CN104099783A - Preparation method of super-hydrophobic modified yak hair - Google Patents
Preparation method of super-hydrophobic modified yak hair Download PDFInfo
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- CN104099783A CN104099783A CN201410333423.5A CN201410333423A CN104099783A CN 104099783 A CN104099783 A CN 104099783A CN 201410333423 A CN201410333423 A CN 201410333423A CN 104099783 A CN104099783 A CN 104099783A
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Abstract
The invention discloses a preparation method of super-hydrophobic modified yak hair. The preparation method mainly comprises the steps as follows: natural yak hair and wool of Tibet Plateau of China are taken as raw materials, and the raw materials are subjected to two-step treatment by organic silicon; dibutyryl chloride is grafted on the fiber surface of hair and wool, so that the fiber surface has high-active groups; the grafted acyl chloride groups and organic silicon react to modify the material surface; basic physical properties of yak hair and wool are researched, and the basic physical properties comprise chemical components, microstructures, surface morphology, waterproofness, thermal insulation property, density and the like of the materials before and after treatment; and super-hydrophobic surfaces of yak hair and wool are tested. The woolen fabric is a natural material, is non-toxic, touches comfortable, has a bionic super-hydrophobic structure, and has the advantages of waterproof and snow preventing functions simultaneously and good air permeability; further, yak hair and wool resources are abundant and convenient to collect; and with the adoption of the preparation method, the economic values of yak products can be effectively increased, and powerful technical support can be provided for wool spinning industry development of western minority areas.
Description
Technical field
The present invention relates to a kind of preparation method of modifying super hydrophobicity yak hair, particularly relate to a kind of preparation method of the waterproof fabrics with ultra-hydrophobicity, belong to textile technology field.
Background technology
Yak is known as yak, is the distinctive ox kind of Tibet alpine steppe, is mainly distributed in the Himalaya and Qinghai-Tibet Platean.Yak whole body is generally pitchy, and health both sides and chest, abdomen, dodds are long and close, and four limbs are short and slightly strong.Yak Growth is at the extremely frigid zones of height above sea level 3000 ~ 5000m, the severe cold that ability is subzero 30 DEG C ~ 40 DEG C, and yak is the mammal that lives in the world height above sea level highest point.Yak is divided into Bos mutus and family yak, and Bos mutus cries again wild ox, and English name wild yak hides name transliteration Asia and returns.Artiodactyla, Bovidae, Niu Yake, Poephagus, be the wild similar of a yak, typical high and cold animal, property is extremely cold-resistant, this and its mao, the high heat-retention that has of suede can have substantial connection.Yak is Qinghai-Tibet peculiar ox kind, for a national class watches for animals.China's consumption ox hair fibre resources is abundant, is mainly distributed in the ground such as Qinghai, Tibet, Sichuan, Gansu.Consumption ox hair fiber major part is made up of scale layer and cortical layer, only contains few medullary substance layer, and brute force is higher, but is close to hair shaft, smoother, cohesive force extreme difference because of its scale.Again because fiber is thick, long, curling less, stiffening, upright and outspoken, bring very big difficulty to spinning.Yakwool fiber good springiness, sliding glutinous, gloss is soft, be difficult for balling-up, warmth retention property is similar to cashmere, and its cost ratio cashmere is low, pure spin or blending have higher economic worth (honor of freely spreading out. yak hair (suede) point comb [J]. wool spinning science and technology, 1986, (3): 49-53.).But on the whole, the production of yak hair, suede is long-term all produces and accounts for sizable proportion in roughing, the labor-intensive that with low content of technology, added value is low, the processing of high added value, high skill content is relatively less, has restricted effective utilization and the related industry development of yak resources.
That hydrophobic fabric can be used for is rainproof/aspects such as snow clothes, tent, military fighting uniform, and its huge potential market and economic benefit become the focus of textile industry research.In order to improve the hydrophobicity of material surface, just must solve surperficial wettability.Wettability is one of key character of the surface of solids, jointly determine (Jiang L by surperficial chemical composition and microstructure, Wang R, Yang B. Binary cooperative complementary nanoscale interfacial materials [J]. Pure Appl. Chem., 2000,72:73-77.).In recent years, super hydrophobic surface has caused people's common concern, as being all widely used in fields such as self-cleaning material, microfluid and harmless fluid transports.Super hydrophobic surface refers to the surface of contact angle >150 ° with water.Contact angle is one of standard of weighing solid hydrophobic surface, but while judging a surperficial hydrophobic effect, also should be taken into account its dynamic process, generally weighs by roll angle.Roll angle is the difference of advancing contact angle (abbreviation advancing angle) and receding contact angle (abbreviation receding angle), has represented the hysteresis of water droplet on the surface of solids.A super hydrophobic surface truly, should both have larger static contact angle, had again less roll angle.Occurring in nature has the example of many super hydrophobic surfaces, as lotus leaf, Rice Leaf, cicada's wings and water skipper leg etc., the special surface structure of these natural materials is manufactured super hydrophobic surface at material surface model (high snowy peak is provided, Jiang Lei. the new development [J] of natural super-hydrophobic biological surface research. physics, 2006,35 (7): 559-564.).Research discovery, the hierarchical structure that micrometer structure combines with nanostructured is the basic reason that causes surface super hydrophobic.To so special biological surface, on textile surface, imitate, by controlling suitable configuration of surface, can obtain super-hydrophobic automatic cleaning surface, rolling anisotropic surface and high-adhesiveness super hydrophobic surface etc. and have the textile material of special surface character.Most typical as feather of the wing of the lepidopterous insects such as lotus leaf surface, butterfly and aquatic bird etc.By observing and study discovery, this type of surface, apart from outside hydrophobic chemical constituent, also has fine coarse structure on micro-scale.Under electron microscope, lotus leaf surface has double-deck microstructure, by the mastoid process of micro-meter scale and the wax-like crystal composition of nanoscale on it; Powder on butterfly class wing is by approximately 100
flat bladder composition, bladder is by countless cuticula (symmetrical chitin form) formation, its surface is not bright and clean, Here it is, and butterfly often has colorful schemochrome and better hydrophobic reason.So preparing super hydrophobic surface just requires: (1) builds coarse structure on hydrophobic material (contact angle >90 °) surface; (2) on rough surface, modify low-surface-energy material.Often by falling low-surface-energy at surface coverage fluorocarbon chain or silane chain.From preparation method, mainly contain induction phase separation method, Electrospinning Method, sol-gel processing etc.
In recent years, carry out super-hydrophobic processing at fabric face, preparing the garment materials such as functional waterproof, antifouling, snow defence is a study hotspot in interface science field and textile industry.And rarely has report in the research that animal fiber fabric face carries out super-hydrophobic processing.
Summary of the invention
The object of the invention is to set up a kind of preparation method of modifying super hydrophobicity yak hair, this polymeric material has the following advantages: this mao of wool fabric is a kind of natural material; Nontoxic, human body contiguous sense is comfortable; There is bionic super-hydrophobic structure; There is waterproof, snow defence function simultaneously; The advantages such as permeability is good.In this patent, intend utilizing cetyl trimethoxy silane (HDTMS) to carry out finishing to yak hair, suede, utilize silicon to reduce fabric face energy as low-surface-energy material, and cetyl builds nano level surface roughness as hydrophobic substance, thereby prepare bionical super hydrophobic surface.In this patent, taking China's natural yak hair in Qinghai-Tibet Platean, suede as raw material, utilize organosilicon to carry out two-step method processing to material, make material surface there is bionic super-hydrophobic structure, thereby prepare a kind of novel waterproof and breathable hair wool fabric.
The technology of preparing scheme of waterproof hair wool fabric is as follows:
1) at hair, suede fiber surface grafting two butyl chlorides
2) hydrolysis of cetyl trimethoxy silane (HDTMS)
3) organosilicon surface modification
By above technical scheme, tool of the present invention has the following advantages: 1) modifying super hydrophobicity yak hair has the advantages such as Nantural non-toxic;
2) anti-modifying super hydrophobicity yak hair has bionic super-hydrophobic structure;
3) modifying super hydrophobicity yak hair has waterproof, snow defence function, and permeability is good;
4) yak hair, suede aboundresources, be convenient to gather, the invention of this fabric can effectively improve the economic worth of Yak product.
Brief description of the drawings
Fig. 1 is the structural representation of this waterproof hair wool fabric.
Wherein, be 1. the long alkyl chain structure of cetyl trimethoxy silane, it grafts on a mao wool fabric surface and has strong hydrophobic effect; 2. for containing silicon face, can effectively reduce hair surface energy, and the super-hydrophobic environment of rough surface; 3. yak hair, suede fiber.
Detailed description of the invention
Provide embodiment below so that the present invention is specifically described; but it is worthy of note that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to the invention described above content and adjustment still belong to protection scope of the present invention.
Embodiment 1:
1. the basic physical property research of yak hair, suede
Section morphology to yak hair, suede, length, fineness, curling, further investigate than the basic physical property such as resistance, frictional behaviour, surface wettability, the microstructure surperficial to it simultaneously, fine structure, the chemical composition that more particularly can affect its surf ace properties are analyzed, and study the correlation between its macroscopical physical property and microstructure.What generally adopt is chemical method, physical method and optical microscopy.Applying electronic microscopy is differentiated various fibers, owing to can observing comparatively clearly its surperficial ultra microstructure and morphological feature, progressively by scientists is paid attention to.Utilize the section morphology of scanning electronic microscope to yak hair, suede, length, fineness etc. to observe and test a kind of comparatively effective method.Crimp elasticity and crimp percent are also mao wool fabric considerable parameters in manufacture process.Wherein crimp elasticity represents the stressed rear curling recovery capability of fiber, and crimp percent represents curling durable fastness.If crimp percent and crimp elasticity are higher, the cohesive force of hair, suede is better, and the plentiful softness of its product is comfortable and easy to wear.Therefore the feel of fabric, elasticity and richness are all relatively good, survey value higher.Frictional behaviour is also an important indicator of reflection fabric product quality, if the forbidden lamella sheet coefficient of friction of the middle fine animal fibre of hair wool fabric is with larger along scale coefficient of friction difference, therefore feltability is better, and with not easily openable of hand, balling-up shape is also better.Be the important indicator whether reflection fabric easily produces electrostatic phenomenon than the height of resistance, should reduce the ratio resistance value of fabric, to increase spinnability as far as possible.Also the mechanical performance that will test yak hair, velvet fabric, because the counter-bending fatigue behaviour of fabric directly affects the quality of material simultaneously.Particularly people's arm is often movable, so the armpit of hair ready-made clothes often there will be disrepair phenomenon.Finally use inorganic acid (as sulfuric acid), Organic Acid and Base material to be carried out to the research of chemical resistance, the comparatively comprehensively chemical stability of Knowing material.
2. yak hair, suede are carried out to the organic-silicon-modified super hydrophobic surface of preparing
Prepare super hydrophobic surface requirement: (1) builds coarse structure on hydrophobic material (contact angle >90 °) surface; (2) on rough surface, modify low-surface-energy material.In recent years, scientists is widely used is by falling low-surface-energy at surface coverage fluorocarbon chain or silane chain.But fluorochemical has larger toxicity, easily cause environmental pollution, replaced by organosilyl use just gradually.Utilize surface can be low, heat endurance is high, avirulence organo-silicon compound carry out surface modification treatment to fabric and receiving in recent years scientist's very big concern.In this project, intend utilizing cetyl trimethoxy silane (HDTMS) to carry out finishing to yak hair, suede, utilize silicon to reduce fabric face energy as low-surface-energy material, and cetyl builds nano level surface roughness as hydrophobic substance, thereby prepare bionical super hydrophobic surface.Organosilyl introducing is mainly divided into two steps: one, at hair, suede fiber surface grafting two butyl chlorides.Because arginine, cystine, serine content in yak hair, suede account for the more than 30% of total amino acid content, in these amino acid, contain-NH ,-SH ,-OH isoreactivity group, these active groups all can be relatively easy to react with two butyl chlorides, so thereby can carry out grafting on these groups makes fiber surface have active higher acid chloride groups.Two, react material surface is carried out to modification with organosilicon by the acid chloride groups of grafting.First HDTMS is dipped into and in methyl alcohol, makes its Si – OCH
3-group is fully hydrolyzed becomes Si – OH silanol, and silanol is because electronegativity difference is large, makes group polarity larger, and reactivity increases.Utilize the substitution reaction between acyl chlorides and silanol to carry out modification to material surface, utilize subsequently dehydration to make to form Si – O key between silanol, fixing hydrophobic alkyl is in material surface.
3. ultra-hydrophobicity test
Wettability is a kind of physical characteristic of material, and it depends on surperficial chemical composition and morphosis, and the many wet processing of textiles relies on the complete wetting of textiles institutional framework to reach satisfied treatment effect.To have good wettability contrary with the wet processing request of textiles, and those require the textiles of waterproof, for example waterproof garment, protective clothing, sportswear, industrial WATERPROOF FABRIC, and indoor decorative fabric etc., needs hydrophobicly especially, preferably has super-hydrophobic ability.Super hydrophobic surface, typically refers to water contact angle and is greater than 150 ° and the very low surface of contact angle hysteresis.For textile material, hydrophobic value is usually only measured Static Water contact angle, is not easy to measure the height roughening being produced by textiles institutional framework and the contact angle hysteresis causing.Wettability depends primarily on surface energy and surface roughness.There are some researches show, there is correlation in the adhesion of surface roughness and particle, some material surfaces due to low surface free energy character produce height water and oil repellant, refuse organic solvent and lubricity obtains practical application.
4. test to organic-silicon-modified yak hair, down material conduct, compression, ventilative, become the test of wind speed heat-insulating property
Heat loss through conduction amount is to weigh the key factor of fabric heat-insulation performance, the possible factor that affects unit are heat loss through conduction amount is the parameter such as fiber net volume under sample thickness, voidage (fiber net volume and flocculus apparent volume percentage), unit are, thereby can carry out the experiment of heat loss through conduction amount to modification yak hair, pile fabric, its heat-insulating property is evaluated.Meanwhile, warming ability and the material thickness of fabric are closely related, and can fabric keep initial thickness just particularly crucial in use, and therefore, the anti-compression properties of the material under reply different disposal condition carries out test analysis.Again, the warming ability of the height of fabric is mainly because inner implicit a large amount of still airs produce high thermal resistance and obtain.The external world has wind to do the used time, and the part air in flocculus is by the static flow regime that transfers to, and its heat loss through convection plays a leading role gradually.Therefore, there is the quality of heat retention of the fabric energy under wind condition to depend mainly on the ability that its inner air is static that maintains.For research has thermal property material modified under wind condition, can test the heat dissipation capacity of the material under different wind speed.
Finally it should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art should understand, can a point technical scheme for invention be modified or be replaced on an equal basis, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (7)
1. a modifying super hydrophobicity yak hair, its architectural feature is: described hair wool fabric is by being prepared from by surface super hydrophobic modification.
2. a method of preparing modifying super hydrophobicity yak hair claimed in claim 1 is carried out as follows:
1) at hair, suede fiber surface grafting two butyl chlorides;
2) cetyl trimethoxy silane is dipped into and in methyl alcohol, makes its Si – OCH
3-group is fully hydrolyzed becomes Si – OH silanol;
3) utilize the substitution reaction between acyl chlorides and silanol to carry out modification to material surface, utilize subsequently dehydration to make to form Si – O key between silanol, fixing hydrophobic alkyl is in material surface.
3. the preparation method of a kind of modifying super hydrophobicity yak hair according to claim 2, is characterized in that the surface super hydrophobic material that in said method, step 1) is used is cetyl trimethoxy silane.
4. the preparation method of a kind of modifying super hydrophobicity yak hair according to claim 2, is further characterized in that the coating material that in said method, step 3) is used is two butyl chlorides.
5. the preparation method of a kind of modifying super hydrophobicity yak hair according to claim 2, be further characterized in that in said method, step 3) is carried out in surface modification reaction, the reaction that need be hydrolyzed, is dipped into cetyl trimethoxy silane in methyl alcohol and makes its hydrolysis become silanol.
6. a kind of modifying super hydrophobicity yak hair according to claim 2, is further characterized in that: the fiber that this mao of wool fabric is yak hair, suede class is made.
7. a kind of modifying super hydrophobicity yak hair according to claim 2, is further characterized in that: this mao of wool fabric has good water resistance, and its surface contact angle should be greater than 120
o.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104947425A (en) * | 2015-07-10 | 2015-09-30 | 成都市龙华新科技有限公司 | Preparation method for novel modified yak plush products |
| CN104975500A (en) * | 2015-07-10 | 2015-10-14 | 成都市龙华新科技有限公司 | Method for carrying out surface modification on woolen fabric by using cetyl |
| CN105463843A (en) * | 2015-11-30 | 2016-04-06 | 无锡新德印染制品有限公司 | Preparation method of waterproof woolen fabric |
| CN111877004A (en) * | 2020-06-18 | 2020-11-03 | 西藏圣信工贸有限公司 | Surface-modified wear-resistant yak hair fabric |
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| CN103147290A (en) * | 2013-03-07 | 2013-06-12 | 中国科学院上海应用物理研究所 | Functional nano textile and preparation method thereof |
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| CN1824884A (en) * | 2005-02-25 | 2006-08-30 | 中科纳米技术工程中心有限公司 | Self-cleaning suiting containing nano-functional material and method for making garment products |
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| CN104947425A (en) * | 2015-07-10 | 2015-09-30 | 成都市龙华新科技有限公司 | Preparation method for novel modified yak plush products |
| CN104975500A (en) * | 2015-07-10 | 2015-10-14 | 成都市龙华新科技有限公司 | Method for carrying out surface modification on woolen fabric by using cetyl |
| CN105463843A (en) * | 2015-11-30 | 2016-04-06 | 无锡新德印染制品有限公司 | Preparation method of waterproof woolen fabric |
| CN111877004A (en) * | 2020-06-18 | 2020-11-03 | 西藏圣信工贸有限公司 | Surface-modified wear-resistant yak hair fabric |
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Application publication date: 20141015 |