CN104961838A - Hydroxypropylated modified starch and preparation method thereof, and glass fiber wetting agent - Google Patents
Hydroxypropylated modified starch and preparation method thereof, and glass fiber wetting agent Download PDFInfo
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- CN104961838A CN104961838A CN201510414989.5A CN201510414989A CN104961838A CN 104961838 A CN104961838 A CN 104961838A CN 201510414989 A CN201510414989 A CN 201510414989A CN 104961838 A CN104961838 A CN 104961838A
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- hydroxypropylation
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000881 Modified starch Polymers 0.000 title abstract description 6
- 239000004368 Modified starch Substances 0.000 title abstract description 6
- 235000019426 modified starch Nutrition 0.000 title abstract description 6
- 239000000080 wetting agent Substances 0.000 title abstract 5
- 229920002472 Starch Polymers 0.000 claims abstract description 102
- 239000008107 starch Substances 0.000 claims abstract description 102
- 235000019698 starch Nutrition 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 230000008595 infiltration Effects 0.000 claims description 30
- 238000001764 infiltration Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- -1 hydroxypropyl Chemical group 0.000 abstract description 20
- 238000006266 etherification reaction Methods 0.000 abstract description 6
- 239000004744 fabric Substances 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000009941 weaving Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000002633 protecting effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011152 fibreglass Substances 0.000 description 9
- 229920002261 Corn starch Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000856 Amylose Polymers 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 235000019759 Maize starch Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001685 Amylomaize Polymers 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/321—Starch; Starch derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B33/00—Preparation of derivatives of amylose
- C08B33/04—Ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention relates to the technical field of starch modification, particularly a hydroxypropylated modified starch and a preparation method thereof, and a glass fiber wetting agent. The hydroxypropyl content of the modified starch is greater than or equal to 7% and smaller than or equal to 12%. The preparation method comprises the following steps: adding an oxidant to oxidize starch, and adding an etherification reagent to perform etherification reaction, thereby preparing the hydroxypropylated modified starch. The oxidize starch has moderate swelling crystal structure and higher hydroxyl reaction activity. The reaction efficiency is enhanced to 60%, and the hydroxypropyl content is enhanced to 7% above. The glass fiber wetting agent uses the hydroxypropylated modified starch as the film former, has the advantages of high binding force, good film-forming property and favorable protecting property, and enhances the mechanical properties of the glass fiber. After the glass fiber subjected to surface treatment by the glass fiber wetting agent is used for weaving cloth, the glass fiber wetting agent has high degradation speed, can not cause unevenness, yellow edges and fluffing on the cloth surface, and enhances the quality of the glass fiber cloth.
Description
Technical field
The present invention relates to starch conversion technical field, particularly relate to fiberglass surfacing processing technology field, be specifically related to a kind of hydroxypropylation treated starch and preparation method thereof, glass fiber infiltration agent.
Background technology
Hydroxypropylated starch is a kind of important chemically modified starch, after its modification, the stability replacing ehter bond due to etherification starch is high, and hydroxypropyl has wetting ability, can weaken the internal hydrogen bonding strength of starch granules structure, it is made to be easy to expand, gelatinization is easy, sticks with paste liquid transparent, good fluidity, retrogradation is weak, and stability is high.Hydroxypropyl corn starch all can be applied in industries such as food, printing, weaving, printing and dyeing, washing composition, papermaking, medicine, metallurgy, petroleum drillings.Hydroxypropyl corn starch, in glass fibre preparation process, is used as the film former component for the treatment of compound usually, for the surface treatment of glass fibre.
In glass fiber wire-drawing process, need in fiberglass surfacing coating a kind of based on the special surface treating agent of the heterogeneous structure of organism milk sap or solution.This applicator can lubrication protection fiberglass surfacing effectively; again can by hundreds of so that thousands of glass monofilament integrated a branch of; the condition of surface of glass fibre can also be changed; so not only meet the requirement to glass precursor performance in subsequent processing operations, and glass fibre and the combination of high molecular polymer be enhanced can also be promoted in the composite.These organic coat things are referred to as glass fiber infiltration agent.Under normal circumstances, treating compound is made up of many materials such as membrane-forming agent, coupling agent, static inhibitor, membrane-forming agent is the key ingredient for the treatment of compound, not only boundling, cohesive action are played to precursor, also determine the processing characteristics of glass when glass filament reinforced plastics is shaping, also determine the film-forming properties for the treatment of compound and the avidity to fiberglass surfacing simultaneously, the treating compound that the membrane-forming agent of excellent performance is made can form high, soft, the wear-resisting film of intensity at fiber surface, and combines together with fiberglass surfacing.
The treating compound used the earliest is paraffin sizing material, and this treating compound not easily moves back solution, but the laking agent warm wash difficulty in formula, make the glass fibre made turn to be yellow or produce obvious brown stripes, reduce product specification.Afterwards, along with the development of fiberglass surfacing treatment technology, engender and adopt starch as treating compound.But unmodified starch is because gelatinization point is high, viscosity is uneven, film-forming properties is poor, the shortcomings such as character is unstable cannot use as membrane-forming agent, and the starch that hydroxypropylation is modified, due to the distinctive wetting ability of hydroxypropyl, improve the performance of starch as membrane-forming agent, and hydroxypropylation degree is higher, its film-forming properties and better with the fusion performance of fiberglass surfacing.
But, crystalline texture due to starch is unfavorable for infiltration and the reaction of chemical reagent, especially the efficiency of etherification reaction is extremely low, therefore increasing research focuses on the preparation feedback efficiency and hydroxypropylation degree aspect that improve hydroxypropylation treated starch at present, as Chinese patent CN102304188A discloses a kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent, adopt and first enzymolysis is carried out to starch, add the preparation method that etherifying reagent carries out hydroxypropylation again, need heating starch gelatinization before enzymolysis in the method, the starch very thickness of gelatinization, be unfavorable for suitability for industrialized production.Even if viscosity reduces after enzymolysis, the reaction efficiency that still there is starch and etherifying reagent is low, the defect that hydroxypropylation degree is low.
Summary of the invention
In order to overcome the defect of prior art, the object of this invention is to provide the hydroxypropylation treated starch that a kind of hydroxypropyl content is high.
Two of object of the present invention is to provide the preparation method of the hydroxypropylation treated starch that a kind of reaction efficiency is high, hydroxypropylation degree is high.
Meanwhile, the present invention is also to provide a kind of glass fiber infiltration agent using hydroxypropylation treated starch of the present invention to prepare, and has excellent film-forming properties, cementability and protective value.
In order to realize above object, the technical solution adopted in the present invention is as follows:
A kind of hydroxypropylation treated starch, 7%≤hydroxypropyl content≤12%.
Above-mentioned hydroxypropylation treated starch, prepared by following preparation method and obtain: comprising following operation steps:
1) starch and swelling inhibitor are added to the water, mixing and stirring, obtained starch solution;
2) starch solution is warming up to 35 DEG C ~ 38 DEG C, adds catalyzer, stir, add oxygenant, carry out oxidizing reaction, obtain solution A;
3) in solution A, add sodium hydroxide solution regulate pH=11 ~ 12, then add catalyzer and etherifying reagent successively, react under 35 DEG C ~ 38 DEG C conditions, obtain solution B;
4) solution B is down to 25 DEG C ~ 30 DEG C, adds pH adjusting agent, regulate pH to 6.5 ~ 7.5, after completion of the reaction, suction filtration obtains solids, obtains described hydroxypropylation treated starch.
Step 3) in the mass concentration of the solution of sodium hydroxide that adds be 2% ~ 6%.
Described catalyzer is sodium-chlor.Sodium-chlor molecular weight is little, and osmotic pressure is high.
Described swelling inhibitor is sodium sulfate.
Described oxygenant is clorox or mass concentration is the hydrogen peroxide of 30%.
Described etherifying reagent is propylene oxide.
Described pH adjusting agent to be mass concentration be 20% hydrochloric acid soln.
Described starch is W-Gum, be preferably amylomaize, more preferably amylose content higher than 70% amylomaize.
Preferably, the quality of starch and water is 1 ~ 2:2 ~ 5; The mass ratio of starch and swelling inhibitor is 20 ~ 40:3 ~ 5; The quality of starch and oxygenant is 5 ~ 24:1 ~ 4; The mass ratio of starch and etherifying reagent is 20 ~ 25:3 ~ 5; Step 2) in the mass ratio of catalyzer and starch be 2 ~ 3:25 ~ 30; Step 3) in the mass ratio of catalyzer and starch be 1 ~ 6:10 ~ 15.
Step 2) in oxidation time be 5 ~ 7 hours; Step 3) in the reaction times be 20 hours.
Step 1) in churning time be 30 ~ 60 minutes; Step 2) churning time is 30 minutes.
In order to obtain the tiny starch of dry granules, also comprising step 4) solids after suction filtration carries out drying and shatters.
A kind of glass fiber infiltration agent, its film former component is above-mentioned hydroxypropylation treated starch.
Above-mentioned glass fiber infiltration agent, described membrane-forming agent consumption is 4 ~ 10% of total formula weight.
Above-mentioned glass fiber infiltration agent, to be mixed with water and emulsifying agent, wet goods auxiliary agent by hydroxypropylation treated starch of the present invention and is made into emulsion and prepares and obtain.
Preferably, above-mentioned glass fiber infiltration agent, is made up of the raw material of following weight percentage: hydroxypropylation treated starch 80 ~ 200 parts, vegetables oil 30 parts, emulsifying agent 1 part, polyoxyethylene glycol 2.5 parts, polyvinyl alcohol 0.5 part, 1766 ~ 1886 parts, water.Wherein polyoxyethylene glycol and polyvinyl alcohol are as reaction promoter, prevent fibre breakage, strengthen plasticity and deflection.
Above-mentioned glass fiber infiltration agent is coated in fiberglass surfacing, for carrying out surface treatment to glass fibre, forming high, soft, the wear-resisting film of intensity, improve the properties for follow of glass fibre at fiberglass surfacing.
Hydroxypropylation treated starch of the present invention, hydroxypropyl content >=7%, is up to 12%, has high hydroxypropyl content, good film-forming property, and viscosity is even, stable performance.
The preparation method of hydroxypropylation treated starch of the present invention, first adds oxidizing starch, then adds etherifying reagent and carry out etherification reaction, makes hydroxypropylation treated starch.The crystalline texture of starch is unfavorable for infiltration and the reaction of chemical reagent, especially the efficiency of etherification reaction is extremely low, the present invention adopts the process means of initial oxidation, make the swelling of the crystalline texture appropriateness of starch, hydroxyl is full of reactive behavior, thus is easy to etherifying reagent reaction, reaction efficiency can be increased to more than 60%, hydroxypropyl content reaches more than 7%, and compare traditional preparation method's reaction efficiency and be enhanced about more than once, hydroxypropyl content improves more than 2 times.
Glass fiber infiltration agent of the present invention; hydroxypropylation treated starch prepared by employing the present invention is as membrane-forming agent; there is high cohesive force, good film-forming properties and protectiveness; be conducive to protection that glass fibre gathers in high-velocity jet and the process of kneading and collection number; enhance productivity, improve the mechanical property of glass fibre.The glass fibre made after adopting glass fiber infiltration agent surface treatment of the present invention is after weaving cotton cloth, move back and separate easily, concavo-convex, yellow limit and the fluffing of cloth cover can not be caused, improve the quality of glasscloth, there is the social benefit of energy-conserving and environment-protective and promote the economic benefit of quality.Meanwhile, compare import starch, the glass fibre after the glass fiber infiltration agent process adopting treated starch of the present invention to make, reduce and resolve Mao Feimao, add stiffness and the physical strength of glass fibre.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
In following embodiment, high-amylose maize starch is purchased from Shandong Hua Nong special corn development corporation, Ltd., Realtek board product; In following embodiment, the consumption of each raw material is weight part; In following embodiment, the account form of reaction efficiency is: reaction efficiency=hydroxypropyl content/propylene oxide addition × 100%.
Embodiment 1
The present embodiment hydroxypropylation treated starch, prepared by following methods and obtain, concrete operation step is:
1) in stainless steel cauldron, add 200 parts of tap water, add high-amylose maize starch and 15 parts of sodium sulfate of 100 parts under constant agitation, stir 30 minutes, obtained starch solution;
2) by step 1) starch solution prepared is warming up to 35 DEG C, and add 8 parts of sodium-chlor, stir 30 minutes, add 20 parts of clorox, carry out oxidizing reaction, react after 5 hours, obtained solution A;
3) in solution A, add the sodium hydroxide solution adjustment pH=11 that mass concentration is 2%, then add 10 parts of sodium-chlor successively, 15 parts of propylene oxide reaction reagent, react after 20 hours under 35 DEG C of conditions, obtained solution B;
4) solution B is cooled to 30 DEG C, adding 16 parts of mass concentrations is the hydrochloric acid soln of 20%, and regulate pH to be 7, after completion of the reaction, suction filtration obtains solids, and dry also comminuted solids thing, obtains hydroxypropylation treated starch.
The hydroxypropyl content of the present embodiment PURE COTE B790 is 7.3%, and carboxyl-content is 1.5%.
The reaction efficiency that the present embodiment prepares hydroxypropylation treated starch is 60.8%.
Embodiment 2
The present embodiment hydroxypropylation treated starch, prepared by following methods and obtain, concrete operation step is:
1) in stainless steel cauldron, add 200 parts of tap water, add high-amylose maize starch and 15 parts of sodium sulfate of 100 parts under constant agitation, stir 60 minutes, obtained starch solution;
2) by step 1) starch solution prepared is warming up to 38 DEG C, and add 8 parts of sodium-chlor, stir 30 minutes, add 20 parts of clorox, carry out oxidizing reaction, react after 7 hours, obtained solution A;
3) in solution A, add the sodium hydroxide solution adjustment pH=12 that mass concentration is 6%, then add 10 parts of sodium-chlor successively, 15 parts of propylene oxide reaction reagent, react after 20 hours under 38 DEG C of conditions, obtained solution B;
4) solution B is cooled to 25 DEG C, adding 16 parts of mass concentrations is the hydrochloric acid soln of 20%, and regulate pH to be 7, after completion of the reaction, suction filtration obtains solids, and dry also comminuted solids thing, obtains hydroxypropylation treated starch.
The hydroxypropyl content of the present embodiment PURE COTE B790 is 7.3%, and carboxyl-content is 1.5%.
The reaction efficiency that the present embodiment prepares hydroxypropylation treated starch is 60.8%.
Embodiment 3
1) in stainless steel cauldron, add 200 parts of tap water, add high-amylose maize starch and 15 parts of sodium sulfate of 100 parts under constant agitation, stir 50 minutes, obtained starch solution;
2) by step 1) starch solution prepared is warming up to 37 DEG C, and add 8 parts of sodium-chlor, stir 30 minutes, add 20 parts of clorox, carry out oxidizing reaction, react after 6 hours, obtained solution A;
3) in solution A, add the sodium hydroxide solution adjustment pH=11 that mass concentration is 5%, then add 10 parts of sodium-chlor successively, 15 parts of propylene oxide reaction reagent, react after 20 hours under 36 DEG C of conditions, obtained solution B;
4) solution B is cooled to 28 DEG C, adding 16 parts of mass concentrations is the hydrochloric acid soln of 20%, and regulate pH to be 7, after completion of the reaction, suction filtration obtains solids, and dry also comminuted solids thing, obtains hydroxypropylation treated starch.
The hydroxypropyl content of the present embodiment PURE COTE B790 is 7.3%, and carboxyl-content is 1.5%.
The reaction efficiency that the present embodiment prepares hydroxypropylation treated starch is 60.8%.
Embodiment 4
1) in stainless steel cauldron, add 200 parts of tap water, add high-amylose maize starch and 13 parts of sodium sulfate of 100 parts under constant agitation, stir 50 minutes, obtained starch solution;
2) by step 1) starch solution prepared is warming up to 37 DEG C, and add 8.9 parts of sodium-chlor, stir 30 minutes, add 30 parts of clorox, carry out oxidizing reaction, react after 6 hours, obtained solution A;
3) in solution A, add the sodium hydroxide solution adjustment pH=11 that mass concentration is 3%, then add 41.7 parts of sodium-chlor successively, 18 parts of propylene oxide reaction reagent, react after 20 hours under 36 DEG C of conditions, obtained solution B;
4) solution B is cooled to 30 DEG C, adding 15 parts of mass concentrations is the hydrochloric acid soln of 20%, and regulate pH to be 7.5, after completion of the reaction, suction filtration obtains solids, and dry also comminuted solids thing, obtains hydroxypropylation treated starch.
The hydroxypropyl content of the present embodiment PURE COTE B790 is 9%, and carboxyl-content is 1.6%.
The reaction efficiency that the present embodiment prepares hydroxypropylation treated starch is 60%.
Embodiment 5
1) in stainless steel cauldron, add 250 parts of tap water, add high-amylose maize starch and 12.5 parts of sodium sulfate of 100 parts under constant agitation, stir 50 minutes, obtained starch solution;
2) by step 1) starch solution prepared is warming up to 37 DEG C, and add 10 parts of sodium-chlor, stir 30 minutes, adding 16.7 parts of mass concentrations is the hydrogen peroxide of 30%, carries out oxidizing reaction, reacts after 6 hours, obtained solution A;
3) in solution A, add the sodium hydroxide solution adjustment pH=12 that mass concentration is 5%, then add 40 parts of sodium-chlor successively, 20 parts of propylene oxide reaction reagent, react after 20 hours under 36 DEG C of conditions, obtained solution B;
4) solution B is cooled to 30 DEG C, adding 17 parts of mass concentrations is the hydrochloric acid soln of 20%, and regulate pH to be 6.5, after completion of the reaction, suction filtration obtains solids, and dry also comminuted solids thing, obtains hydroxypropylation treated starch.
The hydroxypropyl content of the present embodiment PURE COTE B790 is 12%, and carboxyl-content is 1.7%.
The reaction efficiency that the present embodiment prepares hydroxypropylation treated starch is 60%.
Embodiment 6
The present embodiment glass fiber infiltration agent, is made up of the raw material of following parts by weight: hydroxypropylation treated starch 100 parts, hydrogenated vegetable oil 30 parts, span series emulsifying agent 1 part, polyoxyethylene glycol 2.5 parts, polyvinyl alcohol 0.5 part, 1866 parts, water; Wherein hydroxypropylation treated starch is hydroxypropylation treated starch prepared by embodiment 1.
The present embodiment glass fiber infiltration agent is preparation method be specially:
1) treated starch is joined in the water of 500 parts, Heat Gelatinization, obtained solution A;
2) whole hydrogenated vegetable oils, span series emulsifying agent, polyoxyethylene glycol, polyvinyl alcohol are added complete emulsification in the water of 100 parts, obtained solution B;
3) solution B is joined in solution A, and add remaining water, stir, obtain glass fiber infiltration agent.
Comparative example 1
Hydroxypropylation treated starch in embodiment 6 is replaced with import treated starch (suggestion provides production firm), and the method same according to embodiment 7 is prepared into glass fiber infiltration agent.
Comparative example 2
Hydroxypropylation treated starch in embodiment 6 is replaced with paraffin, and the method same according to embodiment 6 is prepared into glass fiber infiltration agent.
Test example
Test method: glass fiber infiltration agent obtained for embodiment 6, comparative example 1 and comparative example 2 is respectively used to glass fiber wire-drawing process, and detects the performance of glass fiber precursor, result is as shown in table 1 below:
The glass fibre performance of the glass fiber infiltration agent process that table 1 adopts embodiment 6, comparative example 1 and comparative example 2 to prepare
| Classification | Precursor convergency | Precursor stiffness | Disconnected hair flies silk | Ultimate strength/CN |
| Comparative example 1 | Good | Better | Lousiness, disconnected hair are less | 2750 |
| Comparative example 2 | Better | Better | Lousiness, disconnected hair are many | 2450 |
| Embodiment 6 | Good | Good | Lousiness, disconnected hair are few | 3000 |
From the data shown in above-mentioned table 1, compare the treating compound that import starch and paraffin are made as membrane-forming agent, glass fiber infiltration agent prepared by the embodiment of the present invention 6, improve convergency and the stiffness of glass fiber precursor; Reduce lousiness and disconnected hair, show that glass fiber infiltration agent prepared by the embodiment of the present invention 6 has better film-forming properties and the provide protection to glass fibre; Improve the breaking tenacity of glass fiber precursor simultaneously, show that glass fiber infiltration agent prepared by the embodiment of the present invention 6 can the defect on filled glass fiber surface and crackle preferably, have and show better affinity with glass fibre, improve the ultimate strength of glass fibre.
Hydroxypropylation treated starch prepared by the embodiment of the present invention 2 ~ 5 also can be used as the film former base of glass fiber infiltration agent, and addition can be 4% ~ 10% of total formula ratio, and the performance of the glass fiber infiltration agent made is suitable with embodiment 6.
Claims (10)
1. a hydroxypropylation treated starch, is characterized in that, 7%≤hydroxypropyl content≤12%.
2. hydroxypropylation treated starch as claimed in claim 1, is characterized in that, prepared and obtain: comprise following operation steps by following preparation method:
1) starch and swelling inhibitor are added to the water, mixing and stirring, obtained starch solution;
2) starch solution is warming up to 35 DEG C ~ 38 DEG C, adds catalyzer, stir, add oxygenant, carry out oxidizing reaction, obtain solution A;
3) in solution A, add sodium hydroxide solution regulate pH=11 ~ 12, then add catalyzer and etherifying reagent successively, react under 35 DEG C ~ 38 DEG C conditions, obtain solution B;
4) solution B is down to 25 DEG C ~ 30 DEG C, adds pH adjusting agent, regulate pH to 6.5 ~ 7.5, after completion of the reaction, suction filtration obtains solids, obtains described hydroxypropylation treated starch.
3. hydroxypropylation treated starch as claimed in claim 2, it is characterized in that, described catalyzer is sodium-chlor.
4. hydroxypropylation treated starch as claimed in claim 2, it is characterized in that, described swelling inhibitor is sodium sulfate.
5. hydroxypropylation treated starch as claimed in claim 2, it is characterized in that, described oxygenant is clorox or mass concentration is the hydrogen peroxide of 30%.
6. hydroxypropylation treated starch as claimed in claim 2, it is characterized in that, described etherifying reagent is propylene oxide.
7. hydroxypropylation treated starch as claimed in claim 2, it is characterized in that, the quality of starch and water is 1 ~ 2:2 ~ 5; The mass ratio of starch and swelling inhibitor is 20 ~ 40:3 ~ 5; The quality of starch and oxygenant is 5 ~ 24:1 ~ 4; The mass ratio of starch and etherifying reagent is 20 ~ 25:3 ~ 5; Step 2) in the mass ratio of catalyzer and starch be 2 ~ 3:25 ~ 30; Step 3) in the mass ratio of catalyzer and starch be 1 ~ 6:10 ~ 15.
8. a preparation method for hydroxypropylation treated starch as claimed in claim 1, is characterized in that, comprises following operation steps:
1) starch and swelling inhibitor are added to the water, mixing and stirring, obtained starch solution;
2) starch solution is warming up to 35 DEG C ~ 38 DEG C, adds catalyzer, stir, add oxygenant, carry out oxidizing reaction, obtain solution A;
3) in solution A, add sodium hydroxide solution regulate pH=11 ~ 12, then add catalyzer and etherifying reagent successively, react under 35 DEG C ~ 38 DEG C conditions, obtain solution B;
4) solution B is down to 25 DEG C ~ 30 DEG C, adds pH adjusting agent, regulate pH to 6.5 ~ 7.5, after completion of the reaction, suction filtration obtains solids, obtains described hydroxypropylation treated starch.
9. a glass fiber infiltration agent, is characterized in that, its film former component is hydroxypropylation treated starch as claimed in claim 1.
10. glass fiber infiltration agent as claimed in claim 9, it is characterized in that, the consumption of described membrane-forming agent accounts for 4% ~ 10% of the total formula ratio of glass fiber infiltration agent.
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| CN109652981A (en) * | 2018-11-22 | 2019-04-19 | 安徽华明太合生物工程有限公司 | A kind of starch base glass fibre infiltration film forming agent and preparation method thereof |
| CN111072790A (en) * | 2019-12-27 | 2020-04-28 | 河南新孚望新材料科技有限公司 | Preparation method of modified starch for glass fiber cloth |
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