CN108821611A - A kind of glass fibre interface fiber size for reinforcemeent and preparation method thereof - Google Patents
A kind of glass fibre interface fiber size for reinforcemeent and preparation method thereof Download PDFInfo
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- CN108821611A CN108821611A CN201810902441.9A CN201810902441A CN108821611A CN 108821611 A CN108821611 A CN 108821611A CN 201810902441 A CN201810902441 A CN 201810902441A CN 108821611 A CN108821611 A CN 108821611A
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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
- C03C25/42—Coatings containing inorganic materials
- C03C25/44—Carbon, e.g. graphite
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Abstract
The present invention provides a kind of glass fibre interface fiber sizes for reinforcemeent and preparation method thereof, are prepared by the raw material of following parts by weight：10-30 parts of film forming agent, 3-8 parts of lubricant, 5-10 parts of coupling agent, 4-9 parts of polyacrylamide emulsion, 2.5-7 parts of polyacrylate dispersion, 2-5 parts of sodium carboxymethylcellulose, 3-9 parts of carbon nanotube, 1-4 parts of antistatic agent, 2-6 parts of PEG, 1-5 parts of polyvinylpyrrolidone, 1-3 parts of triethanolamine, 50-80 parts of deionized water.After size produced by the present invention infiltrates glass fibre, glass fibre shows good precursor cluster performance and still dispersion performance, fiberglass surfacing is without wool yarn simultaneously, yarn surface is smooth, the glass fibre shows good acid and alkali-resistance characteristic simultaneously, therefore size produced by the present invention has important use value in the immersion processing of glass fibre.
Description
Technical field
The present invention relates to a kind of sizes, and in particular to a kind of glass fibre interface fiber size for reinforcemeent and its preparation side
Method.
Background technique
Size refers to the material for applying in glass fibre production process and investing fiberglass surfacing.It determines glass fibers
The purposes and performance of dimension.It is that organic material and inorganic material are combined together the material for applying and investing glass surface.Using it
Glass fibre performance can be changed in chemical action.The coating of size can effectively lubricating glass fiber surface and will be hundreds of
Root or even thousands of glass monofilament integrate a branch of, moreover it is possible to change the surface state of glass fibre, not only meet glass original in this way
The requirement of silk later process processing performance, and glass fibre and enhanced high molecular polymerization can also be promoted in the composite
The combination of object.
Size is all very important the production and application of glass, if the glass mistake superfine in high speed pulling diameter
Cheng Zhong does not coat size in fiber surface, not only wire-drawing operation can be caused complete because of fracture of wire, winged silk caused by serious wear
At.Therefore, the performance of size plays an important role the property of glass and application.However the size of prior art production
It is poor to the effect of impregnation of glass fibre, affect glass fibre surface property and, be unfavorable for further making for glass fibre
With.
Summary of the invention
For the above problem of the existing technology, the purpose of the present invention is to provide a kind of glass fibre interface is enhanced
Size and preparation method thereof.
To achieve the goals above, the present invention provides following technical scheme：
A kind of glass fibre interface fiber size for reinforcemeent, is prepared by the raw material of following parts by weight：10-30 parts of film forming agent, profit
3-8 parts of lubrication prescription, 5-10 parts of coupling agent, 4-9 parts of polyacrylamide emulsion, 2.5-7 parts of polyacrylate dispersion, carboxymethyl cellulose
2-5 parts of sodium, 3-9 parts of carbon nanotube, 1-4 parts of antistatic agent, 2-6 parts of PEG, 1-5 parts of polyvinylpyrrolidone, triethanolamine 1-3
Part, 50-80 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
Preferably, a kind of glass fibre interface fiber size for reinforcemeent of the present invention, by the raw material system of following parts by weight
It is standby to form：20 parts of film forming agent, 5.5 parts of lubricant, 7.5 parts of coupling agent, 7 parts of polyacrylamide emulsion, polyacrylate dispersion 5
Part, 3.5 parts of sodium carboxymethylcellulose, 6 parts of carbon nanotube, 2.5 parts of antistatic agent, 4 parts of PEG, 3 parts of polyvinylpyrrolidone, three
2 parts of ethanol amine, 65 parts of deionized water.
Preferably, the antistatic agent is polyethylene glycol methacrylic acid copolymer body.
Preferably, one kind that the molecular weight of the PEG is 400,600 or 1200.
The preparation method of glass fibre interface of the present invention fiber size for reinforcemeent, includes the following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 5- that mass fraction, which is then added,
2-4h is stirred at room temperature in the carbodiimide of 10wt%, and 3- aminopropyl triethoxysilicane is then added under stirring conditions
Alkane continues to be stirred to react 8-12h, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, and the product after collecting dialysis is gone forward side by side
Row freeze-drying, is made freeze-dried powder；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 50-70 DEG C under stirring conditions, keep this temperature
Degree reaction 1-2h, then sequentially adds lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine, in 35-
Continue to be stirred to react 2-4h at a temperature of 45 DEG C, glass fibre interface fiber size for reinforcemeent is made.
Beneficial effect：The present invention provides a kind of glass fibre interface fiber size for reinforcemeent and preparation method thereof, the present invention
It selects acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester as film forming agent, and passes through three second of 3- aminopropyl
Oxysilane is modified acrylic resin modified starch, so that Si-OH group is contained on acrylic resin modified starch surface,
It is crosslinked with the Si-OH group of fiberglass surfacing by hydrogen bond action realization, further increases glass fibre boundary strength.Season penta
Four alcohol esters and Lauryl Alcohol ester have solvent action outstanding and agglutinating power, improve material system to the wellability of glass fibre
With reinforcing aids to the action intensity of glass fibre.Polyacrylamide emulsion, polyacrylate dispersion and film forming agent act synergistically,
Layer protecting film is formed in fiberglass surfacing, the addition of 1- dodecyl -3- methyl imidazolium tetrafluoroborate is as lubrication
Adhere to while agent in fiberglass surfacing, further enhances the wearability of glass fibre.In the synergistic effect with carbon nanotube
Under, the antistatic property of antistatic agent is greatly improved.The addition of PEG and polyvinylpyrrolidone improves raw material in body
Dispersibility in system further increases the solubility property of raw material, to improve system indirectly to the wellability of glass fibre.
After size produced by the present invention infiltrates glass fibre, glass fibre shows good precursor boundling
Performance and still dispersion performance, while fiberglass surfacing, without wool yarn, yarn surface is smooth, while the glass fibre is shown well
Acid and alkali-resistance characteristic, therefore size produced by the present invention glass fibre immersion processing in have important use value.
Specific embodiment
The invention will now be further described with reference to specific embodiments, but examples are merely exemplary, not to this hair
Bright range constitutes any restrictions.It will be understood by those skilled in the art that without departing from the spirit and scope of the invention
Can with the details and forms of the technical scheme of the invention are modified or replaced, but these modification and replacement each fall within it is of the invention
In protection scope.
Embodiment 1
A kind of glass fibre interface fiber size for reinforcemeent, is prepared by the raw material of following parts by weight：20 parts of film forming agent, lubricant
5.5 parts, 7.5 parts of coupling agent, 7 parts of polyacrylamide emulsion, 5 parts of polyacrylate dispersion, 3.5 parts of sodium carboxymethylcellulose, carbon
6 parts of nanotube, 2.5 parts of antistatic agent, 4 parts of PEG, 3 parts of polyvinylpyrrolidone, 2 parts of triethanolamine, 65 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
The antistatic agent is polyethylene glycol methacrylic acid copolymer body.
The molecular weight of the PEG is 600.
The preparation method of glass fibre interface of the present invention fiber size for reinforcemeent, includes the following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 8wt% that mass fraction, which is then added,
Carbodiimide, 3h is stirred at room temperature, 3-aminopropyltriethoxysilane is then added under stirring conditions, continues to stir
Reaction 10h to be mixed, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, the product after collecting dialysis is simultaneously freeze-dried,
Freeze-dried powder is made；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 60 DEG C under stirring conditions, are kept this temperature anti-
1.5h is answered, lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine are then sequentially added, at 40 DEG C
At a temperature of continue to be stirred to react 3h, be made glass fibre interface fiber size for reinforcemeent.
Embodiment 2
A kind of glass fibre interface fiber size for reinforcemeent, is prepared by the raw material of following parts by weight：10 parts of film forming agent, lubricant
3 parts, 5 parts of coupling agent, 4 parts of polyacrylamide emulsion, 2.5 parts of polyacrylate dispersion, 2 parts of sodium carboxymethylcellulose, carbon nanometer
3 parts of pipe, 1 part of antistatic agent, 2 parts of PEG, 1 part of polyvinylpyrrolidone, 1 part of triethanolamine, 50 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
The antistatic agent is polyethylene glycol methacrylic acid copolymer body.
The molecular weight of the PEG is 400.
The preparation method of glass fibre interface of the present invention fiber size for reinforcemeent, includes the following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 5wt% that mass fraction, which is then added,
Carbodiimide, 2h is stirred at room temperature, 3-aminopropyltriethoxysilane is then added under stirring conditions, continues to stir
Reaction 8h to be mixed, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, the product after collecting dialysis is simultaneously freeze-dried,
Freeze-dried powder is made；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 50 DEG C under stirring conditions, are kept this temperature anti-
1h is answered, lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine are then sequentially added, in 35 DEG C of temperature
Continue to be stirred to react 2h under degree, glass fibre interface fiber size for reinforcemeent is made.
Embodiment 3
A kind of glass fibre interface fiber size for reinforcemeent, is prepared by the raw material of following parts by weight：15 parts of film forming agent, lubricant
4 parts, 6 parts of coupling agent, 5 parts of polyacrylamide emulsion, 4 parts of polyacrylate dispersion, 3 parts of sodium carboxymethylcellulose, carbon nanotube 4
Part, 2 parts of antistatic agent, 3 parts of PEG, 2 parts of polyvinylpyrrolidone, 1.5 parts of triethanolamine, 60 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
The antistatic agent is polyethylene glycol methacrylic acid copolymer body.
The molecular weight of the PEG is 600.
The preparation method of glass fibre interface of the present invention fiber size for reinforcemeent, includes the following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 6wt% that mass fraction, which is then added,
Carbodiimide, 2.5h is stirred at room temperature, 3-aminopropyltriethoxysilane is then added under stirring conditions, continue
It is stirred to react 9h, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, the product after collecting dialysis simultaneously freeze dry
It is dry, freeze-dried powder is made；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 55 DEG C under stirring conditions, are kept this temperature anti-
1.2h is answered, lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine are then sequentially added, at 38 DEG C
At a temperature of continue to be stirred to react 2.5h, be made glass fibre interface fiber size for reinforcemeent.
Embodiment 4
A kind of glass fibre interface fiber size for reinforcemeent, is prepared by the raw material of following parts by weight：30 parts of film forming agent, lubricant
8 parts, 10 parts of coupling agent, 9 parts of polyacrylamide emulsion, 7 parts of polyacrylate dispersion, 5 parts of sodium carboxymethylcellulose, carbon nanotube
9 parts, 4 parts of antistatic agent, 6 parts of PEG, 5 parts of polyvinylpyrrolidone, 3 parts of triethanolamine, 80 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
The antistatic agent is polyethylene glycol methacrylic acid copolymer body.
One kind that the molecular weight of the PEG is 400,600 or 1200.
The preparation method of glass fibre interface of the present invention fiber size for reinforcemeent, includes the following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 10wt% that mass fraction, which is then added,
Carbodiimide, 4h is stirred at room temperature, 3-aminopropyltriethoxysilane is then added under stirring conditions, continues to stir
Reaction 8-12h is mixed, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, the product after collecting dialysis simultaneously freeze dry
It is dry, freeze-dried powder is made；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 70 DEG C under stirring conditions, are kept this temperature anti-
2h is answered, lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine are then sequentially added, in 45 DEG C of temperature
Continue to be stirred to react 4h under degree, glass fibre interface fiber size for reinforcemeent is made.
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that, acrylic resin modified starch is not added in comparative example 1.
Comparative example 2
Comparative example 2 the difference from embodiment 1 is that, be not added with polyacrylamide emulsion and polyacrylate dispersion in comparative example 2.
Size made from embodiment 1-4 and comparative example 1-2 is subjected to infiltration processing to glass fibre, it then will processing
Glass fibre performance and appearance characteristics are observed after glass fibre drying afterwards, test result is as shown in table 1, it is obtained from table 1, this
Invent after size obtained carries out infiltration processing to glass fibre, glass fibre show good precursor cluster performance and but
It is dispersion performance, while fiberglass surfacing, without wool yarn, yarn surface is smooth, while the glass fibre shows good acid and alkali-resistance
Characteristic, therefore size produced by the present invention has important use value in the immersion processing of glass fibre.
Table 1
Claims (5)
1. a kind of glass fibre interface fiber size for reinforcemeent, which is characterized in that be prepared by the raw material of following parts by weight：At
10-30 parts of film, 3-8 parts of lubricant, 5-10 parts of coupling agent, 4-9 parts of polyacrylamide emulsion, polyacrylate dispersion 2.5-7
Part, 2-5 parts of sodium carboxymethylcellulose, 3-9 parts of carbon nanotube, 1-4 parts of antistatic agent, 2-6 parts of PEG, polyvinylpyrrolidone 1-
5 parts, 1-3 parts of triethanolamine, 50-80 parts of deionized water；
The film forming agent is that mass ratio is 8:3:2 acrylic resin modified starch, pentaerythritol resin and Lauryl Alcohol ester；
The coupling agent is that mass ratio is 7:4 3-aminopropyltriethoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane；
The lubricant is that mass ratio is 2:5 1- dodecyl -3- methyl imidazolium tetrafluoroborate and ethylene bis stearamide.
2. a kind of glass fibre interface fiber size for reinforcemeent according to claim 1, which is characterized in that by following weight
The raw material of part is prepared：20 parts of film forming agent, 5.5 parts of lubricant, 7.5 parts of coupling agent, 7 parts of polyacrylamide emulsion, polypropylene
5 parts of acid esters lotion, 3.5 parts of sodium carboxymethylcellulose, 6 parts of carbon nanotube, 2.5 parts of antistatic agent, 4 parts of PEG, polyvinyl pyrrole
3 parts of alkanone, 2 parts of triethanolamine, 65 parts of deionized water.
3. a kind of glass fibre interface fiber size for reinforcemeent according to claim 1, which is characterized in that the antistatic agent
For polyethylene glycol methacrylic acid copolymer body.
4. a kind of glass fibre interface fiber size for reinforcemeent according to claim 1, which is characterized in that point of the PEG
One kind that son amount is 400,600 or 1200.
5. a kind of preparation method of the glass fibre interface fiber size for reinforcemeent as described in claim 1-4, which is characterized in that packet
Include following steps：
（1）Acrylic resin modified starch is added to the one third of deionized water total amount, it is 5- that mass fraction, which is then added,
2-4h is stirred at room temperature in the carbodiimide of 10wt%, and 3- aminopropyl triethoxysilicane is then added under stirring conditions
Alkane continues to be stirred to react 8-12h, is subsequently placed in the PBS buffer solution of pH7.4 and dialyses 3-5 times, and the product after collecting dialysis is gone forward side by side
Row freeze-drying, is made freeze-dried powder；
（2）By step（1）Freeze-dried powder obtained and film forming agent, coupling agent, polyacrylamide emulsion, polyacrylate dispersion,
PEG, polyvinylpyrrolidone, remaining deionized water are mixed, and are heated to 50-70 DEG C under stirring conditions, keep this temperature
Degree reaction 1-2h, then sequentially adds lubricant, sodium carboxymethylcellulose, carbon nanotube, antistatic agent, triethanolamine, in 35-
Continue to be stirred to react 2-4h at a temperature of 45 DEG C, glass fibre interface fiber size for reinforcemeent is made.
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| CN109502996A (en) * | 2018-12-10 | 2019-03-22 | 中国科学院新疆理化技术研究所 | A kind of basalt fibre size and preparation method with conducting function |
| CN115748262A (en) * | 2022-08-27 | 2023-03-07 | 安徽省绩溪华林环保科技股份有限公司 | Surface coating process for prolonging service life of glass fiber |
| WO2023201777A1 (en) * | 2022-04-20 | 2023-10-26 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method therefor, glass fiber product, and application |
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