CN1730732A - Montmorillonite-acrylic acid series nanometer textile glue size and its preparation method - Google Patents
Montmorillonite-acrylic acid series nanometer textile glue size and its preparation method Download PDFInfo
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- CN1730732A CN1730732A CN 200510021353 CN200510021353A CN1730732A CN 1730732 A CN1730732 A CN 1730732A CN 200510021353 CN200510021353 CN 200510021353 CN 200510021353 A CN200510021353 A CN 200510021353A CN 1730732 A CN1730732 A CN 1730732A
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Abstract
The present invention is nanometer montmorillonite-acrylic acid line textile size and its preparation process. The present invention features that sodium-base montmorillonite 1-3 weight portions, the first monomer 6-30 weight portions, the second monomer 0-24 weight portions, molecular weight regulator 0.01-0.1 weight portions and water 65-79 weight portions are ultrasonic vibrated in ultrasonic vibrator of powder 50-8000 W and frequency 10-60 KHz for 10-40 min to realize insertion of monomers to montmorillonite; and initiator in 0.05-0.2 weight portions is then introduced for free radical polymerization at 60-90 deg.c for 3-8 hr to increase the interlaminar interval and interlaminar peeling of montmorillonite to form nanometer particles. Selecting different monomer combination can obtain various kinds of montmorillonite-acrylic acid line textile size with different glass transition temperatures or different polarity for sizing cotton or polyester/cotton warp.
Description
One, technical field
The present invention relates to a kind of montmorillonite-acrylic acid series nanometer textile glue size and preparation method thereof, belong to the spinning sizing agent field.
Two, background technology
In spinning sizing agent, add the existing long history of inorganic particulate.Talcum powder is inorganic filler commonly used in the slurry, very little with the effect of slurry matrix, only play diluting effect, can increase serous coat rigidity and ABRASION RESISTANCE and reduce cost, but will make the intensity decreases of material, the interface of filler and high polymer will become stress concentration point, cause crazing and crackle under stress, and fatigue behaviour also descends; Because general talcum powder particle is thick, and sharp-pointed protrusion is arranged in serous coat, causes the wearing and tearing of warp thread to loom easily; And talcum powder bursts apart after stressed easily, causes the brittle fracture of serous coat; In addition, thick talcum powder and slurry matrix bond are loose, and coming off easily to become is mingled with, and causes abrasive wear in friction pair, also cause the loom wearing and tearing.Therefore, after the eighties in last century, the domestic talcum powder of in the prescription of sizing fabric, having eliminated substantially.
The layer aluminosilicate clay if you would take off soil, attapulgite, sepiolite etc., has nano level layer structure, is the inorganic particulate of the current suitable preparation polymer nanocomposites of finding.Wherein the layer structure of imvite is 2: 1 types, and promptly two-layer silicon-oxy tetrahedron wafer therebetween layer of aluminum oxygen octahedra wafer constitutes unit layer, the about 1nm of its crystal layer thickness, the about 100nm of planar dimension; The imvite crystal layer is oxygen atom up and down, and hydrone enters easily and causes lattice dilatation between the crystal layer; Some metallic atom is replaced by the different metallic atom of other chemical valences in its lattice structure, as the part Si in its tetrahedral structure
4+By Al
3+Replace, or the part A l in its octahedral structure
3+By Mg
2+, Fe
2+, Zn
2+Deng replacement, although its lattice framework remains unchanged, the crystal lamella has produced negative electrical charge, and the CATION that this negative electrical charge can adsorb in the solution on every side reaches charge balance.In the aqueous solution, the CATION of aquation enters between the crystal layer, causes its interlamellar spacing to become big.During the molecular separating force sphere of action, imvite generation disintegration is peeled off between interlamellar spacing increases to above crystal layer, generates the inorganic nano-particle of the about 1nm of lamellar spacing.
Since Japanese Toyota research group in 1987 has at first synthesized the PA6/ Nano composite material of montmorillonite with the intercalation polymeric method, novel nano composite study and product development progress that polymer-matrix contains phyllosilicate, other nano inoganic particles or metal nanoparticle are rapid, and its practical application almost relates to the Application Areas of all high polymers.Polymer based nanocomposites successfully is applied to a lot of engineering materials, almost comprises all spectra that macromolecule is used.Yet regrettably, do not see the bibliographical information that in spinning sizing agent, uses Nano composite material of montmorillonite so far at home and abroad yet.
Starch in the employing sodium bentonite replacement spinning sizing agent is as spinning sizing agent, combine washing/the cotton or existing report of textile warp sizing with chemical sizwe and synthetic slurry, Chinese patent 97105059.7 and 93111225.7 discloses the technology of Yarn sizing powder, relate to the slurry that yarn sizing is used, they adopt bentonite and tertiary sodium phosphate, polyvinyl alcohol, carboxymethyl cellulose, mixing such as potassium permanganate and bisnaphthol with resource bentonite replacement widely or part substituted starch, reduces the starching cost; Chinese patent 00102488.4 discloses the employing sepiolite or kaolin mixes warp sizing with polyvinyl alcohol, starch etc.The common feature of these patented technologies is that clay of laminar silicate is directly mixed mashing off with other slurries and auxiliary agent.In this case, be difficult to guarantee that clay is dissociated into nanometer inorganic in the process of sizing mixing, these thicker inorganic particulates are similar to the talcum powder in traditional sizing in serous coat, and it is few to improve sizing performance, even play the effect that worsens sizing performance sometimes.Chinese patent 02122376.9 has been reported a kind of size composition for textile that contains converted starch and special-purpose nano material, wherein converted starch 20～90%, special-purpose nano material (SiO#-[2], TiO#-[2], Al#-[2] O#-[3] or ZrO#-[2]) 0.05～5%, this size composition for textile has reduced difficulty of weaving to high-count and high-density degree fabric; Chinese patent 03142084.2 discloses another kind of nanometer sizing auxiliary agent, it is by the ultra micro inorganic particulate that accounts for gross weight 1～50%, as SiO#-[2], TiO#-[2], Al#-[2] O#-[3], ZnO or ZrO#-[2], accounting for the dispersant phosphate of gross weight 0.1～10% and the water of surplus forms, this auxiliary agent uses in textile sizing, to the cotton yarn can be fully without polyvinyl alcohol, to cotton wash or the polyester-cotton blend yarn can be more than 1 to 10 replacing for polyvinyl alcohol, be particularly suitable for the production of high-count and high-density fabric; Chinese patent 00110863.8 discloses a kind of fabric size, and it is the composition of a kind of nanoscale colloidal sol and general slurry, and both percentage by weights are 3～5: 1, and the enhancing rate of yarn is 10～15% after the starching.Obviously, these three patents of invention are the difference of essence not, all adopt metal oxide or insoluble inorganic salts nano material directly to join in the conventional formula of size, they are better than the direct mixture of clay and slurry to the improvement degree of sizing performance, but because the commodity price costliness of inorganic nano-particle has hindered them by promotion and application widely.
Three, summary of the invention
The objective of the invention is to propose a kind of montmorillonite-acrylic acid series nanometer textile glue size and preparation method thereof at the deficiencies in the prior art, this size performance is good, and cost is low, can improve the warp sizing performance significantly.
The present inventor selects the predecessor of sodium-based montmorillonite as nano particle for use, mainly based on following reason: 1. China's imvite aboundresources, the sodium-based montmorillonite price has only 1/5 of ative starch, have only 1/50～1/30 of acrylic monomer, can reduce cost of sizing agent significantly as one of component of slurry; 2. sodium-based montmorillonite itself has the natural nano structure, the hydrating capacity height, the mud yield height, suspended dispersed in water easily, sodium ion wherein is easy to by other cation exchange, even neutrality has the organic molecule of polarity also can immerse by the intermediary water that replaces imvite between the lamella of imvite, therefore adopt water-soluble or the easy intercalation of realizing imvite of polar polymer monomer.
The present inventor adopts acrylamide, acrylic acid and esters monomer thereof, in the presence of imvite, pass through free radicals copolymerization reaction synthesis of nano slurry, after water-soluble or polar monomer is to montmorillonite intercalation, under the initator effect, produce free radical in-situ polymerization can take place, enlarge the interlamellar spacing of imvite, even can synthesize the exfoliated montmorillonite-based nano spinning sizing agent of lamella, the resulting product of the inventive method has been separated into nano-scale for transparence suffices to show that imvite at thickness direction after the film forming.Adopt acrylic monomer except easy realization to the montmorillonoid in-situ intercalation polymeric, can also be easily combination by different monomers, obtain the different glass temperature, or the acrylic acid series slurry of opposed polarity, with the starching of the fiber yarn that is adapted to opposed polarity; Compare with polyvinyl alcohol, acrylic acid series water solubility copolymer intermolecular force a little less than, contain a large amount of N, O hetero atom in the Polymer Structure, the biological attack of easier quilt and degrading.By the intermolecular interaction of montmorillonite-based nano lamella and polymer-matrix in the nano pulp of the present invention, the moisture absorption that can reduce the acrylic acid series slurry is viscosity again, increase the brute force and the toughness of serous coat, therefore can substitute or partly substitute the disadvantageous polyvinyl alcohol pulp of environment.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of montmorillonite-acrylic acid series nanometer textile glue size is:
1～3 part of sodium-based montmorillonite
6～30 parts of I monomers
0～24 part of II monomer
0.05～0.2 part of initator
0.01～0.1 part of molecular weight regulator
65～79 parts of soft water
Wherein, sodium-based montmorillonite is required to inhale blue amount 〉=30g/100g soil, granularity≤127 μ m, whiteness 〉=70%, moisture 8～12%.The sodium-based montmorillonite consumption accounts for 3～15% of nano pulp solid part of the present invention.
The I monomer is at least a in acrylic acid, acrylamide and the methacrylic acid, adds these monomers and guarantees the water-soluble of slurries, so that starching and destarch; The II monomer is at least a in methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinylacetate, acrylonitrile and the styrene, makes nano pulp have adhesion, vitrification point and the physical and mechanical properties that adapts to different fiber yarns.
Initator is any in ammonium persulfate, potassium peroxydisulfate or the sodium peroxydisulfate, and they have similar initiation usefulness.
Molecular weight regulator is lauryl mercaptan or mercaptoethanol.
The preparation method of montmorillonite-acrylic acid series nanometer textile glue size:
(1) at room temperature sodium-based montmorillonite 1～3 weight portion, water 20～60 weight portions are joined in the dissolution kettle that has agitator, stir, add I monomer 6～30 weight portions, II monomer 0～24 weight portion, molecular weight regulator 0.01～0.1 weight portion, it is standby to stir;
(2) above-mentioned mixed liquor is joined in the container of ultrasonic oscillation device, start the ultrasonic oscillation device, concussion power 50～8000W, concussion frequency 10～50kHz, ultrasonic Treatment 10～40 minutes;
(3) 1/3～1/6 of imvite-monomer mixed solution total amount that said method is handled, water 10～30 weight portions join and have agitator, in the reactor of thermometer and reflux condenser, initator 0.05～0.2 weight portion water 8～10 weight portions are dissolved, 1/6～1/2 of its total amount is joined in the above-mentioned reactor, in 65～90 ℃ of temperature, in 1～3 hour, drip residue imvite-monomer mixed solution and initiator solution continuously, dropwise simultaneously until monomer and initator, keep 80～90 ℃ of temperature, continue reaction 2～5 hours, under vacuum 50～200mmHg, vacuumize and removed residual monomer in 30 minutes, be cooled to 50 ℃, regulate pH=7～8 with ammoniacal liquor, obtain montmorillonite-acrylic acid series nanometer textile glue size.
The nano pulp of patent of the present invention is yellowish-brown thick liquid or stiff slurry, the monomer-free smell, and solid content 20～35%, pH=7～8,10% solution viscosity, 10～25mPas under 25 ℃, film forming is transparent, and smooth surface is soluble in water; 30～106 ℃ of the high molecular vitrification points of slurry are preferably in 40～60 ℃.In textile and wash/cotton chain sizing instruction, replace traditional acrylic acid series slurry and part polyethylene alcohol slurry.
Four, the specific embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
The recipe ingredient of embodiment is detailed to be shown in Table 1.
The preparation method is that example is described with embodiment 1: with the sodium-based montmorillonite in the above prescription with 30 weight parts water dispersed with stirring, the acrylamide, acrylic acid, methyl acrylate and the mercaptoethanol that add metering respectively, dissolving evenly, putting into the ultrasonic wave container handled 30 minutes under 50kHz, 5000W condition, adding entry 28.5 weight portions again stirs, with the reactor head tank of pump suction belt stirrer and reflux condenser, under agitation 1/5 of its mixing material is put in the reactor.The ammonium persulfate of metering dissolves with 8 weight parts waters, and it 1/3 is joined in the reactor.Under agitation,, in 2 hours, drip monomer and initator continuously, dropwise simultaneously, keep 80 ℃ of reactions of temperature 2 hours, under vacuum 100mmHg, vacuumize and removed residual monomer in 20 minutes, be cooled to 50 ℃ until monomer and initator in 80 ℃ of temperature.Regulate pH=7～8 with ammoniacal liquor, stir, product screen filtration barrelling.
The preparation method of embodiment 2～5 is identical with embodiment 1.According to the raw material of selecting for use, suitable adjusting process parameter.
Application example 1:
The nano pulp of embodiment 1 is applied to wash/cotton chain, fabric specification is T65/JC35 13 * 13tex, 433.0 * 299.1,160cm washs/cotton fine cloth, can replace in the original formulation 50% polyvinyl alcohol (PVA), and no longer need common acrylic acid series slurry (methyl acrylate paste), the prescription contrast is as shown in table 2.
Slurries are not stratified, and low temperature is not tied laitance coating, no slime spots, and the sizing smooth surface, cloth machine opening is clear, and weaving efficiency brings up to 90.2% by 85.7% of original formulation.
Application example 2:
The nano pulp of embodiment 2 is applied to textile warp thread, fabric specification is JC 14.5 * 14.5tex, 523.5 * 283.0,119.5cm textile poplin cloth, can replace in the original formulation 1/3 polyvinyl alcohol (PVA), and no longer need common acrylic acid series slurry (methyl acrylate paste), the prescription contrast is as shown in table 3.
According to the sizing effect contrast of above original formulation and application example 2 prescriptions, the slime spots grey cloth reduces to 0.31% by 0.7% of original formulation, when the cloth machine breaks end by 2.301/platform of original formulation, when reducing to 0.87/platform.
The prescription of table 1 embodiment and technological parameter
| Prescription (weight portion) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Sodium-based montmorillonite | 1.5 | 3.0 | 1.0 | 2.5 | 2.0 | |
| The I monomer | Acrylic acid 2.4 acrylamides 9.0 | Acrylic acid 2.0 acrylamides 10.5 | Methacrylic acid 20.0 | Acrylamide 25.0 | Acrylic acid 10.5 | |
| The II monomer | Methyl acrylate 17.1 | Ethyl acrylate 10.0 | Butyl methacrylate 15.0 | Acrylonitrile 5.0 styrene 1.0 | Vinylacetate 12.5 | |
| Molecular weight regulator | Lauryl mercaptan 0.1 | Mercaptoethanol 0.08 | Mercaptoethanol 0.05 | Mercaptoethanol 0.1 | Lauryl mercaptan 0.08 | |
| Initator | Ammonium persulfate 0.15 | Potassium peroxydisulfate 0.1 | Sodium peroxydisulfate 0.15 | Ammonium persulfate 0.1 | Potassium peroxydisulfate 0.2 | |
| Water | 66.5 | 72.5 | 68.5 | 72.5 | 65.0 | |
| Concussion | Power (W) | 5000 | 5500 | 4000 | 4500 | 6000 |
| Frequency (kHz) | 50 | 40 | 60 | 55 | 40 | |
| Time (min) | 30 | 35 | 20 | 25 | 40 | |
| Reaction temperature (℃) | 80 | 82 | 85 | 88 | 70 | |
| Reaction time (h) | 4 | 5 | 4.5 | 6 | 7.5 | |
| The pH value | 7.5 | 7.0 | 7.2 | 6.8 | 7.2 | |
The sizing prescription of table 2 embodiment 1
| Prescription | PVA/kg | Oxidized starch/kg | Methyl acrylate paste/kg | Emulsification butter/kg | Embodiment 1 nanometer slurry | Preservative agent/m | Slurry volume/M 3 |
| Original formulation | 50 | 25 | 20 | 8 | - | 150 | 0.7 |
| Application example 1 | 25 | 40 | - | 8 | 50 | 150 | 0.7 |
The sizing prescription of table 3 embodiment 2
| Prescription | PVA/kg | Esterification starch/kg | Methyl acrylate paste/kg | Emulsification butter/kg | Embodiment 2 nanometers slurry | Preservative agent/ml | Slurry volume/M 3 |
| Original formulation | 30 | 50 | 36 | 13 | - | 250 | 1 |
| Application example 2 | 20 | 53 | - | 13 | 50 | 250 | 1 |
Claims (7)
1, a kind of preparation method of montmorillonite-acrylic acid series nanometer textile glue size is characterized in that the recipe ingredient of this nanometer textile glue size is by weight:
1～3 part of sodium-based montmorillonite
6～30 parts of I monomers
0～24 part of II monomer
0.05～0.2 part of initator
0.01～0.1 part of molecular weight regulator
65～79 parts of soft water
This nanometer textile glue size prepares as follows:
(1) at room temperature sodium-based montmorillonite 1～3 weight portion, water 20～60 weight portions are joined in the dissolution kettle that has agitating device, stir, add I monomer 6～30 weight portions, II monomer 0～24 weight portion, molecular weight regulator 0.01～0.1 weight portion, it is standby to stir;
(2) above-mentioned mixed liquor is joined in the container of ultrasonic oscillation device, start the ultrasonic oscillation device, concussion power 50～8000W, concussion frequency 10～60kHz, ultrasonic Treatment 10～40 minutes;
(3) 1/3～1/6 of imvite-monomer mixed solution total amount that said method is handled, water 10～30 weight portions join in the reactor that has agitator, thermometer and reflux condenser; With the dissolving of initator 0.05～0.2 weight portion water 8～10 weight portions, 1/6～1/2 of its total amount is joined in the above-mentioned reactor; In 65～90 ℃ of temperature, in 1～3 hour, drip residue imvite-monomer mixed solution and initiator solution continuously, dropwise simultaneously until monomer and initator, keep 80～90 ℃ of temperature, continue reaction 2～5 hours, under vacuum 50～200mmHg, vacuumize and removed residual monomer in 30 minutes, be cooled to 50 ℃, regulate pH=7～8 with ammoniacal liquor, obtain montmorillonite-acrylic acid series nanometer textile glue size.
2, the preparation method of montmorillonite-acrylic acid series nanometer textile glue size according to claim 1 is characterized in that the blue amount 〉=30g/100g soil of suction of sodium-based montmorillonite, granularity≤127 μ m, whiteness 〉=70%, moisture 8～12%.
3, the preparation method of montmorillonite-acrylic acid series nanometer textile glue size according to claim 1, it is characterized in that the I monomer is at least a in acrylic acid, acrylamide and the methacrylic acid, the II monomer is at least a in methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinylacetate, acrylonitrile and the styrene.
4, the preparation method of montmorillonite-acrylic acid series nanometer textile glue size according to claim 1 is characterized in that molecular weight regulator is lauryl mercaptan or mercaptoethanol.
5, the preparation method of montmorillonite-acrylic acid series nanometer textile glue size according to claim 1 is characterized in that initator is a persulfate.
6, the montmorillonite-acrylic acid series nanometer textile glue size for preparing of method according to claim 1.
7,, it is characterized in that this nanometer textile glue size can be used to wash/cotton or textile warp sizing as the purposes of montmorillonite-acrylic acid series nanometer textile glue size as described in the claim 6.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422428C (en) * | 2006-11-09 | 2008-10-01 | 江苏南大紫金科技集团有限公司 | Preparation method of nano-textile sizing agent adjuvant |
| CN101864023A (en) * | 2010-05-25 | 2010-10-20 | 武汉理工大学 | Preparation process of poly-fluorine-containing acrylic ester/ montmorillonite composite emulsion |
| CN101429727B (en) * | 2008-12-22 | 2010-12-08 | 四川大学 | Two-component acrylic acid series polymer/montmorillonite nano composite spinning sizing agent and its preparation method |
| CN102653922A (en) * | 2012-06-04 | 2012-09-05 | 洛阳常龙化工科技发展有限公司 | Starch slurry with acrylic ester copolymer block and preparation method thereof |
| CN103242490A (en) * | 2013-05-03 | 2013-08-14 | 张家港市黎明化工有限公司 | Sulfhydryl-double bond reaction-based acrylate ester/montmorillonite composite and preparation method |
| CN103898762A (en) * | 2013-03-19 | 2014-07-02 | 常州纺织服装职业技术学院 | Size for textile sizing and preparation method of size |
Family Cites Families (1)
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| CN1143868C (en) * | 2001-10-26 | 2004-03-31 | 中国科学院长春应用化学研究所 | In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material |
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- 2005-07-29 CN CNB2005100213530A patent/CN100339533C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422428C (en) * | 2006-11-09 | 2008-10-01 | 江苏南大紫金科技集团有限公司 | Preparation method of nano-textile sizing agent adjuvant |
| CN101429727B (en) * | 2008-12-22 | 2010-12-08 | 四川大学 | Two-component acrylic acid series polymer/montmorillonite nano composite spinning sizing agent and its preparation method |
| CN101864023A (en) * | 2010-05-25 | 2010-10-20 | 武汉理工大学 | Preparation process of poly-fluorine-containing acrylic ester/ montmorillonite composite emulsion |
| CN102653922A (en) * | 2012-06-04 | 2012-09-05 | 洛阳常龙化工科技发展有限公司 | Starch slurry with acrylic ester copolymer block and preparation method thereof |
| CN102653922B (en) * | 2012-06-04 | 2014-03-12 | 洛阳常龙化工科技发展有限公司 | Starch slurry with acrylic ester copolymer block and preparation method thereof |
| CN103898762A (en) * | 2013-03-19 | 2014-07-02 | 常州纺织服装职业技术学院 | Size for textile sizing and preparation method of size |
| CN103242490A (en) * | 2013-05-03 | 2013-08-14 | 张家港市黎明化工有限公司 | Sulfhydryl-double bond reaction-based acrylate ester/montmorillonite composite and preparation method |
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