A scale-inhibiting polypropylene masterbatch for geotextile synthetic material and preparation method thereof

Abstract

The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials of the present invention and the preparation method thereof belong to the technical field of scale-inhibiting polypropylene geotextile. The present invention prepares a novel long-chain aliphatic quaternary ammonium salt, and uses the novel long-chain aliphatic quaternary ammonium salt as the anti-scaling masterbatch, and blends it with polypropylene to prepare a series of scale-inhibiting polypropylene composite fibers. The hydrophobic effect of the aliphatic long chain is utilized to combine it with the polypropylene fiber and play a hydrophobic role. The hydrophilicity of the quaternary ammonium salt is utilized to improve the water permeability, and the positive charge of the quaternary ammonium salt is also utilized to reduce the aggregation of metal ions through the electrostatic repulsion. Through multiple synergistic effects such as lattice distortion and dispersion, the formation and adhesion strength of scale on the surface of the polypropylene composite fiber are affected, so that the scale layer is loose and the adhesion is poor, and the crystal can produce lattice distortion, inhibiting the growth of crystals, and causing the crystallization of the scaling material particles to be loose, thereby achieving the purpose of scale inhibition.

Description

Technical Field

[0001] The invention belongs to the technical field of scale inhibition of polypropylene geotextiles, and specifically relates to a scale inhibition polypropylene masterbatch for geotextile synthetic materials and a preparation method thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Geosynthetics are thin polymer materials widely used in the fields of environment, hydraulics, etc. Compared with steel and cement, geosynthetics have the advantages of good softness and impact resistance, and are suitable for occasions with large deformation, such as soft soil areas, swamps, frozen soil areas, and areas with complex environments. At present, geosynthetics, especially non-woven polypropylene materials, have multiple functions such as anti-filtration, drainage, anti-seepage, reinforcement and protection, and have been widely used in major infrastructure projects such as high-speed railways, highways, water conservancy, environment and ports.

[0004] Polypropylene geotextile has good water permeability and can intercept and filter particles in the water. However, since the geotextile is in a leachate filtration state for a long time and adsorbs microorganisms in the garbage on the surface, inorganic salts such as calcium and magnesium in the water are easy to accumulate on the surface of the polypropylene geotextile, so it is easy to cause scaling, causing its pores to become smaller or even blocked, resulting in obstruction of the diversion function. Further research found that the geotextile is the first part to scale and the most serious scaling. For example, landfill landslides caused by landfill leachate siltation and high internal gas pressure have been reported many times at home and abroad. In addition, if the leachate water level is too high, it will increase the migration rate of pollutants and the leakage rate of leachate, thereby polluting the surrounding environment, especially the groundwater environment. At the same time, the increase in the leachate water level will expand the saturated volume of the garbage body, inhibit its degradation, and delay the stabilization process of the landfill.

[0005] At present, the commonly used industrial methods for preventing scale of polypropylene geotextiles are: (1) improving the pore structure of geotextiles and increasing water permeability. However, this method will also increase the permeability of some harmful substances;

[0006] (2) Chemical scale inhibition, that is, adding scale inhibitors such as trisodium phosphate and sodium hexametaphosphate to water to prevent scale. However, these scale inhibitors will acidify the water and cause irreversible damage to geosynthetics.

[0007] Therefore, it is of great significance to modify the polypropylene geotextile without changing the void structure of the geotextile and acidifying the water body so as to better prevent scaling. Summary of the invention

[0008] The object of the present invention is to provide a scale-inhibiting polypropylene masterbatch for geotextile synthetic materials and a preparation method thereof, so as to solve the above-mentioned technical problems.

[0009] To this end, the present invention provides a scale-inhibiting polypropylene masterbatch for geotextile synthetic materials, comprising the following components in parts by weight: 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of compatibilizer, and 0.2-0.5 parts of antioxidant.

[0010] Preferably, the general structural formula of the long-chain aliphatic quaternary ammonium salt is:

[0011] Preferably, the compatibilizer is at least one of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, styrene grafted polypropylene or chlorinated polypropylene.

[0012] Preferably, the compatibilizer is maleic anhydride grafted polypropylene.

[0013] Preferably, the melt flow rate of the polypropylene resin is 1-100 g / 10 min, and the polypropylene resin is at least one of homopolypropylene or copolymer polypropylene.

[0014] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 330, and antioxidant 168.

[0015] In addition, the present invention also provides a method for preparing a scale-inhibiting polypropylene masterbatch for geotextile synthetic materials. 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of a compatibilizer, and 0.2-0.5 parts of an antioxidant are uniformly mixed, added through the main feeding port of a twin-screw extruder, and melt-dispersed and extruded into granules to obtain a scale-inhibiting polypropylene masterbatch.

[0016] Preferably, the general structural formula of the long-chain aliphatic quaternary ammonium salt is: in Depend on The mixture is fully mixed with hydrochloric acid in a mass ratio of 1000:1-2000:1, and reacted at 25-50°C to obtain the product;

[0017] Depend on The product is prepared by fully mixing with hydrochloric acid at a mass ratio of 1000:1-2000:1 and reacting at 25-50°C.

[0018] Preferably, the Depend on and TsNHNH2(2) in a mass ratio of 50:1-100:1, and NaOH is added to react at 100-150°C to prepare the product.

[0019] Preferably, the Depend on and TsNHNH2(2) in a mass ratio of 50:1-60:1, and NaOH is added to react at 100-150°C to prepare the product.

[0020] Compared with the prior art, the present invention has the following characteristics and beneficial effects:

[0021] (1) The present invention prepares a long-chain aliphatic quaternary ammonium salt, and uses the long-chain aliphatic quaternary ammonium salt as an anti-fouling masterbatch, and blends it with polypropylene to prepare a series of anti-fouling polypropylene composite fibers. The hydrophobic effect of the aliphatic long chain is utilized to combine it with the polypropylene fiber and play a hydrophobic role. The hydrophilicity of the quaternary ammonium salt is utilized to improve the water permeability, and the positive charge of the quaternary ammonium salt is also utilized to reduce the aggregation of metal ions through electrostatic repulsion.

[0022] (2) The present invention affects the formation and adhesion strength of scale on the surface of polypropylene composite fibers through multiple synergistic effects such as lattice distortion and dispersion, making the scale layer loose and having poor adhesion, and can cause lattice distortion of the crystals, inhibiting crystal growth and causing the crystallization of scaling material particles to become loose, thereby achieving the purpose of scale inhibition.

[0023] (3) In the present invention, polyisobutylene-grafted maleic anhydride is used as a raw material to prepare a long-chain aliphatic quaternary ammonium salt, so that the long-chain aliphatic quaternary ammonium salt and the polypropylene resin can be well compatible, and a compatibilizer (such as maleic anhydride grafted polypropylene) is added. At this time, polyisobutylene-grafted maleic anhydride, the long-chain aliphatic quaternary ammonium salt and the compatibilizer (such as maleic anhydride grafted polypropylene) have very good compatibility, so that the scale-inhibiting polypropylene masterbatch has good uniformity.

[0024] (4) The surface of the polypropylene geosynthetics modified with the long-chain aliphatic quaternary ammonium salt of the present invention has certain papillae, which can effectively improve the hydrophobic performance, reduce the contact between scale crystals and the surface of the polypropylene material, reduce scale adhesion, inhibit scale deposition, and at the same time make the formed scale loose and sharp, which is easier to be washed away by water.

[0025] (5) The scale-inhibiting polypropylene geosynthetics prepared by the present invention have the characteristics of high water permeability and low scaling. In addition, under the shear force of the water flow, the precipitated scale can be easily separated from the surface of the geosynthetics and enter the solution system, thereby achieving a good surface scale-inhibiting effect.

[0026] Instruction Manual

[0027] Figure 1is the hydrogen spectrum of compound 3 or 3'.

[0028] Figure 2 is the carbon spectrum of compound 3 or 3'. DETAILED DESCRIPTION

[0029] In order to make the technical means, innovative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below.

[0030] The embodiments described herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention, are illustrative and exemplary, and should not be construed as limiting the embodiments of the present invention and the scope of the present invention. In addition to the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the claims and the contents disclosed in the specification of this application, including technical solutions that adopt any obvious replacement and modification of the embodiments described herein.

[0031] The invention prepares a scale-inhibiting polypropylene masterbatch for geotextile synthetic materials in order to modify the polypropylene geotextile. The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials comprises the following components in parts by weight: 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of compatibilizer, and 0.2-0.5 parts of antioxidant.

[0032] The general structural formula of the long-chain aliphatic quaternary ammonium salt is: in Depend on The mixture is fully mixed with hydrochloric acid in a mass ratio of 1000:1-2000:1, and reacted at 25-50°C to obtain the product; Depend on The product is prepared by fully mixing with hydrochloric acid at a mass ratio of 1000:1-2000:1 and reacting at 25-50°C.

[0033] Said Depend on and TsNHNH2(2) in a mass ratio of 50:1-100:1, and NaOH is added to react at 100-150°C to prepare the product. Depend on and TsNHNH2(2) in a mass ratio of 50:1-60:1, and NaOH is added to react at 100-150°C to prepare the product.

[0034] The specific synthetic route is as follows:

[0035]

[0036] In the above synthetic route, Prepared by reaction with TsNHNH2(2) The preparation method of can refer to the document "Study on the Synthesis of 3-Chloro-4-Methylpyridazine" (Guangzhou Chemical Industry, 2012, 40(9): 121-122.). Different from the document, the present invention replaces citraconic anhydride with

[0037] Prepared by reaction with TsNHNH2(2) The specific preparation method is: The mixture was dissolved in DMF at a molar ratio of 1:1 with p-toluenesulfonhydrazine (i.e., TsNHNH2(2)). An equivalent amount of sodium hydroxide was slowly added to the reaction solution. The mixture was reacted at 60°C for 3 hours. Toluene was then added to extract and concentrate to obtain the target compound.

[0038] use Prepared separately The method is: the compound Dissolve in toluene, slowly add 1.1 equivalents of 1M hydrochloric acid until a white solid is produced, filter and wash the filter cake three times with clean water, and dry the filter cake to obtain a white solid

[0039] The compatibilizer is at least one of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, styrene grafted polypropylene or chlorinated polypropylene. The compatibilizer is preferably maleic anhydride grafted polypropylene. The selection of the compatibilizer in the present invention mainly takes into account the compatibilizer and the long-chain aliphatic quaternary ammonium salt, They are well compatible with each other.

[0040] The melt flow rate of the polypropylene resin is 1-100 g / 10 min, and the polypropylene resin is at least one of homopolymer polypropylene or copolymer polypropylene.

[0041] The antioxidant is at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 330 , and antioxidant 168 .

[0042] The preparation method of the anti-scaling polypropylene masterbatch for the geotextile synthetic material is as follows:

[0043] 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of compatibilizer and 0.2-0.5 parts of antioxidant are mixed evenly, added through the main feeding port of a twin-screw extruder, melt dispersed and extruded into granules to obtain a scale-inhibiting polypropylene masterbatch.

[0044] The present invention is further described below with reference to specific embodiments.

[0045] Example 1

[0046] Preparation of long-chain aliphatic quaternary ammonium salts:

[0047] Will The mixture was dissolved in DMF at a molar ratio of 1:1 with p-toluenesulfonhydrazine (i.e., TsNHNH2(2)). An equivalent amount of sodium hydroxide was slowly added to the reaction solution. The mixture was reacted at 60°C for 3 hours. Toluene was then added to extract and concentrate to obtain the target compound.

[0048] Compound Dissolve in toluene, slowly add 1.1 equivalents of 1M hydrochloric acid until a white solid is produced, filter and wash the filter cake three times with clean water, and dry the filter cake to obtain a white solid

[0049] Scale-inhibiting polypropylene masterbatch for preparing geotextile synthetic materials:

[0050] 93 parts of polypropylene resin, 4 parts of long-chain aliphatic quaternary ammonium salt, 2.5 parts of maleic anhydride grafted polypropylene, and 0.5 parts of antioxidant 1076 were mixed evenly, added through the main feeding port of a twin-screw extruder, melt dispersed, and extruded and granulated at 250°C to obtain a scale-inhibiting polypropylene masterbatch.

[0051] Example 2

[0052] Different from Example 1, the method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials in this example is as follows: 95 parts of polypropylene resin, 3.5 parts of long-chain aliphatic quaternary ammonium salt, 1.3 parts of maleic anhydride grafted polypropylene, and 0.2 parts of antioxidant 1010 are uniformly mixed, added through the main feeding port of the twin-screw extruder, melt dispersed, extruded and granulated at 250° C., and the scale-inhibiting polypropylene masterbatch is obtained. The rest is the same as Example 1.

[0053] Example 3

[0054] Different from Example 1, the method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials in this example is as follows: 97 parts of polypropylene resin, 1.5 parts of long-chain aliphatic quaternary ammonium salt, 1.3 parts of acrylic acid grafted polypropylene, and 0.2 parts of antioxidant 1010 are uniformly mixed, added through the main feeding port of the twin-screw extruder, melt dispersed, extruded and granulated at 250° C., and the scale-inhibiting polypropylene masterbatch is obtained. The rest is the same as Example 1.

[0055] Example 4

[0056] Different from Example 1, the method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials in this example is as follows: 95 parts of polypropylene resin, 3 parts of long-chain aliphatic quaternary ammonium salt, 1.5 parts of maleic anhydride grafted polypropylene, and 0.5 parts of antioxidant 1076 are uniformly mixed, added through the main feed port of the twin-screw extruder, melt dispersed, extruded and granulated at 300° C., and the scale-inhibiting polypropylene masterbatch is obtained. The rest is the same as Example 1.

[0057] Comparative Example 1

[0058] Different from Example 1, the method for preparing the anti-fouling polypropylene masterbatch for geotextile synthetic materials in this comparative example is as follows: 95 parts of polypropylene resin and 0.5 parts of antioxidant 1076 are mixed evenly, added through the main feeding port of the twin-screw extruder, melt dispersed, extruded and granulated at 300° C. to obtain the anti-fouling polypropylene masterbatch. The rest is the same as Example 1.

[0059] Comparative Example 2

[0060] Different from Example 1, the method for preparing anti-scaling polypropylene masterbatch for geotextile synthetic materials in this comparative example is: 95 parts of polypropylene resin, 1.5 parts of maleic anhydride grafted polypropylene, and 0.5 parts of antioxidant 1076 are mixed evenly, added through the main feeding port of the twin-screw extruder, melt dispersed, and extruded and granulated at 300°C to obtain the anti-scaling polypropylene masterbatch.

[0061] Comparative Example 3

[0062] Different from Example 1, the method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials in this comparative example is as follows: 95 parts of polypropylene resin, 3 parts of polyacrylic acid, 0.5 parts of antioxidant 1076, and 1.5 parts of maleic anhydride grafted polypropylene are uniformly mixed, added through the main feed port of the twin-screw extruder, melt dispersed, extruded and granulated at 300° C. to obtain the scale-inhibiting polypropylene masterbatch. The rest is the same as Example 1.

[0063] Scale inhibition performance test

[0064] The scale-inhibiting polypropylene masterbatch obtained in Examples 1-4 and Comparative Examples 1-3 was used to prepare fibers to obtain geotextile synthetic materials, and then the scale-inhibiting performance was tested. The scale-inhibiting performance test method of the scale-inhibiting geosynthetics of the present invention is as follows: CaCl2, MgCl2 and NaHCO3 were used to prepare CaCl2. 2+ Mg 2+ The concentration of hard water is 500mg / L. Cut a sample with a length of 10cm and a width of 10cm and place it in a glass beaker with a capacity of 5L. The cover is equipped with a digital electric stirrer and a mercury thermometer. Stir it in a constant temperature water bath at 25℃ for 3 days, then take it out, dry it, and weigh it. Calculate the weight gain per unit area of ​​each group of samples m / (mg·cm -2 ).

[0065] Table 1 Measurement results of water scaling performance of polypropylene geosynthetics of Examples 1-4 and Comparative Examples 1-3

[0066] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 m 5.3 4.8 6.5 5.0 45.3 40.6 11.9

[0067] As shown in Table 1, the scale-inhibiting polypropylene masterbatch of the present invention is used to make the polypropylene geotextile synthetic material. The obtained polypropylene geotextile synthetic material has good scale-inhibiting performance, and the weight gain per unit area m is as low as 4.8 mg·cm -2 .

[0068] By comparing Example 4 with Comparative Example 1, it can be seen that no long-chain aliphatic quaternary ammonium salt and compatibilizer were added in Comparative Example 1. When the polypropylene geotextile synthetic material was produced, the scale inhibitor and compatibilizer were lacking. The obtained polypropylene geotextile synthetic material had poor uniformity and almost no scale inhibition effect.

[0069] By comparing Example 4 with Comparative Example 2, it can be seen that no long-chain aliphatic quaternary ammonium salt is added as a scale inhibitor in Comparative Example 2, and the obtained polypropylene geotextile synthetic material has almost no scale inhibition effect. However, due to the addition of a compatibilizer, the uniformity of the polypropylene geotextile synthetic material can be improved to a certain extent, so compared with Comparative Example 1, the scale inhibition effect of the polypropylene geotextile synthetic material of Comparative Example 2 is slightly improved.

[0070] By comparing Example 4 with Comparative Example 3, it can be seen that in Comparative Example 3, the long-chain aliphatic quaternary ammonium salt is replaced with a commercially available scale inhibitor, polyacrylic acid, and the scale inhibition effect is relatively poor.

[0071] The above embodiments are only used to explain the present invention and do not constitute a limitation on the scope of the claims. Other alternative means that can be thought of by those skilled in the art based on the contents of the present specification should be within the protection scope of the claims of the present invention.

Claims

1. A scale-inhibiting polypropylene masterbatch for geotextile synthetic materials, characterized in that: The invention comprises the following components in parts by weight: 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of compatibilizer, and 0.2-0.5 parts of antioxidant. The general structural formula of the long-chain aliphatic quaternary ammonium salt is:

2. The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 1, characterized in that: The compatibilizer is at least one of maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, styrene grafted polypropylene or chlorinated polypropylene.

3. The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 2, characterized in that: The compatibilizer is maleic anhydride grafted polypropylene.

4. The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 1, characterized in that: The melt flow rate of the polypropylene resin is 1-100 g / 10 min, and the polypropylene resin is at least one of homopolymer polypropylene or copolymer polypropylene.

5. The scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 330 , and antioxidant 168 .

6. The method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to any one of claims 1 to 5, characterized in that: 93-97 parts of polypropylene resin, 1.5-4 parts of long-chain aliphatic quaternary ammonium salt, 1.3-2.5 parts of compatibilizer and 0.2-0.5 parts of antioxidant are mixed evenly, added through the main feeding port of a twin-screw extruder, melt dispersed and extruded into granules to obtain a scale-inhibiting polypropylene masterbatch.

7. The method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 6, characterized in that: The general structural formula of the long-chain aliphatic quaternary ammonium salt is: in Depend on The mixture is fully mixed with hydrochloric acid in a mass ratio of 1000:1-2000:1, and reacted at 25-50°C to obtain the product; Depend on The product is prepared by fully mixing with hydrochloric acid at a mass ratio of 1000:1-2000:1 and reacting at 25-50°C.

8. The method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 7, characterized in that: Said Depend on and TsNHNH2(2) in a mass ratio of 50:1-100:1, and NaOH is added to react at 100-150°C to prepare the product.

9. The method for preparing the scale-inhibiting polypropylene masterbatch for geotextile synthetic materials according to claim 8, characterized in that: Said Depend on and TsNHNH2(2) in a mass ratio of 50:1-60:1, and NaOH is added to react at 100-150°C to prepare the product.

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