Special material for flame-retardant anti-static hollow plate packaging material as well as preparation and application of special material

Abstract

The invention belongs to the technical field of polymer materials and application, and discloses a special material for a flame-retardant anti-static hollow plate packaging material as well as preparation and application thereof. The preparation method comprises the following steps: carrying out catalytic polymerization reaction on an epoxy silane monomer, a methylsilane monomer and a hydrogen silane end-capping reagent to obtain hydrogen-terminated epoxy polysiloxane, and then carrying out catalytic copolymerization reaction on the hydrogen-terminated epoxy polysiloxane and alpha, omega dialkene to obtain an epoxy polysiloxane modified polyolefin elastomer solution; adding the reinforcing filler subjected to surface modification by the amino silane coupling agent and the antistatic agent for reaction, adding the flame retardant and the foaming agent after the reaction is completed, uniformly mixing, drying and granulating to obtain the flame-retardant and antistatic material special for the hollow plate packaging material. The special material disclosed by the invention can be used for flame-retardant, anti-static, reinforcing and toughening blending modification of a polyolefin hollow plate packaging material.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and their applications, and in particular relates to a special material for flame-retardant and antistatic hollow plate packaging material and its preparation and application. Background Art

[0002] Hollow board, also called Wantong board or corrugated board, is a new type of material that is light (hollow structure), non-toxic, pollution-free, waterproof, shockproof, anti-aging, corrosion-resistant, and colorful. It is mainly made of environmentally friendly, pollution-free, recyclable thermoplastic polypropylene (PP), polyethylene (PE) resin and various auxiliary materials. Compared with paperboard structure products, hollow board has the advantages of moisture resistance and corrosion resistance, so it has a good application prospect in packaging and transportation.

[0003] Hollow boards are made by adding foaming agents and introducing hollow structures to reduce density and weight, but the introduction of hollow structures will lead to reduced strength. Strength can be improved by adding reinforcing fillers such as light calcium carbonate and reinforcing fibers. However, the addition of high-content fillers will lead to a reduction in the continuity of the polyolefin matrix, so its strength is difficult to further improve. At the same time, the toughness of polyolefin materials themselves is slightly poor, and after adding high-content fillers, its toughness is particularly reduced.

[0004] The compatibility problem between fillers and substrates can be improved through masterbatch processing technology and filler modification technology. For example, the invention patent application document with publication number CN118440421A records a preparation process for antistatic and wear-resistant plastic masterbatch, and the addition of modified carbon nanotubes makes the plastic masterbatch have excellent and stable antistatic properties, wear resistance and flame retardancy. However, the preparation process of the modified carbon nanotubes is complicated, the cost is high, and the effect on improving the toughness of the material is limited. Summary of the invention

[0005] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a method for preparing a special material for flame-retardant and antistatic hollow board packaging material.

[0006] Another object of the present invention is to provide a flame retardant and antistatic hollow plate packaging material prepared by the above method.

[0007] Another object of the present invention is to provide an application of the above-mentioned flame-retardant and antistatic hollow board packaging material special material in the preparation of hollow board packaging materials.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0010] (1) heating and polymerizing epoxysilane monomer, methylsilane monomer and hydrogen silane capping agent under silicon alkoxide catalyst conditions to obtain hydrogen-terminated epoxy polysiloxane;

[0011] (2) adding hydrogen-terminated epoxy polysiloxane and α,ω diene into an organic solvent to dissolve them, and then adding a hydrosilylation catalyst to carry out a heating copolymerization reaction to obtain an epoxy polysiloxane-modified polyolefin elastomer solution;

[0012] (3) surface-modifying the reinforcing filler and the antistatic agent using an aminosilane coupling agent to obtain an amino-modified functional additive;

[0013] (4) adding the obtained amino-modified functional additive to the epoxy polysiloxane-modified polyolefin elastomer solution of step (2) and heating and stirring for reaction; after the reaction is completed, adding a flame retardant and a foaming agent and mixing evenly; drying and granulating to obtain a flame retardant and antistatic hollow board packaging material.

[0014] The epoxysilane monomer in step (1) is preferably 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane (KH-563) or 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane (KH-564).

[0015] The methylsilane monomer in step (1) is preferably one or more of octamethylcyclotetrasiloxane (D4), dimethyldimethoxysilane, and dimethyldiethoxysilane.

[0016] The hydrogen silane capping agent in step (1) is preferably one or more of tetramethyldisiloxane (HMM), dimethylmethoxyhydrogensilane, and dimethylethoxyhydrogensilane.

[0017] The added amounts of the epoxysilane monomer, methylsilane monomer and hydrogen silane capping agent in step (1) are controlled so that the weight average molecular weight of the obtained hydrogen-terminated epoxy polysiloxane is 500-3000 and the epoxy group mass percentage is 1%-10%.

[0018] The silicon alkoxide catalyst in step (1) is preferably sodium siliconate or potassium siliconate; the temperature of the heating polymerization reaction is 90-130° C. and the time is 2-8 hours.

[0019] The α,ω diene in step (2) is preferably one or more of 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene and 1,11-dodecadiene.

[0020] The molar ratio of the hydrogen-terminated aminopolysiloxane to the α,ω diene in the step (2) is 1:1-2.

[0021] The organic solvent in step (2) is preferably one or more of isopropanol, ethyl acetate, cyclohexane and petroleum ether.

[0022] The hydrosilylation catalyst in step (2) is chloroplatinic acid isopropanol solution; the temperature of the heating copolymerization reaction is 80-100° C. and the time is 2-8 hours.

[0023] The reinforcing filler in step (3) is preferably one or two of white carbon black and light calcium carbonate, and the amount of the reinforcing filler is 50% to 150% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution; the antistatic agent is preferably one or two of conductive fiber and carbon black, and the amount of the antistatic agent is 2% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution.

[0024] The aminosilane coupling agent in step (3) is preferably one or more of γ-aminopropyltrimethoxysilane (KH-540), γ-aminopropyltriethoxysilane (KH-550), N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane; the amount of the aminosilane coupling agent is 2% to 10% of the total mass of the reinforcing filler and the antistatic agent.

[0025] The surface modification method in step (3) can adopt conventional dry surface modification or wet surface modification in the art, which is a commonly used powder surface modification method in the art.

[0026] The temperature of the heating and stirring reaction in step (4) is 60 to 90° C. and the time is 1 to 3 hours.

[0027] The flame retardant in step (4) is preferably an organic phosphate flame retardant, and the amount of the flame retardant is 5% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution; the foaming agent is preferably one or more of azodicarbonamide, N,N-dinitrosopentamethylenetetramine, and sodium bicarbonate, and the amount of the foaming agent is 5% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution.

[0028] A flame-retardant and antistatic hollow plate packaging material is specially prepared by the method.

[0029] The application of the flame retardant and antistatic hollow board packaging material special material in the preparation of hollow board packaging material, the application method is: add the flame retardant and antistatic hollow board packaging material special material and the polyolefin substrate in a mass ratio of 20 to 60:100 into a mixer and mix them evenly, and then extrude them into a mold for hot pressing and foaming to obtain the flame retardant and antistatic hollow board packaging material.

[0030] The polyolefin substrate is preferably polypropylene (PP) or polyethylene (PE).

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The flame-retardant and antistatic hollow board packaging material special material of the present invention adopts epoxy polysiloxane modified polyolefin elastomer to coat and chemically graft modify amino modified reinforcing filler and antistatic agent, which can significantly improve the dispersibility and bonding force of reinforcing filler and antistatic agent in polyolefin substrate. At the same time, the polysiloxane chain segment contained in it can significantly improve the toughness of the board, thereby achieving good reinforcing and toughening effect. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0034] Example 1

[0035] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0036] (1) 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane (KH-563), octamethylcyclotetrasiloxane (D4), tetramethyldisiloxane (HMM) and potassium trimethylsilanol catalyst were added into a reaction flask in a mass ratio of 30:70:7:0.04 and stirred to mix evenly. Nitrogen was introduced into the reaction flask for replacement protection. The electric heating mantle was heated to 110° C. and stirred for polymerization for 6 hours. Then the temperature was raised to 140° C. and the unreacted raw materials were removed under reduced pressure to obtain hydrogen-terminated epoxy polysiloxane. The obtained product was tested to have a hydrogen content (Si-H) of 0.10%, an epoxy content of 4.96%, a theoretical molecular weight of 2000, and a yield of 87%.

[0037] (2) The hydrogen-terminated epoxy polysiloxane and 1,8-nonadiene in step (1) are added to a reaction flask containing isopropanol solvent in a molar ratio of 1:1.5 to mix and dissolve, and nitrogen is introduced into the reaction flask for replacement protection. Then, a 0.01% chloroplatinic acid isopropanol solution catalyst is added, and the electric heating mantle is heated to 90° C. and stirred for polymerization for 4 hours. The active hydrogen of the product is detected to be completely reacted, and an epoxy polysiloxane-modified polyolefin elastomer solution with a solid content of 25% is obtained.

[0038] (3) By weight, 100 parts of reinforcing filler white carbon black and 10 parts of carbon fiber powder antistatic agent were mixed, and then 6 parts of aminosilane coupling agent KH-540 were used for dry surface modification to obtain an amino-modified functional additive.

[0039] (4) adding the obtained amino-modified functional additive to 400 parts of the epoxy polysiloxane-modified polyolefin elastomer solution of step (2) and dispersing the mixture evenly, heating the mixture to 80° C. and stirring the mixture for reaction for 2 h, adding 10 parts of flame retardant tris(2-chloropropyl) phosphate (TCPP) and 10 parts of foaming agent azodicarbonamide and mixing the mixture evenly, vacuum drying and granulating the mixture to obtain a flame retardant and antistatic hollow board packaging material.

[0040] Example 2

[0041] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0042] (1) 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane (KH-564), octamethylcyclotetrasiloxane (D4), tetramethyldisiloxane (HMM) and potassium trimethylsilanol catalyst were added to a reaction flask in a mass ratio of 40:60:12:0.04 and stirred to mix evenly. Nitrogen was introduced into the reaction flask for replacement protection. The electric heating mantle was heated to 110° C. and stirred for polymerization for 6 hours. Then the temperature was raised to 140° C. and the unreacted raw materials were removed under reduced pressure to obtain hydrogen-terminated epoxy polysiloxane. The obtained product was tested to have a hydrogen content (Si-H) of 0.15%, an epoxy content of 6.65%, a theoretical molecular weight of 1333, and a yield of 82%.

[0043] (2) The hydrogen-terminated epoxy polysiloxane and 1,7-octadiene of step (1) were added to a reaction flask containing isopropanol solvent at a molar ratio of 1:1.8, and mixed and dissolved. Nitrogen was introduced into the reaction flask for replacement protection. Then, a 0.01% chloroplatinic acid isopropanol solution catalyst was added, and the electric heating mantle was heated to 90° C. and stirred for polymerization reaction for 4 hours. The active hydrogen of the product was detected to be completely reacted, and an epoxy polysiloxane-modified polyolefin elastomer solution with a solid content of 25% was obtained.

[0044] (3) By weight, 150 parts of reinforcing filler white carbon black and 20 parts of carbon fiber powder antistatic agent were mixed, and then 10 parts of aminosilane coupling agent KH-540 were used for dry surface modification to obtain an amino-modified functional additive.

[0045] (4) adding the obtained amino-modified functional additive to 400 parts of the epoxy polysiloxane-modified polyolefin elastomer solution of step (2) and dispersing the mixture evenly, heating the mixture to 80° C. and stirring the mixture for reaction for 2 h, adding 10 parts of flame retardant tris(2-chloropropyl) phosphate (TCPP) and 10 parts of foaming agent azodicarbonamide and mixing the mixture evenly, vacuum drying and granulating the mixture to obtain a flame retardant and antistatic hollow board packaging material.

[0046] Example 3

[0047] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0048] (1) 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane (KH-563), octamethylcyclotetrasiloxane (D4), tetramethyldisiloxane (HMM) and potassium trimethylsilanol catalyst were added into a reaction flask in a mass ratio of 20:80:5:0.04 and stirred to mix evenly. Nitrogen was introduced into the reaction flask for replacement protection. The electric heating mantle was heated to 110° C. and stirred for polymerization for 6 hours. Then the temperature was raised to 140° C. and the unreacted raw materials were removed under reduced pressure to obtain hydrogen-terminated epoxy polysiloxane. The obtained product was tested to have a hydrogen content (Si-H) of 0.07%, an epoxy content of 3.07%, a theoretical molecular weight of 2857, and a yield of 91%.

[0049] (2) The hydrogen-terminated epoxy polysiloxane and 1,11-dodecadiene in the step (1) were added to a reaction flask containing an isopropanol solvent in a molar ratio of 1:1.1 to mix and dissolve, and nitrogen was introduced into the reaction flask for replacement protection. Then, a 0.01% chloroplatinic acid isopropanol solution catalyst was added, and the electric heating mantle was heated to 90° C. and stirred for polymerization reaction for 4 hours. The active hydrogen of the product was detected to be completely reacted, and an epoxy polysiloxane-modified polyolefin elastomer solution with a solid content of 25% was obtained.

[0050] (3) By weight, 50 parts of reinforcing filler white carbon black and 5 parts of carbon fiber powder antistatic agent were mixed, and then 3 parts of aminosilane coupling agent KH-540 were used for dry surface modification to obtain an amino-modified functional additive.

[0051] (4) The obtained amino-modified functional additive is added to 400 parts of the epoxy polysiloxane-modified polyolefin elastomer solution of step (2) and dispersed evenly, heated to 80° C. and stirred for reaction for 2 hours. After the reaction is completed, 10 parts of flame retardant tris(2-chloropropyl) phosphate (TCPP) and 20 parts of foaming agent azodicarbonamide are added and mixed evenly, and vacuum dried and granulated to obtain a flame retardant and antistatic hollow board packaging material.

[0052] Comparative Example 1

[0053] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0054] (1) By weight, 100 parts of reinforcing filler white carbon black and 10 parts of carbon fiber powder antistatic agent were mixed, and then 6 parts of aminosilane coupling agent KH-540 were used for dry surface modification to obtain an amino-modified functional additive.

[0055] (2) The obtained amino-modified functional additive, 100 parts of low-density polyethylene substrate (LDPE), 10 parts of flame retardant tris(2-chloropropyl) phosphate (TCPP) and 10 parts of foaming agent azodicarbonamide are added into a mixer and mixed evenly at 160-180° C., and then extruded and granulated to obtain a special material for flame-retardant and antistatic hollow board packaging materials.

[0056] Comparative Example 2

[0057] A method for preparing a flame-retardant and antistatic hollow plate packaging material, comprising the following preparation steps:

[0058] (1) Octamethylcyclotetrasiloxane (D4), tetramethyldisiloxane (HMM) and potassium trimethylsilanol catalyst are added to a reaction flask in a mass ratio of 100:7:0.04 and stirred to mix evenly. Nitrogen is introduced into the reaction flask for replacement protection. The electric heating mantle is heated to 110° C. and stirred for polymerization for 6 hours. The temperature is then raised to 140° C. and the unreacted raw materials are removed under reduced pressure to obtain hydrogen-terminated methyl polysiloxane. The hydrogen content (Si-H) of the obtained product is 0.10% after detection, the theoretical molecular weight is 2000, and the yield is 89%.

[0059] The preparation process of steps (2) to (4) is the same as that of Example 1.

[0060] Example 4

[0061] The application of the special materials (masterbatches) obtained in the above Examples 1 to 3 and Comparative Examples 1 to 2 in the preparation of hollow board packaging materials, the application method is: adding the flame retardant and antistatic hollow board packaging material special material and the low-density polyethylene substrate (LDPE) in a mass ratio of 30:100 into a mixer at 160 to 180°C and mixing evenly, and then extruding into a mold at 200 to 210°C for hot pressing and foaming to obtain a flame retardant and antistatic hollow board.

[0062] The mechanical properties (test thickness 2.5 mm), flame retardancy and antistatic properties (test surface resistivity) of the obtained flame retardant and antistatic hollow board were tested, and the results are shown in Table 1 below.

[0063] Table 1

[0064] performance Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Breaking force, N 190 216 177 143 154 Elongation at break, % 223 181 254 132 238 Tearing force, N 95 104 85 51 56 Plane compression force, N 905 953 871 720 767 Vertical compression force, N 87 90 70 46 68 Flame retardant grade V-0 V-0 V-0 V-0 V-0 Surface resistivity, Ω <![CDATA[1.5×10 5 ]]> <![CDATA[8.6×10 4 ]]> <![CDATA[2.3×10 5 ]]> <![CDATA[2.4×10 5 ]]> <![CDATA[2.2×10 5 ]]>

[0065] It can be seen from the comparison results of Comparative Example 1 in Table 1 that the improvement effect of the special material (masterbatch) prepared without epoxy polysiloxane-modified polyolefin elastomer on the mechanical properties of polyolefin hollow sheet materials is significantly reduced. It can be seen from the comparison results of Comparative Example 2 that the use of polysiloxane-modified polyolefin elastomer without epoxy groups has a significant improvement effect on the toughness of polyolefin hollow sheet materials, but the improvement effect on strength is limited. In addition, it can be seen from the comparison results of Example 1 with Comparative Examples 1 to 2 that the introduction of epoxy polysiloxane-modified polyolefin elastomer also has a certain effect on improving the antistatic properties of polyolefin hollow sheet materials. The reason is that the epoxy groups contained in the epoxy polysiloxane-modified polyolefin elastomer can be chemically connected with the antistatic agent modified by the aminosilane coupling agent surface, thereby improving its dispersion performance in the matrix.

[0066] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a flame retardant and antistatic hollow board packaging material, characterized in that: The method comprises the following preparation steps: (1) heating and polymerizing epoxysilane monomer, methylsilane monomer and hydrogen silane end-capping agent under silicon alkoxide catalyst conditions to obtain hydrogen-terminated epoxy polysiloxane; (2) adding hydrogen-terminated epoxy polysiloxane and α,ω diene into an organic solvent to dissolve them, and then adding a hydrosilylation catalyst to carry out a heating copolymerization reaction to obtain an epoxy polysiloxane-modified polyolefin elastomer solution; (3) surface-modifying the reinforcing filler and the antistatic agent using an aminosilane coupling agent to obtain an amino-modified functional additive; (4) adding the obtained amino-modified functional additive to the epoxy polysiloxane-modified polyolefin elastomer solution of step (2) and heating and stirring for reaction; after the reaction is completed, adding a flame retardant and a foaming agent and mixing evenly; drying and granulating to obtain a flame retardant and antistatic hollow board packaging material.

2. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The epoxysilane monomer in step (1) is 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane or 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane; the methylsilane monomer is one or more of octamethylcyclotetrasiloxane, dimethyldimethoxysilane, and dimethyldiethoxysilane; and the hydrogen silane capping agent is one or more of tetramethyldisiloxane, dimethylmethoxyhydrogensilane, and dimethylethoxyhydrogensilane.

3. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 2, characterized in that: The added amounts of the epoxy silane monomer, the methyl silane monomer and the hydrogen silane end-capping agent are controlled so that the weight average molecular weight of the obtained hydrogen-terminated epoxy polysiloxane is 500-3000, and the mass percentage of the epoxy group is 1%-10%.

4. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The silicon alkoxide catalyst in step (1) is sodium siliconate or potassium siliconate; the temperature of the heating polymerization reaction is 90-130° C. and the time is 2-8 hours.

5. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The α,ω diene in step (2) is one or more of 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene and 1,11-dodecadiene; the molar ratio of the hydrogen-terminated aminopolysiloxane to the α,ω diene is 1:1-2.

6. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The organic solvent in step (2) is one or more of isopropanol, ethyl acetate, cyclohexane, and petroleum ether; the hydrosilylation catalyst is chloroplatinic acid isopropanol solution; the temperature of the heating copolymerization reaction is 80-100° C., and the time is 2-8 hours.

7. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The reinforcing filler in step (3) is one or two of white carbon black and light calcium carbonate, and the amount of the reinforcing filler is 50% to 150% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution; the antistatic agent is one or two of conductive fiber and carbon black, and the amount of the antistatic agent is 2% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution; the aminosilane coupling agent is one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane; the amount of the aminosilane coupling agent is 2% to 10% of the total mass of the reinforcing filler and the antistatic agent.

8. The method for preparing a flame retardant and antistatic hollow board packaging material according to claim 1, characterized in that: The temperature of the heating and stirring reaction in step (4) is 60-90° C., and the time is 1-3 hours; the flame retardant is an organic phosphate flame retardant, and the amount of the flame retardant is 5% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution; the foaming agent is one or more of azodicarbonamide, N,N-dinitrosopentamethylenetetramine, and sodium bicarbonate, and the amount of the foaming agent is 5% to 20% of the solid content of the epoxy polysiloxane modified polyolefin elastomer solution.

9. A flame retardant and antistatic hollow board packaging material, characterized in that: It is prepared by the method according to any one of claims 1 to 8.

10. Use of the flame retardant and antistatic hollow board packaging material special material according to claim 9 in the preparation of hollow board packaging materials, characterized in that: The application method comprises the following steps: adding the flame retardant and antistatic hollow board packaging material special material and the polyolefin substrate into a mixer at a mass ratio of 20 to 60:100, mixing evenly, and then extruding into a mold for hot pressing and foaming to obtain the flame retardant and antistatic hollow board packaging material.