CN111138813A - Corrugated plate tile based on PET (polyethylene terephthalate) broken material and production process thereof - Google Patents

Abstract

The invention discloses a corrugated tile based on PET (polyethylene terephthalate) broken materials, which comprises the following components in parts by weight: 53-62 parts of PET crushed material, 35-41 parts of epoxidized polypropylene, 13-16 parts of glass fiber, 3-4 parts of antioxidant, 2-3 parts of dispersant and 2-4 parts of nano titanium dioxide. According to the epoxidized polypropylene prepared by the invention, free radical polymerization reaction can be carried out on polypropylene and a solubility-increasing modifier in dibenzoyl peroxide, so that epoxy groups are introduced into an epoxidized polypropylene chain, the epoxy groups on the epoxidized polypropylene chain can react with carboxyl groups on a PET material chain, and the epoxidized polypropylene is introduced into the PET chain, so that the epoxidized polypropylene can be uniformly grafted on the PET chain, and further the toughness of the corrugated tile can be improved through the epoxidized polypropylene, and the problems that in the prior art, the compatibility between PET and a polyolefin material is poor, and the PET and the polyolefin material cannot be uniformly dispersed after being directly mixed, so that the toughness of a modified material is reduced are solved.

Description

Corrugated plate tile based on PET (polyethylene terephthalate) broken material and production process thereof

Technical Field

The invention belongs to the field of preparation of corrugated tiles, and relates to a corrugated tile based on PET (polyethylene terephthalate) broken materials and a production process thereof.

Background

The PET material has the advantages of creep resistance, fatigue resistance, abrasion resistance, good dimensional stability, small abrasion, high hardness, maximum toughness in thermoplastic plastics, good electrical insulation performance, small temperature influence, no toxicity, good weather resistance, good chemical resistance stability, low water absorption, weak acid and organic solvent resistance, low price in engineering plastics and high cost performance, but a conjugated system is formed between an ester group in a PET macromolecule and a benzene ring, so that the rigidity of the molecular chain is increased, the impact resistance of the PET is poor, and the corrugated tile needs to be made of a material with high toughness, so that a toughening agent is usually added in the material in the process of preparing the corrugated tile by using the PET material, and the toughening effect is improved.

In the prior art, the toughening modification of the PET material is usually to mix and modify the PET material and materials with higher flexibility such as polyolefin and the like, so as to improve the toughness of the material, but the compatibility between the PET material and the polyolefin material is poor, and the PET material and the polyolefin material cannot be uniformly dispersed after being directly mixed, so that the toughness of the modified material is greatly reduced, and the high-temperature resistance of the polyolefin material is low, while the high-temperature resistance of the PET material is higher, and after the PET material and the polyolefin material are mixed, the addition of the polyolefin material can influence the overall high-temperature resistance of the mixed material. Meanwhile, when the flame retardant property of the existing PET material is improved, the existing PET material is usually directly mixed with the flame retardant for modification, but the flame retardant and the PET material are poor in compatibility, so that the flame retardant property of the material is influenced due to uneven mixing between the flame retardant and the PET material.

Disclosure of Invention

The invention aims to provide a corrugated tile based on a PET crushed material and a production process thereof, the corrugated tile is prepared by melting reaction of epoxy polypropylene and a PET material, the epoxy polypropylene is prepared by free radical polymerization reaction of polypropylene and a dissolution modifier in dibenzoyl peroxide, so that an epoxy group is introduced into an epoxy polypropylene chain, the epoxy group on the epoxy polypropylene chain can react with a carboxyl group on a PET material chain, the epoxy polypropylene is introduced into the PET chain, the epoxy polypropylene can be uniformly grafted on the PET chain, the toughness of the corrugated tile can be improved through the epoxy polypropylene, and the problems that in the prior art, the toughening modification of the PET material is usually mixing modification of materials with higher flexibility such as the PET material and polyolefin and the like, the toughness of the material is improved, but the compatibility between the PET material and the polyolefin material is poor are effectively solved, the two materials can not be uniformly dispersed after being directly mixed, thereby greatly reducing the toughness of the modified material.

The solubility-increasing modifier prepared by the invention contains a large number of siloxane bonds, and when the solubility-increasing modifier is compounded with a polypropylene material through free radical polymerization, the solubility-increasing modifier is uniformly grafted on the polypropylene material, so that the epoxidized polypropylene material prepared after grafting contains a large number of siloxane bonds, the high-temperature resistance of the epoxidized polypropylene can be effectively improved, and after the epoxidized polypropylene material is compounded with a PET (polyethylene terephthalate) material, the high-temperature resistance of the composite material cannot be reduced, so that the problem that the high-temperature resistance of the whole material after mixing is influenced by the addition of the polyolefin material due to the lower high-temperature resistance of the polyolefin material and the higher high-temperature resistance of the PET material is solved.

According to the invention, the olefin group is introduced into the flame retardant modifier, so that the olefin group can be polymerized with polypropylene, phosphate groups are introduced into the prepared epoxidized polypropylene, the flame retardant property of the epoxidized polypropylene can be realized through the action of the phosphate groups, and after the epoxidized polypropylene and the PET material are uniformly compounded, the prepared composite material uniformly contains a large number of phosphate groups, so that the flame retardant property of the material is effectively improved, and the problem that the flame retardant property of the material is influenced due to the fact that the flame retardant and the PET material are not uniformly mixed because the flame retardant and the PET material are poor in compatibility and the flame retardant property is usually directly mixed and modified with each other is solved.

The purpose of the invention can be realized by the following technical scheme:

a corrugated tile based on PET broken materials comprises the following components in parts by weight:

53-62 parts of PET crushed material, 35-41 parts of epoxidized polypropylene, 13-16 parts of glass fiber, 3-4 parts of antioxidant, 2-3 parts of dispersant and 2-4 parts of nano titanium dioxide;

the specific preparation process of the epoxidized polypropylene is as follows: weighing a certain amount of polypropylene, adding the polypropylene into a plasticator, heating to 190 ℃ for smelting for 1min, adding a solubility-enhancing modifier, keeping the temperature unchanged, adding dibenzoyl peroxide after smelting for 4-5min, then mixing for 15-20min, adding a flame-retardant modifier into a reaction container, melting and mixing for 30-40min, and cooling and discharging to obtain epoxidized polypropylene; the dibenzoyl peroxide of the polypropylene can be subjected to free radical polymerization reaction with a solubilizing modifier, and meanwhile, the flame retardant modifier also contains olefin groups, so that the flame retardant modifier can be polymerized with the polypropylene, epoxy groups and phosphate groups are introduced into the prepared epoxidized polypropylene, and the flame retardant property of the epoxidized polypropylene can be realized through the action of the phosphate groups;

the specific preparation process of the solubilizing modifier is as follows:

step 1: weighing a certain amount of acrolein and allyl glycidyl ether, simultaneously adding the acrolein and the allyl glycidyl ether into an acetone solution, then adding an isopropanol-platinum catalyst into the acetone solution, continuously dropwise adding tetramethyldisiloxane into a reaction container after heating to 90-100 ℃, stirring and refluxing for 20-22h at constant temperature after complete dropwise addition, and then carrying out reduced pressure distillation to obtain a product A; wherein the ratio of the amount of acrolein, allyl glycidyl ether and tetramethyldisiloxane is 1: 1: 2, while adding 1.4g of isopropanol-platinum catalyst per mole of allyl glycidyl ether; hydrogen atoms connected with silicon elements in the tetramethyl disiloxane can perform addition reaction with olefin groups in acrolein and allyl glycidyl ether under the action of a catalyst, so that aldehyde groups and epoxy groups are introduced into the product A, and the prepared product A contains a large number of siloxane bonds;

step 2: adding the product A into a reaction kettle, adding acetone and sodium hydroxide into the reaction kettle, adjusting the pH value of the solution to be 13, heating the solution to 60-70 ℃, adding methyl hexadienoate into the reaction vessel, carrying out reflux reaction for 15-17h, then carrying out evaporation concentration, extracting by ethyl acetate, simultaneously carrying out reduced pressure distillation on an organic phase obtained by extraction to obtain a solubility-enhancing modifier, wherein 0.45-0.47g of methyl hexadienoate is added into each gram of the product A, and because a large amount of aldehyde groups are introduced into the product A, the ortho position of the aldehyde groups contains active hydrogen, under alkaline conditions, active hydrogen at the ortho position of aldehyde group can perform addition reaction with one olefin group in the methyl hexadienoate, and the methyl hexadienoate contains two olefin groups, after one of the two is subjected to addition reaction, the other olefin group is grafted on a chain of the solubility-increasing modifier, so that the prepared solubility-increasing modifier contains olefin groups;

the specific preparation process of the flame retardant modifier is as follows: weighing a certain amount of 2-hydroxyethyl acrylate and p-methoxyphenol, adding an acetone solution into a reaction kettle, stirring to dissolve, heating to 50-55 ℃, adding phosphorus pentoxide into the reaction container, heating to 85-90 ℃, stirring and refluxing for 9-10h, and then carrying out reduced pressure distillation to obtain a flame retardant modifier, wherein 0.18-0.19g of phosphorus pentoxide is added into each gram of 2-hydroxyethyl acrylate, and the phosphorus pentoxide can carry out esterification reaction with hydroxyl in the 2-hydroxyethyl acrylate to generate phosphate groups, so that the prepared product contains three phosphate groups and one olefin group;

a production process of a corrugated tile based on PET broken materials comprises the following specific production processes:

firstly, simultaneously adding a certain amount of PET crushed material, epoxidized polypropylene, glass fiber, antioxidant, dispersant and nano titanium dioxide into a screw extruder; one end of the PET material contains carboxyl, so that the carboxyl can react with an epoxy group in the epoxidized polypropylene, the polypropylene is uniformly grafted on a PET chain, the toughness of the PET material can be improved due to the high toughness of the polypropylene, and meanwhile, the flame retardant property of the polymer can be improved due to the phosphate group contained in the epoxidized polypropylene;

and secondly, adding the material melted and extruded in the first step into a forming die, pressurizing the material into the forming die, and then cooling and removing the die to obtain the corrugated plate tile.

The invention has the beneficial effects that:

1. the invention is prepared by the melting reaction of the epoxidized polypropylene and the PET material, because the epoxidized polypropylene is prepared by the free radical polymerization reaction of polypropylene and a dissolution modifier in dibenzoyl peroxide, epoxy groups are introduced on an epoxidized polypropylene chain, the epoxy groups on the epoxidized polypropylene chain can react with carboxyl groups on a PET material chain, and the epoxidized polypropylene is introduced on the PET chain, so that the epoxidized polypropylene can be uniformly grafted on the PET chain, the toughness of the corrugated tile can be improved by the epoxidized polypropylene, and the problems that in the prior art, the toughening modification of the PET material is usually to mix and modify the PET material and materials with higher flexibility such as polyolefin and the like, and further the toughness of the material is improved, but the compatibility between the PET material and the polyolefin material is poor, and the PET material and the polyolefin material can not be uniformly dispersed after being directly mixed are effectively solved, thereby greatly reducing the toughness of the modified material.

2. The solubility-increasing modifier prepared by the invention contains a large number of siloxane bonds, and when the solubility-increasing modifier is compounded with a polypropylene material through free radical polymerization, the solubility-increasing modifier is uniformly grafted on the polypropylene material, so that the epoxidized polypropylene material prepared after grafting contains a large number of siloxane bonds, the high-temperature resistance of the epoxidized polypropylene can be effectively improved, and after the epoxidized polypropylene material is compounded with a PET (polyethylene terephthalate) material, the high-temperature resistance of the composite material cannot be reduced, so that the problem that the high-temperature resistance of the whole material after mixing is influenced by the addition of the polyolefin material due to the lower high-temperature resistance of the polyolefin material and the higher high-temperature resistance of the PET material is solved.

3. According to the invention, the olefin group is introduced into the flame retardant modifier, so that the olefin group can be polymerized with polypropylene, phosphate groups are introduced into the prepared epoxidized polypropylene, the flame retardant property of the epoxidized polypropylene can be realized through the action of the phosphate groups, and after the epoxidized polypropylene and the PET material are uniformly compounded, the prepared composite material uniformly contains a large number of phosphate groups, so that the flame retardant property of the material is effectively improved, and the problem that the flame retardant property of the material is influenced due to the fact that the flame retardant and the PET material are not uniformly mixed because the flame retardant and the PET material are poor in compatibility and the flame retardant property is usually directly mixed and modified with each other is solved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the specific preparation process of the solubility-enhancing modifier is as follows:

step 1: weighing 5.6g of acrolein and 11.4g of allyl glycidyl ether, simultaneously adding the acrolein and the 11.4g of allyl glycidyl ether into 120mL of acetone solution, then adding 0.14g of isopropanol-platinum catalyst into the acetone solution, heating to 90-100 ℃, continuously dropwise adding 13.4g of tetramethyldisiloxane into a reaction vessel, stirring and refluxing for 20-22h at constant temperature after complete dropwise addition, and then carrying out reduced pressure distillation to obtain a product A;

step 2: adding 10g of the product A into a reaction kettle, adding 100mL of acetone and sodium hydroxide into the reaction kettle, adjusting the pH value of the solution to 13, heating to 60-70 ℃, adding 45g of methyl hexadienoate into the reaction container, carrying out reflux reaction for 15-17h, carrying out evaporation concentration, extracting with ethyl acetate, and simultaneously carrying out reduced pressure distillation on an organic phase obtained by extraction to obtain the solubility-increasing modifier.

Example 2:

the specific preparation process of the solubility-enhancing modifier is as follows:

step 1: weighing 22.8g of allyl glycidyl ether, simultaneously adding the allyl glycidyl ether into 120mL of acetone solution, then adding 0.14g of isopropanol-platinum catalyst into the acetone solution, heating to 90-100 ℃, continuously dropwise adding 13.4g of tetramethyldisiloxane into a reaction container, stirring and refluxing for 20-22h at constant temperature after complete dropwise addition, and then carrying out reduced pressure distillation to obtain a product A;

step 2: adding 10g of the product A into a reaction kettle, adding 100mL of acetone and sodium hydroxide into the reaction kettle, adjusting the pH value of the solution to 13, heating to 60-70 ℃, adding 45g of methyl hexadienoate into the reaction container, carrying out reflux reaction for 15-17h, carrying out evaporation concentration, extracting with ethyl acetate, and simultaneously carrying out reduced pressure distillation on an organic phase obtained by extraction to obtain the solubility-increasing modifier.

Example 3:

the specific preparation process of the flame retardant modifier is as follows: weighing 10g of 2-hydroxyethyl acrylate and 1.1g of p-methoxyphenol, adding into a reaction kettle, simultaneously adding 90mL of acetone solution, stirring to dissolve, heating to 50-55 ℃, then adding 1.8g of phosphorus pentoxide into the reaction vessel, heating to 85-90 ℃, stirring and refluxing for 9-10h, and then carrying out reduced pressure distillation to obtain the flame retardant modifier.

Example 4:

the specific preparation process of the epoxidized polypropylene is as follows: weighing 100g of polypropylene, adding the polypropylene into a plasticator, heating to 190 ℃ for melting for 1min, adding 18g of the solubility-enhancing modifier prepared in the embodiment 1, keeping the temperature unchanged, adding 9g of dibenzoyl peroxide after melting for 4-5min, mixing for 15-20min, adding 6g of the flame-retardant modifier prepared in the embodiment 3 into a reaction vessel, melting and mixing for 30-40min, and cooling and discharging to obtain the epoxidized polypropylene.

Example 5:

the specific preparation process of the epoxidized polypropylene is as follows: weighing 100g of polypropylene, adding the polypropylene into a plasticator, heating to 190 ℃ for melting for 1min, adding 18g of the solubility-enhancing modifier prepared in the embodiment 2, keeping the temperature unchanged, adding 9g of dibenzoyl peroxide after melting for 4-5min, mixing for 15-20min, adding 6g of the flame-retardant modifier prepared in the embodiment 3 into a reaction vessel, melting and mixing for 30-40min, and cooling and discharging to obtain the epoxidized polypropylene.

Example 6:

a production process of a corrugated tile based on PET broken materials comprises the following specific production processes:

firstly, simultaneously adding 530g of PET crushed material, 350g of epoxidized polypropylene prepared in example 4, 130g of glass fiber, 30g of antioxidant, 20g of dispersant and 20g of nano titanium dioxide into a screw extruder;

and secondly, adding the material melted and extruded in the first step into a forming die, pressurizing the material into the forming die, and then cooling and removing the die to obtain the corrugated plate tile.

Example 7:

a production process of a corrugated tile based on PET broken materials comprises the following specific production processes:

firstly, simultaneously adding 530g of PET crushed material, 350g of epoxidized polypropylene prepared in example 5, 130g of glass fiber, 30g of antioxidant, 20g of dispersant and 20g of nano titanium dioxide into a screw extruder;

and secondly, adding the material melted and extruded in the first step into a forming die, pressurizing the material into the forming die, and then cooling and removing the die to obtain the corrugated plate tile.

Example 8:

a production process of a corrugated tile based on PET broken materials comprises the following specific production processes:

firstly, simultaneously adding 530g of PET crushed material, 350g of polypropylene, 130g of glass fiber, 30g of antioxidant, 20g of dispersant and 20g of nano titanium dioxide into a screw extruder;

and secondly, adding the material melted and extruded in the first step into a forming die, pressurizing the material into the forming die, and then cooling and removing the die to obtain the corrugated plate tile.

Example 9:

the impact resistance of the corrugated plate tiles prepared in examples 6 to 8 was tested by a pendulum impact tester, and the specific test results are shown in table 1;

table 1 impact resistance measurement results (kj. m) of the corrugated sheet tiles prepared in examples 6 to 8^-2)

	Example 6	Example 7	Example 8
				Impact strength (KJ. M-2)	23.31	20.62	17.71

As can be seen from Table 1, the corrugated tile prepared in example 6 has high impact resistance, and the impact strength reaches 23.31KJ.M^-2While the impact strength of the wave tile in example 7 is reduced, since the solubility-improving modifier used in the preparation process of the epoxidized polypropylene in example 7 has no grafted double bond structure, the polypropylene and the solubility-improving modifier are mixed by physical action, and simultaneously, since the compatibility between the polypropylene and the solubility-improving modifier is poor, further causing the dissolution and modification agent to be unevenly dispersed in the polypropylene, so that epoxy groups in the prepared epoxidized polypropylene are unevenly dispersed, further causing that the epoxidized polypropylene and the PET can not be uniformly dispersed in the PET material when in mixing reaction, so that the impact strength of the prepared corrugated tile is reduced, meanwhile, in the embodiment 8, as the polypropylene and the PET material are directly mixed to prepare the corrugated tile, because the compatibility between polypropylene and PET material is poor, the polypropylene material and the PET material are separated during mixing, and the performance of the mixed material is affected.

Example 10:

according to the vertical burning test method of flammability test, the wave tile samples prepared in examples 6-8 were cut and tested for flame retardant property, and the results are shown in table 2;

table 2 flame retardant performance test results for the corrugated tile samples prepared in examples 6-8

	Example 6	Example 7	Example 8
				The maximum flaming combustion time of the sample after the sample is ignited for 2 times	5s	8s	30s
Whether the molten drops ignite the cotton	Whether or not	Whether or not	Is that
				Flame retardant rating	V0	V0	V2

As can be seen from table 2, the wave tiles prepared in examples 6 and 7 have high flame retardant performance, and the flame retardant rating reaches V0, and meanwhile, the wave tile in example 8 has a flame retardant rating of V2, because the wave tiles prepared in examples 6 and 7 are prepared by mixing and reacting epoxidized polypropylene and PET, and because the epoxidized polypropylene is reacted with the flame retardant modifier through radical polymerization during the preparation process, phosphate groups are introduced into the prepared epoxidized polypropylene, and after the mixing and reacting of the epoxidized polypropylene and PET, the prepared product contains a large amount of phosphate groups, the flame retardant performance of the product is improved, and the wave tile prepared in example 8 is prepared by directly mixing polypropylene and PET materials, and the prepared wave tile does not contain phosphate groups, so that the flame retardant performance is reduced.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (7)

1. The corrugated tile based on the PET broken material is characterized by comprising the following components in parts by weight:

53-62 parts of PET crushed material, 35-41 parts of epoxidized polypropylene, 13-16 parts of glass fiber, 3-4 parts of antioxidant, 2-3 parts of dispersant and 2-4 parts of nano titanium dioxide;

the specific preparation process of the epoxidized polypropylene is as follows: weighing a certain amount of polypropylene, adding the polypropylene into a plasticator, heating to 190 ℃ for smelting for 1min, adding a solubility-enhancing modifier, keeping the temperature unchanged, adding dibenzoyl peroxide after smelting for 4-5min, then mixing for 15-20min, adding a flame-retardant modifier into a reaction container, melting and mixing for 30-40min, and cooling and discharging to obtain the epoxidized polypropylene.

2. The corrugated tile based on PET crumbs as claimed in claim 1, wherein the solubility-enhancing modifier is prepared by the following steps:

step 1: weighing a certain amount of acrolein and allyl glycidyl ether, simultaneously adding the acrolein and the allyl glycidyl ether into an acetone solution, then adding an isopropanol-platinum catalyst into the acetone solution, continuously dropwise adding tetramethyldisiloxane into a reaction container after heating to 90-100 ℃, stirring and refluxing for 20-22h at constant temperature after complete dropwise addition, and then carrying out reduced pressure distillation to obtain a product A;

step 2: adding the product A into a reaction kettle, adding acetone and sodium hydroxide into the reaction kettle, adjusting the pH value of the solution to 13, heating the solution to 60-70 ℃, adding methyl hexadienoate into the reaction container, carrying out reflux reaction for 15-17h, carrying out evaporation concentration, extracting with ethyl acetate, and carrying out reduced pressure distillation on an organic phase obtained by extraction to obtain the solubility-increasing modifier.

3. The corrugated slate tile based on PET regrind of claim 2, wherein the ratio of the amount of acrolein, allyl glycidyl ether and tetramethyldisiloxane in step 1 is 1: 1: 2 while adding 1.4g of isopropanol-platinum catalyst per mole of allyl glycidyl ether.

4. The corrugated slate tile based on PET regrind of claim 2 wherein in step 2, 0.45-0.47g of methyl hexadienoate is added per gram of product A.

5. The corrugated tile based on PET crumbs as claimed in claim 1, wherein the flame retardant modifier is prepared by the following steps: weighing a certain amount of acrylic acid-2-hydroxyethyl ester and p-methoxyphenol, adding into a reaction kettle, simultaneously adding an acetone solution, stirring for dissolving, heating to 50-55 ℃, then adding phosphorus pentoxide into the reaction vessel, heating to 85-90 ℃, stirring for refluxing for 9-10h, and then carrying out reduced pressure distillation to obtain the flame retardant modifier.

6. The corrugated tile based on PET regrind of claim 5 wherein 0.18 to 0.19g of phosphorus pentoxide is added per gram of 2-hydroxyethyl acrylate.

7. The production process of the corrugated tile based on the PET broken materials is characterized by comprising the following specific production processes:

firstly, simultaneously adding a certain amount of PET crushed material, epoxidized polypropylene, glass fiber, antioxidant, dispersant and nano titanium dioxide into a screw extruder;

and secondly, adding the material melted and extruded in the first step into a forming die, pressurizing the material into the forming die, and then cooling and removing the die to obtain the corrugated plate tile.