Plastic filler treating agent and use method thereof

Abstract

The invention belongs to the field of composite materials, and relates to a treating agent for improving strength and hot water resistance of composite plastic filled with filler and a using method. The invention discloses a treating agent for a plastic filler. The treating agent for the plastic filler is prepared from 1-10% of a coupling agent, 5-20% of a compatilizer, 0.01-1% of fluoro acid salt and the balance of a solvent. The preparation method comprises the following steps: hydrolyzing a coupling agent, adding a compatilizer emulsion or solution, then adding fluoroacid salt, fully mixing, coating the surface of the filler with powder according to a weight ratio of (0.1-10): 100, and then removing a solvent through a drying step. The treating agent for the plastic filler is used for treating glass fibers, talcum powder, calcium carbonate or matrix resin, and the mechanical property and the boiling resistance can be remarkably improved.

Description

Technical Field

[0001] The invention belongs to the field of composite materials, and particularly relates to a treatment agent for improving the strength and hot water resistance of composite plastics filled with fillers and a use method thereof. Background Art

[0002] Filling with inorganic fillers or reinforcing materials is a very effective way to reduce product costs while improving product strength, heat resistance and other properties. Due to the large difference in polarity between conventional thermoplastic or thermosetting resins and inorganic fillers, compatibilizer resins are often added to the formula, or surface-modified fillers are used, or both of the above methods are used to improve the dispersibility of inorganic fillers and the interface strength between resin and inorganic fillers, thereby obtaining better mechanical strength and fatigue performance.

[0003] However, in some service scenarios, composite materials are exposed to hot water for a long time, and their strength will decrease significantly. This decrease is usually caused by two factors. One is the degradation of the matrix resin itself. For example, products such as nylon and polyester resins with high water absorption undergo hydrolysis under the action of hot water and acid and alkali, which reduces the molecular weight and reduces the overall strength. The other is that the matrix resin itself is resistant to hydrolysis, such as polypropylene and polyphenylene sulfide, but the interface between the filler and the resin has reduced interface strength due to the long-term action of hot water. The filler that originally had a certain reinforcing effect has been transformed into an inert filler after long-term boiling, thereby greatly reducing the performance of the composite material.

[0004] Usually, inorganic fillers are treated with coupling agents, especially silane coupling agents with amino groups, while the more common compatibilizers in resins are mostly maleic anhydride. Amino groups and maleic anhydride react under temperature to form covalent bonds, which form a strong interaction between resin and inorganic fillers, thereby effectively improving the strength of the composite material. After long-term boiling, water hydrolyzes the amide bond formed by amino groups and maleic anhydride, leaving only part of the hydrogen bonding effect, and the reinforcing material becomes an inert filler, so the strength is greatly reduced. Summary of the invention

[0005] An object of the present invention is to provide a treating agent for plastic fillers, which can simultaneously improve the mechanical properties and hydrolysis resistance of plastic materials.

[0006] Another purpose of the present invention is to apply it to resin to effectively improve the strength of composite materials.

[0007] Based on the above problems, the present invention provides a treatment agent for plastic fillers and a method for using the same. The treatment agent is composed of 1-10% coupling agent, 5-60% compatibilizer, 0.01-1% fluoroacid salt, and the rest is solvent.

[0008] Wherein, the coupling agent is one or a combination of silane coupling agent, aluminate coupling agent or titanate coupling agent; preferably, it is a silane coupling agent or titanate coupling agent with amino group or glycidyl group. The content of the coupling agent is 1-10%, preferably 2-8%, more preferably 3-5%, such as 1.5%, 2.5%, 3.5%, 4.0%, 4.5%, 5.5%, 6.0%, 7.0%, 7.5%, 9.0%, and so on.

[0009] The compatibilizer is a polymer with a molecular weight of >1000 that has strong interactions such as chemical bonding with the plastic matrix and the coupling agent, preferably a polyolefin polymer with maleic anhydride or acrylic acid. The content of the compatibilizer is 5-60%, preferably 10-50%, more preferably 20-35%, such as 15%, 25%, 30%, 40%, etc.

[0010] Wherein, the chemical formula of the fluorosalt is X a BF b , where X is a cation, and B is any non-metal or metal element that can form a covalent bond; the cation X in the fluoroacid salt can be selected from lithium, sodium, potassium, ammonium, etc., and the solubility of the formed salt in water is >0.1g / 100g water. B in the fluoroacid anion is preferably selected from elements such as boron, silicon, phosphorus, aluminum, and zirconium.

[0011] Wherein, the solvent is one or a combination of water, an organic solvent with carbon elements less than 6 in the molecule.

[0012] The method of using the treatment agent for plastic fillers is to hydrolyze the coupling agent in a solvent, add a compatibilizer emulsion or solution, and then add a fluoro acid salt, fully mix, and then mix or coat with the filler at a weight ratio of 0.1-20:100, and then fully dry, and then mix with the matrix resin for melt modification to obtain the desired modified plastic. Preferably, the mixing ratio of the coupling agent, the fluoro acid salt and the filler is (0.5-15):100, and more preferably (1-10):100, such as 1.5:100, 2:100, 3:100, 5:100, 8:100, 9:100, and the like.

[0013] In another aspect, the present invention provides a novel method for treating inorganic fillers in plastics.

[0014] Generally, non-polar resins and fillers have poor compatibility. By adding compatibilizers to the resin and modifying the functional groups on the filler surface, the mechanical properties can be improved. However, this effect is often limited by the modification method of the filler surface and cannot maximize its performance. Secondly, after long-term boiling in water, the original polar bonds on the interface are eroded by water and hydrolyzed, and the interfacial force is weakened, so the strength of the composite material decreases.

[0015] The present invention further processes the filler, adds a compatibilizer to the treating agent while treating with a conventional coupling agent, increases the action density of maleic anhydride by in-situ action, and uses a very small amount of fluorosalt to improve the hydrolysis resistance of the interface, thereby obtaining a filler-filled composite material with hot water resistance. The present invention can be used to process materials such as glass fiber, talcum powder, calcium carbonate and inorganic color powder, and is applied to most base resins. DETAILED DESCRIPTION

[0016] Treatment agent ingredients:

[0017] Silane coupling agent: A1100, Momentive;

[0018] Compatibilizer emulsion: Hydrosize PP270, Michelman;

[0019] Potassium hexafluorophosphate: CAS number: 17084-13-8, Sigma-aldrich.

[0020] Resin: Polypropylene Moplen EP540P, LyondellBasell;

[0021] Compatibilizer: PP-g-MAH, CA100, SK, Korea;

[0022] Talc: 1250 mesh, Jiangyin Guangyuan Superfine Powder Co., Ltd.

[0023] Fiberglass: ECS13-3-508A, Boulder.

[0024] Talc-filled polypropylene: 20% talc was mixed with 80% polypropylene particles, extruded at 230°C by a twin-screw extruder, and injection molded into tensile specimens at 250°C. The specimens were prepared and tested according to ISO-527 and ISO179 / 1eA. Hot water resistance test: Boiled in 90°C water for 1000 hours.

[0025] Glass fiber filled polypropylene: Polypropylene and compatibilizer are mixed in a ratio of 96:4, and then fed from the main feed of a twin-screw extruder, and 30% of glass fiber is fed from the side, extruded into particles at 250°C, and then specimens are prepared and tested according to ISO-527 and ISO179 / 1eA. Water boiling resistance test: boiled in water at 95°C for 1000 hours.

[0026] Embodiment 1:

[0027] 3g of silane coupling agent was dissolved in 36.99g of water and mixed and hydrolyzed, then 60g of compatibilizer emulsion was poured in and stirred evenly, and finally 0.01g of potassium hexafluorophosphate was added and stirred evenly to obtain the treatment agent. 1kg of talcum powder was added to the high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0028] Embodiment 2:

[0029] 5g of silane coupling agent was dissolved in 64g of water and mixed and hydrolyzed, then 30g of compatibilizer emulsion was poured in and stirred evenly, and finally 1g of potassium hexafluorophosphate was added and stirred evenly to obtain the treatment agent. 1kg of talcum powder was added to the high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0030] Embodiment 3:

[0031] 10g of silane coupling agent was dissolved in 84g of water and mixed and hydrolyzed, then 5g of compatibilizer emulsion was poured in and stirred evenly, and finally 1g of potassium hexafluorophosphate was added and stirred evenly to obtain the treatment agent. 1kg of talcum powder was added to the high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0032] Embodiment 4:

[0033] 1g of silane coupling agent was dissolved in 93g of water and mixed and hydrolyzed, then 5g of compatibilizer emulsion was poured in and stirred evenly, and finally 1g of potassium hexafluorophosphate was added and stirred evenly to obtain the treating agent. 100g of the agent was sprayed per kilogram of glass fiber, stirred evenly by rollers, and dried in a vibrating fluidized bed at 200°C for 5 minutes.

[0034] Embodiment 5:

[0035] 1g of silane coupling agent was dissolved in 39.99g of water and mixed and hydrolyzed thoroughly, then 20g of compatibilizer emulsion was poured in and stirred thoroughly, and finally 1g of potassium hexafluorophosphate was added and stirred to obtain the treating agent. 20g was sprayed per kilogram of glass fiber, stirred evenly by rollers, and dried in a vibrating fluidized bed at 200°C for 5 minutes.

[0036] Embodiment 6:

[0037] 3g of silane coupling agent was dissolved in 56g of water and mixed and hydrolyzed, then 40g of compatibilizer emulsion was poured in and stirred evenly, and finally 1g of potassium hexafluorophosphate was added and stirred evenly to obtain the treatment agent. 10g was sprayed per kilogram of glass fiber, stirred evenly by rollers, and dried in a vibrating fluidized bed at 200°C for 5 minutes.

[0038] Comparative Example 1: Untreated talcum powder.

[0039] Comparative Example 2: 5g of silane coupling agent was dissolved in 95g of water and mixed and hydrolyzed to obtain a treatment agent. 1kg of talcum powder was added to a high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0040] Comparative Example 3: 10g of silane coupling agent was dissolved in 85g of water and mixed and hydrolyzed, then 5g of compatibilizer emulsion was poured in and stirred evenly to obtain the treatment agent. 1kg of talcum powder was added to the high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0041] Comparative Example 4: 1 g potassium hexafluorophosphate was dissolved in 99 g water and mixed thoroughly to obtain a treatment agent. 1 kg talcum powder was added to a high-speed mixer, and the temperature of the high-speed mixer was set to 100°C. While stirring at a speed of 1000 rpm, the treatment agent was sprayed from the top. After the spraying was completed, it was stirred for 5 minutes to make it completely dry.

[0042] Comparative Example 5: Untreated glass fiber.

[0043] Comparative Example 6: 1g of silane coupling agent was dissolved in 79g of water and mixed and hydrolyzed, then 20g of compatibilizer emulsion was poured in and stirred to obtain a treatment agent. 100g of the agent was sprayed per kilogram of glass fiber, stirred evenly by rollers, and dried in a vibrating fluidized bed at 200°C for 5 minutes.

[0044] Comparative Example 7: Pour 40g of the compatibilizer emulsion into 59g of water and mix and hydrolyze thoroughly, then stir thoroughly and evenly, finally add 1g of potassium hexafluorophosphate and stir evenly to obtain a treating agent. Spray 10g per kilogram of glass fiber, stir evenly by rollers, and dry in a vibrating fluidized bed at 200°C for 5 minutes.

[0045] Table 1 Properties of 20% talc-filled PP composites

[0046]

[0047] By comparing Example 1 with Comparative Example 1, it can be seen that the talc-filled polypropylene treated with the treating agent can obtain better tensile strength and notched impact strength, and after being boiled in water, its tensile strength and notched impact strength are significantly higher than those of the untreated sample.

[0048] By comparing Example 2 with Comparative Example 2, it can be seen that the initial performance of the talc-filled polypropylene treated with only the silane coupling agent is slightly lower than that of the talc-filled polypropylene treated with the treating agent, and after boiling, the difference is more significant.

[0049] By comparing Example 3 with Comparative Example 3, it can be seen that the initial performance of the talc-filled polypropylene treated with silane coupling agent and compatibilizer emulsion is close to or even slightly higher than that of the talc-filled polypropylene treated with the treating agent, but after boiling in water, the performance is significantly lower than that of the talc-filled polypropylene treated with the treating agent.

[0050] By comparing Examples 1, 2, 3 and Comparative Example 4, it can be seen that the addition of potassium hexafluorophosphate alone does not help the performance in the initial state or after boiling in water. It is necessary to use potassium hexafluorophosphate together with a silane coupling agent and a compatibilizer emulsion to achieve better boiling resistance.

[0051] Table 2 Properties of 30% glass fiber filled PP composites

[0052]

[0053] By comparing Example 4 with Comparative Example 5, it can be seen that the glass fiber-filled polypropylene treated with the treating agent can obtain better tensile strength and notched impact strength, and after being boiled in water, its tensile strength and notched impact strength are significantly higher than those of the untreated sample.

[0054] By comparing Example 5 with Comparative Example 6, it can be seen that the glass fiber filled polypropylene treated with the treating agent can obtain better tensile strength and notched impact strength, and has significantly higher tensile strength after boiling and notched impact strength than the glass fiber using only coupling agent and compatibilizer.

[0055] By comparing Example 6 with Comparative Example 7, it can be seen that the initial performance of the treatment agent after removing the silane coupling agent is not much different, but after boiling in water, it is significantly lower than the performance of glass fiber filled polypropylene treated with the treatment agent containing the coupling agent.

[0056] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A treatment agent for plastic fillers, characterized in that: The treating agent for the plastic filler is composed of 1-10% of coupling agent, 5-20% of compatibilizer, 0.01-1% of fluorosalt, and the rest of solvent.

2. The treating agent for plastic fillers according to claim 1, characterized in that: The coupling agent is one or a combination of silane coupling agent, aluminate coupling agent or titanate coupling agent.

3. The treating agent for plastic fillers according to claim 1, characterized in that: The compatibilizer is a polymer with a molecular weight greater than 1000 and having strong interactions such as chemical bonding with the plastic matrix and the coupling agent.

4. The treating agent for plastic fillers according to claim 1, characterized in that: The chemical formula of the fluoroacid salt is X a BF b , where X is a cation and B is any non-metal or metal element that can form a covalent bond.

5. The treating agent for plastic fillers according to claim 1, characterized in that: The cation X in the fluorosalt is selected from lithium, sodium, potassium, and ammonium, and the solubility of the formed salt in water is > 0.01 g / 100 g water.

6. The treating agent for plastic fillers according to claim 1, characterized in that: The B in the fluoroacid anion in the fluoroacid salt is preferably selected from boron, silicon, phosphorus, aluminum and zirconium.

7. The treating agent for plastic fillers according to claim 1, characterized in that: The solvent is water, an organic solvent with carbon elements less than 6 in the molecule, or a combination of several thereof.

8. A method for using a treatment agent for plastic fillers, characterized in that: The method for using the plastic filler treating agent is to hydrolyze the coupling agent, add a compatibilizer emulsion or solution, and then add a fluorosalt, mix them thoroughly, and then apply them to the filler surface in a weight ratio of (0.1-20):100 with the powder, and then remove the solvent through a drying step.

9. The use of the treating agent for plastic fillers according to claim 1, characterized in that: The treating agent for plastic fillers is used for treating glass fiber, talcum powder, calcium carbonate or matrix resin to improve mechanical properties and water boiling resistance.

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