CN113004680A

CN113004680A - Wear-resisting corrosion-resistant TPU super-permeable membrane

Info

Publication number: CN113004680A
Application number: CN202110279722.5A
Authority: CN
Inventors: 张国荣
Original assignee: Zhejiang Rock New Material Co ltd
Current assignee: Zhejiang Rock New Material Co ltd
Priority date: 2021-03-16
Filing date: 2021-03-16
Publication date: 2021-06-22

Abstract

The invention belongs to the technical field of TPU modified films, and provides a wear-resistant corrosion-resistant TPU super-permeable film which comprises the following components in parts by weight: 120 parts of TPU resin particles 110-3 parts of glass fiber, 10-16 parts of POE maleic anhydride graft, 1-1.5 parts of tackifier, 1-2 parts of wear-resistant agent, 1-3 parts of chain extender, 0.5-1.5 parts of light shielding agent, 0.5-1.5 parts of light absorbent, 0.5-1.5 parts of hindered amine and 1-2 parts of corrosion resistant agent. The invention improves the TPU film, adds maleic anhydride grafted polyolefin and chain extender on the basis of the original TPU resin particles, changes the molding effect of the formed TPU resin particles through the grafted components, embeds the performance of the polyolefin in the TUP polymer, changes the chain performance of the high molecular polymer, increases the stability of the high molecular polymer through the increased C-C bond, and reduces the separation and oxidation of chemical bonds caused by external force.

Description

Wear-resisting corrosion-resistant TPU super-permeable membrane

Technical Field

The invention relates to the technical field of TPU modified films, in particular to a wear-resistant corrosion-resistant TPU super-permeable film.

Background

The TPU is increasingly popular with people due to the excellent performance and the environmental protection concept, not only has the excellent characteristics of high tension, high tensile force, toughness and aging resistance, but also is a mature environmental protection material, and at present, the TPU is widely applied to: shoe materials, ready-made clothes, inflatable toys, aquatic and underwater sports equipment, medical equipment, fitness equipment, automobile seat materials, umbrellas, leather suitcases, leather bags and the like.

The TPU film in the current market has no corrosion resistance, is easily corroded by light, air, rainwater, external acid and alkali and the like in the using process, destroys chemical bonds in high molecular polymers in the TPU film, decomposes the high molecular polymers, and further has no better corrosion resistance; and the corrosion resistance of the TPU film is more general, so that the service life of the TPU film is shortened, and the practicability is greatly reduced.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a wear-resistant corrosion-resistant TPU (thermoplastic polyurethane) super-permeable film, which solves the problem that a TPU film in the prior art is not ideal in corrosion resistance and wear resistance.

According to the embodiment of the invention, the wear-resistant corrosion-resistant TPU ultra-permeable film comprises the following components in parts by weight: 120 parts of TPU resin particles 110-3 parts of glass fiber, 10-16 parts of POE maleic anhydride graft, 1-1.5 parts of tackifier, 1-2 parts of wear-resistant agent, 1-3 parts of chain extender, 0.5-1.5 parts of light shielding agent, 0.5-1.5 parts of light absorbent, 0.5-1.5 parts of hindered amine and 1-2 parts of corrosion resistant agent.

Preferably, the tackifier is PVC or a cycloaliphatic petroleum resin.

Preferably, the hindered amine comprises one of GW-622, GW-944, poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate, bis (2,2,6, 6-tetramethylpiperidinol sebacate), bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.

Preferably, the wear-resisting agent is formed by mixing potassium stearate, polyacrylonitrile, modified buckwheat flour, polyvinyl alcohol and polyacrylate, and the weight ratio of the potassium stearate to the polyacrylonitrile to the modified buckwheat flour to the polyvinyl alcohol to the polyacrylate is 1.1:1.2:1:1: 1.

Preferably, the chain extender comprises one of 1, 3-propanediol, 1, 5-pentanediol, hydroquinone dihydroxyethyl ether, 1, 4-cyclohexanedimethanol and bisphenol A modified polyethylene glycol diallyl ester.

Preferably, the corrosion resistant agent is polyoxymethylene.

Preferably, the light-shielding agent includes one of titanium dioxide, zinc oxide, and zinc barium.

Preferably, the light absorber comprises one of hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, N- (2-ethoxyphenyl) -N' - (2-ethylphenyl) -ethanediamide, 2- (2 "-hydroxy-3", 5 "-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol.

Preferably, the TPU semipermeable membrane is prepared by:

s1: weighing 120 parts of TPU resin particles 110-3 parts, 2-3 parts of glass fiber, 10-16 parts of POE maleic anhydride graft, 1-1.5 parts of tackifier, 1-2 parts of wear-resistant agent, 1-3 parts of chain extender, 0.5-1.5 parts of light shielding agent, 0.5-1.5 parts of light absorbent, 0.5-1.5 parts of hindered amine and 1-2 parts of corrosion-resistant agent for later use;

s2: grinding and mixing the TPU resin particles weighed in the step S1, POE maleic anhydride grafting and a chain extender to form a mixture for later use;

s3: adding the mixture obtained in the step S2 into a high-speed kneader, blending and kneading to form colloid, and then putting the colloid into a double-screw extruder for granulation to obtain mixed granules;

s4: and (4) mixing the mixed particles in the step S3 with the glass fiber, the tackifier, the wear-resisting agent, the corrosion-resisting agent, the light-shielding agent, the light absorbing agent and the hindered amine in the step S1, introducing the mixture into a double-screw extruder to obtain molten colloid, and then introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Compared with the prior art, the invention has the following beneficial effects: the invention improves the TPU super-permeable membrane, adds maleic anhydride grafted polyolefin and a chain extender on the basis of the original TPU resin particles, changes the molding effect of the TPU resin particles after molding through the grafted components, embeds the performance of the polyolefin in the TUP polymer, changes the chain performance of the high molecular polymer, increases the stability of the high molecular polymer through the added C-C bond, and reduces the separation and oxidation of the chemical bond caused by external force.

The tackifier that increases can be compacter with high polymer, reduces the inside possibility of air admission high polymer, reduces the external force influence, and then makes high polymer oxidation corrosion from inside.

The addition of the light-shielding agent, the light absorbing agent and the hindered amine can reduce the phenomenon of light corrosion; the light shielding agent can prevent ultraviolet light from entering the interior of the high polymer, limit the photo-oxidative aging reaction, and enable the reaction to stay on the surface of the high polymer, so that the high polymer is protected; the light absorbent has an absorption effect on ultraviolet light, can convert excitation energy into vibration energy harmless to high polymers, and can also transmit light-activated macromolecule excitation energy out in modes of collision and the like for extinction; the hindered amine is a light stabilizer with heat oxidation resistance.

The corrosion resistance of the added corrosion-resistant agent to the high polymer film can be reduced, and the added wear-resistant agent can improve the wear resistance of the prepared TPU film.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples.

The wear-resistant corrosion-resistant TPU super-permeable film comprises the following components in parts by weight: 120 parts of TPU resin particles 110-3 parts of glass fiber, 10-16 parts of POE maleic anhydride graft, 1-1.5 parts of tackifier, 1-2 parts of wear-resistant agent, 1-3 parts of chain extender, 0.5-1.5 parts of light shielding agent, 0.5-1.5 parts of light absorbent, 0.5-1.5 parts of hindered amine and 1-2 parts of corrosion resistant agent.

Preferably, the tackifier is PVC or a cycloaliphatic petroleum resin.

Preferably, the corrosion resistant agent is polyoxymethylene.

Preferably, the TPU semipermeable membrane is prepared by:

Wherein the TPU resin particles are polyester TPU pellets, JM-1020 (Luoyangjiming chemical Co., Ltd.), and the relative viscosity is 2.12.

Example 1

The wear-resistant corrosion-resistant TPU super-permeable film is prepared by the following steps:

s1: preparing a wear-resisting agent: weighing potassium stearate, polyacrylonitrile, modified buckwheat flour, polyvinyl alcohol and polyacrylate according to the weight ratio of 1.1:1.2:1:1:1, and mixing all the weighed components in a mixer to obtain the wear-resisting agent for later use;

s2: weighing the following components in parts by weight:

110 parts of TPU resin particles, namely TPU resin particles,

2 parts of glass fiber, namely 2 parts of glass fiber,

10 parts of POE maleic anhydride is grafted,

1 parts of PVC (polyvinyl chloride),

1 part of a wear-resistant agent, namely,

1 part of hydroquinone dihydroxyethyl ether,

0.5 part of titanium dioxide, namely,

0.5 part of 3, 5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester,

GW-6220.5 portions of (by weight portions),

1 part of polyformaldehyde for later use;

s3: grinding the TPU resin particles, POE maleic anhydride grafting and chain extender weighed in the step S2 into powder of 30-50 meshes, and mixing to form a mixture for later use;

s4: adding the mixture obtained in the step S3 into a high-speed kneader, blending and kneading to form colloid; the high-speed kneader kneads the mixed material under the condition of 110 ℃, and the stirring rake of high-speed kneader constantly stirs the mixed material and acts on shearing force to the mixed material for the mixed material further disperses, thereby forms even colloid, puts into twin-screw extruder granulation subsequently with the colloid, obtains the mixturely. Wherein the extrusion temperature is controlled in one zone of the screw machine: 180 ℃; and a second zone: 200 ℃; a three-zone is 210 ℃; four areas are 220 ℃; five regions are 240 ℃; six regions are 220 ℃; seven areas are 220 ℃; eight regions are 210 ℃; nine areas are 200 ℃; ten zones 200 ℃.

S5: and (3) mixing the mixed particles in the step S4 with the glass fiber, the tackifier, the wear-resistant agent, the corrosion-resistant agent, the light-shielding agent, the light absorbent and the hindered amine in the step S2 in a mixer, controlling the mixing temperature at 100 ℃ and 110 ℃, stirring at a low speed, stirring at 200r/min for 1 hour, keeping the temperature at 90-100 ℃, introducing into a double-screw extruder to obtain molten colloid, and introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Example 2

s2: weighing the following components in parts by weight:

115 parts of TPU resin particles, namely 115 parts of TPU resin particles,

2.5 parts of glass fiber, namely,

13 parts of POE maleic anhydride grafted by 13 parts,

1.2 parts of alicyclic petroleum resin,

1.5 parts of a wear-resisting agent,

1.8 parts of bisphenol A modified polyethylene glycol diallyl ester,

0.8 part of titanium dioxide, namely,

0.8 part of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole,

0.8 portion of poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate,

1.6 parts of polyformaldehyde for later use;

s4: adding the mixture obtained in the step S3 into a high-speed kneader, blending and kneading to form colloid; the high-speed kneader kneads the mixed material under the condition of 110 ℃, and the stirring rake of high-speed kneader constantly stirs the mixed material and acts on shearing force to the mixed material for the mixed material further disperses, thereby forms even colloid, puts into twin-screw extruder granulation subsequently with the colloid, obtains the mixturely. Wherein the extrusion temperature is controlled in one zone of the screw machine: 190 ℃; and a second zone: at 210 ℃; a three area is 220 ℃; four areas are 230 ℃; five regions are 250 ℃; six areas are 230 ℃; seven areas are 230 ℃; an eight area is 220 ℃; nine zones at 210 ℃; ten zones 210 ℃.

S5: and (3) mixing the mixed particles in the step S4 with the glass fiber, the tackifier, the wear-resistant agent, the corrosion-resistant agent, the light-shielding agent, the light absorbent and the hindered amine in the step S2 in a mixer, controlling the mixing temperature at 100 ℃ and 110 ℃, stirring at a low speed, stirring at 250r/min for 1 hour, keeping the temperature at 90-100 ℃, introducing into a double-screw extruder to obtain molten colloid, and introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Example 3

s2: weighing the following components in parts by weight:

120 parts of TPU resin particles, namely, TPU resin particles,

3 parts of glass fiber, namely 3 parts of glass fiber,

16 parts of POE maleic anhydride grafted by POE maleic anhydride,

1.5 parts of PVC (polyvinyl chloride),

2 parts of a wear-resisting agent, namely,

3 parts of 1, 4-cyclohexanedimethanol,

1.5 parts of zinc oxide, namely zinc oxide,

1.5 parts of N- (2-ethoxyphenyl) -N' - (2-ethylphenyl) -oxalamide,

GW-9441.5 portions of (by weight portions),

2 parts of polyformaldehyde for later use;

S5: and (3) mixing the mixed particles in the step S4 with the glass fiber, the tackifier, the wear-resistant agent, the corrosion-resistant agent, the light-shielding agent, the light absorbent and the hindered amine in the step S2 in a mixer, controlling the mixing temperature at 100 ℃ and 110 ℃, stirring at a low speed, stirring at 180r/min for 1 hour, keeping the temperature at 90-100 ℃, introducing into a double-screw extruder to obtain molten colloid, and introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Example 4

s2: weighing the following components in parts by weight:

112 parts of TPU resin particles, namely 112 parts of TPU resin particles,

2 parts of glass fiber, namely 2 parts of glass fiber,

10 parts of POE maleic anhydride is grafted,

1 part of alicyclic petroleum resin, namely 1 part of alicyclic petroleum resin,

1 part of a wear-resistant agent, namely,

1 part of 1, 3-propylene glycol,

1.5 parts of zinc oxide, namely zinc oxide,

0.5 part of 2- (2H-benzotriazole-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol,

0.5 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate,

1 part of polyformaldehyde for later use;

s4: adding the mixture obtained in the step S3 into a high-speed kneader, blending and kneading to form colloid; the high-speed kneader kneads the mixed material under the condition of 110 ℃, and the stirring rake of high-speed kneader constantly stirs the mixed material and acts on shearing force to the mixed material for the mixed material further disperses, thereby forms even colloid, puts into twin-screw extruder granulation subsequently with the colloid, obtains the mixturely. Wherein the extrusion temperature is controlled in one zone of the screw machine: 200 ℃; and a second zone: 200 ℃; a three area is 220 ℃; four areas are 220 ℃; five regions are 250 ℃; a sixth area is 240 ℃; seven areas are 230 ℃; an eight area is 220 ℃; nine zones at 210 ℃; ten zones 200 ℃.

Example 5

s2: weighing the following components in parts by weight:

118 parts of TPU resin particles, namely TPU resin particles,

the glass fiber is 2.9 of the glass fiber,

15.8 parts of POE maleic anhydride graft,

1.5 parts of PVC (polyvinyl chloride),

2 parts of a wear-resisting agent, namely,

1 part of 1, 5-pentanediol,

0.5 part of zinc and barium,

0.5 part of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol,

0.5 part of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate,

1.6 parts of polyformaldehyde for later use;

S5: and (3) mixing the mixed particles in the step S4 with the glass fiber, the tackifier, the wear-resistant agent, the corrosion-resistant agent, the light-shielding agent, the light absorbent and the hindered amine in the step S2 in a mixer, controlling the mixing temperature at 110 ℃ and stirring at low speed, controlling the stirring speed at 250r/min for 1 hour, keeping the temperature at 90-100 ℃ and introducing into a double-screw extruder to obtain molten colloid, and introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Comparative example 1

s1: weighing a certain amount of TPU resin particles for later use according to the parts by weight;

s2: and (4) stirring the TPU resin particles weighed in the step S1 in a mixer, controlling the stirring temperature at 100-110 ℃, stirring at a low speed, keeping the stirring speed at 250r/min, stirring for 1 hour, keeping the temperature at 90-100 ℃, introducing into a double-screw extruder to obtain molten colloid, and introducing the molten colloid into a casting machine for molding to obtain the finished TPU super-permeable film.

Experiment one:

equal amounts of the TPU semipermeable films of examples 1-5 and the TPU semipermeable film of the comparative example were placed in the same corrosive environment for 5 hours, 10 hours, and 15 hours, respectively, and the data was recorded.

As a result:

the TPU super-permeable films in the examples 1 and 3 have no obvious reaction in a corrosive environment for 5 hours, 10 hours and 15 hours;

the TPU ultra-permeable films in the examples 2 and 5 have no obvious reaction after 5 hours in a corrosive environment, have slight corrosion reaction after 10 hours and have moderate corrosion reaction after 15 hours;

the TPU super-permeable film in example 4 has a slight corrosion reaction in a corrosive environment for 5 hours, and has a moderate corrosion reaction in 10 and 15 hours;

the TPU ultra-permeable film in the comparative example has moderate corrosion reaction within 5 hours and 10 hours in a corrosive environment, and has severe corrosion reaction within 15 hours.

Experiment two:

the equivalent amount of the TPU super-permeable films of examples 1 to 5 and the TPU super-permeable film of the comparative example were taken out after 1 hour at 60 degrees celsius, 100 degrees celsius, and 140 degrees celsius, respectively, and the data were recorded.

As a result:

the TPU super-transparent film in the example 3 is taken out after being placed in an environment at 60 ℃ for 1 hour and has no obvious damage mark, slight foaming and wrinkling marks are generated after being placed in an environment at 100 ℃ for 1 hour, and moderate foaming and wrinkling marks are generated after being placed in an environment at 140 ℃ for 1 hour;

the TPU super-transparent films in the examples 1 and 4 have no obvious damage mark after being taken out after being placed in the environment of 60 ℃ and 100 ℃ for 1 hour, and have slight marks of foaming and wrinkling after being placed in the environment of 140 ℃ for 1 hour;

the TPU super-transparent films in the embodiments 2 and 5 are placed in the environment of 60 ℃, 100 ℃ and 140 ℃ for 1 hour and then taken out without obvious damage traces;

the TPU super-permeable film in the comparative example was removed with moderate marks of blistering and wrinkling after being left at 60 degrees celsius and 100 degrees celsius for 1 hour, and with severe marks of blistering and wrinkling after being left at 140 degrees celsius for 1 hour.

Experiment three:

the surfaces of the TPU super-permeable films of examples 1 to 5 and the TPU super-permeable film of the comparative example were coated with an oxidizing agent at three concentrations of low, medium and high for one hour and observed, and data were recorded.

As a result:

the TPU super-permeable films in the examples 2 and 3 have no obvious oxidation trace on the surface after being coated with a low-concentration oxidizing agent and placed for one hour, have a slight oxidation trace on the surface after being coated with a medium-concentration oxidizing agent and placed for one hour, and have a moderate oxidation trace on the surface after being coated with a high-concentration oxidizing agent and placed for one hour;

the TPU super-permeable film in the embodiment 4 has no obvious oxidation trace on the surface after being coated with low and medium concentration oxidants and being placed for one hour, and has slight oxidation trace on the surface after being coated with high concentration oxidants and being placed for one hour;

the TPU super-permeable films in the examples 1 and 5 have no obvious oxidation traces on the surfaces after being coated with low, medium and high concentration oxidants and placed for one hour;

the TPU super-permeable film in the comparative example shows moderate oxidation on the surface after being coated with low and medium-concentration oxidizing agents and placed for one hour, and the TPU film in the comparative example shows severe oxidation on the surface after being coated with high-concentration oxidizing agents and placed for one hour.

The experiments show that the TPU super-permeable membrane is improved, the maleic anhydride grafted polyolefin and the chain extender are added on the basis of the original TPU resin particles, the molding effect of the TPU resin particles after molding is changed through the grafted components, the performance of the polyolefin is embedded in the TUP polymer, the chain performance of the high molecular polymer is changed, the stability of the high molecular polymer is improved through the added C-C bond, and the separation and oxidation of chemical bonds caused by external force are reduced.

Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims

1. The wear-resistant corrosion-resistant TPU super-permeable film is characterized in that: the paint comprises the following components in parts by weight: 120 parts of TPU resin particles 110-3 parts of glass fiber, 10-16 parts of POE maleic anhydride graft, 1-1.5 parts of tackifier, 1-2 parts of wear-resistant agent, 1-3 parts of chain extender, 0.5-1.5 parts of light shielding agent, 0.5-1.5 parts of light absorbent, 0.5-1.5 parts of hindered amine and 1-2 parts of corrosion resistant agent.

2. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the tackifier is PVC or alicyclic petroleum resin.

3. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the hindered amine comprises one of GW-622, GW-944, poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate, bis (2,2,6, 6-tetramethylpiperidineethanol) sebacate and bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.

4. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the wear-resisting agent is formed by mixing potassium stearate, polyacrylonitrile, modified buckwheat flour, polyvinyl alcohol and polyacrylate, and the weight ratio of the potassium stearate to the polyacrylonitrile to the modified buckwheat flour to the polyvinyl alcohol to the polyacrylate is 1.1:1.2:1:1: 1.

5. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the chain extender comprises one of 1, 3-propylene glycol, 1, 5-pentanediol, hydroquinone dihydroxyethyl ether, 1, 4-cyclohexanedimethanol and bisphenol A modified polyethylene glycol diallyl ester.

6. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the corrosion resistant agent is polyformaldehyde.

7. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the light shielding agent comprises one of titanium dioxide, zinc oxide and zinc barium.

8. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: the light absorber comprises one of 3, 5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, N- (2-ethoxyphenyl) -N '- (2-ethylphenyl) -ethanediamide, 2- (2' -hydroxy-3 ', 5' -di-tert-butylphenyl) -5-chlorobenzotriazole, and 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxy-phenol.

9. The wear and corrosion resistant TPU semipermeable membrane according to claim 1, wherein: is prepared by the following steps: