A kind of aging-resistant PVC composite material

Abstract

The invention relates to the technical field of polymer material preparation, and discloses an anti-aging PVC composite material. The PVC composite material comprises the following raw materials: polyvinyl chloride, anti-aging filler, modified castor oil, lubricant and dispersant; wherein the anti-aging filler is talcum powder with hindered amine groups coated on the surface; and the modified castor oil is castor oil containing organic fluorine in its structure. The invention prepares the anti-aging filler and the modified castor oil and participates in the preparation process of the PVC composite material, thereby enhancing the stability of the PVC composite material to light and high temperature, so that the prepared PVC composite material has excellent high temperature resistance and anti-aging performance, and also has the characteristics of strong toughness and easy processing, and also has the effect of hydrophobicity and antifouling, can meet the needs of different fields, and has a long service life.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material preparation, and in particular to an anti-aging PVC composite material. Background Art

[0002] Polymer materials are materials based on polymer compounds, including plastics, rubber, fibers, coatings, etc., and are usually used in clothing, shoes, construction, medical treatment, packaging and other fields. Among plastics, PVC is a common polymer material with good corrosion resistance and weather resistance, as well as excellent insulation and antistatic properties. PVC materials are widely available and have extremely high economic benefits, making it one of the most widely used polymer materials in all walks of life. However, PVC materials have poor stability to light and heat, and long-term use at high temperatures may cause deformation or damage to the material. When used outdoors, PVC materials are prone to accumulate stains, especially outdoors (rainy days, muddy, workwear environments) and indoors (kitchen and bathroom environments). The accumulation of stains affects the appearance of the building, and timely cleaning is difficult and poses a safety hazard. Under the influence of ultraviolet light, the material will age faster, affecting the service life of the material and causing economic losses.

[0003] Therefore, when PVC materials are applied to various industries, they need to be modified. One of the simplest methods is to compound PVC materials with other materials into PVC composite materials, thereby changing their properties and giving them additional functionality. For example, the patent with publication number CN109971096B discloses a method for preparing a high-toughness PVC composite film, in which aramid nanofibers are alkylated and added to a PVC matrix as a reinforcing material, and the PVC is toughened by linear aramid nanofibers. At the same time, the mechanical strength of the material is enhanced by mutual entanglement with PVC macromolecules, and the Young's modulus, yield strength and fracture toughness of the composite material are improved. At the same time, the compatibility with the matrix is ​​good, and there is no decrease in the interface mechanical properties. However, the PVC composite material is still unstable to light and heat, which affects the service life of the composite material.

[0004] The patent with publication number CN102453289B discloses a light-resistant, low-cost, renewable PVC foam composite material and its preparation method. The composite material has excellent light-resistant and mechanical properties. A large amount of wood powder is added to the composite material to enhance the recyclability of the composite material, which has good economic value. However, the PVC composite material does not have the ability of hydrophobic self-cleaning and is prone to accumulate stains when used for a long time. Summary of the invention

[0005] The purpose of the present invention is to provide an anti-aging PVC composite material, which solves the following technical problems: (1) the ordinary PVC material has poor light and heat stability and is prone to aging; (2) the ordinary PVC material is prone to accumulate stains and has low anti-fouling performance.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] An anti-aging PVC composite material comprises the following raw materials in parts by weight: 50-80 parts of polyvinyl chloride, 5-10 parts of anti-aging filler, 8-10 parts of modified castor oil, 3-5 parts of lubricant, and 1-3 parts of dispersant; the anti-aging filler is talcum powder with hindered amine groups coated on the surface; the modified castor oil is castor oil containing organic fluorine in its structure.

[0008] Furthermore, the lubricant is any one of stearic acid, paraffin, and white oil; the dispersant is any one of tetraethyl ethylene diphosphate and benzyl ethylene diphosphate.

[0009] Furthermore, the preparation method of the aging-resistant filler comprises the following steps:

[0010] S1: placing talcum powder in deionized water, ultrasonically dispersing for 10-15 min, adding 4,4′-diisocyanate dicyclohexylmethane, heating to react, filtering, washing, and vacuum drying to obtain modified talcum powder;

[0011] S2: Place the modified talc in deionized water, add 4-amino-2,2,6,6-tetramethylpiperidine and a catalyst, heat to 50-55°C and react for 3-5h, filter, wash and vacuum dry to obtain an aging-resistant filler.

[0012] Through the above technical scheme, the hydroxyl groups on the surface of talcum powder react with the isocyanate groups at one end of the 4,4′-diisocyanate dicyclohexylmethane structure to obtain modified talcum powder, and then under the action of a catalyst, the isocyanate groups on the surface of the modified talcum powder react with the amino groups in the 4-amino-2,2,6,6-tetramethylpiperidine structure to obtain an aging-resistant filler. The surface of this anti-aging filler is coated with a layer of organic matter. After mixing with the PVC material, it can be evenly dispersed in the composite material and is not easy to agglomerate. At the same time, the filler can fill the pores in the composite material and increase the density of the material, thereby increasing the thermal deformation temperature of the composite material and enhancing its high temperature resistance. The surface of the filler is coated with hindered amine groups, which can effectively absorb ultraviolet rays to prevent ultraviolet rays from damaging the composite material. At the same time, the secondary amine groups in the hindered amine can react with free radicals to remove free radicals and improve the anti-aging ability of the composite material. The hindered amine groups are fixed in the composite material by chemical bonding, which can prevent the beneficial components of the composite material from migrating and precipitating when used for a long time, and can exert a long-term anti-aging effect, so that the composite material has a long service life.

[0013] Furthermore, in step S1, the temperature-raising reaction is to raise the temperature to 75-85° C. and react for 2-5 hours.

[0014] Furthermore, in step S2, the catalyst is dibutyltin dilaurate.

[0015] Furthermore, the preparation method of the modified castor oil comprises the following steps:

[0016] SS1: Place castor oil in ethanol, add glycidyl methacrylate and initiator, heat to 60-65°C and react for 5-8h, wash the product and perform vacuum distillation to obtain epoxidized castor oil;

[0017] SS2: Place epoxidized castor oil in toluene, add 1H,1H,2H,2H-tridecafluoro-1-octanol and catalyst ①, heat to 65-75°C and react for 5-10h, remove the solvent by rotary evaporation to obtain modified castor oil.

[0018] Through the above technical scheme, under the action of an initiator, the double bonds in the castor oil structure react with the double bonds in the glycidyl methacrylate structure to produce a free radical polymerization reaction to obtain epoxidized castor oil, and under the action of a catalyst, the epoxy groups in the epoxidized castor oil structure react with the hydroxyl groups in the 1H, 1H, 2H, 2H-tridecafluoro-1-n-octanol structure to produce a ring-opening reaction to obtain modified castor oil. The modified castor oil structure has multiple hydroxyl groups, and after being blended with a PVC material, the hydroxyl groups in its structure interact with the active chlorine in the molecular chain of the PVC material, and its molecular chain can be mutually entangled with the molecular chain of PVC to form a network structure, significantly enhancing the compatibility of the two and the toughness of the composite material, and at the same time, a CF bond with extremely low surface energy can be introduced into the network structure to enhance the hydrophobic and antifouling ability of the composite material, so that it has a self-cleaning effect, so that the PVC composite material is not easy to accumulate oil during use, has a long-term self-cleaning effect, saves time and effort, and has a long service life.

[0019] Furthermore, in step SS1, the initiator is any one of dibenzoyl peroxide and diisopropylbenzene peroxide.

[0020] Furthermore, in step SS2, the catalyst ① is any one of tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium acetate.

[0021] Furthermore, the method for preparing the composite material comprises the following steps:

[0022] Step 1, placing weight parts of polyvinyl chloride, aging-resistant filler, modified castor oil, lubricant, and dispersant in a high-speed mixer, setting the mixer speed to 600-700 r / min, heating to 105-115° C., stirring for 1-3 hours, and discharging after cooling to room temperature to obtain a mixture;

[0023] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 165-185° C., the screw speed to 200-300 r / min, extrude and cool to granulate, and obtain a composite material.

[0024] Beneficial effects of the present invention:

[0025] The invention prepares aging-resistant fillers and modified castor oil and participates in the preparation process of PVC composite materials, thereby enhancing the stability of the PVC composite materials to light and high temperature, so that the prepared PVC composite materials have excellent high temperature resistance and aging resistance, strong toughness and easy processing, and additionally have the effect of hydrophobicity and antifouling, and have a long service life.

[0026] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0028] Figure 1 This is a thermal weight loss curve of talc, modified talc and antioxidant filler in Example 1 of the present invention;

[0029] Figure 2 The infrared spectra of castor oil, epoxidized castor oil and modified castor oil in Example 1 of the present invention are shown in FIG.

[0030] Figure 3 This is a scanning electron microscope analysis diagram of the PVC composite material in Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] 1. Preparation of aging-resistant filler

[0034] S1: 2 g of talc was placed in 100 ml of deionized water, and ultrasonically dispersed for 10-15 min, 1.5 g of 4,4′-diisocyanate dicyclohexylmethane was added, and the temperature was raised to 75° C. for reaction for 2 h, and the modified talc was obtained after filtering, washing, and vacuum drying;

[0035] S2: Place 2 g of modified talc in 120 ml of deionized water, add 3 ml of 4-amino-2,2,6,6-tetramethylpiperidine and 0.03 g of dibutyltin dilaurate, heat to 50°C and react for 3 h, filter, wash and vacuum dry to obtain an aging-resistant filler.

[0036] The talc, modified talc and aging-resistant fillers were characterized by thermogravimetric analysis. Figure 1It can be seen that at high temperature, the final mass retention rate of talcum powder is 96.8%, and the lost part is due to the thermal decomposition of the crystalline water in the talcum powder structure. The final mass retention rate of modified talcum powder is 54.8%, and the reduced part is due to the thermal decomposition of 4,4′-diisocyanate dicyclohexylmethane grafted on the surface of modified talcum powder. The final mass retention rate of aging-resistant filler is 33.6%, and the lost part is due to the thermal decomposition of organic matter coated on the surface of aging-resistant filler.

[0037] 2. Preparation of modified castor oil

[0038] SS1: 3.5 ml of castor oil was placed in 60 ml of ethanol, 2 ml of glycidyl methacrylate and 0.5 g of benzoyl peroxide were added, the temperature was raised to 60°C for reaction for 5 h, the product was washed and subjected to reduced pressure distillation to obtain epoxidized castor oil;

[0039] SS2: Place 3 ml of epoxidized castor oil in 50 ml of toluene, add 2 ml of 1H,1H,2H,2H-tridecafluoro-1-octanol and 0.2 g of tetrabutylammonium bromide, heat to 65°C and react for 5 h. After removing the solvent by rotary evaporation, modified castor oil is obtained.

[0040] Castor oil, epoxidized castor oil and modified castor oil were characterized by infrared spectroscopy. Figure 2 It can be seen that in the infrared spectrum of castor oil, 3367cm -1 The absorption peak of hydroxyl group is 3010cm -1 The absorption peak of the carbon-hydrogen bond in the olefin group is 1723 cm -1 The absorption peak of the carbon-oxygen double bond in the ester group is at 915cm -1 The characteristic absorption peak of epoxy group appeared at 1256cm -1 The absorption peak of carbon-oxygen bond in epoxy group appeared at 3010cm -1 The absorption peak of the carbon-hydrogen bond in the olefin group basically disappeared, indicating that the double bond in the castor oil structure underwent a free radical polymerization reaction to form epoxidized castor oil; in the infrared spectrum of modified castor oil, 915cm -1 The characteristic absorption peak of epoxy group at 1246 cm -1 The absorption peak of the carbon-oxygen bond in the epoxy group basically disappeared, indicating that the epoxy group in the epoxidized castor oil structure and the hydroxyl group in the 1H,1H,2H,2H-tridecafluoro-1-n-octanol structure underwent a ring-opening reaction.

[0041] 3. Preparation of composite materials

[0042] Step 1, placing 50 parts of polyvinyl chloride, 5 parts of aging-resistant fillers, 8 parts of modified castor oil, 3 parts of stearic acid, and 1 part of ethylene diphosphate tetraethyl in a high-speed mixer, setting the mixer speed to 600 r / min, heating to 105° C., stirring for 1 hour, cooling to room temperature and then discharging to obtain a mixture;

[0043] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 165° C., the screw speed to 200 r / min, extrude and cool to granulate, and obtain a composite material.

[0044] The morphology of the composites was analyzed by scanning electron microscopy. Figure 3 It can be seen that the composite material is composed of a cross-linked network structure, which is formed by the interaction between multiple hydroxyl groups in the modified castor oil structure and the active chlorine in the polyvinyl chloride molecular chain at high temperature, and the molecular chains of the two are entangled with each other.

[0045] Example 2

[0046] Preparation of composite materials

[0047] Step 1, placing 65 parts of polyvinyl chloride, 8 parts of aging-resistant filler, 9 parts of modified castor oil, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate in a high-speed mixer, setting the mixer speed to 650 r / min, heating to 110° C., stirring for 2 hours, cooling to room temperature and then discharging to obtain a mixture;

[0048] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0049] Wherein, the preparation method of the aging-resistant filler and modified castor oil is the same as that in Example 1.

[0050] Example 3

[0051] Preparation of composite materials

[0052] Step 1, placing 80 parts of polyvinyl chloride, 10 parts of aging-resistant filler, 10 parts of modified castor oil, 5 parts of white oil, and 3 parts of ethylene diphosphate in a high-speed mixer, setting the mixer speed to 700 r / min, heating to 115° C., stirring for 3 hours, cooling to room temperature and then discharging to obtain a mixture;

[0053] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 185° C., the screw speed to 300 r / min, extrude and cool to granulate, and obtain a composite material.

[0054] Wherein, the preparation method of the aging-resistant filler and modified castor oil is the same as that in Example 1.

[0055] Comparative Example 1

[0056] Preparation of composite materials

[0057] Step 1, 65 parts of polyvinyl chloride, 9 parts of modified castor oil, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate are placed in a high-speed mixer, the mixer speed is set to 650r / min, the temperature is raised to 110°C, stirred for 2h, cooled to room temperature and then discharged to obtain a mixture;

[0058] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0059] Wherein, the preparation method of modified castor oil is the same as that in Example 1.

[0060] Comparative Example 2

[0061] Preparation of composite materials

[0062] Step 1, place 65 parts of polyvinyl chloride, 8 parts of aging-resistant filler, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate in a high-speed mixer, set the mixer speed to 650r / min, heat to 110°C, stir for 2h, cool to room temperature and then discharge to obtain a mixture;

[0063] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0064] Wherein, the preparation method of the aging-resistant filler is the same as that in Example 1.

[0065] Comparative Example 3

[0066] Preparation of composite materials

[0067] Step 1, place 65 parts of polyvinyl chloride, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate in a high-speed mixer, set the mixer speed to 650r / min, heat to 110°C, stir for 2h, cool to room temperature and then discharge to obtain a mixture;

[0068] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0069] Comparative Example 4

[0070] Preparation of composite materials

[0071] Step 1, placing 65 parts of polyvinyl chloride, 8 parts of talc, 9 parts of modified castor oil, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate in a high-speed mixer, setting the mixer speed to 650 r / min, heating to 110° C., stirring for 2 hours, cooling to room temperature and then discharging to obtain a mixture;

[0072] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0073] Wherein, the preparation method of modified castor oil is the same as that in Example 1.

[0074] Comparative Example 5

[0075] Preparation of composite materials

[0076] Step 1, placing 65 parts of polyvinyl chloride, 8 parts of aging-resistant filler, 9 parts of castor oil, 4 parts of paraffin wax, and 2 parts of ethylene diphosphate in a high-speed mixer, setting the mixer speed to 650 r / min, heating to 110° C., stirring for 2 hours, cooling to room temperature and then discharging to obtain a mixture;

[0077] Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 175° C., the screw speed to 250 r / min, extrude and cool to granulate, and obtain a composite material.

[0078] Wherein, the preparation method of the aging-resistant filler is the same as that in Example 1.

[0079] Performance Testing

[0080] The PVC composite materials prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were pressed into sheets and cut into samples that met the specifications. The samples were subjected to a Vicat softening temperature test according to the reference standard GB / T1633-2000 to determine the high temperature resistance of the samples. The samples were subjected to a bending elastic modulus test according to the reference standard GB / T9341-2008 to determine the toughness of the samples. The samples were subjected to an irradiation test at a wavelength of 313 nm and an irradiance of 0.72 / m 2 The samples treated in the UV aging box for 48 hours were subjected to tensile strength test to determine the aging resistance of the samples; the water contact angle test was performed on the samples using the JC2000D2G contact angle tester to determine the hydrophobic and antifouling properties of the samples; the specific test results are shown in the table below:

[0081]

[0082]

[0083] As can be seen from the above table, the samples prepared in Examples 1 to 3 have good toughness and good high temperature resistance, aging resistance and hydrophobic self-cleaning properties. The sample prepared in Comparative Example 1 does not have aging-resistant fillers added, so the aging resistance and high temperature resistance are poor, but because modified castor oil is added therein, the sample has good toughness and has excellent hydrophobic and antifouling properties. The sample prepared in Comparative Example 2 does not have modified castor oil added therein, so the toughness is not strong and the hydrophobic and antifouling ability is poor, but aging-resistant fillers are added to the sample, so the aging resistance is excellent and the high temperature resistance is good. The sample prepared in Comparative Example 3 has good toughness and excellent hydrophobic and antifouling properties. The sample has neither aging-resistant filler nor modified castor oil added, has poor toughness, and is at a poor level in terms of high temperature resistance, aging resistance, and hydrophobic and antifouling properties. The sample prepared in Comparative Example 4 directly adds unmodified talcum powder, has good high temperature resistance, and average aging resistance, but adds modified castor oil, so has good toughness, and has excellent hydrophobic and antifouling properties. The sample prepared in Comparative Example 5 directly adds unmodified castor oil, has poor hydrophobic and antifouling ability, but good toughness. Due to the addition of aging-resistant filler, the sample has excellent high temperature resistance and aging resistance.

[0084] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0085] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An aging-resistant PVC composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 50-80 parts of polyvinyl chloride, 5-10 parts of anti-aging filler, 8-10 parts of modified castor oil, 3-5 parts of lubricant, and 1-3 parts of dispersant; the anti-aging filler is talcum powder with hindered amine groups coated on the surface; the modified castor oil is castor oil containing organic fluorine in its structure; The preparation method of the aging-resistant filler comprises the following steps: S1: placing talc in deionized water, ultrasonically dispersing for 10-15 min, adding 4,4′-diisocyanate dicyclohexylmethane, heating to react, filtering, washing, and vacuum drying to obtain modified talc; S2: Place the modified talc in deionized water, add 4-amino-2,2,6,6-tetramethylpiperidine and a catalyst, heat to 50-55° C. for reaction for 3-5 hours, filter, wash, and vacuum dry to obtain an aging-resistant filler; The preparation method of the modified castor oil comprises the following steps: SS1: Place castor oil in ethanol, add glycidyl methacrylate and initiator, heat to 60-65°C and react for 5-8h, wash the product and perform vacuum distillation to obtain epoxidized castor oil; SS2: Place epoxidized castor oil in toluene, add 1H,1H,2H,2H-tridecafluoro-1-octanol and catalyst ①, heat to 65-75°C and react for 5-10h, remove the solvent by rotary evaporation to obtain modified castor oil.

2. The aging-resistant PVC composite material according to claim 1, characterized in that: The lubricant is any one of stearic acid, paraffin and white oil; the dispersant is any one of tetraethyl ethylene diphosphate and benzyl ethylene diphosphate.

3. The aging-resistant PVC composite material according to claim 1, characterized in that: In step S1, the temperature is raised to 75-85°C for 2-5h.

4. The aging-resistant PVC composite material according to claim 1, characterized in that: In step S2, the catalyst is dibutyltin dilaurate.

5. The aging-resistant PVC composite material according to claim 1, characterized in that: In step SS1, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

6. The aging-resistant PVC composite material according to claim 1, characterized in that: In step SS2, the catalyst ① is any one of tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium acetate.

7. The aging-resistant PVC composite material according to claim 1, characterized in that: The method for preparing the composite material comprises the following steps: Step 1, placing parts by weight of polyvinyl chloride, aging-resistant filler, modified castor oil, lubricant, and dispersant in a high-speed mixer, setting the mixer speed to 600-700 r / min, heating to 105-115° C., stirring for 1-3 hours, and discharging after cooling to room temperature to obtain a mixture; Step 2: Add the mixed material into a twin-screw extruder, set the temperature of the twin-screw extruder to 165-185° C., the screw speed to 200-300 r / min, extrude and cool to granulate, and obtain a composite material.

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