A kind of impact-resistant additive based on silicone and its preparation method and application

Abstract

The invention discloses an organosilicon-based impact-resistant additive, a preparation method and application thereof, and belongs to the technical field of resin additive preparation. The invention comprises the following components by weight: 18-50 parts of an organosilicon compound, 5-30 parts of a hydroxy silicone oil, 2-20 parts of a boride, 0.1-5 parts of a dimethyl silicone oil, 0.1-5 parts of a vinyl silicone oil, 0.1-5 parts of white carbon black, 0.1-10 parts of calcium carbonate, 0.1-6 parts of titanium dioxide and 0.1-3 parts of an aluminum oxide powder. The organosilicon compound is heptamethylcyclotetrasiloxane or a modified derivative of heptamethylcyclotetrasiloxane. Based on the existing impact-resistant additive, the invention prepares an impact-resistant additive applicable to a variety of thermoplastic resins by modifying and adjusting the components, and the impact-resistant additive has an excellent modification effect.

Description

Technical Field

[0001] The invention relates to the technical field of resin additive preparation, and in particular to an organosilicon-based impact-resistant additive and a preparation method and application thereof. Background Art

[0002] Thermoplastic resins are widely used in our daily lives, such as films, sidings, sheets, tubes, window profiles, fences, covers and pipes, but most thermoplastic resins are usually brittle and do not have the appropriate impact strength for various end uses. It is usually necessary to adjust and improve the impact resistance of the resin to meet different application scenarios so that it is not easy to fail when impacted.

[0003] The existing technology usually blends thermoplastic resin with impact modifier to improve its impact resistance, but the existing impact modifiers generally have defects such as poor modification effect or complex structure and preparation method. There is an urgent need for an impact modifier with a wide range of applications and better modification effect. Summary of the invention

[0004] In view of the above problems, the present invention provides an organosilicon-based impact-resistant additive and a preparation method and application thereof.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] An organosilicon-based impact-resistant additive, comprising the following components by weight: 18-50 parts of organosilicon compound, 5-30 parts of hydroxy silicone oil, 2-20 parts of boride, 0.1-5 parts of dimethyl silicone oil, 0.1-5 parts of vinyl silicone oil, 0.1-5 parts of white carbon black, 0.1-10 parts of calcium carbonate, 0.1-6 parts of titanium dioxide, and 0.1-3 parts of aluminum oxide powder;

[0007] Wherein, the organosilicon compound is heptamethylcyclotetrasiloxane or a modified derivative of heptamethylcyclotetrasiloxane, and the modified derivative of heptamethylcyclotetrasiloxane is a first modified derivative or a second modified derivative;

[0008] The preparation method of the first modified derivative comprises the following steps:

[0009] Weigh heptamethylcyclotetrasiloxane and dissolve it in xylene solvent, add trivinylmethylsilane, stir and mix thoroughly, then add platinum catalyst, stir and heat to 30-50° C. and keep warm for 0.5-2 hours, cool to room temperature after the reaction is completed, filter out the precipitate, and evaporate the solvent under reduced pressure to obtain the first modified derivative;

[0010] Wherein, the mass ratio of the heptamethylcyclotetrasiloxane to the trivinylmethylsilane is (6.7-6.9):1;

[0011] The preparation method of the second modified derivative comprises the following steps:

[0012] (1) Weigh 3,4,9,10-perylenetetracarboxylic dianhydride and dissolve it in dimethylformamide solvent, heat it to 50-60°C, slowly add allylamine dimethylformamide solution under heat preservation and stirring conditions, continue to heat preservation and stirring for 1-2 hours after the addition is completed, then heat it to 120-130°C and continue to heat preservation and stirring for 3-8 hours, after the reaction is completed, cool it to room temperature, separate the precipitate and wash it with solvent to obtain a precursor product;

[0013] Wherein, the mass ratio of the 3,4,9,10-perylenetetracarboxylic dianhydride to the allylamine is 1:(1.4-1.5);

[0014] (2) dissolving the precursor product in xylene solvent, adding heptamethylcyclotetrasiloxane, stirring and mixing thoroughly, adding platinum catalyst, stirring and heating to 30-50° C. and keeping the temperature to react for 0.5-2 hours, cooling to room temperature after the reaction is completed, filtering off the precipitate, and evaporating the solvent under reduced pressure to obtain the second modified derivative;

[0015] Wherein, the mass ratio of the precursor product to the heptamethylcyclotetrasiloxane is 1:(1.4-1.45).

[0016] In some preferred embodiments, the hydroxy silicone oil is α,ω-dihydroxy-terminated polydimethylsiloxane with a viscosity of 20-3000 mPa·s.

[0017] In some preferred embodiments, the boride is selected from one of pyroboric acid, boric acid, sodium tetraborate, potassium tetraborate, ammonium borate, methyl borate, ethyl borate, propyl borate or butyl borate.

[0018] In some preferred embodiments, the dimethyl silicone oil is polydimethylsiloxane with a viscosity of 20-7000 mpa·s.

[0019] In some preferred embodiments, the vinyl silicone oil is α,ω-divinyl-terminated polydimethylsiloxane with a viscosity of 20-5000 mPa·s.

[0020] In some preferred embodiments, the particle size of the white carbon black, the calcium carbonate, the titanium dioxide, and the aluminum oxide powder is 0.1-100 μm.

[0021] The second aspect of the present invention is to provide a method for preparing the silicone-based impact-resistant additive, which specifically comprises the following steps:

[0022] S1, preparing the organosilicon compound;

[0023] S2, weigh the raw materials according to the ratio and set aside;

[0024] S3. Add the organosilicon compound, hydroxy silicone oil, boride, dimethyl silicone oil, vinyl silicone oil, white carbon black, calcium carbonate, titanium dioxide and aluminum oxide powder into the container in sequence for physical mixing; start the vacuum system at 0.08-0.098 MPa, start the heating system, stir the materials at 110-160° C. for 1-4 hours, and naturally cool to room temperature to obtain the impact-resistant additive.

[0025] The third aspect of the present invention is to provide an application method of the silicone-based impact-resistant additive, specifically, adding the silicone-based impact-resistant additive to PC or PE to improve its impact resistance.

[0026] The beneficial effects of the present invention are:

[0027] In view of the defects of poor modification effect or complex structure and preparation method of impact-resistant additives in the prior art, the present invention, on the basis of the existing impact-resistant additives, proposes an impact-resistant additive with excellent modification effect that can be applied to a variety of thermoplastic resins through component modification and adjustment. Specifically, the present invention introduces cyclotetrasiloxane with a ring structure and obtains a modified organic silicon compound through an olefinic crosslinking agent, which can further improve the toughness of the material on the basis of the "particle cluster" formed in the material. At the same time, the present invention also uses the nucleophilic reaction product of trivinylmethylsilane or allylamine and 3,4,9,10-perylenetetracarboxylic dianhydride as a crosslinking agent, and performs hydrosilylation under a platinum catalyst to obtain a modified organic silicon compound, which improves the toughness and impact resistance of the resin while reducing the influence of the modification on its tensile strength and flexural strength, thereby further improving the application performance of the modified resin. DETAILED DESCRIPTION

[0028] The present invention is further described in conjunction with the following examples.

[0029] Example 1

[0030] A silicone-based impact-resistant additive, the preparation method of which comprises the following steps:

[0031] Weigh 38 parts of organosilicon compound, 12 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (viscosity of 100 mpa·s), 9 parts of boric acid, 2 parts of polydimethylsiloxane (viscosity of 180 mpa·s), 2 parts of α,ω-divinyl-terminated polydimethylsiloxane (viscosity of 200 mpa·s), 1 part of white carbon black, 0.8 parts of light calcium carbonate, 1 part of titanium dioxide, and 1.5 parts of alumina powder in parts by weight, and add the raw materials into a kneader in turn for stirring; start the vacuum system -0.096 MPa, start the heating system, make the material dehydrated under vacuum at 120°C, stir for 2 hours, and naturally cool to room temperature to obtain the impact-resistant additive;

[0032] Wherein, the organosilicon compound is heptamethylcyclotetrasiloxane; the particle sizes of the white carbon black, the light calcium carbonate, the titanium dioxide, and the aluminum oxide powder are all in the range of 1-100 μm;

[0033] The PC was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, the PC and the impact-resistant additive were mixed at a weight ratio of 100:5.8, blended and granulated in a twin-screw extruder, and then injection molded to form a standard test strip; and the impact resistance thereof was measured.

[0034] The PE was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, PE and the impact-resistant additive were mixed at a weight ratio of 100:4.6, blended and granulated in a twin-screw extruder, and then injection-molded to form a standard test strip; and the impact resistance thereof was measured.

[0035] Example 2

[0036] A silicone-based impact-resistant additive, the preparation method of which comprises the following steps:

[0037] Weigh 38 parts of organosilicon compound, 12 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (viscosity of 100 mpa·s), 9 parts of boric acid, 2 parts of polydimethylsiloxane (viscosity of 180 mpa·s), 2 parts of α,ω-divinyl-terminated polydimethylsiloxane (viscosity of 200 mpa·s), 1 part of white carbon black, 0.8 parts of light calcium carbonate, 1 part of titanium dioxide, and 1.5 parts of alumina powder in parts by weight, and add the raw materials into a kneader in turn for stirring; start the vacuum system -0.096 MPa, start the heating system, make the material dehydrated under vacuum at 120°C, stir for 2 hours, and naturally cool to room temperature to obtain the impact-resistant additive;

[0038] Wherein, the organosilicon compound is a first modified derivative; the particle sizes of the white carbon black, the light calcium carbonate, the titanium dioxide, and the aluminum oxide powder are all in the range of 1-100 μm;

[0039] The preparation method of the first modified derivative comprises the following steps:

[0040] Weigh heptamethylcyclotetrasiloxane and dissolve it in xylene solvent, add trivinylmethylsilane, stir and mix thoroughly, add platinum catalyst, stir and heat to 40° C. and keep warm for 1 hour, cool to room temperature after the reaction is completed, filter out the precipitate, and evaporate the solvent under reduced pressure to obtain the first modified derivative;

[0041] Wherein, the mass ratio of the heptamethylcyclotetrasiloxane to the trivinylmethylsilane is 6.8:1;

[0042] The PC was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, the PC and the impact-resistant additive were mixed at a weight ratio of 100:5.8, blended and granulated in a twin-screw extruder, and then injection molded to form a standard test strip; and the impact resistance thereof was measured.

[0043] The PE was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, PE and the impact-resistant additive were mixed at a weight ratio of 100:4.6, blended and granulated in a twin-screw extruder, and then injection-molded to form a standard test strip; and the impact resistance thereof was measured.

[0044] Example 3

[0045] A silicone-based impact-resistant additive, the preparation method of which comprises the following steps:

[0046] Weigh 38 parts of organosilicon compound, 12 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (viscosity of 100 mpa·s), 9 parts of boric acid, 2 parts of polydimethylsiloxane (viscosity of 180 mpa·s), 2 parts of α,ω-divinyl-terminated polydimethylsiloxane (viscosity of 200 mpa·s), 1 part of white carbon black, 0.8 parts of light calcium carbonate, 1 part of titanium dioxide, and 1.5 parts of alumina powder in parts by weight, and add the raw materials into a kneader in turn for stirring; start the vacuum system -0.096 MPa, start the heating system, make the material dehydrated under vacuum at 120°C, stir for 2 hours, and naturally cool to room temperature to obtain the impact-resistant additive;

[0047] Wherein, the organosilicon compound is a second modified derivative; the particle sizes of the white carbon black, the light calcium carbonate, the titanium dioxide, and the aluminum oxide powder are all in the range of 1-100 μm;

[0048] The preparation method of the second modified derivative comprises the following steps:

[0049] (1) Weigh 3,4,9,10-perylenetetracarboxylic dianhydride and dissolve it in dimethylformamide solvent, heat it to 50°C, slowly add allylamine dimethylformamide solution under heat preservation and stirring conditions, continue to heat preservation and stirring for 1 hour after the addition, then heat it to 120°C and continue to heat preservation and stirring for 6 hours. After the reaction is completed, cool it to room temperature, separate the precipitate and wash it with solvent to obtain a precursor product;

[0050] Wherein, the mass ratio of the 3,4,9,10-perylenetetracarboxylic dianhydride to the allylamine is 1:1.45;

[0051] (2) dissolving the precursor product in xylene solvent, adding heptamethylcyclotetrasiloxane, stirring and mixing thoroughly, adding platinum catalyst, stirring and heating to 40° C. and keeping the temperature to react for 1 hour, cooling to room temperature after the reaction is completed, filtering off the precipitate, and evaporating the solvent under reduced pressure to obtain the second modified derivative;

[0052] Wherein, the mass ratio of the precursor product to the heptamethylcyclotetrasiloxane is 1:1.42;

[0053] The PC was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, the PC and the impact-resistant additive were mixed at a weight ratio of 100:5.8, blended and granulated in a twin-screw extruder, and then injection molded to form a standard test strip; and the impact resistance thereof was measured.

[0054] The PE was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, PE and the impact-resistant additive were mixed at a weight ratio of 100:4.6, blended and granulated in a twin-screw extruder, and then injection-molded to form a standard test strip; and the impact resistance thereof was measured.

[0055] Example 4

[0056] A silicone-based impact-resistant additive, the preparation method of which comprises the following steps:

[0057] Weigh 12 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (viscosity of 100 mpa·s), 9 parts of boric acid, 2 parts of polydimethylsiloxane (viscosity of 180 mpa·s), 2 parts of α,ω-divinyl-terminated polydimethylsiloxane (viscosity of 200 mpa·s), 1 part of white carbon black, 0.8 parts of light calcium carbonate, 1 part of titanium dioxide, and 1.5 parts of alumina powder by weight, and add the raw materials into a kneader in turn for stirring; start the vacuum system -0.096 MPa, start the heating system, make the materials dehydrated under vacuum at 120°C, stir for 2 hours, and naturally cool to room temperature to obtain the impact-resistant additive;

[0058] Wherein, the particle sizes of the white carbon black, the light calcium carbonate, the titanium dioxide, and the aluminum oxide powder are all in the range of 1-100 μm;

[0059] The PC was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, the PC and the impact-resistant additive were mixed at a weight ratio of 100:5.8, blended and granulated in a twin-screw extruder, and then injection molded to form a standard test strip; and the impact resistance thereof was measured.

[0060] The PE was dried at 110° C. for 12 hours, the impact-resistant additive was dried at 80° C. for 6 hours, PE and the impact-resistant additive were mixed at a weight ratio of 100:4.6, blended and granulated in a twin-screw extruder, and then injection-molded to form a standard test strip; and the impact resistance thereof was measured.

[0061] The notched impact strength was tested according to GB / T1843-2008 (23°C); the tensile performance test was carried out according to ASTM D 638-2003, with a tensile rate of 10 mm / min; the bending performance test was carried out according to ASTM D 790-2003, with a bending rate of 2 mm / min; the impact resistance test results of each embodiment are shown in Table 1.

[0062] Table 1 Test results of impact resistance of the impact-resistant additives described in Examples 1-4 in different resin matrices

[0063] <![CDATA[Impact strength (kJ·m 2 ).]]> Tensile strength (MPa) Bending strength (MPa) PC 8.4 65.7 69.2 PE 3.9 19.2 22.4 Example 1 (PC) 19.5 58.4 60.8 Example 1 (PE) 8.9 14.5 17.3 Example 2 (PC) 32.4 61.6 62.4 Example 2 (PE) 14.7 15.8 18.9 Example 3 (PC) 40.1 63.5 65.7 Example 3 (PE) 21.4 17.7 20.5 Example 4 (PC) 10.6 57.8 58.9 Example 4 (PE) 6.3 12.3 14.9

[0064] The present invention respectively tests and compares the impact resistance of the impact-resistant additives described in Examples 1-4 before and after adding them to PC and PE. The test results are shown in Table 1. It can be seen from the table that the introduction of heptamethylcyclotetrasiloxane, the first modified derivative or the second modified derivative into the PC and PE resin matrices can improve their impact resistance to varying degrees. According to the test results of Examples 1 and 4 and PC and PE without modification, the additive with heptamethylcyclotetrasiloxane as the organic silicon compound can improve the impact resistance of the matrix, but at the same time, its tensile strength and flexural strength are reduced to varying degrees; according to the test results of Example 1 and 4, the impact resistance of the matrix can be improved by adding heptamethylcyclotetrasiloxane as the organic silicon compound, but at the same time, its tensile strength and flexural strength are reduced to varying degrees; The results of Examples 2 and 3 show that the modified derivatives prepared by adding the nucleophilic reaction product of trivinylmethylsilane or allylamine with 3,4,9,10-perylenetetracarboxylic dianhydride as a crosslinking agent can improve the impact resistance of the substrate while reducing the loss of its tensile strength and flexural strength caused by the modification. Among them, the comprehensive performance of the additive using the nucleophilic reaction product of allylamine with 3,4,9,10-perylenetetracarboxylic dianhydride as a crosslinking agent is better than that of trivinylmethylsilane; the impact resistance of the impact-resistant additives described in Examples 1-4 before and after addition to PE has a modification result similar to that of PC.

[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A silicone-based impact-resistant additive, It is characterized in that The composition is as follows, by weight: 18-50 parts of organic silicon compound, 5-30 parts of hydroxy silicone oil, 2-20 parts of boride, 0.1-5 parts of dimethyl silicone oil, 0.1-5 parts of vinyl silicone oil, 0.1-5 parts of white carbon black, 0.1-10 parts of calcium carbonate, 0.1-6 parts of titanium dioxide, and 0.1-3 parts of aluminum oxide powder; Wherein, the organosilicon compound is a modified derivative of heptamethylcyclotetrasiloxane, and the preparation method of the modified derivative of heptamethylcyclotetrasiloxane comprises the following steps: (1) Weigh 3,4,9,10-perylenetetracarboxylic dianhydride and dissolve it in dimethylformamide solvent, heat it to 50-60° C., slowly add the dimethylformamide solution of allylamine under heat preservation and stirring conditions, continue to heat preservation and stirring for 1-2 hours after the addition is completed, then heat it to 120-130° C. and continue to heat preservation and stirring for 3-8 hours, after the reaction is completed, cool it to room temperature, separate the precipitate and wash it with a solvent to obtain a precursor product; Wherein, the mass ratio of the 3,4,9,10-perylenetetracarboxylic dianhydride to the allylamine is 1:(1.4-1.5); (2) dissolving the precursor product in xylene solvent, adding heptamethylcyclotetrasiloxane, stirring and mixing thoroughly, adding platinum catalyst, stirring and heating to 30-50° C. and keeping the temperature to react for 0.5-2 hours, cooling to room temperature after the reaction is completed, filtering off the precipitate, and distilling off the solvent under reduced pressure to obtain the modified derivative of heptamethylcyclotetrasiloxane; Wherein, the mass ratio of the precursor product to the heptamethylcyclotetrasiloxane is 1:(1.4-1.45).

2. A silicone-based impact-resistant additive according to claim 1, It is characterized in that The hydroxy silicone oil is α,ω-dihydroxy-terminated polydimethylsiloxane with a viscosity of 20-3000 mpa·s.

3. The silicone-based impact-resistant additive according to claim 1, It is characterized in that The boride is selected from one of pyroboric acid, boric acid, sodium tetraborate, potassium tetraborate, ammonium borate, methyl borate, ethyl borate, propyl borate or butyl borate.

4. The silicone-based impact-resistant additive according to claim 1, It is characterized in that The dimethyl silicone oil is polydimethylsiloxane with a viscosity of 20-7000 mpa·s.

5. The silicone-based impact-resistant additive according to claim 1, It is characterized in that The vinyl silicone oil is α,ω-divinyl-terminated polydimethylsiloxane with a viscosity of 20-5000 mpa·s.

6. The silicone-based impact-resistant additive according to claim 1, It is characterized in that The particle sizes of the white carbon black, the calcium carbonate, the titanium dioxide and the aluminum oxide powder are 0.1-100 μm.

7. A method for preparing a silicone-based impact-resistant additive according to any one of claims 1 to 6, It is characterized in that The following steps are involved: S1, preparing the organosilicon compound; S2, weigh the raw materials according to the ratio and set aside; S3. Add the organosilicon compound, hydroxy silicone oil, boride, dimethyl silicone oil, vinyl silicone oil, white carbon black, calcium carbonate, titanium dioxide and aluminum oxide powder into the container in sequence for physical mixing; start the vacuum system at 0.08-0.098 MPa, start the heating system, stir the materials at 110-160° C. for 1-4 hours, and naturally cool to room temperature to obtain the impact-resistant additive.

8. Use of an organosilicon-based impact-resistant additive according to any one of claims 1 to 6, It is characterized in that Applications added to PC or PE.