CN102493192A - Spinning size and preparation method thereof - Google Patents
Spinning size and preparation method thereof Download PDFInfo
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- CN102493192A CN102493192A CN2011104148057A CN201110414805A CN102493192A CN 102493192 A CN102493192 A CN 102493192A CN 2011104148057 A CN2011104148057 A CN 2011104148057A CN 201110414805 A CN201110414805 A CN 201110414805A CN 102493192 A CN102493192 A CN 102493192A
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- 238000009987 spinning Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920002472 Starch Polymers 0.000 claims abstract description 49
- 239000007908 nanoemulsion Substances 0.000 claims abstract description 43
- 239000008107 starch Substances 0.000 claims abstract description 41
- 235000019698 starch Nutrition 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 238000004513 sizing Methods 0.000 claims description 40
- 241000196324 Embryophyta Species 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 235000019890 Amylum Nutrition 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229940117958 vinyl acetate Drugs 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 5
- 229960003237 betaine Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 5
- 239000008267 milk Substances 0.000 claims description 5
- 210000004080 milk Anatomy 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- -1 sodium alkyl benzene Chemical class 0.000 claims description 5
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 230000021736 acetylation Effects 0.000 claims description 4
- 238000006640 acetylation reaction Methods 0.000 claims description 4
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 4
- 238000006011 modification reaction Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002261 Corn starch Polymers 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 229940099112 cornstarch Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000009990 desizing Methods 0.000 abstract 1
- 239000011118 polyvinyl acetate Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 19
- 238000009413 insulation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004753 textile Substances 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses spinning size and a preparation method thereof. The spinning size comprises modified plant starch which is obtained by performing graft modification of plant starch and graft monomers, and nano emulsion, wherein the nano emulsion is a liquid phase system of polymer which is formed by reacting composite emulsifier, a dispersing agent, a composite monomer, and an initiator in 100 weight parts of water. During preparation, the modified plant starch and the nano emulsion which are used as raw materials are fully mixed uniformly; and the nano emulsion can be obtained by the steps of adding the composite monomer and the initiator into mixture of the composite emulsifier, the dispersing agent, and water, and then performing polymerization. The spinning size has a wide application range, the size obtained after size mixing is high in affinity and permeability and degradability, and is good in stable adhesion performance, film-forming performance, and desizing performance, and a half amount of the size can completely replace polyvinyl acetate (PVA).
Description
Technical field
The present invention relates to the slurry that starching is used in a kind of process of textile production, and the preparation method of this slurry.
Background technology
The existing long history of warp sizing technology during weaving is produced, thereby spinning sizing agent is widely used in the warp thread process.PVA (polyvinyl alcohol) once was the indispensable sizing raw material of textile industry; But because of its cost height; And the environmental pollution that can not degrade and bring, can not adapt at present and improved constantly with economic development and textile industry level, and to the requirements at the higher level of energy-saving and emission-reduction and environmental protection in the weaving processing.Because the spinning sizing agent of single prescription often is difficult to satisfy the multinomial quality requirements of sizing process, to existing at present many researchs of the composite mortar that contains multiple composition and report.
The CN101597861A document provides a kind of composite textile pulp by nanometer polymer emulsion, employing be in polymer emulsion, to introduce the spinning sizing agent that nano silicon forms nanometer polymer emulsion.A kind of spinning sizing agent of being made up of the plant amylum and the nanoemulsions of graft modification has been proposed in the CN101550658A document.Because the nanoemulsions performance of different composition forms has than big-difference; The concrete form of the not clear and definite wherein used nanoemulsions of the document, and in the slurry of its preparation, also used the polyester slurry of significant proportion amount, thus can make particle particle aggregation in the slurry, become big; Permeability variation to warp thread; Serous coat thickening and coarse causes its process for preparation comparatively complicated, and it is bigger to control difficulty; Be difficult to accurate grasp, all be difficult to satisfy fully demand of practical production aspect many in the design of the prescription of the process of sizing mixing and the control of sizing mixing etc.
Summary of the invention
To above-mentioned situation, the present invention at first provides a kind of spinning sizing agent, and further the preparation method of this spinning sizing agent is provided also, can address the above problem satisfactorily.
In the spinning sizing agent of the present invention; Used equally as in the above-mentioned CN101550658A document by the improved plant starch after plant amylum and the grafted monomers graft modification; And the nanoemulsions composition, composition form is: improved plant starch 10 ~ 15 weight portions, nanoemulsions 20 weight portions.Wherein, said nanoemulsions by in the water of 100 weight portions by following ingredients reaction the liquid-phase system of one-tenth polymer:
Compound emulsifying agent 2 ~ 4 weight portions,
Dispersant 1 ~ 2 weight portion,
Compound monomer 30 ~ 40 weight portions,
Initator 0.2 ~ 0.3 weight portion.
In the composition of above-mentioned nanoemulsions, said compound emulsifying agent is the mixture by polyethers sodium sulphate 1 weight portion, sodium alkyl benzene sulfonate 0.8 ~ 1.2 weight portion, methyl sodiosul foaliphatate 0.5 ~ 0.7 weight portion and betaine 0.8 ~ 1.2 weight portion;
Dispersant be the degree of polymerization be 1000 with alcoholysis degree be 99% polyvinyl alcohol (can select commercial goods or preparation voluntarily for use);
Compound monomer is the mixed liquor of being made up of methyl acrylate 1 weight portion, butyl acrylate 2.6 ~ 3.2 weight portions, styrene 1.1 ~ 1.2 weight portions, methacrylic acid 1.1 ~ 1.2 weight portions;
Initator is at least a in ammonium persulfate, sodium peroxydisulfate, sodium hydrogensulfite, sodium thiosulfate, ammonium ceric nitrate, the ferrous nitrate ammonium.
Preferably, the polymer in the above-mentioned said nanoemulsions is the droplet of particle diameter≤50nm.
Spinning sizing agent of the present invention can be the homogeneous mixture by said improved plant starch and nanoemulsions.
The basic preparation method of the above-mentioned form spinning sizing agent of the present invention, can be with said improved plant starch and the full and uniform mixing of nanoemulsions raw material.Wherein, said nanoemulsions can adopt following manner to prepare:
1': in mixture by said compound emulsifying agent 2 ~ 4 weight portions and dispersant 1 ~ 2 weight portion and 100 weight parts waters; In 60 ~ 66 ℃ with stirring condition under; The aqueous solution of the 15 ~ 25w% that drips 30 ~ 40 weight portion compound monomers and be mixed with by 0.2 ~ 0.3 weight portion initator
2': the mixed material system after adding is after carrying out polymerisation under 70 ℃ ~ 80 ℃ conditions; Regulate pH value 8 ~ 8.5; Obtain to be used for preparing the nanoemulsions of spinning sizing agent after the filtration, or further become the solid product that can be used for the preparation of nano emulsion after the drying with said improved plant starch.
Prepare in the process at above-mentioned nanoemulsions, further optimal way can also have respectively:
, preferably be adopted as earlier and be uniformly mixed into said mixture at 35 ℃ ~ 40 ℃ in the step at said 1' by said compound emulsifying agent and dispersant and water, be warming up to then said temperature and with stir under adding compound monomer and initiator solution.Result of the test shows, the mode that adopts segmentation and/or heat up gradually can help the more good dissolving of emulsifying agent and dispersant.
In step, said polymerization reaction time is 3 ~ 4 hours at 2'.
In actual the enforcement, above-mentioned optimal way can single employing or is adopted jointly with associated form.
Except that nanoemulsions; Improved plant starch in the said raw material; Can directly adopt as provide in the above-mentioned CN101550658A document by the improved plant starch after plant amylum and the grafted monomers graft modification; Or the corresponding improved plant starch that adopts the mode with the document to prepare, its basic preparation method is:
1': plant amylum and deionized water are mixed with the starch milk of 25 ~ 40w%, react under the condition of 30 ~ 40 ℃ and pH=7 ~ 9 with the acetylation composition again, obtain acetate starch;
2': acetate starch and grafted monomers and the initator that will go up the step collected solid constituent after carrying out the graft modification reaction 40 ~ 60 ℃ and pH=7 ~ 9, is said improved plant starch product.
Wherein, said plant amylum comprises any in cornstarch, tapioca, the wheaten starch; The acetylation composition is at least a in acetic acid, acetic anhydride, the vinyl acetate; Grafted monomers is at least a in acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, vinylacetate, styrene, methacrylic acid, the methyl methacrylate; Initator is at least a in ammonium persulfate, sodium peroxydisulfate, sodium hydrogensulfite, sodium thiosulfate, ammonium ceric nitrate, the ferrous nitrate ammonium.
As preferably, in above-mentioned graft modification reaction, be 100 weight portion timing with the consumption of acetate starch, used grafted monomers is 8 ~ 30 weight portions, initator is 0.5 ~ 2 weight portion.
Result of the test shows that the present invention through the spinning sizing agent that this particular form nanoemulsions co-formulated with said ratio obtains, can obtain good and satisfied effect on the improved plant starch basis of adopting the same form of aforementioned documents.Because compound emulsifying agent and dispersant among the present invention in said this nanoemulsions can make each copolymerization component in the preparation process, reach nanoscale; Can help it with the compound preparation of improved plant starch the time, can permeate more fully in wherein; Thereby help performance synergy better between each component, make slurry have more excellent performance.Particularly when the droplet of polymer was particle diameter≤50nm, the particle diameter of its droplet in the nanoemulsions system was very little, and to the infiltration of yarn diffusion inside, sizing uniformity, the rate of sizing, and serous coat is level and smooth and aspect such as pliability all is superior to common spinning sizing agent.Because it can also also save use polyester paste composition, has further practiced thrift cost.Spinning sizing agent applied range of the present invention, the compatibility of the rear slurry of sizing mixing, permeance property are good, and good sticking stability ability, filming performance, destarch performance and degradability are arranged, and can realize fully in the use replacing PVA fully with half amount.
Below again foregoing of the present invention is done further to specify through the specific embodiment of embodiment.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following instance.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
The specific embodiment
Embodiment 1
The preparation of nanoemulsions: 170g water is stirred intensification; In the time of 35 ~ 37 ℃, add 3.6g compound emulsifying agent (polyethers sodium sulphate 1g, sodium alkyl benzene sulfonate 1g, methyl sodiosul foaliphatate 0.6g and betaine 1g) and 1.7g dispersant (degree of polymerization is 1000, alcoholysis degree is 99% polyvinyl alcohol); Continue to stir and be warming up to 60 ℃; Temperature control Dropwise 5 0g compound monomer (methyl acrylate 8g, butyl acrylate 24g, styrene 9g, methacrylic acid 9g) and initiator solution (being mixed with by 0.4g ammonium persulfate and 3.5g water) dripped off in about 1 hour simultaneously.Dropwise 75 ℃ of hierarchies of control reaction 3.5 hours, regulation system pH value is 8, filters after being cooled to the temperature of being convenient to operate, and obtains the about 230g of nanoemulsions.
100g cornstarch and deionized water 200g added be mixed with 33% starch milk in the reactor that has agitator and thermometer, 35 ℃ of temperature, dropping 6g acetic acid; Control pH7 ~ 8; Dropwise the back insulation reaction 2 hours, and then, be warming up to 50 ℃; With 1 hour dropping 15g mix monomer (butyl acrylate 9g, styrene 3g, acrylic acid 3g); Drip initiator solution 16.5g (ammonium persulfate 1.2g, sodium hydrogensulfite 0.3g, water 15g) with another feeder simultaneously, insulation reaction 4 hours is filtered.
Above-mentioned nanoemulsions and improved plant starch are fully mixed down at 60 ℃, dry, pulverize the nanoemulsions composite modified starch spinning sizing agent of the usefulness of sizing mixing when obtaining supplying to spin.
Embodiment 2
The preparation of nanoemulsions: 180g water is stirred intensification; In the time of 35 ~ 40 ℃, add 7.2g compound emulsifying agent (polyethers sodium sulphate 2g, sodium alkyl benzene sulfonate 2g, methyl sodiosul foaliphatate 1.2g and betaine 2g) and 3.6g dispersant (degree of polymerization is 1000, alcoholysis degree is 99% polyvinyl alcohol); Continue to stir and be warming up to 60 ℃; The beginning temperature control drips 72g compound monomer (methyl acrylate 12g, butyl acrylate 32g, styrene 14g, methacrylic acid 14g) and initiator solution (by 0.54g ammonium persulfate and the preparation of 10g water), drips off in about 1.5 hours.Dropwise 70 ℃ of reactions of the hierarchy of control 4 hours, regulation system pH value is 8, and cooling is filtered, and promptly gets the about 260g of nanoemulsions.
100g tapioca and deionized water 300g added be mixed with 25% starch milk in the reactor that has agitator and thermometer, 40 ℃ of temperature, dropping 2g acetic anhydride; Control pH7.5 ~ 8.5; Dropwise the back insulation reaction 4 hours, and then, be warming up to 60 ℃; With 1 hour dropping 30g mix monomer (butyl acrylate 10g, vinylacetate 14g, methacrylic acid 6g); Drip initiator solution 15.5g (ammonium persulfate 0.3g, ammonium ceric nitrate 0.2g, water 15g) with another feeder simultaneously, insulation reaction 3 hours is filtered.
Above-mentioned nanoemulsions and improved plant starch are fully mixed under 50 ℃, dry, pulverize, get operational nanoemulsions composite modified starch spinning sizing agent.
Embodiment 3
The preparation of nanoemulsions: 130g water is stirred intensification; In the time of 35 ℃, add 4g compound emulsifying agent (polyethers sodium sulphate 1.1g, sodium alkyl benzene sulfonate 1.1g, methyl sodiosul foaliphatate 0.7g and betaine 1.1g) and 2g dispersant (degree of polymerization is 1000, alcoholysis degree is 99% polyvinyl alcohol); Continue to stir and be warming up to 60 ℃; The beginning temperature control drips 45g compound monomer (methyl acrylate 7g, butyl acrylate 22g, styrene 8g, methacrylic acid 8g) and initiator solution (by 0.26g ammonium persulfate and the preparation of 4g water), drips off in about 1.2 hours.Dropwise 80 ℃ of reactions of the hierarchy of control 3 hours, regulation system pH value is 8, and cooling is filtered, and promptly gets the about 177g of nanoemulsions.
100g wheaten starch and deionized water 150g are added be mixed with 40% starch milk in the reactor of belt stirrer and thermometer, 30 ℃ of temperature, the mixture of dropping 4g acetic anhydride and 8g vinylacetate; Control pH8 ~ 9; Dropwise the back insulation reaction 3 hours, and then, be warming up to 40 ℃; With 1 hour dropping 8g mix monomer (styrene 2g, ethyl acrylate 2g, methacrylic acid 2g, butyl acrylate 2g); Drip initiator solution 17g (ammonium persulfate 1.5g, sodium thiosulfate 0.5g, water 15g) with another feeder simultaneously, insulation reaction 5 hours is filtered.
With above-mentioned nanoemulsions and improved plant starch fully mix down at 50 ℃, oven dry, pulverize, obtain supplying the nanoemulsions composite modified starch spinning sizing agent of sizing mixing and using.
Slurry with the above-mentioned embodiment of the invention is as shown in table 1 with existing multi-form slurry carries out sizing after the reality preparation contrast and experiment.Yarn variety wherein is: 65 " T/C 65/35 45s * 45s 133 * 70." document prescription " in the table is from " the highly dense kind of polyester-cotton blend is used the craft discussion of PVA starching less " literary composition in " national slurry and sizing technology 2011 can "; " document control formula " wherein is the slurry that this article is recommended for using the existing conventional formula of size that compares, " document recommended formula " in this article; " the present invention fills a prescription 1 ~ 3 " is respectively the preparation that the spinning sizing agent that adopts the foregoing description 1 ~ 3 carries out.
The performance comparison experimental result of the different spinning sizing agents of table 1
| Project | The document control formula | The document recommended formula | The present invention fills a prescription 1 | The present invention fills a prescription 2 | The present invention fills a prescription 3 |
| Etherification starch (kg) | 50 | 25 | 82 | 80 | 76 |
| PVA（kg） | 50 | 25 | — | — | — |
| CL-08 | — | 50 | — | — | — |
| AE (solid propenoic acid) (kg) | 5 | 5 | — | — | — |
| SLMO-96 I（kg） | 2 | 2 | 2 | 2 | 2 |
| Embodiment 1 slurry (kg) | — | — | 24.5 | — | — |
| Embodiment 2 slurries (kg) | — | — | — | 25 | — |
| Embodiment 2 slurries (kg) | — | — | — | — | 26.5 |
| Supply slurry viscosity (s) | 10.5~11.5 | 10~11 | 10~11 | 10~11 | 10~11 |
| Slurry groove temperature (℃) | 95.6 | 95.5 | 95~96 | 95~96 | 95~96 |
| Stock tank viscosity (s) | 8.8 | 8.3 | 8.4 | 8.5 | 8.5 |
| Loom efficiency (%) | 89.19 | 92.5 | 92.5 | 92.7 | 92.7 |
| Warp-wise broken end when platform (root /) | 0.68 | 0.57 | 0.56 | 0.45 | 0.44 |
| Hundred meters sizing costs (rice) | 23.96 | 22.85 | 22.72 | 22.65 | 22.63 |
Among table 1 result, etherification starch is to be used for modulating one of slashing size starch based filling/modulation material commonly used at present, and cheap, its consumption what directly influence and reflected the cost of slurry therewith.Contrast and experiment shows, under equal sizing condition, and when adopting spinning sizing agent preparation of the present invention, its performance, and end breakage rate all is superior to existing conventional slurry and document recommendation slurry with efficient, sizing costs is significantly reduction also.
Claims (8)
1. spinning sizing agent; Contain by the improved plant starch after plant amylum and the grafted monomers graft modification; It is characterized in that also containing the nanoemulsions composition; It consists of improved plant starch 10 ~ 15 weight portions, nanoemulsions 20 weight portions, wherein said nanoemulsions by in the water of 100 weight portions by following ingredients reaction the liquid-phase system of one-tenth polymer:
Compound emulsifying agent 2 ~ 4 weight portions,
Dispersant 1 ~ 2 weight portion,
Compound monomer 30 ~ 40 weight portions,
Initator 0.2 ~ 0.3 weight portion,
Wherein, compound emulsifying agent is the mixture by polyethers sodium sulphate 1 weight portion, sodium alkyl benzene sulfonate 0.8 ~ 1.2 weight portion, methyl sodiosul foaliphatate 0.5 ~ 0.7 weight portion and betaine 0.8 ~ 1.2 weight portion;
Dispersant be the degree of polymerization be 1000 with alcoholysis degree be 99% polyvinyl alcohol;
Compound monomer is the mixed liquor of being made up of methyl acrylate 1 weight portion, butyl acrylate 2.6 ~ 3.2 weight portions, styrene 1.1 ~ 1.2 weight portions, methacrylic acid 1.1 ~ 1.2 weight portions;
Initator is at least a in ammonium persulfate, sodium peroxydisulfate, sodium hydrogensulfite, sodium thiosulfate, ammonium ceric nitrate, the ferrous nitrate ammonium.
2. spinning sizing agent as claimed in claim 1 is characterized in that the polymer in the said nanoemulsions is the droplet of particle diameter≤50nm.
3. according to claim 1 or claim 2 spinning sizing agent is characterized in that being the homogeneous mixture by said improved plant starch and nanoemulsions.
4. the preparation method of the said spinning sizing agent of one of claim 1 to 3 is characterized in that with said improved plant starch and nanoemulsions be the full and uniform mixing of raw material, and nanoemulsions wherein is for to prepare through following manner:
1': in mixture by said compound emulsifying agent 2 ~ 4 weight portions and dispersant 1 ~ 2 weight portion and 100 weight parts waters; In 60 ~ 66 ℃ with stirring condition under; The aqueous solution of the 15 ~ 25w% that drips 30 ~ 40 weight portion compound monomers and be mixed with by 0.2 ~ 0.3 weight portion initator
2': the mixed material system after adding is after carrying out polymerisation under 70 ℃ ~ 80 ℃ conditions; Regulate pH value 8 ~ 8.5; Obtain to be used for preparing the nanoemulsions of spinning sizing agent after the filtration, or further become the solid product that can be used for the preparation of nano emulsion after the drying with said improved plant starch.
5. like preparation method as claimed in claim 4; It is characterized in that at 1' in the step; Earlier be uniformly mixed into said mixture at 35 ℃ ~ 40 ℃ by said compound emulsifying agent and dispersant and water, be warming up to then said temperature and with stir following adding compound monomer and initiator solution.
6. preparation method as claimed in claim 4 is characterized in that the polymerization reaction time in said 2' step is 3 ~ 4 hours.
7. like the preparation method of one of claim 4 to 6, it is characterized in that said improved plant starch prepares by following mode:
1': plant amylum and deionized water are mixed with the starch milk of 25 ~ 40w%, react under the condition of 30 ~ 40 ℃ and pH=7 ~ 9 with the acetylation composition again, obtain acetate starch;
2': acetate starch and grafted monomers and the initator that will go up the step collected solid constituent after carrying out the graft modification reaction 40 ~ 60 ℃ and pH=7 ~ 9, is the improved plant starch product,
Wherein, said plant amylum comprises any in cornstarch, tapioca, the wheaten starch; The acetylation composition is at least a in acetic acid, acetic anhydride, the vinyl acetate; Grafted monomers is at least a in acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, vinylacetate, styrene, methacrylic acid, the methyl methacrylate; Initator is at least a in ammonium persulfate, sodium peroxydisulfate, sodium hydrogensulfite, sodium thiosulfate, ammonium ceric nitrate, the ferrous nitrate ammonium.
8. preparation method as claimed in claim 7 is characterized in that in said graft modification reaction, is 100 weight portions in the consumption of acetate starch, and used grafted monomers is 8 ~ 30 weight portions, and initator is 0.5 ~ 2 weight portion.
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