7:10.
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.45g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 8:
1) preparation of hollow silica nano particle:
The softex kw (CTAB) of 0.09g and the Dodecyl trimethyl ammonium chloride of 0.01g are joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the 3-aminopropyl triethoxysilane (APTES) of 0.4mL and 0.6mL mass concentration are 26% ~ 28% is added after stirring, 1h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 5:10;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.15g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
Embodiment 9:
1) preparation of hollow silica nano particle:
The octadecyl trimethyl ammonium chloride (OTAC) of 0.07g is joined in the mixed liquor A that 45mL mixes by second alcohol and water, the commercially available concentrated ammonia liquor that the vinyltriethoxysilane (A-151) of 0.3mL, the 3-aminopropyl triethoxysilane (APTES) of 0.2mL and 0.45mL mass concentration are 26% ~ 28% is added after stirring, 4h is reacted under room temperature, through centrifugal, washing after reaction terminates, then in an oven in 60 DEG C of dryings, the good hollow silica nano particle of regularity is obtained; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is 4:10.
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by the hollow silica nano particle of 0.45g in the mixed liquid B that 15mL mixes by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; By 30g solid content be 30% aqueous polyurethane (WPU) join in 100mL there-necked flask, then in the 100mL there-necked flask filling aqueous polyurethane, hollow silica nano particle turbid liquid is added, 6h is stirred with the speed of 350rpm again at 75 DEG C, make it to mix with aqueous polyurethane, obtain hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1.
As can be seen from Fig. 1-Fig. 2, the hollow silica nano particle that step 1) of the present invention obtains is the nano particle of hollow-core construction, and even particle size, smooth surface, the particle diameter of hollow silica is about 500nm, and wall thickness is about 150nm.
The hollow silica prepared according to the present invention/aqueous polyurethane composite mortar excellent performance, compared with water-based polyurethane, its water vapor permeability improves 49.57%, and resistance to water improves 18.31%, and elongation at break and tensile strength improve 17.45% and 24.51% respectively.
The film performance of table 1 hollow silica/aqueous polyurethane composite mortar and pure WPU
Wherein, hollow SiO
2the hollow silica that/WPU and the present invention obtain/aqueous polyurethane composite mortar.
Claims (1)
1. a preparation method for use for synthetic leather hollow silica/aqueous polyurethane composite mortar, is characterized in that:
1) preparation of hollow silica nano particle:
Cationic surface active agent is joined in the mixed liquor A mixed by second alcohol and water, after stirring, add silicon source and concentrated ammonia liquor, under room temperature, react 0.5h ~ 6h, through centrifugal, washing after reaction terminates, then dry, obtain hollow silica nano particle; Wherein, in the mixed liquor A added, the volume ratio of second alcohol and water is (3 ~ 7): 10; The cationic surface active agent of every 0.06g ~ 0.10g needs the concentrated ammonia liquor adding 0.3mL ~ 0.7mL silicon source and 0.4mL ~ 0.6mL; The cationic surface active agent of 0.06g ~ 0.10g is added in every 45mL mixed liquor A;
2) preparation of hollow silica/aqueous polyurethane composite mortar:
Added by hollow silica nano particle in the mixed liquid B mixed by second alcohol and water, ultrasonic disperse is even, obtains hollow silica nano particle turbid liquid; It is in the aqueous polyurethane of 30% that hollow silica nano particle turbid liquid is joined solid content, then stirs at 75 DEG C, obtains hollow silica/aqueous polyurethane composite mortar; Wherein, in the mixed liquid B added, the volume ratio of second alcohol and water is 2:1; Hollow silica nano particle accounts for 0.5% ~ 2% of aqueous polyurethane quality, adds the hollow silica nano particle of 0.15g ~ 0.6g in the mixed liquid B of every 15mL.
2. the preparation method of use for synthetic leather hollow silica/aqueous polyurethane composite mortar according to claim 1, is characterized in that: described step 1) cationic surfactant is the mixture of one or more arbitrary proportions in Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride, softex kw.
3. the preparation method of use for synthetic leather hollow silica/aqueous polyurethane composite mortar according to claim 1, is characterized in that: the silicon source in described step 1) is the mixture of one or more arbitrary proportions in ethyl orthosilicate, tetramethoxy-silicane, 3-aminopropyl triethoxysilane, vinyltriethoxysilane.
4. the preparation method of use for synthetic leather hollow silica/aqueous polyurethane composite mortar according to claim 1, is characterized in that: the drying in described step 1) is carried out in an oven, and baking temperature is 60 DEG C.
5. the preparation method of use for synthetic leather hollow silica/aqueous polyurethane composite mortar according to claim 1, is characterized in that: described step 2) in mixing speed be 350rpm.
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CN111100542B (en) * | 2019-12-23 | 2021-10-08 | 中国皮革和制鞋工业研究院(晋江)有限公司 | Antibacterial Ag-ZnO-TiO2Preparation method of/waterborne polyurethane composite slurry |
CN117139115B (en) * | 2023-10-31 | 2024-01-09 | 江苏康士格新材料科技有限公司 | High-strength aluminum veneer and processing technology thereof |
CN117987067A (en) * | 2024-03-29 | 2024-05-07 | 四川汇利实业有限公司 | Preparation method of polyurethane adhesive for medicine packaging composite film and composition of polyurethane adhesive |
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