Weather-resistant and aging-resistant PVC material and preparation method thereof

Abstract

The application relates to the field of PVC material preparation, in particular to a weather-resistant and aging-resistant PVC material and a preparation method thereof, which are mainly prepared from the following raw materials in parts by weight: 50-60 parts of PVC master batch, 5-8 parts of filler, 2-5 parts of plasticizer and 3-8 parts of anti-aging agent; the preparation method of the anti-aging agent comprises the following steps: S11, stirring, standing and preparing pre-reaction material by adding ethyl silicate, ethanol solution and ammonia water at 25-40 DEG C; S12, adding silane coupling agent and N-isopropyl-N-phenyl-p-phenylenediamine into the pre-reaction material prepared in the step S11, uniformly mixing, reacting in inert gas, taking out, filtering, separating, drying and obtaining. The application has the advantages of improving the anti-aging performance of the PVC material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of PVC material preparation, in particular to a weather-resistant and aging-resistant PVC material and a preparation method thereof. BACKGROUND

[0002] PVC (polyvinyl chloride) is a kind of polymer material with low price, good physical and mechanical properties, dielectric properties and solvent resistance. Since PVC material has good compatibility with various polymers, it can be mixed with other polymers to combine the advantages of various polymers and prepare various products with good properties. At present, there are more and more PVC materials prepared in industry, such as PVC pipes, films, coated products, foamed plastics, profiled materials, etc. However, due to the existence of some unstable structures such as oxygen-containing groups, chain branching, unsaturated functional groups and allyl groups in the PVC molecular chain, the PVC material is easy to decompose under the environment of oxygen and ultraviolet light, which leads to the breakage of PVC molecular chain and the aging of PVC products or products containing PVC material during use, thereby shortening the service life.

[0003] In the above related technology, the inventors believe that the existing PVC material is easy to age during use, and the anti-aging performance needs to be improved. SUMMARY

[0004] In order to improve the anti-aging performance of PVC material, the present application provides a weather-resistant and aging-resistant PVC material and a preparation method thereof.

[0005] In a first aspect, the present application provides a weather-resistant and aging-resistant PVC material, which adopts the following technical solution:

[0006] A weather-resistant and aging-resistant PVC material is prepared mainly from the following raw materials in parts by weight: 50-60 parts of PVC masterbatch, 5-8 parts of filler, 2-5 parts of plasticizer and 3-8 parts of anti-aging agent. The preparation method of the anti-aging agent comprises the following steps:

[0007] S11: stirring, standing, and preparing a pre-reaction material from tetraethyl orthosilicate, an ethanol solution and ammonia water at 25-40℃;

[0008] S12: adding a silane coupling agent and N-isopropyl-N-phenyl-p-phenylenediamine to the pre-reaction material prepared in step S11, mixing uniformly, and then reacting in an inert gas. The product is obtained by filtering, separating and drying.

[0009] By adopting the technical scheme, the raw materials are matched, and the anti-aging agent is prepared. After the tetraethyl orthosilicate is mixed with the ethanol solution, the tetraethyl orthosilicate is partially hydrolyzed to generate silicic acid and corresponding alcohol products. After the addition of ammonia water, in the alkaline environment, the condensation reaction occurs between the silicic acids or between the silicic acid and the tetraethyl orthosilicate, to generate the pre-reaction material containing the nano-silica sol. The nano-silica sol has the small size effect and the macro quantum tunnel effect, so that, after being added into the PVC material, the nano-silica sol has the electron cloud effect with the unsaturated bond in the PVC, to improve the thermal stability and the light stability of the PVC material, thereby improving the aging resistance of the prepared PVC material.

[0010] Meanwhile, due to the large specific surface area of the nano-silica sol, the surface of the nano-silica sol has the hydroxyl group and has the high reactivity. By adding the silane coupling agent into the pre-reaction material, one end of the silane coupling agent is first hydrolyzed and then combined with the silicon hydroxyl group on the surface of the nano-silica sol, and the other end of the silane coupling agent is connected with the N-isopropyl-N-phenyl-p-phenylenediamine. The N-isopropyl-N-phenyl-p-phenylenediamine itself has the anti-aging effect. After being grafted onto the surface of the nano-silica sol through the chemical bond, the nano-silica sol has the loading and fixing effects on the N-isopropyl-N-phenyl-p-phenylenediamine, so that the N-isopropyl-N-phenyl-p-phenylenediamine is not easy to volatilize and migrate in the preparation process of the PVC material, to improve the stability of the N-isopropyl-N-phenyl-p-phenylenediamine in the PVC material. Meanwhile, due to the long molecular chain of the N-isopropyl-N-phenyl-p-phenylenediamine, the nano-silica particles can be dispersed in the PVC material, and through the mutual separation effect, the nano-silica particles are not easy to agglomerate in the PVC material. After the prepared anti-aging agent is added into the PVC material, the anti-aging agent can have the better anti-aging effect on the PVC material.

[0011] Optionally, the mass ratio of the silane coupling agent to the tetraethyl orthosilicate in the step S12 is (0.1-0.2):(3-5).

[0012] By adopting the technical scheme, due to the large amount of hydroxyl groups on the surface of the nano-silica particles, the use amount of the silane coupling agent is adjusted. When the use amount of the silane coupling agent is small, the connection effect of the silane coupling agent with the nano-silica particles is insufficient, so that the nano-silica particles have the insufficient fixing and loading effects on the N-isopropyl-N-phenyl-p-phenylenediamine, to affect the subsequent anti-aging effect on the PVC material. However, when the use amount of the silane coupling agent is too large, the silane coupling agents are easy to crosslink, so that the nano-silica particles are easy to agglomerate, to affect the anti-aging effect on the prepared PVC material. Therefore, by adjusting the mass ratio of the silane coupling agent to the tetraethyl orthosilicate, the prepared anti-aging agent has the better anti-aging effect on the PVC material.

[0013] Optionally, the preparation method of the filler comprises the following steps:

[0014] 1) mixing anhydrous ethylenediamine, water, lysine and tetrabutyl titanate to prepare a premix, adding a pH regulator to the premix to adjust the pH value of the premix to be alkaline, and preparing a mixture;

[0015] 2) heating the mixture prepared in step 1), washing and drying to prepare a pre-product;

[0016] 3) mixing the pre-product prepared in step 2) with an antioxidant, and sealing and heating to obtain the product; the antioxidant is at least one of 3,5-di-tert-butyl-4-benzoic acid and hydroquinone monobenzoate.

[0017] By adopting the above technical scheme, tetrabutyl titanate is used as a titanium source, the premix prepared contains nanometer titanium dioxide particles, lysine is used as a modifier, the amino group in lysine modifies the nanometer titanium dioxide in an alkaline environment, so that the pre-product contains amino-modified nanometer titanium dioxide particles, and then the antioxidant reacts with the pre-product, so that the antioxidant is grafted on the pre-product. Since 3,5-di-tert-butyl-4-benzoic acid has anti-aging properties, it can assist the amino-modified nanometer titanium dioxide to have better anti-ultraviolet properties. Hydroquinone monobenzoate has good ultraviolet absorption properties and can assist the amino-modified nanometer titanium dioxide particles to have good light stability effects after being connected to the pre-product. The filler prepared is filled into the PVC material, fills the pores in the PVC material, and also absorbs and resists ultraviolet rays, further having an anti-aging effect on the PVC material.

[0018] Optionally, the antioxidant consists of 3,5-di-tert-butyl-4-benzoic acid and hydroquinone monobenzoate in a mass ratio of (2-3):(3-5).

[0019] By adopting the above technical scheme, since 3,5-di-tert-butyl-4-benzoic acid has good nitrogen radical scavenging ability, it can scavenge free radicals generated due to chain scission in the aging process of the PVC material after being connected to the surface of the amino-modified nanometer titanium dioxide particles, inhibit the generation of HCI gas in the aging process, and slow down the aging process of the PVC material. Hydroquinone monobenzoate has good ultraviolet absorption and good light stability effects, and can cooperate with the amino-modified nanometer titanium dioxide particles to make the PVC material have good ultraviolet absorption and resistance when subjected to ultraviolet radiation. Under the combined action of 3,5-di-tert-butyl-4-benzoic acid and hydroquinone monobenzoate, the anti-aging properties of the prepared PVC material are improved.

[0020] Optionally, the mass ratio of lysine to tetrabutyl titanate in step 1) is (1-2):(14-20).

[0021] By adopting the above technical solution, the mass ratio of lysine to tetrabutyl titanate is adjusted. When lysine is continuously added to the filler, the positively charged lysine and the negatively charged tetrabutyl titanate can recognize each other, so that the amino group on the surface of nano-titanium dioxide continuously increases, and the content of aminated nano-titanium dioxide continuously increases. However, with the continuous addition of lysine, the addition of a large amount of organic groups is not conducive to the synergistic effect of tetrabutyl titanate and anhydrous ethylenediamine, which affects the preparation of aminated nano-titanium dioxide, and further affects the filling and anti-aging effect of the subsequent filler on the PVC material. Therefore, by adjusting the mass ratio of lysine to tetrabutyl titanate, the yield of aminated nano-titanium dioxide prepared is higher, and then the antioxidant is more easily connected to the aminated nano-titanium dioxide, so that the prepared filler has better anti-aging effect on the PVC material.

[0022] Optionally, the pH regulator is added in step 1) to adjust the pH value of the premixture to 9-11.

[0023] By adopting the above technical solution, since there is only one butyl group connected to the oxygen atom around the titanium ion in the tetrabutyl titanate molecule, the pH value of the premixture is adjusted to 9-11 by adding a pH regulator, so that tetrabutyl titanate can lose electrons and hydrolyze in an alkaline environment. However, when the pH value is small, the amino group in lysine is not easy to dissociate, so that nano-titanium dioxide is not easy to be aminated, which affects the subsequent connection with the antioxidant. With the gradual increase of the pH value, after the amino group in lysine is dissociated, it is connected to nano-titanium dioxide through electrostatic attraction, and the generated aminated nano-titanium dioxide continuously increases. However, as the pH value continues to increase, the electrostatic interaction between nano-titanium dioxide and the amino group weakens, so that the amount of aminated nano-titanium dioxide no longer increases. Therefore, by adjusting the pH value of the premixture, the amount of aminated nano-titanium dioxide prepared is increased, and then the filling and anti-aging effect of the subsequently prepared filler on the PVC material is better.

[0024] Optionally, after the prepared pre-product is mixed with the antioxidant in step 3), the heating temperature is 80-110℃.

[0025] By adopting the above technical solution, the temperature of the mixture is adjusted. When the temperature is low, the hydrolysis rate of lysine is slow, and the generated amino group is small. With the continuous increase of the temperature, the content of the amino group continuously increases. However, when the temperature continues to increase, the denaturation of lysine caused by the high temperature leads to the decrease of the content of the amino group, which further affects the yield of the prepared aminated nano-titanium dioxide, and leads to the decrease of the filling and anti-aging effect of the prepared filler on the PVC material.

[0026] In a second aspect, the application provides a preparation method of a weather-resistant and aging-resistant PVC material.

[0027] The preparation method of the weather-resistant and aging-resistant PVC material mainly comprises the following steps:

[0028] S1: mixing PVC masterbatch, filler, plasticizer and anti-aging agent to prepare a premix;

[0029] S2: melt extruding the premix prepared in step S1 to obtain granules.

[0030] By using the above technical solution, the PVC masterbatch, filler, plasticizer and anti-aging agent are mixed, and then melt extruded to make the anti-aging agent uniformly dispersed in the prepared PVC material. After the anti-aging agent is added to the PVC material, the N-isopropyl-N-phenyl-p-phenylenediamine is loaded on the nano-silicon dioxide, so that the N-isopropyl-N-phenyl-p-phenylenediamine is not easy to migrate out of the PVC material. At the same time, through the separation effect of the N-isopropyl-N-phenyl-p-phenylenediamine, the nano-silicon dioxide particles are not easy to agglomerate. The mutual synergistic effect between the nano-silicon dioxide and the N-isopropyl-N-phenyl-p-phenylenediamine plays a good anti-aging effect on the PVC material.

[0031] Optionally, maleic anhydride is added to the premix before melt extrusion in step S2; the mass ratio of the maleic anhydride to the PVC masterbatch is (0.8-1.3):(86-97).

[0032] By using the above technical solution, the PVC material is easy to release HCI under heat during use, forming a conjugated polyene. By adding maleic anhydride, which contains double bonds, the maleic anhydride can undergo an addition reaction with the conjugated double bonds formed by the molecular chain rupture of the PVC after being heated, thereby improving the mechanical strength of the PVC material, delaying the aging rate of the PVC material under heat, and improving the anti-aging effect of the PVC material.

[0033] In summary, the application has the following beneficial effects:

[0034] The application adds an anti-aging agent in the preparation raw material of the PVC material, and the anti-aging agent is prepared by reacting tetraethyl orthosilicate, an ethanol solution and ammonia water. The pre-reaction material containing nanometer silicon dioxide sol is prepared, and the N-isopropyl-N-phenyl-p-phenylenediamine is connected to the nanometer silicon dioxide particles through the connecting action of the silane coupling agent, so as to play a separating role on the nanometer silicon dioxide particles and prevent the agglomeration of the nanometer silicon dioxide particles. Meanwhile, the nanometer silicon dioxide is fixed by loading the N-isopropyl-N-phenyl-p-phenylenediamine, so as to reduce the volatilization of the N-isopropyl-N-phenyl-p-phenylenediamine in the preparation process. The anti-aging performance of the prepared PVC material is improved through the joint action of the N-isopropyl-N-phenyl-p-phenylenediamine and the nanometer silicon dioxide particles. DETAILED DESCRIPTION

[0035] The application will be further described in detail in combination with examples and comparative examples.

[0036] The raw materials of the examples and the comparative examples of the application are all ordinary commercial products except for special description.

[0037] Preparation example

[0038] Anti-aging agent preparation example 1

[0039] The preparation method of the anti-aging agent in the preparation example includes the following steps:

[0040] S11: A mixed barrel is taken, the ethanol solution is placed in the mixed barrel, the tetraethyl orthosilicate and the ammonia water are jointly added in the ethanol solution, and the materials in the mixed barrel are stirred uniformly at 35℃ and then are left to stand for 3h to prepare a pre-reaction material. The mass ratio of the used tetraethyl orthosilicate to the ammonia water is 5:1.5. The mass concentration of ethanol in the used ethanol solution is 50%. The ammonia concentration of the used ammonia water is 26%. The mass ratio of the used ethanol solution to the tetraethyl orthosilicate is 3:1.

[0041] S12: The silane coupling agent and the N-isopropyl-N-phenyl-p-phenylenediamine are added in the mixed barrel containing the pre-reaction material in step S11, and are stirred and mixed uniformly. Then the mixed barrel is sealed, nitrogen is introduced, and the reaction is carried out for 4h. The product is obtained by filtering, separating and drying. The mass ratio of the used silane coupling agent to the tetraethyl orthosilicate is 0.1:5. The mass ratio of the used N-isopropyl-N-phenyl-p-phenylenediamine to the tetraethyl orthosilicate is 2:5. The silane coupling agent used in the application is γ-aminopropyl triethoxysilane.

[0042] Anti-aging agent preparation example 2

[0043] The difference between the anti-aging agent preparation example and the anti-aging agent preparation example 1 is that the mass ratio of the silane coupling agent to the tetraethyl orthosilicate used in step S12 is 0.2:3.

[0044] Anti-aging agent Preparation Example 3

[0045] The difference between the present anti-aging agent preparation example and Anti-aging agent Preparation Example 1 is that the mass ratio of silane coupling agent to tetraethyl orthosilicate used in step S12 is 0.15:4.

[0046] Filler Preparation Example 1

[0047] 1) Take a reaction bucket, add anhydrous ethylenediamine, water, lysine and tetrabutyl titanate into the reaction bucket, mix uniformly to prepare a premix, add a pH adjuster to the premix to adjust the pH value of the premix to 9, and prepare a mixture; the mass ratio of anhydrous ethylenediamine, water and lysine used is 3:8:2; the mass ratio of lysine to tetrabutyl titanate used is 1:20; and the pH adjuster used is sodium hydroxide;

[0048] 2) Heat the mixture prepared in step 1) at 100°C for 10h, cool, wash and dry to prepare a pre-product;

[0049] 3) Take a reaction kettle, add an ethanol solution as a solvent into the reaction kettle, put the pre-product prepared in step 2) and an antioxidant into the reaction kettle, mix uniformly, seal and heat at 80°C for 2h, take out and cool to obtain the product; the antioxidant used is 3,5-di-tert-butyl-4-benzoic acid; the mass ratio of antioxidant to pre-product used is 1:10; and the mass concentration of ethanol in the ethanol solution used is 30%.

[0050] Filler Preparation Example 2

[0051] The difference between the present filler preparation example and Filler Preparation Example 1 is that the mass ratio of lysine to tetrabutyl titanate used in step 1) is 2:14.

[0052] Filler Preparation Example 3

[0053] The difference between the present filler preparation example and Filler Preparation Example 1 is that the mass ratio of lysine to tetrabutyl titanate used in step 1) is 1.5:17.

[0054] Filler Preparation Example 4

[0055] The difference between the present filler preparation example and Filler Preparation Example 3 is that the pH value of the premix is adjusted to 11 by using a pH adjuster in step 1).

[0056] Filler Preparation Example 5

[0057] The difference between the present filler preparation example and Filler Preparation Example 3 is that the pH value of the premix is adjusted to 10 by using a pH adjuster in step 1).

[0058] Filler Preparation Example 6

[0059] The difference between the present filler preparation example and filler preparation example 5 is that the temperature of heating after mixing the prepared pre-product with the antioxidant in step 3) is 110°C.

[0060] Filler preparation example 7

[0061] The difference between the present filler preparation example and filler preparation example 5 is that the temperature of heating after mixing the prepared pre-product with the antioxidant in step 3) is 95°C.

[0062] Filler preparation example 8

[0063] The difference between the present filler preparation example and filler preparation example 7 is that the antioxidant used in step 3) is m-phenylenediamine monobenzoate.

[0064] Filler preparation example 9

[0065] The difference between the present filler preparation example and filler preparation example 1 is that the antioxidant used in step 3) is composed of 3,5-di-tert-butyl-4-benzoic acid and o-hydroxybenzoic acid according to a mass ratio of 2.5:4.

[0066] Example

[0067] Example 1

[0068] The weather-resistant and aging-resistant PVC material in the present example mainly includes the following raw materials by weight: PVC masterbatch 50 kg, filler 5 kg, plasticizer 2 kg, and anti-aging agent 3 kg; the filler used is prepared in filler preparation example 1; the anti-aging agent used is prepared in anti-aging agent preparation example 1; and the plasticizer used is dioctyl phthalate;

[0069] The preparation method of the weather-resistant and aging-resistant PVC material in the present example mainly includes the following steps:

[0070] S1: Take a mixing barrel, and put the PVC masterbatch, filler, plasticizer, and anti-aging agent in the above weight portions into the mixing barrel to mix uniformly and prepare a pre-mixture;

[0071] S2: Put the pre-mixture prepared in step S1 into a twin-screw extruder to melt extrude and granulate to obtain the product.

[0072] Example 2

[0073] The preparation method of the weather-resistant and aging-resistant PVC material in the present example is different from that in example 1 in that the weather-resistant and aging-resistant PVC material mainly includes the following raw materials by weight: PVC masterbatch 60 kg, filler 8 kg, plasticizer 5 kg, and anti-aging agent 8 kg.

[0074] Example 3

[0075] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 1 in that the weather-resistant and aging-resistant PVC material mainly comprises the following raw materials by weight: 55 kg of PVC master batch, 6 kg of filler, 3.5 kg of plasticizer, and 6 kg of anti-aging agent.

[0076] Embodiment 4

[0077] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 3 in that maleic anhydride is additionally added to the premix in step S2 before melt extrusion; the mass ratio of the maleic anhydride to the PVC master batch is 1:90.

[0078] Embodiment 5

[0079] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 4 in that the anti-aging agent used in step S1 is prepared in Anti-aging Agent Preparation Example 2.

[0080] Embodiment 6

[0081] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 4 in that the anti-aging agent used in step S1 is prepared in Anti-aging Agent Preparation Example 3.

[0082] Embodiment 7

[0083] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 2.

[0084] Embodiment 8

[0085] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 3.

[0086] Embodiment 9

[0087] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 4.

[0088] Embodiment 10

[0089] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 5.

[0090] Embodiment 11

[0091] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 6.

[0092] Embodiment 12

[0093] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 7.

[0094] Embodiment 13

[0095] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 8.

[0096] Embodiment 14

[0097] The preparation method of the weather-resistant and aging-resistant PVC material in the embodiment is different from that in Embodiment 6 in that the filler used in step S1 is prepared in Filler Preparation Example 9.

[0098] Comparative Example

[0099] Comparative Example 1

[0100] The preparation method of the weather-resistant and aging-resistant PVC material in the comparative example is different from that in Embodiment 1 in that the preparation method of the anti-aging agent in the raw material used comprises the following steps: taking a mixing barrel, placing an ethanol solution in the mixing barrel, adding tetraethyl orthosilicate and ammonia water into the ethanol solution together, stirring the materials in the mixing barrel uniformly at 35°C, and then standing for 3h, filtering, and drying to obtain the anti-aging agent; the mass ratio of the tetraethyl orthosilicate to the ammonia water used is 5:1.5; the mass concentration of ethanol in the ethanol solution used is 50%; the concentration of ammonia in the ammonia water used is 26%; and the mass ratio of the ethanol solution to the tetraethyl orthosilicate used is 3:1.

[0101] Comparative Example 2

[0102] The preparation method of the weather-resistant and aging-resistant PVC material in the comparative example is different from that in Embodiment 1 in that the anti-aging agent used in the raw material used is N-isopropyl-N-phenyl-p-phenylenediamine.

[0103] Comparative Example 3

[0104] The preparation method of the weather-resistant and aging-resistant PVC material in the comparative example is different from that in Embodiment 1 in that the anti-aging agent used in the raw material used is a commercially available silicon dioxide powder provided by Jinan Baoda Dye Chemical Co., Ltd.

[0105] Detection Method

[0106] The PVC material was prepared as an experimental sample according to the preparation method of the weather-resistant and aging-resistant PVC material in Examples 1-14 and Comparative Examples 1-3. First, the impact strength of each experimental sample was tested and recorded as an original value. Then, the experimental sample was placed in a 60℃ ultraviolet light irradiation environment for 8h, and the ultraviolet light intensity was 80μW / cm 2 After 12h, the experimental sample was taken out and rested for 12h, and the test was repeated 30 times to obtain a post-experiment sample. The impact strength of the post-experiment sample was tested and recorded as a post-experiment value. The impact strength loss value was calculated, and the data was recorded in Table 1:

[0107] Impact strength loss value = (original value - post-experiment value) / original value * 100%

[0108] Table 1 Impact strength loss value of the PVC material prepared in Examples 1-14 and Comparative Examples 1-3

[0109] No. Impact strength loss value (%) Example 1 13.6 Example 2 13.9 Example 3 13.1 Example 4 12.5 Example 5 12.8 Example 6 12.0 Example 7 12.1 Example 8 11.3 Example 9 11.5 Example 10 10.8 Example 11 10.5 Example 12 10.0 Example 13 9.8 Example 14 8.9 Comparative Example 1 16.6 Comparative Example 2 18.4 Comparative Example 3 19.2

[0110] As can be seen from Examples 1-4 and Table 1, by adjusting the ratio of each raw material in the PVC material, the prepared PVC material has good mechanical properties, and thus has good impact resistance under ultraviolet light irradiation. As can be seen from Example 4, the addition of maleic anhydride can add to the double bond inside the PVC material after fracture under ultraviolet light irradiation, preventing the aging of the PVC material and enhancing the impact resistance of the PVC material.

[0111] As can be seen from Examples 3-6, Comparative Examples 1-3 and Table 1, by mixing tetraethyl orthosilicate with an ethanol solution and ammonia water, promoting the condensation of tetraethyl orthosilicate, and making the pre-reaction material contain a large amount of nanometer silica sol, and by connecting the silane coupling agent, the N-isopropyl-N-phenyl-p-phenylenediamine is grafted on the surface of the nanometer silica sol. Through the interaction of the grafted N-isopropyl-N-phenyl-p-phenylenediamine and the nanometer silica sol, the nanometer silica sol is not easy to agglomerate in the PVC material, and the grafted N-isopropyl-N-phenyl-p-phenylenediamine is also not easy to migrate out of the PVC material, thereby improving the anti-aging effect of the prepared anti-aging agent on the PVC material. Compared with Comparative Examples 2-3, the anti-aging agent prepared in the present application has better anti-aging effect, and the impact strength loss value of the PVC material after ultraviolet light irradiation is smaller.

[0112] It can be seen from the combination of embodiments 7-12 and Table 1 that the amino-modified nano-titanium dioxide particles are prepared by mixing anhydrous ethylenediamine, water, lysine and tetrabutyl titanate to prepare a premix, using tetrabutyl titanate as a titanium source and lysine as a modifier. The nano-titanium dioxide itself has good ultraviolet light absorption and reflection effects. Then, by adjusting the mass ratio of lysine to tetrabutyl titanate in the filler preparation process, adjusting the pH value of the premix with a pH adjuster, and heating the mixture to graft the antioxidant onto the surface of the nano-titanium dioxide, the prepared filler can improve the compactness of the internal structure of the PVC material after filling into the PVC material, so that the ultraviolet light is not easy to penetrate into the interior of the PVC material, reducing the aging damage caused by the ultraviolet light, and cooperating with the resistance effect of nano-titanium dioxide on ultraviolet light and the scavenging effect of the antioxidant on the free radicals during the oxidation of the PVC material, to alleviate the oxidation aging of the PVC material and further improve the anti-aging effect of the prepared PVC material.

[0113] In combination with embodiments 13-14, by selecting 3,5-di-tert-butyl-4-benzoic acid and o-hydroxybenzoic acid to form an antioxidant with a mass ratio of 2.5:4, the 3,5-di-tert-butyl-4-benzoic acid can scavenge the free radicals generated by the aging of the PVC chain segment, inhibit the aging of the PVC material, and cooperate with the o-hydroxybenzoic acid to absorb ultraviolet light, while improving the light stability of the prepared PVC material, and further improving the anti-aging performance of the prepared PVC material.

[0114] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, as long as the modifications are within the scope of the claims of the present application.

Claims

1. A weather and age resistant PVC material, characterized in that: It is mainly prepared from the following raw materials in parts by weight: 50-60 parts of PVC masterbatch, 5-8 parts of filler, 2-5 parts of plasticizer, and 3-8 parts of anti-aging agent; the preparation method of the anti-aging agent comprises the following steps: S11: stirring, standing, and preparing a pre-reaction material from tetraethyl orthosilicate, an ethanol solution, and ammonia water at 25-40℃; S12: adding a silane coupling agent and N-isopropyl-N-phenyl-p-phenylenediamine to the pre-reaction material prepared in step S11, mixing uniformly, and then reacting in an inert gas, and then taking out, filtering, and drying to obtain the anti-aging agent; The preparation method of the filler comprises the following steps: 1) mixing anhydrous ethylenediamine, water, lysine, and tetrabutyl titanate to prepare a premix, adding a pH adjuster to the premix to adjust the pH value of the premix to be alkaline, and preparing a mixture; 2) heating, washing, and drying the mixture prepared in step 1) to prepare a pre-product; 3) mixing the pre-product prepared in step 2) with an antioxidant, and then sealing and heating to obtain the filler; the antioxidant is at least one of 3,5-di-tert-butyl-4-benzoic acid and resorcinol monobenzoate.

2. The weatherable and age-resistant PVC material according to claim 1, characterized in that: The mass ratio of the silane coupling agent to tetraethyl orthosilicate in step S12 is (0.1-0.2):(3-5).

3. The weatherable and age-resistant PVC material according to claim 1, characterized in that: The antioxidant is composed of 3,5-di-tert-butyl-4-benzoic acid and resorcinol monobenzoate in a mass ratio of (2-3):(3-5).

4. The weatherable and age-resistant PVC material according to claim 1, characterized in that: The mass ratio of lysine to tetrabutyl titanate in step 1) is (1-2):(14-20).

5. The weatherable and age resistant PVC material according to claim 1, characterized in that: The pH adjuster is added in step 1) to adjust the pH value of the premix to be 9-11.

6. The weatherable and age-resistant PVC material according to claim 1, characterized in that: In step 3), the temperature for heating the prepared pre-product after mixing with the antioxidant is 80-110℃.

7. A process for the preparation of weather and ageing resistant PVC material according to claim 1, characterized by: It mainly comprises the following steps: S1: mixing PVC masterbatch, filler, plasticizer, and anti-aging agent to prepare a premix; S2: melt extruding and granulating the premix prepared in step S1 to obtain the PVC material.

8. The process for the preparation of weather and ageing resistant PVC material according to claim 7, characterized by the fact that: In step S2, maleic anhydride is also added to the premix before melt extrusion; the mass ratio of maleic anhydride to PVC masterbatch is (0.8-1.3):(86-97).