CN103936873A - Preparation method of modified high amylose starch for glass fiber wetting agent - Google Patents
Preparation method of modified high amylose starch for glass fiber wetting agent Download PDFInfo
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- CN103936873A CN103936873A CN201410188873.XA CN201410188873A CN103936873A CN 103936873 A CN103936873 A CN 103936873A CN 201410188873 A CN201410188873 A CN 201410188873A CN 103936873 A CN103936873 A CN 103936873A
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Abstract
The invention relates to modified high amylose starch. The modified high amylose starch is prepared on the basis of a solvent method through etherification of epoxypropane and crosslinking modification of epoxy chloropropane by using high amylose starch (the amylose content is greater than 70%) and using a catalyst formed by compounding emulsifier alkylol polyethenoxy ether, polyethyleneglycol and the like. The invention has the following advantages: under alkaline conditions, the compound catalyst has catalytic action on the modification reaction of the high amylose starch, so that the substitution degree of the starch can be increased (MS value is 0.1-0.2), and the reaction time can be shortened; and the modified starch meets the use requirements of glass fiber wetting agent.
Description
Technical field
The invention belongs to glass fibre starch-type treating compound field, particularly high amylose starch modification and preparation method thereof.
Background technology
Along with industry transfer, China has become the maximum glass fibre producing country in the whole world.China's glass annual accumulative total glass fibre yarn output in 2011 reaches 2,790,000 tons, and within 2012, glass fiber yarn output is 2,880,000 tons, and 2012 glass-fiber industry main business incomes reach 1,040 hundred million yuan of left and right.China's Fiberglass Industry develop rapidly, large tank furnace used continuous construction, hardware technology class and technology maturity improve constantly, but owing to existing the bottleneck for the treatment of compound starting material and formula technique, China's glass fiber product kind, capability and performance are in the international market in middle and lower reaches status.Specifically, i.e. China's treating compound starting material and formula technique differentiation, personalization and the degree that becomes more meticulous are not high, so that glass fiber product is simple in structure, and bulk product is many, and high-end product is few, and it is more severe that product structure contradiction will become.The task of top priority finds a kind of Novel electronic grade glass to infiltrate collecting agent exactly.High straight chain treated starch type treating compound is good to glass fiber bundling provide protection, move back solution while weaving lousiness few.Its advantages of nontoxic raw materials, to human body nonirritant.Its major advantage is that warm wash is easy, and decomposition temperature is low, pure white, smooth through aftertreatment cloth cover, without chocolate striped, and remaining carbon is low, can reach n*10
-4(n is 1-9) level, product is widely used in electrically insulating material, and its bulk product is robot calculator, instrument, the required printed wiring PCB metal clad board glass base cloth of domestic electronic device, if ASTM standard is 7628 cloth, 2116 cloth etc.
High amylose starch modification infiltrates collecting agent as glass fibre and sees Chinese patent ZL0315249.5, ZL03818934.8, Japanese Patent JP9227174, JP1072243, JP10167772.The method that JP9227174 prepares treated starch is that dry method (reaction does not need solvent) is prepared treated starch glass fibre to infiltrate collecting agent modification high amylose starch specification of quality high, and ash content, basicity need to control, and starch is difficult for mixing with raw material, and quality does not ensure.For obtaining high-quality modification high amylose starch, adopt wet method (using solvent and water when reaction), add phase-transfer catalyst, speed of response is accelerated, the reaction times shortens, and cost, obtains stay-in-grade modification high amylose starch.
Summary of the invention
The object of the invention is the modification high amylose starch that does not have at present glass fiber treating compound to use for domestic, adopt composite catalyst reaction to improve stability and the substitution value of treated starch, Reaction time shorten, does not add catalyst reaction time need 30 hours, adds composite catalyst reaction to reduce to 16 hours; Optimized production process condition, prepares and has high performance modification high amylose starch simultaneously.
The present invention prepares modification high amylose starch by following method and technical scheme, its principal feature is: having in whipping appts, thermometer, manometric sealing load reactor, add the high amylose starch (straight chain content is greater than 70%) of 1 weight part), (solvent can be methyl alcohol for the solvent of 2～5 weight parts, ethanol, Virahol, one or more in acetone.) and 10% aqueous sodium hydroxide solution of 0.01～0.05 weight part, stirring at room temperature 0.5～1h, fully alkalizes starch; By the composite catalyst of 0.1～0.5% weight part, (catalyzer is polyoxyethylene glycol, and the mixture of fatty alcohol-polyoxyethylene ether is preferably the mixture of Polyethylene Glycol-600 or polyoxyethylene glycol 800 and fatty alcohol-polyoxyethylene ether.) and the propylene oxide of 0.1～0.3 weight part add respectively in alkalization starch, sealed reactor, passes into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 10 hours; The epoxy chloropropane of 0.1～1% weight part is added in starch, and sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours; Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch; The thick product of white powder treated starch, with deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.
Synthetic product analysis the results are shown in following table.
Embodiment
Further illustrate the embodiment of the present invention below.
Embodiment 1:
Having in whipping appts, thermometer, manometric 1 liter of sealing load reactor, add high amylose starch, the methyl alcohol of 400g and 15% aqueous sodium hydroxide solution of 25g of 200g, stirring at room temperature 0.5～1h, fully alkalizes starch.Then 0.5g polyoxyethylene glycol 800 and 40g propylene oxide are added respectively in alkalization starch, sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 24 hours.0.6g epoxy chloropropane is added in starch, sealed reactor, passes into nitrogen again, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.26%, ash content 0.18%, substitution value MS=0.12.
Embodiment 2:
Having in whipping appts, thermometer, manometric 1 liter of sealing load reactor, add high amylose starch, the methyl alcohol of 400g and 15% aqueous sodium hydroxide solution of 25g of 200g, stirring at room temperature 0.5～1h, fully alkalizes starch.Then 0.5g alkyl alcohol Soxylat A 25-7 and 40g propylene oxide are added respectively in alkalization starch, sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 20 hours.0.6g epoxy chloropropane is added in starch, sealed reactor, passes into nitrogen again, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.13%, ash content 0.13%, substitution value MS=0.13.
Embodiment 3:
Having in whipping appts, thermometer, manometric 1 liter of sealing load reactor, add high amylose starch, the methyl alcohol of 400g and 15% aqueous sodium hydroxide solution of 25g of 200g, stirring at room temperature 0.5～1h, fully alkalizes starch.Then by 0.3g alkyl alcohol Soxylat A 25-7,0.2g polyoxyethylene glycol 800 and 40g propylene oxide add respectively in alkalization starch, sealed reactor, pass into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, keep temperature of reaction at 40～60 DEG C, react 10 hours.0.6g epoxy chloropropane is added in starch, sealed reactor, passes into nitrogen again, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.23%, ash content 0.18%, substitution value MS=0.21.
Embodiment 4:
Having in whipping appts, thermometer, manometric 1 liter of sealing load reactor, add high amylose starch, the methyl alcohol of 400g and 15% aqueous sodium hydroxide solution of 25g of 200g, stirring at room temperature 0.5～1h, fully alkalizes starch.Then by 0.3g alkyl alcohol Soxylat A 25-7,0.2g Polyethylene Glycol-600 and 40g propylene oxide add respectively in alkalization starch, sealed reactor, pass into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, keep temperature of reaction at 40～60 DEG C, react 10 hours.0.6g epoxy chloropropane is added in starch, sealed reactor, passes into nitrogen again, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.63%, ash content 0.16%, substitution value MS=0.19.
Embodiment 5:
Having in whipping appts, thermometer, manometric 1 liter of sealing load reactor, add high amylose starch, the acetone of 400g and 15% aqueous sodium hydroxide solution of 25g of 200g, stirring at room temperature 0.5～1h, fully alkalizes starch.Then by 0.2g alkyl alcohol Soxylat A 25-7,0.3g Polyethylene Glycol-600 and 40g propylene oxide add respectively in alkalization starch, sealed reactor, pass into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, keep temperature of reaction at 40～60 DEG C, react 10 hours.0.6g epoxy chloropropane is added in starch, sealed reactor, passes into nitrogen again, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.54%, ash content 0.16%, substitution value MS=0.18.
Embodiment 6:
Having in whipping appts, thermometer, manometric 10 liters of sealing load reactors, add high amylose starch, the methyl alcohol of 4kg and 15% aqueous sodium hydroxide solution of 250g of 2kg, stirring at room temperature 0.5～1h, fully alkalizes starch.Then by 4g alkyl alcohol Soxylat A 25-7,6g polyoxyethylene glycol 800 and 0.6kg propylene oxide add respectively in alkalization starch, sealed reactor, pass into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, keep temperature of reaction at 40～60 DEG C, react 10 hours.Continue 6g epoxy chloropropane to add in starch, sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.48%, ash content 0.16%, substitution value MS=0.21.
Embodiment 7:
Having in whipping appts, thermometer, manometric 10 liters of sealing load reactors, add high amylose starch, the ethanol of 4kg and 15% aqueous sodium hydroxide solution of 250g of 2kg, stirring at room temperature 0.5～1h, fully alkalizes starch.Then by 4g alkyl alcohol Soxylat A 25-7,6g Polyethylene Glycol-600 and 0.6kg propylene oxide add respectively in alkalization starch, sealed reactor, pass into nitrogen, reactor pressure, at 0.1～0.5MPa, is opened and is stirred, keep temperature of reaction at 40～60 DEG C, react 10 hours.Continue 6g epoxy chloropropane to add in starch, sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reacts 6 hours.Reaction finishes rear releasing reactor internal pressure, through filtering the thick product that obtains white powder treated starch.With deionized water solution immersion, with hydrochloric acid neutralization, washing, filtration, the dry Powdered treated starch of pure white that obtains.The water content of product is 5.21%, ash content 0.13%, substitution value MS=0.19.
The product of embodiment 6 and embodiment 7 is measured by the service requirements of Fiberglass Industry, met the requirement of starch-type treating compound in Fiberglass Industry.
Claims (6)
1. the preparation method of a modification high amylose starch, it is characterized in that: having in whipping appts, thermometer, manometric sealing load reactor, add high amylose starch (W-Gum that straight chain content is greater than 70%), the solvent of 2～5 weight parts and 10% aqueous sodium hydroxide solution of 0.01～0.05 weight part of 1 weight part, stirring at room temperature 0.5～1h, fully alkalizes starch; The propylene oxide of the complexed surfactant of 0.1～0.5% weight part and 0.1～0.3 weight part is added respectively in alkalization starch, and sealed reactor, passes into nitrogen, reactor pressure is at 0.1～0.5MPa, open and stir, keep temperature of reaction at 40～60 DEG C, react 10～12 hours; The epoxy chloropropane of 0.1～1% weight part is added in starch, and sealed reactor, passes into nitrogen, and reactor pressure, at 0.1～0.5MPa, is opened and stirred, and keeps temperature of reaction at 40～60 DEG C, reaction 6-8 hour; After reaction finishes, through filtering the thick product that obtains white powder treated starch, drying obtains modification high amylose starch.
2. solvent according to claim 1, is characterized in that solvent is methyl alcohol, ethanol, Virahol, one or more in acetone.
3. composite catalyst according to claim 1, is characterized in that composite catalyst is polyoxyethylene glycol, and the mixture of fatty alcohol-polyoxyethylene ether is preferably the mixture of Polyethylene Glycol-600 or polyoxyethylene glycol 800 and fatty alcohol-polyoxyethylene ether.
4. after adding according to claim 1 composite catalyst, shortened the reaction times, composite catalyst makes the reaction times reduce to 16 hours from 30 hours.
5. the viscosity of modification high amylose starch according to claim 1 (50 DEG C, 5% the aqueous solution) 5 ~ 20mPaS, pH6 ~ 7, ash content≤0.2%, surface tension 45 ~ 50mN/m.
6. modification high amylose starch according to claim 1 infiltrates collecting agent for glass fibre.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961838A (en) * | 2015-07-15 | 2015-10-07 | 漯河市恒瑞化工有限公司 | Hydroxypropylated modified starch and preparation method thereof, and glass fiber wetting agent |
| CN106316158A (en) * | 2016-08-31 | 2017-01-11 | 郭舒洋 | Method for preparing impregnating compound from compound modified tapioca starch |
| CN107869056A (en) * | 2017-11-30 | 2018-04-03 | 天峨县平昌生态农业有限公司 | A kind of preparation method of preparation method for sizing agent cassava modified starch |
| CN108529900A (en) * | 2018-04-20 | 2018-09-14 | 刘凡领 | A kind of preparation method of glass fiber infiltration agent |
| CN110482545A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method and its usage of high-crosslinking-degree starch |
| CN111072791A (en) * | 2019-12-27 | 2020-04-28 | 河南新孚望新材料科技有限公司 | Preparation method of high amylose starch for coating agent |
| CN111116764A (en) * | 2019-12-30 | 2020-05-08 | 河南新孚望新材料科技有限公司 | Method for preparing cast iron coating by using high amylose corn starch as raw material |
-
2014
- 2014-05-07 CN CN201410188873.XA patent/CN103936873A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961838A (en) * | 2015-07-15 | 2015-10-07 | 漯河市恒瑞化工有限公司 | Hydroxypropylated modified starch and preparation method thereof, and glass fiber wetting agent |
| CN106316158A (en) * | 2016-08-31 | 2017-01-11 | 郭舒洋 | Method for preparing impregnating compound from compound modified tapioca starch |
| CN107869056A (en) * | 2017-11-30 | 2018-04-03 | 天峨县平昌生态农业有限公司 | A kind of preparation method of preparation method for sizing agent cassava modified starch |
| CN108529900A (en) * | 2018-04-20 | 2018-09-14 | 刘凡领 | A kind of preparation method of glass fiber infiltration agent |
| CN110482545A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method and its usage of high-crosslinking-degree starch |
| CN111072791A (en) * | 2019-12-27 | 2020-04-28 | 河南新孚望新材料科技有限公司 | Preparation method of high amylose starch for coating agent |
| CN111116764A (en) * | 2019-12-30 | 2020-05-08 | 河南新孚望新材料科技有限公司 | Method for preparing cast iron coating by using high amylose corn starch as raw material |
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