CN102304188B - Preparation method of starch type film-forming agent for glass fiber wetting agent - Google Patents
Preparation method of starch type film-forming agent for glass fiber wetting agent Download PDFInfo
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- CN102304188B CN102304188B CN 201110200636 CN201110200636A CN102304188B CN 102304188 B CN102304188 B CN 102304188B CN 201110200636 CN201110200636 CN 201110200636 CN 201110200636 A CN201110200636 A CN 201110200636A CN 102304188 B CN102304188 B CN 102304188B
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Abstract
The invention discloses a preparation method of a starch type film-forming agent for a glass fiber wetting agent, which is characterized by comprising the following steps: feeding 40 mass parts of pea starch into a reaction vessel, adding 300-500 mass parts of water, heating to 75-90 DEG C while stirring, carrying out gelation reaction for 0.5-2 hours, and then cooling to 35-50 DEG C; adjusting the pH value to 4-6.5, adding 1-4 mass parts of isoamylase, reacting for 6-30 hours, and then heating to 75-90 DEG C to carry out enzyme inactivation for 5-30 minutes; cooling to 30-55 DEG C, adding 3-6 mass parts of expansion inhibitor, and keeping the temperature for 10-20 minutes; and adding 0.3-0.5 mass part of catalyst and 4-10 mass parts of etherifying agent, reacting for 10-24 hours, adjusting the pH value to 6-8, cooling to room temperature, then carrying out vacuum filtration, and drying the solid to obtain the film-forming agent product. The product is used for a glass fiber wetting agent, and has the characteristics of good film forming performance, convenient post treatment process and the like.
Description
Technical field
The invention belongs to the preparation method for the chemically modified starch of fiberglass surface treating agent, relate to a kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent.The product that makes is specially adapted to the surface treatment agent in the glass fiber wire-drawing process---make membrane-forming agent in the glass fiber infiltration agent (wire drawing treating compound).
Background technology
In the glass fiber wire-drawing process, need to apply a kind of special surface treating agent take organism milk sap or solution as the heterogeneous structure of main body at fiberglass surfacing.This applicator is the lubrication protection fiberglass surfacing effectively, again can hundreds of and even thousands of glass monofilament are integrated a branch of, can also change the condition of surface of glass fibre.So not only satisfy in the following process operation requirement to glass precursor performance, and in matrix material, can also promote the combination of glass fibre and the high molecular polymer that is enhanced.These organic coat things are referred to as glass fiber infiltration agent (being called for short the wire drawing treating compound).
Moulding process to various glass fiber material, must there be equally special-purpose treating compound supporting with it, giving fiberglass products necessary properties, such as flowability of penetrance, impregnability, stiffness, cutting, dispersiveness, tapability and chopped yarn etc.Can say that the development for the treatment of compound technology is one of prerequisite of fiber glass industry development.
Generally, treating compound is comprised of many materials such as membrane-forming agent, coupling agent, lubricant, static inhibitor.From production cost and security consideration, generally be made into 5～10% the aqueous solution.Membrane-forming agent is the key ingredient for the treatment of compound, also is the foundation that determines treating compound performance, classification.Its consumption in treating compound is maximum, not only precursor is played boundling, cohesive action, also determines the processing performance of glass when the glass filament reinforced plastics moulding.In the prior art, the quality of membrane-forming agent and stability are all more undesirable, especially soak into antistatic performance relatively poor.
At the beginning of China's fiber glass industry is original, just require textile size must guarantee the textile process performance, guarantee final product quality.So treating compound should form high, soft, the wear-resisting film of intensity at fiber, the component for the treatment of compound must have avidity with fiberglass surfacing, combines together with fiberglass surfacing.Along with increasing and the application of high-effect Weaving device of textile strand monofilament radical, industrial protective value to textile size requires more and more higher.The paraffin wax type weaving treating compound of early application is because of the laking agent warm wash difficulty in its prescription, so that cloth cover turns to be yellow or produces obvious brown striped, its consumption also significantly reduces, and is replaced by starch-oils treating compound gradually.
Starch-oils textile size mostly is foreign study and uses, and its advantages of nontoxic raw materials is to the human body nonirritant.Domestic research work for textile size still is in the starting stage.In actual production, if with common starch directly as the membrane-forming agent in the treating compound component, aspect of performance does not reach production requirement far away.Its maximum shortcoming is that straight chain content is not high enough, and the treating compound of making can not be well forms fine and close film and plays the effects such as protection to glass fibre, boundling on the glass yarn surface, thereby must carry out modification to it.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, utilize common domestic low-cost pea starch, process and the chemical modification means such as hydroxypropyl etherificate by isoamylase, a kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent is provided.Kind and the quantity of the molecular structure of the present invention by changing pea starch, molecular size range, leading functional group, improve film-forming properties, viscosity of common pea starch etc., make it be able to applications well in the treating compound field, and production technique is easy, cost is low, environmental benefit is outstanding.
The membrane-forming agent production cost that the present invention is directed to the Present Domestic glass fiber treating compound is high, domestic starch performance does not reach the shortcoming of membrane-forming agent performance requriements, under low temperature, acidic conditions, pea starch is carried out pre-treatment with isoamylase first, then under neutrallty condition, by expansion inhibitor, catalyzer, etherifying agent etc., so that pea starch generation etherification, make a kind of starch-type membrane-forming agent that is used for glass fiber infiltration agent of excellent performance.
Content of the present invention is: a kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent is characterized in that comprising the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300～500 mass parts distilled water or deionized water (also starch can be mixed with part water be made into 5～15% the aqueous solution after, mix with the water of remaining part again), stir lower, be warming up to 75～90 ℃, behind gelatinization reaction 0.5～2h, cooling down to 35～50 ℃ make starch fluid again;
B, regulate the pH value to 4 of starch fluid～6.5 with pH adjusting agent, add isoamylase 1～4 mass parts, react 6～30h after, be warming up to 75～90 ℃ of enzyme 5～30min that go out, make reaction solution;
C, reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again 0.3～0.5 mass parts of catalyst, then (rapidly) add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described expansion inhibitor is that sodium sulfate is or/and sodium-chlor;
Described catalyzer is one or more the mixture in sodium hydroxide, sodium sulfate or the sodium-chlor;
Described etherifying agent is one or more the mixture in oxyethane, propylene oxide or the chloroethanol.
In the content of the present invention: described step c can replace with: reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again catalyst solution, then (rapidly) add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described catalyst solution is that 0.3～0.5 mass parts of catalyst is dissolved in the solution that is made in 5～10 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
In the content of the present invention: described pH adjusting agent can be the acid regulator SODIUM PHOSPHATE, MONOBASIC or/and potassium primary phosphate or/and the alkaline conditioner Sodium phosphate dibasic or/and dipotassium hydrogen phosphate.
In the content of the present invention: described pea starch can for commercially available crape skin pea starch or/and smooth pea starch.
When the membrane-forming agent product that the present invention makes is used in glass fiber wire drawing technique, the membrane-forming agent product that the present invention can be made mixes, is made into the form treating compound of emulsion, is coated to fiberglass surfacing again with water and (multiple) organic additive (existing commercially available prod), and the consumption of the membrane-forming agent product that the present invention makes can be 3～8% of prescription gross weight.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) adopt the present invention, pea starch is as key ingredient---the membrane-forming agent for the treatment of compound.Because starch is carbohydrate, heat decomposition temperature is low, and resistates is few after decomposing, so be easy to remove in the warm wash operation, pure white, smooth through the aftertreatment cloth cover, without the chocolate striped, remaining carbon is low;
Among the present invention, can be divided into two portions to the chemical modification of pea starch, at first be with isoamylase it to be processed; Isoamylase is that a class can be cut the α-1 in the amylopectin tapping point single-mindedly, thereby 6 glycosidic links are cut the enzyme of whole Lateral shoot formation amylose starch; The amylose starch that the obtains Zulkovsky starch that is otherwise known as, crystalline structure is tight and particle is smaller, and the polar group in the molecule is closely arranged mutually, and in gelatinization process, water molecules is difficult to into the people to its inside; Therefore, amylose content is higher, and its gelatinization degree is larger, and the film made from this amylose starch has good transparency, snappiness, tensile strength and water-insoluble, can realize fully the provide protection to glass fibre;
Among the present invention, be above-mentioned enzymolysis starch to be carried out etherificate process to the second section of pea starch chemical modification; Process through etherificate, the hydroxyl on the starch glucose unit and etherifying agent effect, thereby in the one or more hydroxypropyls of starch chain upper joint unit; Ehter bond with strong stability between the hydroxypropyl of nonionic and the starch molecule connects so that hydroxypropylated starch has very outstanding alkaline resistance properties and viscosity stability; The process of etherificate can effectively prevent the generation of the heavy situation of membrane-forming agent wadding, is conducive to preparation and the storage of membrane-forming agent; Consider the use properties of membrane-forming agent and the relation of its surface tension and contact angle, when pea starch is carried out etherificate, selected the little membrane-forming agent prescription of contact angle θ; In drawing process, treating compound can relatively easily launch, infiltrate at fiberglass surfacing, forms the film of continuous whole like this;
The present invention has considered enzymolysis and etherificate to the advantage of starch conversion, and it is effectively combined; The processing of isoamylase can improve the straight chain content of starch, and then improve preferably the film-forming properties of starch, make domestic starch can be effectively form the film of one deck densification at fiberglass surfacing, play protection to glass, the effect such as toughness reinforcing, prevent the mechanical wear of glass in the drawing process; Etherificate is processed then and is promoted the viscosity of starch and stability further to improve in original performance basis, fully satisfies glass-fiber industry to the performance requriements of starch treating compound; Simultaneously, by the inventive method domestic pea starch is carried out modification, be prepared into film, the film-forming components as in the glass fiber infiltration agent when satisfying the glass performance requirement, can reduce the production cost of glass greatly; Compare with the Japanese starch of import, the starch membrane-forming agent raw material sources of modification of the present invention are extensive, with low cost, have more superior performance than the resulting starch membrane-forming agent of traditional method of modifying simultaneously.
(2) the present invention adopts isoamylase that pea starch is carried out pre-treatment, by cutting off the amylopectin structure, improves amylose content in the sample, thereby has greatly improved the film-forming properties of starch, guarantees that treating compound can be coated on the glass fibre preferably; Simultaneously, use for reference the achievement in research of hydroxypropyl etherificate starch, introduce starch substituting group ether structure in the short chain behind enzymolysis, improve viscosity stability and the alkali resistance of membrane-forming agent;
(3) membrane-forming agent of the present invention's preparation is used for glass fiber infiltration agent, overcome traditional paraffin wax type weaving treating compound, laking agent warm wash difficulty in the prescription, cloth cover jaundice or produce the shortcoming such as obvious brown striped, products obtained therefrom is removed in the warm wash operation easily, pure white, smooth through the aftertreatment cloth cover, without the chocolate striped, remaining carbon is low, has reduced the production cost in the whole technique;
(4) the starch-type film forming of the present invention preparation is applicable to the wire drawing production technique of glass fibre, has improved the precursor convergency, reduces and resolves Mao Feisi, has increased simultaneously the stiffness of precursor, guarantees that glass fibre can finish smoothly postorder and process;
(5) product of the present invention is produced under normal pressure, low temperature, and manufacturing condition is easy to control, and equipment is simple, realizes easily scale industrialization production; Preparation technology is simple, and operation is practical easily.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
Get 40 mass parts pea starches and drop in the reactor, add 400 mass parts distilled water, stir, be warming up to 85 ℃, behind the gelatinization 1h, be cooled to 50 ℃, regulate pH value to 6 with alkaline conditioner.Add 3 mass parts isoamylases, reaction 24h is after solution is crossed 80 mesh sieve, be warming up to 85 ℃, reaction 15min is cooled to 50 ℃ again, add 4 mass parts anhydrous sodium sulphate, insulation 10min adds 0.32 mass parts sodium hydroxide again, then add rapidly 4 mass parts propylene oxide, sealed vessel, reaction 16h, react complete, be down to room temperature, suction filtration, solids makes pale powder shape treated starch---membrane-forming agent product through lyophilize.
Prepare and use treating compound by the prior art mode: get membrane-forming agent product that 40 mass parts embodiment 1 make, mix (the quality percentage composition of membrane-forming agent product is 5%) with 800 mass parts deionized waters and become solution, solution is heated to 90 ℃, constant temperature 30min gelatinization, temperature-rise period should not be too fast.After gelatinization is finished, add again an amount of warm water and adjust the temperature to that (to become starch paste) about 75 ℃ stand-by.According to the prior art formula requirement, take by weighing auxiliary agent NBL-e-201, Sofbon GF-1, L-44, Newlon GF-101, Newlon GF-100 in the emulsification container, be heated to 80 ℃, auxiliary agent GW-18 is dissolved into separately the aqueous solution more than 80 ℃.Use 5000r/min high-speed shearing machine (being a kind of whipping appts of the prior art) under high-speed stirring, to add gradually the GW-18 aqueous solution.The material thick paste that is that becomes sticky when phase inversion point continues to add hot water more than 80 ℃, makes it to be transformed into stable O/w emulsion.About 4 minutes of high speed shear churning time.In the starch paste that the finish emulsion adding that emulsification is good is 75 ℃.Take by weighing the auxiliary agent NBL-70 that prescription requires, be dissolved in 80 ℃ of hot water, add in the starch paste.Quantitatively extremely require the treating compound total amount of preparation with 70 ℃ of left and right sides hot water.The treating compound that makes is used for the glass fiber wire-drawing process, and surveys performance, the results are shown in Table 1, table 2.
Embodiment 2:
Get 40 mass parts pea starches and drop in the reactor, add 300 mass parts distilled water, stir, be warming up to 80 ℃, behind the gelatinization 1.5h, be cooled to 45 ℃, regulate pH value to 5 with alkaline conditioner.Add 2 mass parts isoamylases, reaction 30h is after solution is crossed 80 mesh sieve, be warming up to 90 ℃, reaction 10min is cooled to 40 ℃ again, add 3 mass parts anhydrous sodium sulphate, insulation 10min adds 0.48 mass parts sodium hydroxide again, then add rapidly 4 mass parts propylene oxide, sealed vessel, reaction 12h, react complete, be down to room temperature, suction filtration, solids makes pale powder shape treated starch---membrane-forming agent product through lyophilize.
Get membrane-forming agent product that 40 mass parts embodiment 2 make, mix (the quality percentage composition of membrane-forming agent product is 5%) with 800 parts of deionized waters and become solution, solution is heated to 90 ℃, constant temperature 30min gelatinization, temperature-rise period should not be too fast.After gelatinization is finished, adjust the temperature to that (to become starch paste) about 70 ℃ stand-by.According to the prior art formula requirement, take by weighing auxiliary agent NBL-e-201, Sofbon GF-1, L-44, Newlon GF-101, Newlon GF-100 in the emulsification container, be heated to 80 ℃, GW-18 is dissolved into separately the aqueous solution more than 75 ℃.Use the 5000r/min high-speed shearing machine under high-speed stirring, to add gradually the GW-18 aqueous solution.The material thick paste that is that becomes sticky when phase inversion point continues to add hot water more than 85 ℃, makes it to be transformed into stable O/w emulsion.About 5 minutes of high speed shear churning time.In the starch paste that the finish emulsion adding that emulsification is good is 75 ℃.Take by weighing the NBL-70 that prescription requires, be dissolved in 80 ℃ of hot water, add in the starch paste.Quantitatively extremely require the treating compound total amount of preparation with 70 ℃ of left and right sides hot water.The treating compound that makes is used for the glass fiber wire-drawing process, and surveys performance, the results are shown in Table 1, table 2.
The addition of auxiliary agent is with reference to following table (consumption in the preparation 100kg treating compound) among the embodiment 1 and 2:
| NBL-e-201 | 0.80-1.50 kg |
| Sofbon GF-1 | 0.50-0.85 kg |
| L-44 | 0.05-0.15 kg |
| Newlon GF-101 | 0.02-0.08 kg |
| Newlon GF-100 | 0.05-0.15 kg |
| GW-18 | 0.25-0.65 kg |
| NBL-70 | 0.70-1.20 kg |
Embodiment 1 and 2 membrane-forming agent, treating compound the performance test results:
The performance perameter of the membrane-forming agent that table 1: embodiment 1 and 2 makes
Table 2: embodiment 1 and 2: the wire-drawing performance of the treating compound that makes
Embodiment 3:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent comprises the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 400 mass parts distilled water or deionized waters, stir down, are warming up to 80 ℃, and behind the gelatinization reaction 1.2h, cooling down to 40 ℃ makes starch fluid again;
B, with the pH value to 5 that pH adjusting agent is regulated starch fluid, add isoamylase 2.5 mass parts, react 18h after, be warming up to 80 ℃ of enzyme 18min that go out, make reaction solution;
C, reaction solution is cooled to 45 ℃, adds 4.5 mass parts expansion inhibitor, insulation 15min; Add again 0.4 mass parts of catalyst, then (rapidly) add 7 mass parts etherifying agents, react again 17h, regulate pH value to 7 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Embodiment 4:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent comprises the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300 mass parts distilled water or deionized waters, stir down, are warming up to 90 ℃, and behind the gelatinization reaction 0.5h, cooling down to 35 ℃ makes starch fluid again;
B, with the pH value to 4 that pH adjusting agent is regulated starch fluid, add isoamylase 1 mass parts, react 6h after, be warming up to 90 ℃ of enzyme 5min that go out, make reaction solution;
C, reaction solution is cooled to 30 ℃, adds 3 mass parts expansion inhibitor, insulation 10min; Add again 0.3 mass parts of catalyst, then add 4 mass parts etherifying agents, react again 10h, regulate pH value to 6 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Embodiment 5:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent comprises the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300 mass parts distilled water or deionized waters, stir down, are warming up to 90 ℃, and behind the gelatinization reaction 2h, cooling down to 50 ℃ makes starch fluid again;
B, with the pH value to 6.5 that pH adjusting agent is regulated starch fluid, add isoamylase 4 mass parts, react 30h after, be warming up to 75 ℃ of enzyme 30min that go out, make reaction solution;
C, reaction solution is cooled to 55 ℃, adds 6 mass parts expansion inhibitor, insulation 20min; Add again 0.5 mass parts of catalyst, then add 10 mass parts etherifying agents, react again 24h, regulate pH value to 8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Embodiment 6:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent comprises the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300～500 mass parts distilled water or deionized water (also starch can be mixed with part water be made into 5～15% the aqueous solution after, mix with the water of remaining part again), stir lower, be warming up to 75～90 ℃, behind gelatinization reaction 0.5～2h, cooling down to 35～50 ℃ make starch fluid again;
B, regulate the pH value to 4 of starch fluid～6.5 with pH adjusting agent, add isoamylase 1～4 mass parts, react 6～30h after, be warming up to 75～90 ℃ of enzyme 5～30min that go out, make reaction solution;
C, reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again 0.3～0.5 mass parts of catalyst, then add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Embodiment 7-13:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent comprises the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300～500 mass parts distilled water or deionized water (also starch can be mixed with part water be made into 5～15% the aqueous solution after, mix with the water of remaining part again), stir lower, be warming up to 75～90 ℃, behind gelatinization reaction 0.5～2h, cooling down to 35～50 ℃ make starch fluid again;
B, regulate the pH value to 4 of starch fluid～6.5 with pH adjusting agent, add isoamylase 1～4 mass parts, react 6～30h after, be warming up to 75～90 ℃ of enzyme 5～30min that go out, make reaction solution;
C, reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again 0.3～0.5 mass parts of catalyst, then add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
The concrete consumption (mass parts) of each component sees the following form among each embodiment:
Embodiment 14:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent,
Described step c replaces with: reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again catalyst solution, then (rapidly) add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described catalyst solution is that 0.3～0.5 mass parts of catalyst is dissolved in the solution that is made in 5～10 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
Arbitrary in the other the same as in Example 3-13, omit.
Embodiment 15:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent,
Described step c replaces with: reaction solution is cooled to 45 ℃, adds 4.5 mass parts expansion inhibitor, insulation 15min; Add catalyst solution, then (rapidly) adding 7 mass parts etherifying agents react 17h more again, regulate pH value to 7 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described catalyst solution is that 0.4 mass parts of catalyst is dissolved in the solution that is made in the 7 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
Arbitrary in the other the same as in Example 3-13, omit.
Embodiment 16:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent,
Described step c replaces with: reaction solution is cooled to 30 ℃, adds 3 mass parts expansion inhibitor, insulation 10min; Add catalyst solution, then (rapidly) adding 4 mass parts etherifying agents react 10h more again, regulate pH value to 6 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described catalyst solution is that 0.3 mass parts of catalyst is dissolved in the solution that is made in the 5 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
Arbitrary in the other the same as in Example 3-13, omit.
Embodiment 17:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent,
Described step c replaces with: reaction solution is cooled to 55 ℃, adds 6 mass parts expansion inhibitor, insulation 20min; Add again catalyst solution, then (rapidly) add 10 mass parts etherifying agents, react again 24h, regulate pH value to 8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Described catalyst solution is that 0.5 mass parts of catalyst is dissolved in the solution that is made in the 10 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
Arbitrary in the other the same as in Example 3-13, omit.
Embodiment 18:
A kind of preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent,
Described step c replaces with: reaction solution is cooled to 35 ℃, adds 5 mass parts expansion inhibitor, insulation 16min; Add catalyst solution, then (rapidly) adding 6 mass parts etherifying agents react 15h more again, regulate pH value to 7 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, solids namely makes (canescence treated starch) membrane-forming agent product through (freezing or other prior art mode) drying;
Arbitrary in the other the same as in Example 3-13, omit.
Described catalyst solution is that 0.35 mass parts of catalyst is dissolved in the solution that is made in the 6 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
In above-described embodiment 3-18: described expansion inhibitor is that sodium sulfate is or/and sodium-chlor;
In above-described embodiment 3-18: described catalyzer is one or more the mixture in sodium hydroxide, sodium sulfate or the sodium-chlor;
In above-described embodiment 3-18: described etherifying agent is one or more the mixture in oxyethane, propylene oxide or the chloroethanol.
In above-described embodiment 3-18: described pH adjusting agent be the acid regulator SODIUM PHOSPHATE, MONOBASIC or/and potassium primary phosphate or/and the alkaline conditioner Sodium phosphate dibasic or/and dipotassium hydrogen phosphate.
In above-described embodiment 3-18: described pea starch is that commercially available crape skin pea starch is or/and smooth pea starch.
In above-described embodiment: described NBL-e-201, Sofbon GF-1, L-44, Newlon GF-101, Newlon GF-100, GW-18, NBL-70 are the existing commercially available prod of Japanese NBL KCC production and sales.
When the membrane-forming agent product that content of the present invention and above-described embodiment make is used in glass fiber wire drawing technique as treating compound, the membrane-forming agent product that makes and water and (multiple) organic additive (existing commercially available prod) can be mixed, are made into the form of emulsion treating compound, be coated to fiberglass surfacing, the consumption of membrane-forming agent product in treating compound that the present invention makes can be treating compound 3～8% of the gross weight of filling a prescription.
Described raw material in content of the present invention and above-described embodiment is existing marketable material, and the consumption unit of the feed composition that does not indicate especially is with the mass parts (can all be gram or kilogram etc.) of adjacent other component same units, the ratio of feed composition and is mass ratio; In the percentage that adopts, do not indicate especially, be the mass percent example.
In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, content of the present invention is described all can implement and have described good result.
Claims (4)
1. a preparation method who is used for the starch-type membrane-forming agent of glass fiber infiltration agent is characterized in that comprising the following steps:
A, the pea starch of getting 40 mass parts are put in the reaction vessel, add 300～500 mass parts distilled water or deionized waters, stir down, are warming up to 75～90 ℃, and behind gelatinization reaction 0.5～2h, cooling down to 35～50 ℃ make starch fluid again;
B, regulate the pH value to 4 of starch fluid～6.5 with pH adjusting agent, add isoamylase 1～4 mass parts, react 6～30h after, be warming up to 75～90 ℃ of enzyme 5～30min that go out, make reaction solution;
C, reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again 0.3～0.5 mass parts of catalyst, then add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, the solids drying namely makes the membrane-forming agent product;
Described expansion inhibitor is that sodium sulfate is or/and sodium-chlor;
Described catalyzer is sodium hydroxide;
Described etherifying agent is one or more the mixture in oxyethane, propylene oxide or the chloroethanol.
2. by the preparation method of the starch-type membrane-forming agent for glass fiber infiltration agent claimed in claim 1, it is characterized in that: described step c replaces with: reaction solution is cooled to 30～55 ℃, adds 3～6 mass parts expansion inhibitor, insulation 10～20min; Add again catalyst solution, then add 4～10 mass parts etherifying agents, react again 10～24h, regulate pH value to 6～8 with pH adjusting agent, react complete, be down to room temperature after, suction filtration, the solids drying namely makes the membrane-forming agent product;
Described catalyst solution is that 0.3～0.5 mass parts of catalyst is dissolved in the solution that is made in 5～10 mass parts water, and this catalyst solution is added drop-wise in the reaction system.
3. by the preparation method of claim 1 or 2 described starch-type membrane-forming agents for glass fiber infiltration agent, it is characterized in that: described pH adjusting agent be the acid regulator SODIUM PHOSPHATE, MONOBASIC or/and potassium primary phosphate or/and the alkaline conditioner Sodium phosphate dibasic or/and dipotassium hydrogen phosphate.
4. by the preparation method of claim 1 or 2 described starch-type membrane-forming agents for glass fiber infiltration agent, it is characterized in that: described pea starch is that commercially available crape skin pea starch is or/and smooth pea starch.
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| CN103420621A (en) * | 2012-05-23 | 2013-12-04 | 台嘉玻璃纤维有限公司 | Glass fiber yarn impregnating compound and preparation method |
| CN103012608A (en) * | 2012-11-21 | 2013-04-03 | 西南科技大学 | Method for preparing etherification linear-chain dextrin starch film-forming agent for glass fiber infiltration |
| CN103232548B (en) * | 2013-04-12 | 2015-12-09 | 西南科技大学 | A kind of preparation method of glass fibre infiltration esterification starch membrane-forming agent |
| CN104861212B (en) * | 2015-05-06 | 2017-06-06 | 西南科技大学 | A kind of preparation method of silica gel modified starch type size |
| CN104911891B (en) * | 2015-05-28 | 2017-05-31 | 句容市申兔工艺针织厂 | A kind of pre-treating method of glass fabric wire drawing |
| CN104961838B (en) * | 2015-07-15 | 2017-03-01 | 河南恒瑞淀粉科技股份有限公司 | A kind of hydroxypropylation modified starch and preparation method thereof |
| CN110983772A (en) * | 2019-12-27 | 2020-04-10 | 河南新孚望新材料科技有限公司 | Formaldehyde crosslinked starch for glass fibers and preparation method thereof |
| CN112679624B (en) * | 2021-03-18 | 2021-07-20 | 华南理工大学 | Life nutrition capsule |
| CN114933419B (en) * | 2022-04-29 | 2023-09-29 | 北京仿生界面科学未来技术研究院 | Method for preparing ultrathin flexible glass by using bionic weathering enzyme composite glass thinning agent |
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| US7081261B2 (en) * | 2002-05-14 | 2006-07-25 | National Starch And Chemical Investment Holding Corporation | Resistant starch prepared by isoamylase debranching of low amylose starch |
| CN100509854C (en) * | 2007-04-19 | 2009-07-08 | 成都新柯力化工科技有限公司 | Method for preparing amylose |
| CN101759808B (en) * | 2010-01-14 | 2011-12-07 | 同济大学 | Method for preparing modified polyamine porous starch |
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