CN115897244A - Bio-based polyurethane sizing agent and preparation method thereof - Google Patents
Bio-based polyurethane sizing agent and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 238000004513 sizing Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 27
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- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
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- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 8
- 235000002906 tartaric acid Nutrition 0.000 claims description 8
- 239000011975 tartaric acid Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 3
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- 239000004917 carbon fiber Substances 0.000 abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 30
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- 239000011159 matrix material Substances 0.000 abstract description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A bio-based polyurethane sizing agent and a preparation method thereof, belonging to the technical field of sizing agents. The sizing agent comprises the following components in parts by weight: 1-5 parts of high-solid content bio-based polyurethane, 0.5-10 parts of neutralizing agent and 90-98.5 parts of deionized water; the invention also provides a preparation method of the bio-based polyurethane sizing agent. The sizing agent utilizes the synergistic effect of the anionic groups and the nonionic hydrophilic chain segments in polyurethane molecules on improving the hydrophilicity, wherein the anionic groups form a double-electron-layer structure to generate electrostatic repulsion, the nonionic hydrophilic chain segments reduce the surface tension of latex particles, the dispersibility of emulsion is improved, the solid content of the sizing agent is obviously improved, and the interface binding capacity of the carbon fiber nylon 6 matrix resin composite material can also be effectively improved.
Description
Technical Field
The invention belongs to the technical field of sizing agents, and particularly relates to a bio-based polyurethane sizing agent and a preparation method thereof.
Background
Carbon fibers are an ideal material for reinforcing polymer matrix composites and have a series of excellent properties. The carbon fiber reinforced polymer composite material has excellent performances of light weight, high specific strength, corrosion resistance and the like, and has wide application prospects in aerospace, military, wind power equipment and high-grade civil products.
The carbon fiber reinforced polymer composite material is characterized in that carbon fibers are used as a reinforcement body, a polymer is used as a matrix, and the fibers are bonded together to protect the carbon fibers from the environment. The interface performance is an important factor influencing the mechanical performance of the composite material, and is directly related to the effective transmission and dispersion of load between the matrix and the reinforcement, thereby determining the strength and toughness of the composite material. However, carbon fiber is a disordered graphite structure, has a smooth surface, is chemically inert, has low surface energy, and thus has poor interfacial properties between carbon fiber and resin, and the application of carbon fiber reinforced polymer composite materials is greatly limited. Therefore, surface treatment of carbon fibers is often required to improve the mechanical properties of the composite material; the carbon fiber surface modification method is various and comprises electrochemical modification, sizing treatment, oxidation treatment, high-energy radiation treatment and the like. In various treatment methods, the sizing method can not only prevent the surface of the carbon fiber from being polluted, protect the activity of surface groups, improve the bundling property of the fiber, but also infiltrate the carbon fiber, reduce the surface tension between the carbon fiber and matrix resin, enhance the interface bonding degree between the carbon fiber and the matrix resin, and improve the interlaminar shear strength, thereby improving the overall performance of the composite material.
The bio-based polymer is widely concerned because of no pollution of raw material sources and low cost. According to the similar compatibility principle, because the structure of the bio-based polyurethane is similar to that of the nylon matrix, the bio-based polyurethane and the nylon have good compatibility, and a good interface layer can be formed between the carbon fiber and the nylon 6 resin after polyurethane is coated on the surface of the carbon fiber, so that the mechanical property of the carbon fiber/nylon composite material is effectively improved; in addition, the solid content of the waterborne polyurethane sold in China is generally between 20% and 35%, mainly because most of the waterborne polyurethane adopts carboxylate as a hydrophilic group, the cost is increased, the energy consumption is reduced, the transportation cost and the drying cost are increased, and therefore the high-solid-content polyurethane has great application value. Therefore, the development of the high-solid-content bio-based aqueous thermoplastic sizing agent suitable for nylon 6 resin has important significance for the development of the carbon fiber industry; meanwhile, the carbon fiber treated by the water-based sizing agent has good dispersibility in water, and can be used in various fields, such as: preparing carbon paper, friction-resistant materials and sports equipment.
Disclosure of Invention
The invention aims to provide a bio-based polyurethane sizing agent and a preparation method thereof, wherein the bio-based polyurethane sizing agent can effectively improve the interface bonding capability of a carbon fiber nylon 6 matrix resin composite material and has higher solid content.
The bio-based polyurethane sizing agent comprises the following components in parts by weight:
1-5 parts of autocatalytic bio-based polyurethane, 0.5-10 parts of neutralizing agent and 90-98.5 parts of deionized water;
the structural formula of the autocatalytic bio-based polyurethane is shown as formula 1:
in the formula 1, R 2 Is composed of
R 1 Is composed of
The neutralizing agent is triethylamine.
A preparation method of a bio-based polyurethane sizing agent comprises the following steps:
the method comprises the following steps: preparation of high solid content bio-based polyurethane:
dissolving polyethylene glycol and diisocyanate in a solvent, introducing nitrogen, reacting for 2-4 hours at 80-90 ℃ to obtain a polyurethane prepolymer, adding a bio-based raw material tartaric acid as a chain extender, reacting for 1-3 hours, adding sodium lignosulfonate, continuously reacting for 0.5-1 hour, performing rotary evaporation to remove the solvent, and drying to obtain the bio-based polyurethane;
step two: preparation of high-solid content bio-based polyurethane sizing agent with anionic/nonionic synergy:
and (3) continuously stirring the bio-based polyurethane obtained in the step one for 20-30min at the rotating speed of 1600rpm, dispersing the bio-based polyurethane in water, and dropwise adding a neutralizer to react to obtain the bio-based polyurethane sizing agent.
The polyethylene glycol of the first step is selected from one of polyethylene glycol-1000, polyethylene glycol-1500 or polyethylene glycol-2000.
The molar ratio of the polyethylene glycol to the diisocyanate in the first step is (10-15): (20-30).
The bio-based raw material in the step one is tartaric acid.
And the diisocyanate in the first step is isophorone diisocyanate.
In the first step, the molar ratio of polyethylene glycol, diisocyanate, a chain extender and sodium lignosulfonate is (1-10): (2-20): (1-10): (1-10): (2-20).
The solvent in the first step is selected from one of acetone, N-dimethylformamide or tetrahydrofuran.
Compared with the prior art, the invention has the following beneficial effects:
the bio-based polyurethane obtained by the invention has the characteristics of high solid content and high quantity of oxygen-containing functional groups, is beneficial to forming a uniform coating with high surface energy on the surface of carbon fiber, and enables the carbon fiber composite material to have better mechanical property.
Drawings
FIG. 1 is an infrared spectrum of a bio-based polyurethane of the present invention.
Fig. 2 is a schematic diagram of the water-soluble sizing agent of bio-based polyurethane prepared by the present invention.
Detailed Description
The bio-based polyurethane sizing agent comprises the following components in parts by weight:
1-5 parts of bio-based polyurethane, 0.5-10 parts of neutralizing agent and 90-98.5 parts of deionized water;
the structural formula of the autocatalytic bio-based polyurethane is shown as formula 1:
in the formula 1, R 2 Is composed of
R 1 Is composed of
The neutralizing agent is preferably triethylamine.
A preparation method of a bio-based polyurethane sizing agent comprises the following steps:
the method comprises the following steps: preparation of high solid content bio-based polyurethane:
dissolving polyethylene glycol and diisocyanate in a solvent, introducing nitrogen, reacting for 2-4 hours at 80-90 ℃ to obtain a polyurethane prepolymer, adding a bio-based raw material tartaric acid as a chain extender, reacting for 1-3 hours, adding sodium lignosulfonate, continuously reacting for 0.5-1 hour, performing rotary evaporation to remove the solvent, and drying to obtain the bio-based polyurethane;
step two: preparation of high-solid content bio-based polyurethane sizing agent with anionic/nonionic synergy:
and (3) continuously stirring the bio-based polyurethane obtained in the step one for 20-30min at the rotating speed of 1600rpm, dispersing the bio-based polyurethane in water, and dropwise adding a neutralizer to react to obtain the bio-based polyurethane sizing agent.
The polyethylene glycol in the step one is selected from one of polyethylene glycol-1000, polyethylene glycol-1500 or polyethylene glycol-2000.
The molar ratio of the polyethylene glycol to the diisocyanate in the first step is (10-15): (20-30).
The bio-based raw material in the step one is tartaric acid.
And the diisocyanate in the first step is isophorone diisocyanate.
In the first step, the molar ratio of polyethylene glycol, diisocyanate, chain extender and sodium lignosulfonate is (1-10): (2-20): (1-10): (1-10): (2-20).
The solvent in the first step is selected from one of acetone, N-dimethylformamide or tetrahydrofuran.
The raw materials referred to in the examples are all commercially available.
Comparative example 1:
the nylon 6/carbon fiber composite material with the size of 100mm multiplied by 0.3mm is prepared by adopting a thermal compression technology after 8 layers of nylon 6 films and 7 layers of carbon fiber plain cloth are interwoven and stacked, and the interlaminar shear strength is 56.3MPa and the bending strength is 564.2MPa through the test of a universal testing machine.
The solids content of the polyurethane sizing agent was determined by the weight difference before and after water evaporation, and about 2g of the sizing agent was placed on a polyfluortetraethylene plate and evaporated to a constant weight in an oven at 110 ℃ for 2 hours, the average of three determinations of the solids content of the polyurethane sizing agent being 55.2%, as shown in table 1.
Example 1:
the preparation method of the bio-based polyurethane water sizing agent comprises the following steps:
1. weighing 4.44g of isophorone diisocyanate, adding 1000 g of polyethylene glycol and 10g of isophorone diisocyanate, introducing nitrogen, heating to 80 ℃ for reacting for 2 hours to generate a bio-based polyurethane prepolymer, adding 1.5g of tartaric acid as a chain extender, reacting for 1 hour, cooling to 40 ℃, adding 10.6g of sodium lignosulfonate, continuing to react for 0.5 hour, performing rotary evaporation to remove a solvent, and drying to obtain the bio-based polyurethane with the infrared spectrum shown in figure 1.
2. And (2) taking 5g of the bio-based polyurethane obtained in the step (1), dispersing the bio-based polyurethane in 500ml of water under the high-speed stirring action at the rotating speed of 1600rpm, slowly dropwise adding 2ml of triethylamine, and reacting for 30 minutes to obtain the bio-based polyurethane sizing agent with high solid content.
The solid content of the polyurethane was determined by the difference in weight before and after evaporation of the water, and about 2g of the sizing agent was placed on a polyfluortetraethylene plate and evaporated to a constant weight in an oven at 110 ℃ for 2 hours, the solid content of the polyurethane sizing agent being 57.2% on average of three determinations.
Dipping carbon fibers in the sizing agent prepared in the embodiment 1 at a speed of 15m/min, interweaving and stacking 8 layers of nylon 6 films and 7 layers of carbon fiber plain cloth, and preparing the carbon fibers into a nylon 6/carbon fiber composite material with the size of 100mm multiplied by 0.3mm by adopting a hot compression technology; cutting the obtained composite material into bending and interlaminar shear test sample strips, and testing by a universal tester to obtain the interlaminar shear strength of 56.3MPa and the bending strength of 564.2MPa; specifically, as shown in table 1, the results show that the mechanical properties are significantly improved compared with the unsized carbon fiber/nylon 6 composite material.
Example 2:
the preparation method of the bio-based polyurethane water sizing agent comprises the following steps:
1. weighing 2.22g of isophorone diisocyanate, adding 1000,5g of polyethylene glycol, introducing nitrogen, heating to 80 ℃ for reacting for 2 hours to generate a bio-based polyurethane prepolymer, adding 0.75g of tartaric acid as a chain extender, reacting for 1 hour, cooling to 40 ℃, adding 5.3g of sodium lignosulfonate, continuously reacting for 0.5 hour, performing rotary evaporation to remove the solvent, and drying to obtain the bio-based polyurethane with the infrared spectrum shown in figure 1.
2. And (3) taking 3g of the bio-based polyurethane obtained in the step (1), dispersing the bio-based polyurethane in 500ml of water under the high-speed stirring action at the rotating speed of 1600rpm, slowly dropwise adding 1ml of triethylamine, and reacting for 25 minutes to obtain the bio-based polyurethane sizing agent with high solid content.
The solid content of the polyurethane was determined by the difference in weight before and after evaporation of the water, and about 2g of the sizing agent was placed on a polyfluortetraethylene plate and evaporated to a constant weight in an oven at 110 ℃ for 2 hours, the solid content of the polyurethane sizing agent being 55.2% on average of three determinations.
The carbon fiber is soaked in the sizing agent prepared in the embodiment 2 and is run at the speed of 15m/min, 8 layers of nylon 6 films and 7 layers of carbon fiber plain cloth are interwoven and stacked, then the nylon 6/carbon fiber composite material with the size of 100mm multiplied by 0.3mm is prepared by adopting a hot compression technology, the obtained composite material is cut into bending and interlaminar shear test sample strips, and the interlaminar shear strength is 50.5MPa and the bending strength is 492.1MPa through the test of a universal testing machine, and the results are shown in table 1 specifically, and the mechanical property is obviously improved compared with the carbon fiber/nylon 6 composite material which is not sized.
Example 3:
the preparation method of the bio-based polyurethane water sizing agent comprises the following steps:
1. weighing 8.88g of isophorone diisocyanate, adding polyethylene glycol-1000, 20g, introducing nitrogen, heating to 80 ℃ for reacting for 2 hours to generate a bio-based polyurethane prepolymer, adding 3.0g of tartaric acid as a chain extender, reacting for 1 hour, cooling to 40 ℃, adding 21.2g of sodium lignosulfonate, continuing to react for 0.5 hour, performing rotary evaporation to remove the solvent, and drying to obtain the bio-based polyurethane with the infrared spectrum shown in figure 1.
2. And (3) taking 10g of the bio-based polyurethane obtained in the step (1), dispersing the bio-based polyurethane in 500ml of water under the high-speed stirring action at the rotating speed of 1600rpm, slowly dropwise adding 4ml of triethylamine, and reacting for 20 minutes to obtain the bio-based polyurethane sizing agent with high solid content.
The solid content of the polyurethane was determined by the difference in weight before and after evaporation of the water, and about 2g of the sizing agent was placed on a polyfluortetraethylene plate and evaporated to a constant weight in an oven at 110 ℃ for 2 hours, the solid content of the polyurethane sizing agent being 54.8% on average of three determinations.
Dipping carbon fibers in the sizing agent prepared in the embodiment 3, running at the speed of 15m/min, interweaving and stacking 8 layers of nylon 6 films and 7 layers of carbon fiber plain cloth, preparing the carbon fiber plain cloth into a nylon 6/carbon fiber composite material with the size of 100mm multiplied by 0.3mm by adopting a thermal compression technology, cutting the obtained composite material into bending and interlaminar shear test sample strips, and testing by using a universal testing machine to obtain the interlaminar shear strength of 53.8MPa and the bending strength of 552.2MPa; specifically, as shown in table 1, the results show that the mechanical properties are significantly improved compared with the unsized carbon fiber/nylon 6 composite material.
FIG. 1 is an infrared spectrum of a high solids biobased polyurethane of the present invention wherein the characteristic absorption peak of isocyanate groups is completely disappeared and the characteristic peak of hydroxyl groups is appeared at 3346cm -1 Here, the diisocyanate reaction is complete; at 1707cm -1 The strong absorption peak can be attributed to the characteristic peak of ester group generated after the neutralizing agent reacts with the anion group; furthermore, at 1645cm -1 The absorption peak at (a) is the presence of a C = O bond in the ureido structure, indicating that-OH and NCO-groups have reacted; these results demonstrate that the prepared bio-based polyurethane structure is as expected.
Fig. 2 is a physical diagram of the water-soluble sizing agent of the bio-based polyurethane prepared by the invention.
TABLE 1
The results in table 1 illustrate that: compared with carbon fiber composite materials which are not sized, the mechanical property of the composite materials prepared by the sizing agent is obviously improved, and the solid content of the composite materials is obviously improved compared with that of common anionic polyurethane sizing agents (20-30 percent).
Claims (7)
1. A bio-based polyurethane sizing agent is characterized in that: according to the parts by weight, the high-solid content bio-based polyurethane comprises 1-5 parts of high-solid content bio-based polyurethane, 0.5-10 parts of neutralizing agent and 90-98.5 parts of deionized water;
the structural formula of the high-solid content bio-based polyurethane is shown as a formula 1:
in the formula 1, R 2 Is as follows;
R 1 is composed of
2. The bio-based polyurethane sizing agent according to claim 1, wherein: the neutralizing agent is triethylamine.
3. The method for preparing the bio-based polyurethane sizing agent according to claim 1, wherein the method comprises the following steps:
the method comprises the following steps: preparation of high solid content bio-based polyurethane:
dissolving polyethylene glycol and diisocyanate in a solvent, introducing nitrogen, reacting for 2-4 hours at 80-90 ℃ to obtain a polyurethane prepolymer, adding a bio-based raw material as a chain extender, reacting for 1-3 hours, adding sodium lignosulfonate, continuously reacting for 0.5-1 hour, performing rotary evaporation to remove the solvent, and drying to obtain bio-based polyurethane;
step two: preparation of high solid content bio-based polyurethane sizing agent with anionic/nonionic synergy:
and (3) continuously stirring the bio-based polyurethane obtained in the step one for 20-30min at the rotating speed of 1600rpm, dispersing the bio-based polyurethane in water, and dropwise adding a neutralizer to react to obtain the bio-based polyurethane sizing agent.
4. The method for preparing a bio-based polyurethane sizing agent according to claim 3, wherein the method comprises the following steps: the bio-based raw material in the first step is tartaric acid.
5. The method for preparing a bio-based polyurethane sizing agent according to claim 3, wherein the method comprises the following steps: and the diisocyanate in the first step is isophorone diisocyanate.
6. The method for preparing a bio-based polyurethane sizing agent according to claim 3, wherein the bio-based polyurethane sizing agent comprises the following steps: the molar ratio of the polyethylene glycol, the diisocyanate, the chain extender and the sodium lignin sulfonate in the first step is (1-10): (2-20): (1-10): (1-10): (2-20).
7. The method for preparing a bio-based polyurethane sizing agent according to claim 3, wherein the method comprises the following steps: the solvent in the first step is selected from one of acetone, N-dimethylformamide or tetrahydrofuran.
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| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN113201112A (en) * | 2021-04-06 | 2021-08-03 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
| CN113550148A (en) * | 2021-08-03 | 2021-10-26 | 长春工业大学 | High-surface-energy carbon fiber water-soluble sizing agent for carbon paper and preparation method thereof |
| CN114716643A (en) * | 2022-04-22 | 2022-07-08 | 福州大学 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
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2022
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201112A (en) * | 2021-04-06 | 2021-08-03 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN113550148A (en) * | 2021-08-03 | 2021-10-26 | 长春工业大学 | High-surface-energy carbon fiber water-soluble sizing agent for carbon paper and preparation method thereof |
| CN114716643A (en) * | 2022-04-22 | 2022-07-08 | 福州大学 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
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