CN105481989B - Glass fiber impregnating compound added with modified starch - Google Patents
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- CN105481989B CN105481989B CN201510942752.4A CN201510942752A CN105481989B CN 105481989 B CN105481989 B CN 105481989B CN 201510942752 A CN201510942752 A CN 201510942752A CN 105481989 B CN105481989 B CN 105481989B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
The invention relates to the technical field of glass fiber surface treatment, in particular to a glass fiber impregnating compound added with modified starch. The film forming agent component is hydroxypropyl modified starch, wherein the hydroxypropyl content in the hydroxypropyl modified starch is more than or equal to 7% and less than or equal to 12%. The glass fiber impregnating compound added with the modified starch has high bonding force, good film forming property and protectiveness, and improves the mechanical property of glass fiber. The glass fiber prepared by adopting the glass fiber sizing agent added with the modified starch to perform surface treatment is easy to be degraded after weaving, does not cause concave-convex, yellow edge and fluffy cloth surface, and improves the quality of the glass fiber cloth.
Description
The application is a divisional application of a hydroxypropylated modified starch, a preparation method thereof and a glass fiber sizing agent, wherein the application number is 201510414989.5, the application date is 2015, 7 and 15
Technical Field
The invention relates to the technical field of glass fiber surface treatment, in particular to a glass fiber impregnating compound added with modified starch.
Background
Hydroxypropyl starch is an important chemically modified starch, and after modification, due to the high stability of ether bonds substituted by etherified starch, the hydroxypropyl has hydrophilicity, can weaken the internal hydrogen bond strength of a starch particle structure, and is easy to expand, easy to gelatinize, transparent in paste liquid, good in fluidity, weak in retrogradation and high in stability. The hydroxypropyl corn starch can be applied to the industries of food, printing, spinning, printing and dyeing, detergents, papermaking, medicine, metallurgy, petroleum drilling and the like. Hydroxypropyl corn starch is commonly used as a film forming agent component of a sizing agent in the preparation process of glass fibers and is used for surface treatment of the glass fibers.
During the glass fiber drawing process, a special surface treating agent with a multiphase structure mainly comprising organic emulsion or solution is required to be coated on the surface of the glass fiber. The coating not only can effectively lubricate and protect the surface of the glass fiber, but also can integrate hundreds or even thousands of glass fiber monofilaments into one bundle, and can change the surface state of the glass fiber, thereby not only meeting the requirements on the performance of the glass fiber protofilament in the subsequent processing procedures, but also promoting the combination of the glass fiber and the reinforced high molecular polymer in the composite material. These organic coatings are collectively referred to as glass fiber size with added modified starch. Generally, the sizing agent is composed of a film forming agent, a coupling agent, an antistatic agent and other substances, wherein the film forming agent is a key component of the sizing agent, plays a role in bundling and bonding strands, determines the processability of glass fibers during the molding of glass fiber reinforced plastics, determines the film forming property and the affinity to the surfaces of the glass fibers, and can form a high-strength, soft and wear-resistant film on the surfaces of the fibers and be integrated with the surfaces of the glass fibers.
The most used impregnating compound is paraffin type impregnating compound which is not easy to degrade, but the color fixing agent in the formula is difficult to thermally clean, so that the prepared glass fiber is yellow or generates obvious brown stripes, and the grade of the product is reduced. Later, with the development of glass fiber surface treatment technology, the use of starch as a sizing agent gradually appeared. However, unmodified starch cannot be used as a film forming agent due to the defects of high gelatinization temperature, non-uniform viscosity, poor film forming property, unstable property and the like, and the hydroxypropyl modified starch improves the performance of the starch as the film forming agent due to the specific hydrophilicity of hydroxypropyl, and the higher the hydroxypropyl degree is, the better the film forming property and the fusion property with the surface of the glass fiber are.
However, since the crystalline structure of starch is not favorable for permeation and reaction of chemical reagents, especially the efficiency of etherification reaction is extremely low, more and more researches are focused at present on improving the preparation reaction efficiency and the hydroxypropylation degree of hydroxypropylated modified starch, for example, chinese patent CN102304188A discloses a preparation method of starch type film forming agent for glass fiber sizing agent added with modified starch, which adopts a preparation method of firstly carrying out enzymolysis on starch and then adding an etherification reagent for hydroxypropylation, wherein starch needs to be heated and gelatinized before the enzymolysis, and the gelatinized starch is very viscous, thus being not favorable for industrial production. Even if the viscosity is reduced after enzymolysis, the defects of low reaction efficiency of starch and an etherification reagent and low degree of hydroxypropylation still exist.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a glass fiber sizing agent added with modified starch, which uses hydroxypropylated modified starch with high hydroxypropyl content and has excellent film forming property, caking property and protective property.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a hydroxypropylated modified starch, the hydroxypropyl content is more than or equal to 7 percent and less than or equal to 12 percent.
The hydroxypropylated modified starch is prepared by the following preparation method: the method comprises the following operation steps:
1) adding starch and a swelling inhibitor into water, and mixing and stirring uniformly to prepare a starch solution;
2) heating the starch solution to 35-38 ℃, adding a catalyst, uniformly stirring, adding an oxidant, and carrying out an oxidation reaction to obtain a solution A;
3) adding a sodium hydroxide solution into the solution A to adjust the pH value to 11-12, sequentially adding a catalyst and an etherification reagent, and reacting at 35-38 ℃ to obtain a solution B;
4) and (3) cooling the solution B to 25-30 ℃, adding a pH regulator, regulating the pH to 6.5-7.5, and after the reaction is finished, carrying out suction filtration to obtain a solid substance, thus obtaining the hydroxypropylated modified starch.
The mass concentration of the solution of sodium hydroxide added in the step 3) is 2-6%.
The catalyst is sodium chloride. The sodium chloride has small molecular weight and high osmotic pressure.
The swelling inhibitor is sodium sulfate.
The oxidant is sodium hypochlorite or hydrogen peroxide with the mass concentration of 30%.
The etherification reagent is propylene oxide.
The pH regulator is a hydrochloric acid solution with the mass concentration of 20%.
The starch is corn starch, preferably high amylose corn starch, and more preferably high amylose corn starch with an amylose content of more than 70%.
Preferably, the mass of the starch and the water is 1-2: 2-5; the mass ratio of the starch to the swelling inhibitor is 20-40: 3-5; the mass of the starch and the oxidant is 5-24: 1-4; the mass ratio of the starch to the etherification reagent is 20-25: 3-5; the mass ratio of the catalyst to the starch in the step 2) is 2-3: 25-30; the mass ratio of the catalyst to the starch in the step 3) is 1-6: 10 to 15.
The oxidation reaction time in the step 2) is 5-7 hours; the reaction time in step 3) was 20 hours.
The stirring time in the step 1) is 30-60 minutes; step 2) the stirring time was 30 minutes.
In order to obtain dry starch with fine particles, the method also comprises the step of drying and crushing the solid matters obtained after the suction filtration in the step 4).
The glass fiber impregnating compound added with the modified starch comprises the film forming agent component of the hydroxypropyl modified starch.
The glass fiber impregnating compound added with the modified starch is characterized in that the dosage of the film forming agent is 4-10% of the total weight of the formula.
The glass fiber impregnating compound added with the modified starch is prepared by mixing the hydroxypropylated modified starch of the invention with water, an emulsifier, oil and other auxiliaries to prepare an emulsion.
Preferably, the glass fiber impregnating compound added with the modified starch is prepared from the following raw materials in percentage by weight: 80-200 parts of hydroxypropylated modified starch, 30 parts of vegetable oil, 1 part of emulsifier, 2.5 parts of polyethylene glycol, 0.5 part of polyvinyl alcohol and 1766-1886 parts of water. Wherein, the polyethylene glycol and the polyvinyl alcohol are used as reaction auxiliary agents to prevent fiber from breaking and enhance plasticity and stiffness.
The glass fiber impregnating compound added with the modified starch is coated on the surface of glass fiber and used for carrying out surface treatment on the glass fiber to form a high-strength, soft and wear-resistant film on the surface of the glass fiber, so that the subsequent processing performance of the glass fiber is improved.
The hydroxypropyl modified starch has the hydroxypropyl content of more than or equal to 7 percent and up to 12 percent, has high hydroxypropyl content, good film forming property, uniform viscosity and stable performance.
The preparation method of the hydroxypropylated modified starch comprises the steps of firstly adding an oxidant to oxidize starch, and then adding an etherification reagent to carry out etherification reaction to prepare the hydroxypropylated modified starch. The invention adopts the treatment means of oxidation first to ensure that the crystalline structure of the starch is moderately swelled, and hydroxyl is fully filled with the reaction activity, so that the etherification reagent reaction is easy, the reaction efficiency can be improved to more than 60 percent, the hydroxypropyl content reaches more than 7 percent, and compared with the traditional preparation method, the reaction efficiency is improved by more than one time, and the hydroxypropyl content is improved by more than 2 times.
The glass fiber impregnating compound added with the modified starch has high cohesive force, good film forming property and protectiveness by adopting the hydroxypropylated modified starch prepared by the invention as a film forming agent, is beneficial to the protection and the collection of the glass fiber in the high-speed spraying and twisting processes, improves the production efficiency and improves the mechanical property of the glass fiber. The glass fiber prepared by adopting the glass fiber sizing agent added with the modified starch for surface treatment is easy to be degraded after weaving, does not cause concave-convex, yellow edge and fluffy cloth surface, improves the quality of glass fiber cloth, and has social benefits of energy conservation and environmental protection and economic benefits of quality improvement. Meanwhile, compared with imported starch, the glass fiber treated by the glass fiber impregnating compound added with the modified starch prepared by the modified starch of the invention reduces broken wool and fly, and increases the stiffness and mechanical strength of the glass fiber.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
In the following examples, high-chain corn starch was obtained from Ri Yi brand product, Towa Nongchun Special corn development Co., Ltd., in which the raw materials were used in parts by weight, and the reaction efficiency was calculated by the reaction efficiency of hydroxypropyl content/propylene oxide content of × 100% by weight.
Example 1
The hydroxypropylated modified starch of the embodiment is prepared by the following steps:
1) adding 200 parts of tap water into a stainless steel reaction kettle, adding 100 parts of high-chain corn starch and 15 parts of sodium sulfate under the condition of continuous stirring, and stirring for 30 minutes to prepare a starch solution;
2) heating the starch solution prepared in the step 1) to 35 ℃, adding 8 parts of sodium chloride, stirring for 30 minutes, adding 20 parts of sodium hypochlorite, carrying out oxidation reaction, and reacting for 5 hours to obtain a solution A;
3) adding a sodium hydroxide solution with the mass concentration of 2% into the solution A to adjust the pH value to 11, sequentially adding 10 parts of sodium chloride and 15 parts of propylene oxide reaction reagent, and reacting at 35 ℃ for 20 hours to obtain a solution B;
4) and cooling the solution B to 30 ℃, adding 16 parts of hydrochloric acid solution with the mass concentration of 20%, adjusting the pH to 7, performing suction filtration after the reaction is finished to obtain a solid, drying and crushing the solid to obtain the hydroxypropylated modified starch.
The hydroxypropyl modified starch of this example had a hydroxypropyl content of 7.3% and a carboxyl content of 1.5%.
The reaction efficiency for the preparation of hydroxypropylated modified starch in this example was 60.8%.
Example 2
The hydroxypropylated modified starch of the embodiment is prepared by the following steps:
1) adding 200 parts of tap water into a stainless steel reaction kettle, adding 100 parts of high-chain corn starch and 15 parts of sodium sulfate under the condition of continuous stirring, and stirring for 60 minutes to prepare a starch solution;
2) heating the starch solution prepared in the step 1) to 38 ℃, adding 8 parts of sodium chloride, stirring for 30 minutes, adding 20 parts of sodium hypochlorite, carrying out oxidation reaction, and reacting for 7 hours to obtain a solution A;
3) adding a sodium hydroxide solution with the mass concentration of 6% into the solution A to adjust the pH value to 12, sequentially adding 10 parts of sodium chloride and 15 parts of propylene oxide reaction reagent, and reacting at 38 ℃ for 20 hours to obtain a solution B;
4) and cooling the solution B to 25 ℃, adding 16 parts of hydrochloric acid solution with the mass concentration of 20%, adjusting the pH to 7, performing suction filtration after the reaction is finished to obtain a solid, drying and crushing the solid to obtain the hydroxypropylated modified starch.
The hydroxypropyl modified starch of this example had a hydroxypropyl content of 7.3% and a carboxyl content of 1.5%.
The reaction efficiency for the preparation of hydroxypropylated modified starch in this example was 60.8%.
Example 3
1) Adding 200 parts of tap water into a stainless steel reaction kettle, adding 100 parts of high-chain corn starch and 15 parts of sodium sulfate under the condition of continuous stirring, and stirring for 50 minutes to prepare a starch solution;
2) heating the starch solution prepared in the step 1) to 37 ℃, adding 8 parts of sodium chloride, stirring for 30 minutes, adding 20 parts of sodium hypochlorite, carrying out oxidation reaction, and reacting for 6 hours to obtain a solution A;
3) adding a sodium hydroxide solution with the mass concentration of 5% into the solution A to adjust the pH value to 11, sequentially adding 10 parts of sodium chloride and 15 parts of propylene oxide reaction reagent, and reacting at 36 ℃ for 20 hours to obtain a solution B;
4) and cooling the solution B to 28 ℃, adding 16 parts of hydrochloric acid solution with the mass concentration of 20%, adjusting the pH to 7, performing suction filtration after the reaction is finished to obtain a solid, drying and crushing the solid to obtain the hydroxypropylated modified starch.
The hydroxypropyl modified starch of this example had a hydroxypropyl content of 7.3% and a carboxyl content of 1.5%.
The reaction efficiency for the preparation of hydroxypropylated modified starch in this example was 60.8%.
Example 4
1) Adding 200 parts of tap water into a stainless steel reaction kettle, adding 100 parts of high-chain corn starch and 13 parts of sodium sulfate under the condition of continuous stirring, and stirring for 50 minutes to prepare a starch solution;
2) heating the starch solution prepared in the step 1) to 37 ℃, adding 8.9 parts of sodium chloride, stirring for 30 minutes, adding 30 parts of sodium hypochlorite, carrying out oxidation reaction, and reacting for 6 hours to obtain a solution A;
3) adding a sodium hydroxide solution with the mass concentration of 3% into the solution A to adjust the pH value to 11, sequentially adding 41.7 parts of sodium chloride and 18 parts of propylene oxide reaction reagent, and reacting at 36 ℃ for 20 hours to obtain a solution B;
4) and cooling the solution B to 30 ℃, adding 15 parts of hydrochloric acid solution with the mass concentration of 20%, adjusting the pH to 7.5, after the reaction is finished, performing suction filtration to obtain a solid, drying and crushing the solid to obtain the hydroxypropylated modified starch.
The hydroxypropyl modified starch of this example had a hydroxypropyl content of 9% and a carboxyl content of 1.6%.
The reaction efficiency for the preparation of hydroxypropylated modified starch in this example was 60%.
Example 5
1) Adding 250 parts of tap water into a stainless steel reaction kettle, adding 100 parts of high-chain corn starch and 12.5 parts of sodium sulfate under the condition of continuous stirring, and stirring for 50 minutes to prepare a starch solution;
2) heating the starch solution prepared in the step 1) to 37 ℃, adding 10 parts of sodium chloride, stirring for 30 minutes, adding 16.7 parts of hydrogen peroxide with the mass concentration of 30%, performing oxidation reaction, and reacting for 6 hours to obtain a solution A;
3) adding a sodium hydroxide solution with the mass concentration of 5% into the solution A to adjust the pH value to 12, sequentially adding 40 parts of sodium chloride and 20 parts of propylene oxide reaction reagent, and reacting at 36 ℃ for 20 hours to obtain a solution B;
4) and cooling the solution B to 30 ℃, adding 17 parts of hydrochloric acid solution with the mass concentration of 20%, adjusting the pH to 6.5, after the reaction is finished, performing suction filtration to obtain a solid, drying and crushing the solid to obtain the hydroxypropylated modified starch.
The hydroxypropyl modified starch of this example had a hydroxypropyl content of 12% and a carboxyl content of 1.7%.
The reaction efficiency for the preparation of hydroxypropylated modified starch in this example was 60%.
Example 6
The glass fiber impregnating compound added with the modified starch is prepared from the following raw materials in parts by weight: 100 parts of hydroxypropylated modified starch, 30 parts of hydrogenated vegetable oil, 1 part of span series emulsifier, 2.5 parts of polyethylene glycol, 0.5 part of polyvinyl alcohol and 1866 parts of water; wherein the hydroxypropylated modified starch is the hydroxypropylated modified starch prepared in example 1.
The preparation method of the glass fiber impregnating compound added with the modified starch comprises the following specific steps:
1) adding the modified starch into 500 parts of water, and heating and pasting to prepare a solution A;
2) adding all hydrogenated vegetable oil, span series emulsifier, polyethylene glycol and polyvinyl alcohol into 100 parts of water for complete emulsification to prepare a solution B;
3) and adding the solution B into the solution A, adding the rest water, and uniformly stirring to obtain the glass fiber impregnating compound added with the modified starch.
Comparative example 1
The hydroxypropylated modified starch in example 6 was replaced with imported modified starch (recommended by the manufacturer), and a modified starch-added glass fiber sizing agent was prepared in the same manner as in example 7.
Comparative example 2
A glass fiber sizing material containing modified starch was prepared in the same manner as in example 6, except that the modified hydroxypropylated starch in example 6 was replaced with paraffin.
Test examples
The test method comprises the following steps: the glass fiber sizing agents with the addition of the modified starch prepared in example 6, comparative example 1 and comparative example 2 were respectively used in the glass fiber drawing process, and the performance of the glass fiber strands was tested, and the results are shown in the following table 1:
TABLE 1 Properties of glass fibers treated with modified starch-containing glass fiber sizing Agents prepared in example 6, comparative example 1 and comparative example 2
| Categories | Strand integrity | Stiffness of raw yarn | Broken hair fly silk | Breaking Strength/CN |
| Comparative example 1 | Good taste | Is preferably used | Has less broken filaments and broken hairs | 2750 |
| Comparative example 2 | Is preferably used | Is preferably used | Many broken hairs and filaments | 2450 |
| Example 6 | Good taste | Good taste | Little broken wool and broken wool | 3000 |
As can be seen from the data shown in table 1, compared with the sizing agent prepared by using imported starch and paraffin as film forming agents, the glass fiber sizing agent added with modified starch prepared in example 6 of the present invention improves the bundling property and stiffness of glass fiber strands; the broken filaments and broken hairs are reduced, and the glass fiber impregnating compound added with the modified starch prepared in the embodiment 6 of the invention has better film-forming property and protective effect on glass fibers; meanwhile, the breaking strength of the glass fiber strands is improved, which shows that the glass fiber impregnating compound added with the modified starch prepared in the embodiment 6 of the invention can well fill the defects and cracks on the surfaces of the glass fibers, has better affinity with the glass fibers and improves the breaking strength of the glass fibers.
The hydroxypropylated modified starch prepared in the embodiments 2-5 of the invention can also be used as a raw material of a film forming agent of the glass fiber sizing agent added with the modified starch, the addition amount can be 4-10% of the total formula amount, and the performance of the prepared glass fiber sizing agent added with the modified starch is equivalent to that of the embodiment 6.
Claims (7)
1. The glass fiber impregnating compound added with the modified starch is characterized in that a film forming agent component is hydroxypropyl modified starch, wherein the hydroxypropyl content in the hydroxypropyl modified starch is more than or equal to 7% and less than or equal to 12%;
the preparation method comprises the following steps: the method comprises the following operation steps:
1) adding starch and a swelling inhibitor into water, and mixing and stirring uniformly to prepare a starch solution;
2) heating the starch solution to 35-38 ℃, adding a catalyst, uniformly stirring, adding an oxidant, and carrying out an oxidation reaction to obtain a solution A;
3) adding a sodium hydroxide solution into the solution A to adjust the pH value to 11-12, sequentially adding a catalyst and an etherification reagent, and reacting at 35-38 ℃ to obtain a solution B;
4) and (3) cooling the solution B to 25-30 ℃, adding a pH regulator, regulating the pH to 6.5-7.5, and after the reaction is finished, carrying out suction filtration to obtain a solid substance, thus obtaining the hydroxypropylated modified starch.
2. The modified starch added glass fiber sizing agent according to claim 1, wherein said catalyst is sodium chloride.
3. The modified starch added glass fiber sizing agent according to claim 1, wherein said swelling inhibitor is sodium sulfate.
4. The glass fiber impregnating compound added with the modified starch as described in claim 1, wherein the oxidizing agent is sodium hypochlorite or hydrogen peroxide with a mass concentration of 30%.
5. The modified starch added glass fiber sizing agent according to claim 1, wherein said etherification agent is propylene oxide.
6. The glass fiber impregnating compound added with the modified starch as claimed in claim 1, wherein the mass ratio of the starch to the water is 1-2: 2-5; the mass ratio of the starch to the swelling inhibitor is 20-40: 3-5; the mass of the starch and the oxidant is 5-24: 1-4; the mass ratio of the starch to the etherification reagent is 20-25: 3-5; the mass ratio of the catalyst to the starch in the step 2) is 2-3: 25-30; the mass ratio of the catalyst to the starch in the step 3) is 1-6: 10 to 15.
7. The glass fiber sizing agent added with the modified starch as claimed in claim 1, wherein the amount of the film forming agent is 4-10% of the total formula amount of the glass fiber sizing agent added with the modified starch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510942752.4A CN105481989B (en) | 2015-07-15 | 2015-07-15 | Glass fiber impregnating compound added with modified starch |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510414989.5A CN104961838B (en) | 2015-07-15 | 2015-07-15 | A kind of hydroxypropylation modified starch and preparation method thereof |
| CN201510942752.4A CN105481989B (en) | 2015-07-15 | 2015-07-15 | Glass fiber impregnating compound added with modified starch |
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| CN201510414989.5A Division CN104961838B (en) | 2015-07-15 | 2015-07-15 | A kind of hydroxypropylation modified starch and preparation method thereof |
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| CN105481989A CN105481989A (en) | 2016-04-13 |
| CN105481989B true CN105481989B (en) | 2020-07-03 |
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| CN201510414989.5A Active CN104961838B (en) | 2015-07-15 | 2015-07-15 | A kind of hydroxypropylation modified starch and preparation method thereof |
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| CN105315379B (en) * | 2015-12-04 | 2018-05-08 | 东莞建泰生物科技有限公司 | A kind of grease proofing starch and its production technology and application |
| CN106316158A (en) * | 2016-08-31 | 2017-01-11 | 郭舒洋 | Method for preparing impregnating compound from compound modified tapioca starch |
| CN107759110A (en) * | 2017-10-31 | 2018-03-06 | 常州菲胜图自动化仪器有限公司 | A kind of preparation method of good beaming type glass fiber infiltration agent |
| CN108585547A (en) * | 2018-07-19 | 2018-09-28 | 安徽省绩溪县华宇防火滤料有限公司 | A kind of glass fibre high efficiency infiltration agent composition |
| CN109652981B (en) * | 2018-11-22 | 2021-11-30 | 蒋洪新 | Starch-based glass fiber soaking film-forming agent and preparation method thereof |
| 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 |
| 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 |
| CN111100215A (en) * | 2019-12-30 | 2020-05-05 | 河南新孚望新材料科技有限公司 | Preparation method of hydroxypropyl high amylose starch for water-based paint |
| CN111535029B (en) * | 2020-04-17 | 2022-10-11 | 安徽工程大学 | Sizing glass filament yarn and sizing method thereof |
| CN111977990B (en) * | 2020-09-08 | 2021-02-09 | 清远忠信电子材料有限公司 | High-performance impregnating compound for superfine electronic yarn and preparation method thereof |
| CN112813561A (en) * | 2020-12-31 | 2021-05-18 | 南京玻璃纤维研究设计院有限公司 | Flat glass fiber fabric and preparation method thereof |
| CN116099030B (en) * | 2022-11-15 | 2024-08-02 | 青岛海诺生物工程有限公司 | Chitosan breathable adhesive bandage and preparation method thereof |
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| CN104961838B (en) | 2017-03-01 |
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