A high-resistance composite hose and its production process

Abstract

The present invention relates to a high-tolerance composite hose and a production process thereof, belonging to the technical field of polymer composite materials. The composite hose comprises an aluminum foil and a high-tolerance inner film composited on its surface. The high-tolerance inner film is a copolymer of low molecular weight polyethylene, monomer 1, and monomer 2. The monomer 1 molecule contains branched fluorine-containing groups and double bonds. After copolymerization, fluorine groups are introduced on the outside of the main chain to protect the main chain and improve tolerance to organic solvents. Monomer 2 uses diethanolamine and diallyl sulfide as raw materials, and undergoes an addition reaction under the catalysis of sodium ethoxide to produce an intermediate containing branched hydroxyl groups. Subsequently, double bonds are introduced into the ends using acryloyl chloride for modification. The double bonds participate in copolymerization. The sulfur-containing and nitrogen-containing structures in the middle of the monomer 2 molecule have a chelating effect with the aluminum foil, forming an anchoring effect on the polymer after composite, so that the high-tolerance inner film has a strong adhesion strength to the aluminum foil.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer composite materials, and in particular relates to a high-resistance composite hose and a production process thereof. Background Art

[0002] Hair dye is a cosmetic used to dye hair. It contains p-phenylenediamine, ammonia, and some organic solvents. To ensure the stability and protective reliability of hair dye, traditional hair dye is packaged in pure aluminum tubes with high barrier properties. However, due to the low toughness of pure aluminum and the high packaging cost, it is gradually being replaced by aluminum-plastic packaging materials.

[0003] The so-called aluminum-plastic packaging material is a multi-layer composite material composed of plastic film, aluminum foil and adhesive. The general process includes: cleaning the aluminum foil, brushing the adhesive, pre-baking and shaping, film pasting and hot pressing. The process is relatively complicated, and the plastic film and the aluminum foil are bonded with adhesive. There is a problem of peeling during use. The aluminum foil cannot be formed into a film layer at the peeling point, and it is easy to bend, crack and leak. In addition, the plastic film used is mostly made of polyethylene film with higher flexibility to meet the repeated extrusion and use of hair dye. However, the polyethylene film has general tolerance to alkaline substances and organic solvents in hair dye, and it is difficult to meet stable storage requirements.

[0004] Based on the above technical defects, the present application starts from improving the tolerance of the film layer and the bonding strength of the film layer to develop a high-resistance aluminum-plastic composite material suitable for packaging of hair dye. Summary of the Invention

[0005] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a high-resistance composite hose and a production process thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A production process for a high-resistance composite hose specifically includes the following steps:

[0008] Step S1: After cleaning the surface of the aluminum foil, a high-resistance inner film is laminated on the surface, followed by roll lamination at a temperature of 220-230°C and a pressure of 4-6 kg, and spray-cooled to room temperature to form a composite sheet;

[0009] Step S2: The composite sheet is cut into pieces, then rolled and high-frequency welded to form a high-resistance composite hose.

[0010] The high-tolerance inner membrane is prepared by the following method:

[0011] Step A1: Tetrafluoropropanol and triethylamine were mixed and kept constant temperature in an ice-water bath. Then, the stirring rate was set to 120-180 rpm, and 2,3-dichloropropylene was slowly added dropwise. The mixing time was controlled to be 5-8 hours. Then, the stirring rate was increased to 360-480 rpm, and the temperature was raised to 95-100°C and refluxed for 20-30 minutes to obtain monomer 1;

[0012] Furthermore, the usage ratio of 2,3-dichloropropylene, tetrafluoropropanol and triethylamine is 0.1 mol: 0.25-0.28 mol: 15-20 mL, and the excess tetrafluoropropanol and 2,3-dichloropropylene are subjected to substitution reaction, and after the reaction, the excess tetrafluoropropanol and triethylamine are quickly removed by rotary evaporation under reduced pressure.

[0013] Step A2: Diethanolamine, sodium ethoxide, and anhydrous ethanol were mixed, diallyl sulfide was added, the stirring rate was set at 240-360 rpm, the temperature was raised to 85-95°C, and the reaction was refluxed for 2-4 hours to obtain a branched intermediate;

[0014] Furthermore, the dosage ratio of diallyl sulfide, diethanolamine, sodium ethoxide and anhydrous ethanol is 0.1 mol: 0.22-0.25 mol: 0.3-0.4 g: 50-80 mL, and the double bond of diallyl sulfide and the secondary amine of diethanolamine undergo nucleophilic addition under the catalysis of sodium ethoxide. After the reaction is completed, low-boiling substances are removed by rotary evaporation.

[0015] Step A3: Mix the branched intermediate, potassium hydroxide, and DMF, set the stirring rate to 180-300 rpm, and add acryloyl chloride dropwise at room temperature. Control the total dropwise reaction time to be 2-3 hours to obtain monomer 2;

[0016] Furthermore, the usage ratio of the branched intermediate, acryloyl chloride, potassium hydroxide and DMF is 0.1 mol: 0.41-0.42 mol: 2.5-3.5 g: 120-160 mL. After the reaction is completed, deionized water is added and the mixture is evaporated under reduced pressure several times to remove DMF.

[0017] Step A4: low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant are added to a high pressure reactor and mixed, nitrogen is introduced to increase the pressure to 1.8-2.2 MPa, the temperature is raised to 240-260° C., the reaction is carried out for 6.5-7.2 minutes, the binder is discharged, and the film is cast to obtain a high-tolerance inner film;

[0018] Furthermore, the usage ratio of low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant is 1 kg: 80-100 g: 165-190 g: 320-380 mL: 5.5-6.2 g: 1-2 g.

[0019] Furthermore, the antioxidant is antioxidant 300.

[0020] Furthermore, the initiator is a catalyst MMAO.

[0021] Furthermore, the average molecular weight of the low molecular weight polyethylene is 5,000.

[0022] Beneficial effects of the present invention:

[0023] The present invention prepares a high-tolerance inner membrane, which is composited with aluminum foil to reduce the cost of pure aluminum tubes while having high tolerance. The high-tolerance inner membrane is a copolymer of low-molecular-weight polyethylene, monomer 1, and monomer 2, wherein monomer 1 uses tetrafluoropropanol and 2,3-dichloropropylene as raw materials for substitution reaction, and the obtained monomer 1 molecule contains branched fluorine-containing groups and double bonds. After copolymerization, fluorine groups are introduced on the outside of the main chain to protect the main chain, thereby improving tolerance to organic solvents. At the same time, the introduction of the fluorine-containing groups gives the high-tolerance inner membrane water and oil repellency, which can reduce the residue of hair dye in the tube body; monomer 2 uses diethanolamine and diallyl sulfide as raw materials, undergoes an addition reaction under the catalysis of sodium ethoxide, and is prepared into an intermediate containing branched hydroxyl groups. Thereafter, double bonds are introduced into the end of the monomer 2 for modification, and the double bonds participate in copolymerization. The sulfur-containing and nitrogen-containing structure in the middle of the monomer 2 molecule has a chelating effect with the aluminum foil, and forms an anchoring effect on the polymer after composite, so that the high-tolerance inner membrane has strong adhesion strength with the aluminum foil, thereby avoiding delamination of the high-tolerance inner membrane and the aluminum foil during use. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] Example 1

[0026] This embodiment prepares a high-resistance composite hose, and the specific implementation process is as follows:

[0027] 1) Preparation of high-tolerance endometrium

[0028] a1. Tetrafluoropropanol and triethylamine were added to a reactor and stirred for 10 minutes. The mixture was placed in an ice-water bath and kept at a constant temperature. The stirring rate was set to 180 rpm. 2,3-dichloropropylene was slowly and uniformly added dropwise over 1 hour. The overall dropping and mixing time was controlled to 5 hours. The stirring rate was then increased to 480 rpm. The temperature was raised to 100°C and refluxed for 20 minutes to produce monomer 1. After the reaction, the pressure was reduced to below 10 mmHg, and the mixture was rotary evaporated at 50°C to quickly remove excess low-boiling-point substances such as tetrafluoropropanol and triethylamine. The amount ratio of 2,3-dichloropropylene, tetrafluoropropanol, and triethylamine was 0.1 mol:0.28 mol:20 mL.

[0029] a2. Diethanolamine, sodium ethoxide, and anhydrous ethanol were added to a reactor and stirred to dissolve the sodium ethoxide. Diallyl sulfide was then added and mixed for 5 minutes. The stirring rate was set to 360 rpm, and the temperature was raised to 95°C and refluxed for 2 hours to produce a branched intermediate. After the reaction was completed, anhydrous ethanol was removed by rotary evaporation under reduced pressure. The ratio of diallyl sulfide, diethanolamine, sodium ethoxide, and anhydrous ethanol was 0.1 mol: 0.25 mol: 0.4 g: 80 mL.

[0030] a3. The branched intermediate, potassium hydroxide, and DMF were added to a reactor and stirred for 15 minutes. The stirring rate was set to 300 rpm. Acryloyl chloride was slowly added dropwise over 1 hour at room temperature. The total dropwise reaction time was controlled to 2 hours to produce monomer 2. After the reaction, deionized water twice the mass of the reaction solution was added in three portions. The pressure was reduced to below 20 mmHg and the temperature was set to 80°C for rotary evaporation to remove DMF. The amount ratio of the branched intermediate, acryloyl chloride, potassium hydroxide, and DMF was 0.1 mol:0.42 mol:3.5 g:160 mL.

[0031] a4. Low molecular weight polyethylene (provided by Jilin Petrochemical Polyethylene Plant, with an average molecular weight of 5000, and the following examples use the same raw materials), monomer 1, monomer 2, NMP, an initiator, and an antioxidant are added to an autoclave and mixed for 20 minutes. The mixture is decompressed to 5 mmHg, and then high-purity nitrogen is introduced to increase the pressure to 2.2 MPa. The temperature is raised to 260° C. and the reaction is carried out for 6.5 minutes. After the reaction, the rubber is discharged to a casting machine, and the rubber is cast into a film, which is air-cooled and shaped to form a high-tolerance inner membrane. The low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator (selected from catalyst MMAO, and the following examples use the same raw materials) and antioxidant (selected from antioxidant 300, and the following examples use the same raw materials) are used in a ratio of 1 kg:80 g:190 g:380 mL:6.2 g:2 g.

[0032] 2) Preparation of high-resistance composite hose

[0033] s1. Take aluminum foil (provided by Henan Mingtai Aluminum Co., Ltd., 8011 aluminum foil, the following examples use the same batch of raw materials), immerse the aluminum foil in 10% sodium carbonate solution to remove oil, rinse with clean water, then immerse it in 5% sulfuric acid to wash, rinse with clean water, and dry it to clean the aluminum foil. Then, unwind the high-tolerance inner film and laminate it on the treated surface of the aluminum foil. Place it in a rolling mill, control the temperature to 230°C, and the rolling pressure to 4kg. Laminate the high-tolerance inner film on the surface of the aluminum foil, and then spray cool it to room temperature to make a composite sheet;

[0034] a2. Cut the composite sheet into pieces, roll the tube so that the ends overlap, and weld the overlapping seams by high frequency to make a high-resistance composite hose.

[0035] Example 2

[0036] This embodiment prepares a high-resistance composite hose, and the specific implementation process is as follows:

[0037] 1) Preparation of high-tolerance endometrium

[0038] a1. Tetrafluoropropanol and triethylamine were added to a reactor and stirred for 10 minutes. The mixture was placed in an ice-water bath to maintain constant temperature. The stirring rate was set to 120 rpm. 2,3-dichloropropylene was slowly and uniformly added dropwise over 1 hour. The overall dropping and mixing time was controlled to 8 hours. The stirring rate was then increased to 360 rpm. The temperature was raised to 95°C and refluxed for 30 minutes to produce monomer 1. After the reaction, the pressure was reduced to below 10 mmHg, and the mixture was rotary evaporated at 50°C to quickly remove excess tetrafluoropropanol, triethylamine and other low-boiling substances. The amount ratio of 2,3-dichloropropylene, tetrafluoropropanol and triethylamine was 0.1 mol:0.25 mol:15 mL.

[0039] a2. Diethanolamine, sodium ethoxide, and anhydrous ethanol were added to a reactor and stirred to dissolve the sodium ethoxide. Diallyl sulfide was then added and mixed for 5 minutes. The stirring rate was set to 240 rpm, and the temperature was raised to 85°C and refluxed for 4 hours to produce a branched intermediate. After the reaction was completed, anhydrous ethanol was removed by rotary evaporation under reduced pressure. The ratio of diallyl sulfide, diethanolamine, sodium ethoxide, and anhydrous ethanol was 0.1 mol: 0.22 mol: 0.3 g: 50 mL.

[0040] a3. The branched intermediate, potassium hydroxide, and DMF were added to a reactor and stirred for 15 minutes. The stirring rate was set to 180 rpm. Acryloyl chloride was slowly added dropwise over 1.5 hours at room temperature, and the total dropwise reaction time was controlled to 3 hours to produce monomer 2. After the reaction, deionized water twice the mass of the reaction solution was added in three portions, and the pressure was reduced to below 20 mmHg. The temperature was set to 80°C and rotary evaporation was performed to remove DMF. The amount ratio of the branched intermediate, acryloyl chloride, potassium hydroxide, and DMF was 0.1 mol:0.41 mol:2.5 g:120 mL.

[0041] a4. Low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant are added to a high-pressure reactor and mixed for 20 minutes. The pressure is reduced to 5 mmHg, and high-purity nitrogen is introduced to increase the pressure to 1.8 MPa. The temperature is raised to 240°C and the reaction is carried out for 7.2 minutes. After the reaction, the rubber is discharged to a casting machine, and the rubber is cast into a film. The film is air-cooled and shaped to form a high-tolerance inner film. The usage ratio of low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant is 1 kg:100 g:165 g:320 mL:5.5 g:1 g.

[0042] 2) Preparation of high-resistance composite hose

[0043] s1. Take the aluminum foil and immerse it in 10% sodium carbonate solution to remove oil, rinse it with clean water, then immerse it in 5% sulfuric acid to wash it, rinse it with clean water again, and dry it to clean the aluminum foil. Then, unwind the high-tolerance inner film and laminate it on the treated aluminum foil surface. Place it in a rolling mill, control the temperature to 220°C, and the rolling pressure to 6kg. Laminate the high-tolerance inner film on the aluminum foil surface, and then spray cool it to room temperature to make a composite sheet.

[0044] a2. Cut the composite sheet into pieces, roll the tube so that the ends overlap, and weld the overlapping seams by high frequency to make a high-resistance composite hose.

[0045] Example 3

[0046] This embodiment prepares a high-resistance composite hose, and the specific implementation process is as follows:

[0047] 1) Preparation of high-tolerance endometrium

[0048] a1. Tetrafluoropropanol and triethylamine were added to a reactor and stirred for 10 minutes. The mixture was placed in an ice-water bath to maintain constant temperature. The stirring rate was set to 180 rpm. 2,3-dichloropropylene was slowly and uniformly added dropwise over 1 hour. The total dropping and mixing time was controlled to 6.5 hours. The stirring rate was then increased to 360 rpm. The temperature was raised to 100°C and refluxed for 22 minutes to produce monomer 1. After the reaction, the pressure was reduced to below 10 mmHg, and the mixture was rotary evaporated at 50°C to quickly remove excess low-boiling-point products such as tetrafluoropropanol and triethylamine. The amount ratio of 2,3-dichloropropylene, tetrafluoropropanol, and triethylamine was 0.1 mol:0.26 mol:17 mL.

[0049] a2. Diethanolamine, sodium ethoxide, and anhydrous ethanol were added to a reactor and stirred to dissolve the sodium ethoxide. Diallyl sulfide was then added and mixed for 5 minutes. The stirring rate was set to 240 rpm, and the temperature was raised to 90°C and refluxed for 3 hours to produce a branched intermediate. After the reaction was completed, anhydrous ethanol was removed by rotary evaporation under reduced pressure. The ratio of diallyl sulfide, diethanolamine, sodium ethoxide, and anhydrous ethanol was 0.1 mol: 0.24 mol: 0.35 g: 70 mL.

[0050] a3. The branched intermediate, potassium hydroxide, and DMF were added to a reactor and stirred for 15 minutes. The stirring rate was set to 300 rpm. Acryloyl chloride was slowly added dropwise over 1.2 hours at room temperature, and the total dropwise reaction time was controlled to 2.8 hours to produce monomer 2. After the reaction, deionized water twice the mass of the reaction solution was added three times in batches, and the pressure was reduced to below 20 mmHg. The temperature was set to 80°C and rotary evaporation was performed to remove DMF. The amount ratio of the branched intermediate, acryloyl chloride, potassium hydroxide, and DMF was 0.1 mol:0.42 mol:2.9 g:140 mL.

[0051] a4. Low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant are added to a high-pressure reactor and mixed for 20 minutes. The pressure is reduced to 5 mmHg, and high-purity nitrogen is introduced to increase the pressure to 2.0 MPa. The temperature is raised to 250°C and the reaction is carried out for 6.8 minutes. After the reaction, the rubber is discharged to a casting machine, and the rubber is cast into a film. The film is air-cooled and shaped to form a high-tolerance inner film. The usage ratio of low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant is 1 kg:90 g:180 g:350 mL:5.8 g:1.3 g.

[0052] 2) Preparation of high-resistance composite hose

[0053] s1. Take the aluminum foil and immerse it in 10% sodium carbonate solution to remove oil, rinse it with clean water, then immerse it in 5% sulfuric acid to wash it, rinse it with clean water again, and dry it to clean the aluminum foil. Then, unwind the high-tolerance inner film and laminate it on the treated aluminum foil surface. Place it in a rolling mill, control the temperature to 230°C, and the rolling pressure to 5.2kg. Laminate the high-tolerance inner film on the aluminum foil surface, and then spray cool it to room temperature to make a composite sheet;

[0054] a2. Cut the composite sheet into pieces, roll the tube so that the ends overlap, and weld the overlapping seams by high frequency to make a high-resistance composite hose.

[0055] Example 4

[0056] This embodiment prepares a high-resistance composite hose, and the specific implementation process is as follows:

[0057] 1) Preparation of high-tolerance endometrium

[0058] a1. Tetrafluoropropanol and triethylamine were added to a reactor and stirred for 10 minutes. The mixture was placed in an ice-water bath to maintain constant temperature. The stirring rate was set to 120 rpm. 2,3-dichloropropylene was slowly and uniformly added dropwise over 1 hour. The total dropping and mixing time was controlled to 7.5 hours. The stirring rate was then increased to 360 rpm. The temperature was raised to 98°C and refluxed for 26 minutes to produce monomer 1. After the reaction, the pressure was reduced to below 10 mmHg, and the mixture was rotary evaporated at 50°C to quickly remove excess low-boiling-point substances such as tetrafluoropropanol and triethylamine. The amount ratio of 2,3-dichloropropylene, tetrafluoropropanol, and triethylamine was 0.1 mol:0.28 mol:18 mL.

[0059] a2. Diethanolamine, sodium ethoxide, and anhydrous ethanol were added to a reactor and stirred to dissolve the sodium ethoxide. Diallyl sulfide was then added and mixed for 5 minutes. The stirring rate was set to 360 rpm, and the temperature was raised to 92°C and refluxed for 3.6 hours to produce a branched intermediate. After the reaction was completed, anhydrous ethanol was removed by rotary evaporation under reduced pressure. The ratio of diallyl sulfide, diethanolamine, sodium ethoxide, and anhydrous ethanol was 0.1 mol:0.23 mol:0.35 g:60 mL.

[0060] a3. The branched intermediate, potassium hydroxide, and DMF were added to a reactor and stirred for 15 minutes. The stirring rate was set to 300 rpm. Acryloyl chloride was slowly added dropwise over 1.3 hours at room temperature, and the total dropwise reaction time was controlled to 3.6 hours to produce monomer 2. After the reaction, deionized water twice the mass of the reaction solution was added in three portions, and the pressure was reduced to below 20 mmHg. The temperature was set to 80°C and rotary evaporation was performed to remove DMF. The amount ratio of the branched intermediate, acryloyl chloride, potassium hydroxide, and DMF was 0.1 mol:0.41 mol:3.2 g:150 mL.

[0061] a4. Take low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant, add them into a high-pressure reactor and mix for 20 minutes, reduce the pressure to 5 mmHg, then introduce high-purity nitrogen to increase the pressure to 2.2 MPa, raise the temperature to 250°C, and react for 7.0 minutes. After the reaction, discharge the glue into a casting machine, cast the glue into a film, and air-cool and shape it to make a high-tolerance inner film. Among them, the usage ratio of low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator and antioxidant is 1 kg:88 g:185 g:370 mL:6.0 g:1.5 g.

[0062] 2) Preparation of high-resistance composite hose

[0063] s1. Take the aluminum foil and immerse it in 10% sodium carbonate solution to remove oil, rinse it with clean water, then immerse it in 5% sulfuric acid to wash it, rinse it with clean water again, and dry it to clean the aluminum foil. Then, unwind the high-tolerance inner film and laminate it on the treated aluminum foil surface. Place it in a rolling mill, control the temperature to 230°C, and the rolling pressure to 5.5kg. Laminate the high-tolerance inner film on the aluminum foil surface, and then spray cool it to room temperature to make a composite sheet;

[0064] a2. Cut the composite sheet into pieces, roll the tube so that the ends overlap, and weld the overlapping seams by high frequency to make a high-resistance composite hose.

[0065] Comparative Example

[0066] Take the aluminum foil treated in Example 1, brush YH-T855 glue on the surface, adhere to a low-density polyethylene film (provided by Jinzhiyang (Guangzhou) New Materials Co., Ltd.), and let it stand and cure at room temperature for 12 hours to make a composite sheet. Then, it is slit, rolled and high-frequency welded to make a composite hose.

[0067] The high-tolerance inner films prepared in Examples 1 to 4 and the low-density polyethylene films provided in the comparative example were taken as samples, and p-phenylenediamine, ammonia water (15%) and anhydrous ethanol were prepared into a solution at a ratio of 1 g: 8 mL: 100 mL, recorded as an etching solution, and the sample was immersed in the etching solution. After soaking for 30 days, it was taken out and dried at 40 ° C for 20 minutes. The tensile strength and elongation at break of the sample before and after treatment were tested with reference to GB / T 1040.1-2018 standard. The specific test data are shown in Table 1:

[0068] Table 1

[0069]

[0070]

[0071] From the data in Table 1, it can be seen that the tensile strength of the high-tolerance inner film prepared by the present invention is slightly higher than that of the existing low-density polyethylene film, and the elongation at break is slightly lower than that of the low-density polyethylene film. Analysis shows that this is caused by the cross-linking effect of monomer 2, and the mirror cabinet

[0072] The composite sheets prepared in Examples 1 to 4 and the comparative example were subjected to peeling tests in accordance with GB / T31294-2014. The test temperatures were 5°C, 25°C, and 50°C, respectively. The specific test data are shown in Table 2:

[0073] Table 2

[0074]

[0075] It can be seen from the data in Table 2 that the film layer of the composite sheet prepared by the present invention has good peeling resistance at room temperature, and the peeling strength does not change much at low and high temperatures, and has a stable anti-peeling effect, avoiding delamination of the film layer and the aluminum foil during use.

[0076] The composite hoses prepared in Examples 1 to 4 and the comparative example were filled with Mela Red 8-45 hair dye, and nitrogen was introduced for protection. The hoses were left standing at room temperature for 12 months. After being taken out, the blackening of the hair dye was observed. At the same time, the hose was opened and the hair dye was discharged inverted. The hose was left standing inverted for 10 minutes, weighed, cleaned, and the residual amount in the hose was calculated. The specific test data are shown in Table 3:

[0077] Table 3

[0078]

[0079] As can be seen from the data in Table 3, the composite hose prepared in the present invention has a good barrier effect on hair dye and is less likely to leave hair dye residue.

[0080] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0081] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A high-resistance composite hose, characterized in that: It includes aluminum foil and a high-resistance inner film laminated on the surface thereof; The high-tolerance inner membrane is prepared by the following method: Step A1: Tetrafluoropropanol and triethylamine are mixed and kept constant temperature in an ice-water bath, and 2,3-dichloropropylene is added dropwise with stirring. The dropping and mixing time is controlled to be 5-8 hours. The temperature is further raised to 95-100°C and stirred under reflux for 20-30 minutes. The amount ratio of 2,3-dichloropropylene, tetrafluoropropanol, and triethylamine is 0.1 mol: 0.25-0.28 mol: 15-20 mL to obtain monomer 1 containing branched fluorine-containing groups and double bonds; Step A2: Diethanolamine, sodium ethoxide, and anhydrous ethanol were mixed, diallyl sulfide was added, and the stirring rate was set to 240-360 rpm. The temperature was raised to 85-95°C and refluxed for 2-4 hours. The ratio of diallyl sulfide, diethanolamine, sodium ethoxide, and anhydrous ethanol was 0.1 mol: 0.22-0.25 mol: 0.3-0.4 g: 50-80 mL to obtain a branched intermediate containing branched hydroxyl groups. Step A3: Mix the branched intermediate, potassium hydroxide, and DMF, and add acryloyl chloride dropwise under stirring at room temperature. The total dropwise reaction time is controlled to be 2-3 hours. The ratio of the branched intermediate, acryloyl chloride, potassium hydroxide, and DMF is 0.1 mol: 0.41-0.42 mol: 2.5-3.5 g: 120-160 mL to obtain monomer 2 containing sulfur and nitrogen structures. Step A4: mixing low molecular weight polyethylene, monomer 1, monomer 2, NMP, an initiator, and an antioxidant, introducing nitrogen to increase the pressure to 1.8-2.2 MPa, raising the temperature to 240-260° C., reacting for 6.5-7.2 minutes, debinding, and casting into a film, wherein the amount ratio of low molecular weight polyethylene, monomer 1, monomer 2, NMP, initiator, and antioxidant is 1 kg: 80-100 g: 165-190 g: 320-380 mL: 5.5-6.2 g: 1-2 g, and the average molecular weight of the low molecular weight polyethylene is 5000, to obtain a high-tolerance inner film made of a copolymer of low molecular weight polyethylene, monomer 1, and monomer 2; The initiator is catalyst MMAO, and the antioxidant is antioxidant 300.

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