Silicon core pipe and method for manufacturing the same

Abstract

The application relates to the technical field of silicon core pipe materials, in particular to a silicon core pipe material and a preparation method thereof. The silicon core pipe material comprises a silicon core pipe material body, the outer wall of the silicon core pipe material body is formed with a flame-retardant antibacterial reinforcing layer; the flame-retardant antibacterial reinforcing layer is prepared from a flame-retardant antibacterial reinforcing type prepreg tape; the flame-retardant antibacterial reinforcing type prepreg tape comprises flame-retardant antibacterial type prepreg resin and reinforcing type mesh cloth; the ratio of the thickness of the silicon core pipe material body to the thickness of the flame-retardant antibacterial reinforcing layer is 100:(1-5); and the mass ratio of the flame-retardant antibacterial type prepreg resin to the reinforcing type mesh cloth in the flame-retardant antibacterial reinforcing type prepreg tape is (10-25):10. The flame-retardant antibacterial reinforcing layer formed on the outer wall of the silicon core pipe material body by UV curing improves the overall flame retardance, antibacterial hygiene and tensile resistance, and the preparation method of the prepreg tape-winding-UV curing type is good in environmental protection, high in curing efficiency and convenient for batch manufacturing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silicon core pipe, in particular to a silicon core pipe and a preparation method thereof. BACKGROUND

[0002] The existing silicon core pipe includes an HDPE outer pipe and a lubricating inner pipe with a silica solid lubricant on the inner wall of the HDPE outer pipe. The lubricating inner pipe has a low friction coefficient, and has the advantages of simple construction, convenient cable threading, good sealing performance, and chemical corrosion resistance. It has replaced traditional cement pipes, PVC plastic pipes, PE pipes, and corrugated pipes to become a mainstream sheath pipe for cables, and is widely used in optical cable communication network systems of highways and railways. With the rapid development of 5G technology and power and information technology, the use of cables has increased rapidly, and the use of silicon core pipes has also increased significantly. However, the flame-retardant protection performance of the existing silicon core pipe cannot meet market demand, and the protection performance of high-end cables needs to be further improved. Therefore, the present application provides a silicon core pipe and a preparation method thereof. SUMMARY

[0003] To solve the above technical problems, the present application provides a silicon core pipe and a preparation method thereof.

[0004] The present application provides a silicon core pipe, which is realized by the following technical scheme:

[0005] The silicon core pipe comprises a silicon core pipe body, and a flame-retardant and antibacterial reinforcing layer is formed on the outer wall of the silicon core pipe body. The flame-retardant and antibacterial reinforcing layer is prepared from a flame-retardant and antibacterial reinforcing type prepreg. The flame-retardant and antibacterial reinforcing type prepreg comprises a flame-retardant and antibacterial type prepreg resin and a reinforcing type mesh cloth. The ratio of the thickness of the silicon core pipe body to the thickness of the flame-retardant and antibacterial reinforcing layer is 100:(1-5).

[0006] The present application is a post-treatment of an HDPE silicon core pipe to meet the high-level protection requirements of the market for the flame-retardant, antibacterial, and high-tensile-strength HDPE silicon core pipe. The commercially available HDPE silicon core pipe is cleaned, the prepreg is wound, hot pressing is performed, and UV curing is performed to form a flame-retardant and antibacterial reinforcing layer, thereby improving the overall flame-retardant, antibacterial, and tensile properties of the silicon core pipe.

[0007] Preferably, the mass ratio of the flame-retardant and antibacterial type prepreg resin to the reinforcing type mesh cloth in the flame-retardant and antibacterial reinforcing type prepreg is (10-25):10.

[0008] Preferably, the reinforcing type mesh cloth is one of a glass fiber mesh cloth, an aramid fiber mesh cloth, a carbon fiber mesh cloth, and an UHMWPE mesh cloth.

[0009] Further preferably, the reinforcing type mesh cloth is a glass fiber mesh cloth, the thickness of the glass fiber mesh cloth is 50-150 pm, and the grammage is 45-166 g / m2.2 .

[0010] The low-cost glass fiber mesh cloth is used in the application, the production cost of the finished product silicon core pipe material is reduced, the flame retardancy, antibacterial hygiene and tensile resistance of the finished product silicon core pipe material are improved, and the market competitiveness of the product is improved.

[0011] Preferably, the flame-retardant antibacterial type pre-impregnated resin is made of 100 parts of UV glue, 1-2 parts of methacryloxy silane, 0.5-2 parts of antibacterial nano filler, 3-6 parts of nano molybdenum disulfide and 10-20 parts of flame-retardant filler composition.

[0012] Preferably, the flame-retardant filler composition is composed of 4-8% of organically modified montmorillonite, 36-42% of ammonium polyphosphate and 50-60% of melamine phosphate.

[0013] By adopting the above technical scheme, the finished product silicon core pipe material is endowed with good antibacterial hygiene and flame retardancy.

[0014] Preferably, the UV glue is made of 6-10 parts of hexafunctional polyurethane modified acrylate resin, 14-20 parts of bifunctional polyurethane modified acrylate resin, 50-70 parts of UV active diluent, 2-5 parts of photoinitiator, 0.25-0.50 parts of leveling agent, 0.25-0.50 parts of defoaming agent and 0.25-0.50 parts of wetting agent; the UV active diluent is composed of trimethylolpropane triacrylate, tetrahydrofurfuryl methacrylate and propoxylated neopentyl glycol diacrylate in a mass ratio of (5-10):10:(10-25).

[0015] By adopting the above technical scheme, the finished product silicon core pipe material is endowed with good wear resistance and chemical corrosion resistance.

[0016] Preferably, the bifunctional polyurethane modified acrylate resin contains 4-8 wt% of phosphorus-containing polyol in the synthetic raw material, and the phosphorus-containing polyol is at least one of tri(dipropylene glycol) phosphite, phosphorus-containing polyol Exolit 550 and 560.

[0017] The use of phosphorus-containing polyol in the application can ensure the flame retardant performance of the finished product silicon core pipe while reducing the use amount of the flame retardant filler composition, optimize the use cost of the flame retardant filler and improve the overall bending toughness.

[0018] The application provides a preparation method of a silicon core pipe material.

[0019] The preparation method of the silicon core pipe material comprises the following steps.

[0020] Step one, cleaning the surface of the silicon core pipe body;

[0021] Step two, preparation of the flame-retardant and antibacterial reinforced type prepreg tape;

[0022] Step three, seamless winding of the flame-retardant and antibacterial reinforced type prepreg tape on the outer wall of the silicon core pipe body, and then hot pressing of the silicon core pipe material with the wound flame-retardant and antibacterial reinforced type prepreg tape, with a mold pressing force of 25-100 kg / m 2 , a temperature of 60-80 DEG C, and a hot pressing time of 15-30 s, to obtain a semi-finished silicon core pipe material;

[0023] Step four, UV curing treatment of the semi-finished silicon core pipe material after hot pressing, with a unit light energy of 50-100 mW / cm² and a cumulative light energy of 500-600 mJ / cm², to obtain a finished silicon core pipe material.

[0024] The preparation method in the application can realize batch production of high-performance silicon core pipe materials in an environmentally friendly manner, and ensure the quality and batch stability of the silicon core pipe materials.

[0025] Preferably, in the step two, preparation of the flame-retardant and antibacterial reinforced type prepreg tape, a UV adhesive is first prepared by uniformly mixing a metered amount of a six-functional polyurethane modified acrylate resin, a double-functional polyurethane modified acrylate resin, a UV active diluent, a photoinitiator, a leveling agent, a defoaming agent, and a wetting agent, and vacuum defoaming; then, 100 parts of the UV adhesive is mixed with 1-2 parts of methacryloxy silane, 0.5-2 parts of antibacterial nano filler, 3-6 parts of nano molybdenum disulfide, and 10-20 parts of flame-retardant filler composition to obtain a flame-retardant and antibacterial type prepreg resin after uniform mixing and vacuum defoaming; the flame-retardant and antibacterial type prepreg resin is then scraped onto a release paper and subjected to UV pre-curing treatment, with a unit light energy of 10-20 mW / cm² and a cumulative light energy of 150-200 mJ / cm², to obtain a flexible flame-retardant and antibacterial type prepreg sheet; finally, a reinforcing type mesh cloth is laid between two pieces of the flexible flame-retardant and antibacterial type prepreg sheet, and then subjected to hot pressing, cooling, and winding to obtain the flame-retardant and antibacterial reinforced type prepreg tape.

[0026] The preparation method of the flame-retardant and antibacterial reinforced type prepreg tape provided in the application is relatively simple and facilitates batch production, which can reduce the production cost of the flame-retardant and antibacterial reinforced type prepreg tape.

[0027] In summary, the application has the following advantages:

[0028] 1. The flame-retardant and antibacterial reinforcing layer formed on the outer wall of the silicon core pipe body by UV curing improves the flame retardance, antibacterial hygiene, and tensile resistance of the silicon core pipe as a whole.

[0029] 2、The production mode of the pre-impregnated tape-winding-UV curing can realize batch production, environmentally-friendly production and manufacturing of high-performance silicon core pipes, and guarantees the quality and batch quality stability of the silicon core pipes. DETAILED DESCRIPTION

[0030] In order to further understand the creativity and technical progress of the present application, the preferred embodiments of the present application are discussed in detail below in combination with examples and comparative examples.

[0031] Embodiment: A silicon core pipe includes a silicon core pipe body, which is a commercially available HDPE silicon core pipe. The present application is a post-treatment of the HDPE silicon core pipe to meet the market demand for flame-retardant, hygienic and high-strength HDPE silicon core pipes. To this end, the inventors form a flame-retardant and antibacterial reinforcing layer on the outer wall of the silicon core pipe body by winding a flame-retardant and antibacterial reinforcing type pre-impregnated tape, hot pressing and UV curing, thereby endowing the HDPE silicon core pipe with good flame-retardant performance, antibacterial and mildew-proof hygienic performance and high tensile strength performance.

[0032] The flame-retardant and antibacterial reinforcing type pre-impregnated tape includes a flame-retardant and antibacterial type pre-impregnated resin and a reinforcing type grid cloth. The ratio of the thickness of the silicon core pipe body to the thickness of the flame-retardant and antibacterial reinforcing layer is 100:(1-5). The mass ratio of the flame-retardant and antibacterial type pre-impregnated resin to the reinforcing type grid cloth in the flame-retardant and antibacterial reinforcing type pre-impregnated tape is (10-20):10.

[0033] According to the customer's demand for the tensile strength of the silicon core pipe, different thicknesses of the flame-retardant and antibacterial reinforcing type pre-impregnated tape can be selected for reinforcement. The higher the thickness of the flame-retardant and antibacterial reinforcing type pre-impregnated tape, the greater the increase in the flame-retardant and antibacterial performance and the mechanical properties of the silicon core pipe, but it will inevitably lead to an increase in the overall production cost and the overall weight of the silicon core pipe. Therefore, in industrial production, it is necessary to balance the thickness of the flame-retardant and antibacterial reinforcing type pre-impregnated tape and the silicon core pipe to endow them with good flame-retardant and antibacterial reinforcing performance while optimizing the production cost and the total weight. In addition, for the silicon core pipe with high demand for tensile strength, the HDPE silicon core pipe can be double-wrapped. Specifically, the first layer of flame-retardant and antibacterial reinforcing type pre-impregnated tape is wrapped in the S direction, and the second layer of flame-retardant and antibacterial reinforcing type pre-impregnated tape is wrapped in the Z direction. The HDPE silicon core pipe after wrapping is hot-pressed and completely cured by UV to obtain a finished silicon core pipe with high flame retardance and high tensile strength.

[0034] The reinforcing type grid cloth in the flame-retardant and antibacterial reinforcing type pre-impregnated tape mainly plays a role in reinforcement and flame breakthrough prevention, and can be selected from one of glass fiber grid cloth, aramid grid cloth, carbon fiber grid cloth and UHMWPE grid cloth. From the perspective of performance increase and lightweight, UHMWPE grid cloth is most suitable as a reinforcing type grid cloth. From the perspective of production cost, glass fiber grid cloth is most suitable as a reinforcing type grid cloth.

[0035] Preferably, the reinforcing mesh cloth is a glass fiber mesh cloth, the thickness of the glass fiber mesh cloth is 50-150 μm, and the grammage is 45-166 g / m 2 . Specifically, 1080 glass fiber cloth (thickness 53 μm, grammage 46.8 g / m 2 ), 2114 glass fiber cloth (thickness 84 μm, grammage 90.9 g / m 2 ), 1504 glass fiber cloth (thickness 125 μm, grammage 148 g / m 2 ) of Nan Asia Plastic are selected.

[0036] Taking the flame-retardant antibacterial reinforcing prepreg tape prepared from 1080 glass fiber cloth as an example, the overall thickness of the flame-retardant antibacterial reinforcing prepreg tape is 100 μm, the content of the flame-retardant antibacterial prepreg resin is 58.0%, the amount of 1080 glass fiber cloth is 46.8 g / m 2 , and the amount of flame-retardant antibacterial prepreg resin is 89.7 g / m 2 .

[0037] Taking the flame-retardant antibacterial reinforcing prepreg tape prepared from 2114 glass fiber cloth as an example, the overall thickness of the flame-retardant antibacterial reinforcing prepreg tape is 150 μm, the content of the flame-retardant antibacterial prepreg resin is 61.8%, the amount of 2114 glass fiber cloth is 90.9 g / m 2 , and the amount of flame-retardant antibacterial prepreg resin is 125.6 g / m 2 .

[0038] Taking the flame-retardant antibacterial reinforcing prepreg tape prepared from 1504 glass fiber cloth as an example, the overall thickness of the flame-retardant antibacterial reinforcing prepreg tape is 200 μm, the content of the flame-retardant antibacterial prepreg resin is 51.3%, the amount of 1504 glass fiber cloth is 148 g / m 2 , and the amount of flame-retardant antibacterial prepreg resin is 155.9 g / m 2 .

[0039] The formula of the flame-retardant antibacterial prepreg resin includes the following raw materials in parts by weight: 100 parts of UV glue, 1-2 parts of methacryloyloxysilane, 0.5-2 parts of antibacterial nano filler, 3-6 parts of nano molybdenum disulfide, and 10-20 parts of flame-retardant filler composition. The flame-retardant filler composition is composed of 4-8% of organically modified montmorillonite (BYK organic bentonite CLAYTONE 40, average particle size 10 μm), 36-42% of ammonium polyphosphate APP (Langbo Wan, APP1000, CAS: 68333-79-9), and 50-60% of melamine phosphate (Sunfeda, CAS: 15541-60-3, molecular formula: C3H 10 N6O7P2). The above flame-retardant filler composition can ensure excellent flame retardancy at a low addition amount.

[0040] Methacryloxy silane is γ-methacryloxy propyl trimethoxy silane KH-570 (CAS: 2530-85-0). Nano molybdenum disulfide is selected from the average particle size of 100 nm of flaky nano molybdenum disulfide of Tianan nano. Antibacterial nano filler is selected from the antibacterial formaldehyde removal additive of Lianke Huaxin Material Co., Ltd. of Guangxi.

[0041] The UV glue is made of the following raw materials by weight: 6-10 parts of hexafunctional polyurethane modified acrylate resin, 14-20 parts of bifunctional polyurethane modified acrylate resin, 50-70 parts of UV active diluent, 2-5 parts of photoinitiator, 0.25-0.50 parts of leveling agent, 0.25-0.50 parts of defoaming agent, 0.25-0.50 parts of wetting agent.

[0042] The photoinitiator is photoinitiator 184 (CAS: 947-19-3), photoinitiator TPO (CAS: 75980-60-8). The leveling agent is BYK-3500. The defoaming agent is BYK-1788. The wetting agent is EBECRYL 436.

[0043] The hexafunctional polyurethane modified acrylate resin is Songda SD7566.

[0044] The bifunctional polyurethane modified acrylate resin is Songda SD6238, SD7541.

[0045] Among them, the UV active diluent is trimethylolpropane triacrylate (CAS: 15625-89-5), methyl methacrylate tetrahydrofurfuryl (CAS: 2455-24-5), propoxylated neopentyl glycol diacrylate (CAS: 84170-74-1) with mass ratio (5-10):10:(10-25).

[0046] In order to improve the flame retardance of the UV glue, the bifunctional polyurethane modified acrylate resin contains 4-8wt% of phosphorus-containing polyol in the synthesis raw material, and the phosphorus-containing polyol is at least one of tri (one shrink di propylene glycol) phosphite (CAS: 36788-39-3, Kogyo Weston 430), phosphorus-containing polyol Exolit 550 (Germany Clariant), and phosphorus-containing polyol Exolit 560 (Germany Clariant).

[0047] Preparation Example 1: The flame-retardant modified polyurethane modified acrylate resin is mainly prepared from dicyclohexyl methane diisocyanate HMDI (CAS: 5124-30-1), BASF polytetrahydrofuran diol PoiyTHF 1000 with a molecular weight of 1000, phosphorus-containing polyol Exolit 550, 1,4-butanediol, and blocking agent hydroxyethyl methacrylate (CAS: 868-77-9). The content of phosphorus-containing polyol Exolit 550 in the flame-retardant modified polyurethane modified acrylate resin is 6.98%. The preparation method of the flame-retardant modified polyurethane modified acrylate resin is as follows:

[0048] Step one, 1800g of BASF polytetrahydrofuran diol PoiyTHF 1000 with a molecular weight of 1000, 204g of phosphorus-containing polyol Exolit 550 are vacuum dehydrated at 120°C for 2 hours to obtain a mixed polyol, which is ready for use;

[0049] Step two, place the dehydrated mixed polyol into a reaction kettle, and heat to 80°C under nitrogen protection. Add 787.1g of dicyclohexyl methane diisocyanate HMDI, 0.1g of dibutyltin dilaurate, and 600g of acetone into the reaction kettle. Heat to 90°C under a rotation speed of 200rpm, and maintain the temperature at 90°C until the -NCO content in the system reaches a stable value to obtain a HMDI blocked polyurethane prepolymer.

[0050] Step three, adjust the temperature in the reaction kettle to 70°C, and add 5g of hydroquinone, 8g of tetrabutyl titanate, and 78.2g of hydroxyethyl acrylate. Carry out esterification blocking reaction under nitrogen protection for 2h. After the NCO content is 0, remove the acetone by distillation under reduced pressure to obtain the flame-retardant modified polyurethane modified acrylate resin.

[0051] Preparation Example 2 is different from Preparation Example 1 in that the phosphorus-containing polyol Exolit 550 is replaced by an equimolar amount of tris(dipropylene glycol) phosphite, and the content of tris(dipropylene glycol) phosphite is 6.2%.

[0052] The content of phosphorus-containing polyol Exolit 550 in the flame-retardant modified polyurethane modified acrylate resin is 6.98%. The preparation method of the flame-retardant modified polyurethane modified acrylate resin is as follows:

[0053] Step one, 1800g of polytetrahydrofuran diol PoiyTHF 1000, and 172.2g of tris(dipropylene glycol) phosphite are vacuum dehydrated at 120°C for 2 hours to obtain a mixed polyol, which is ready for use;

[0054] Step two, the mixed polyol after dehydration was placed in the reaction kettle, and was heated to 80°C under nitrogen protection. 787.1 g of dicyclohexyl methane diisocyanate HMDI, 0.1 g of dibutyl tin dilaurate, 500 g of acetone were added into the reaction kettle, and was heated to 90°C under the rotation speed of 200 rpm. The temperature was maintained at 90°C until the -NCO content in the system reached a stable value, and a HMDI capped polyurethane prepolymer was obtained.

[0055] Step three, the temperature in the reaction kettle was adjusted to 70°C, 5 g of hydroquinone, 8 g of tetrabutyl titanate, and 78.2 g of hydroxyethyl acrylate were added, and the esterification capping reaction was carried out for 2 h under nitrogen protection. After the NCO content was 0, the acetone was removed by distillation under reduced pressure, and a flame-retardant modified polyurethane modified acrylate resin was obtained.

[0056] Example 1: A method for preparing a silicon core pipe, comprising the following steps:

[0057] Step one, the surface of the purchased silicon core pipe body (HDPE silicon core pipe specification: outer diameter 40 mm, inner diameter 33 mm) was cleaned: after washing with deionized water, it was wiped with ethanol, and the surface of the silicon core pipe body was cleaned in a dust-free environment and naturally dried.

[0058] Step two, preparation of flame-retardant antibacterial reinforced pre-impregnated tape:

[0059] S2.1, nitrogen was used to exhaust the air in the dispersion kettle, and then 80 g of six functional polyurethane modified acrylate resin-Songda SD7566, 60 g of double functional polyurethane modified acrylate resin-Songda SD6238, 120 g of double functional polyurethane modified acrylate resin-SD7541, 120 g of trimethylolpropane triacrylate, 250 g of methyltetrahydrofurfuryl methacrylate, 320 g of propoxylated neopentyl glycol diacrylate, 15 g of photoinitiator 184, 25 g of photoinitiator TPO, 3 g of leveling agent BYK-3500, 4 g of defoaming agent BYK-1788, and 3 g of wetting agent EBECRYL 436 were accurately measured and placed in the dispersion kettle. Mixed for 15 min at 4°C temperature and 400 rpm rotation speed under nitrogen protection, vacuum to 0.5 bar gauge pressure, vacuum defoaming for 5 min, vacuum to 0.8 bar gauge pressure, vacuum defoaming for 10 min, nitrogen was filled to restore normal pressure, and the material was discharged to obtain a UV glue. The obtained UV glue needs to be stored in a low temperature and light shielding environment;

[0060] S2.2, 10 g of KH-570, 40 g of flaky nanometer molybdenum disulfide with an average particle size of 100 nm, 10 g of Lifakewei-antibacterial formaldehyde removal additive, 9 g of organically modified montmorillonite (BYK organic bentonite CLAYTONE 40), 60 g of ammonium polyphosphate APP 1000, 81 g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture, another dispersion kettle is selected, the air in the dispersion kettle is exhausted by nitrogen, 1000 g of the UV glue in S2.1 is weighed and added to the dispersion kettle, then the prepared mixture is added to the dispersion kettle in four times at a speed of 400 rpm, the interval time of the mixture addition is 5 min, after the addition is completed, the mixing is continued at a speed of 400 rpm for 10 min, vacuum is applied to a gauge pressure of 0.5 bar, vacuum defoaming is performed for 5 min, vacuum is applied to a gauge pressure of 0.8 bar, vacuum defoaming is performed for 10 min, nitrogen is filled to restore normal pressure, and the material is discharged to obtain a flame-retardant antibacterial type prepreg resin;

[0061] S2.3, the flame-retardant antibacterial type prepreg resin prepared in S2.2 is coated on release paper and then subjected to UV pre-curing treatment, the coating amount is 89.7 g / 2m 2 , the unit light energy is 20 mW / cm², the cumulative light exposure time is 8 s, the cumulative light energy is 160 mJ / cm², a flexible flame-retardant antibacterial type prepreg sheet is obtained, and the flexible flame-retardant antibacterial type prepreg sheet is cut and rolled according to the use requirement, and the specific width thereof in this embodiment is 12.0 mm;

[0062] S2.4, 1080 glass fiber cloth is laid between two pieces of the flexible flame-retardant antibacterial type prepreg sheet, and then hot pressing is performed: the hot pressing roller distance is 0.10 mm, and the roller surface temperature is 80°C, cooling is performed after the hot pressing is completed: the cooling roller distance is 0.10 mm, and the roller surface temperature is 10°C, and the winding is completed to obtain a flame-retardant antibacterial reinforcing type prepreg tape;

[0063] Step three, the flame-retardant antibacterial reinforcing type prepreg tape is wound on the outer wall of the silicon core pipe material body in the S direction without seams, and then the silicon core pipe material with the flame-retardant antibacterial reinforcing type prepreg tape wound thereon is subjected to hot pressing, the die inner diameter is 40.2 mm, the die pressure is 65 kg / m 2 , the temperature is 75°C, and the hot pressing time is 20 s, and a semi-finished silicon core pipe material is obtained;

[0064] Step four, the semi-finished silicon core pipe material is subjected to UV curing treatment, the unit light energy is 80 mW / cm², the cumulative light exposure time is 7 s, and the cumulative light energy is 560 mJ / cm², and a finished silicon core pipe material is obtained.

[0065] The difference between Example 2 and Example 1 is that S2.3, the flame-retardant antibacterial type prepreg resin prepared in S2.2 is coated on release paper and then subjected to UV pre-curing treatment, the coating amount is 125.6 g / 2m2 S2.3, the flexible flame-retardant and antibacterial type prepreg sheet with a width of 12.0 mm was obtained by cutting and rolling after the flame-retardant and antibacterial type prepreg resin prepared in S2.2 was coated on the release paper and then UV pre-cured; S2.4, 1504 glass fiber cloth was laid between two pieces of the flexible flame-retardant and antibacterial type prepreg sheet, and then hot pressing was performed: hot roller distance 0.20 mm, roller surface temperature 80°C, after hot pressing, cooling was performed: cooling roller distance 0.20 mm, roller surface temperature 10°C, and the flame-retardant and antibacterial reinforced prepreg tape was obtained by winding; the remaining steps were the same.

[0066] Example 3 differs from Example 1 in that: S2.3, the flame-retardant and antibacterial type prepreg resin prepared in S2.2 was coated on the release paper and then UV pre-cured, the coating amount was 155.9 g / 2m 2 S2.3, the flexible flame-retardant and antibacterial type prepreg sheet with a width of 12.0 mm was obtained by cutting and rolling after the flame-retardant and antibacterial type prepreg resin prepared in S2.2 was coated on the release paper and then UV pre-cured; S2.4, 1504 glass fiber cloth was laid between two pieces of the flexible flame-retardant and antibacterial type prepreg sheet, and then hot pressing was performed: hot roller distance 0.20 mm, roller surface temperature 80°C, after hot pressing, cooling was performed: cooling roller distance 0.20 mm, roller surface temperature 10°C, and the flame-retardant and antibacterial reinforced prepreg tape was obtained by winding; the remaining steps were the same.

[0067] Example 4 differs from Example 1 in that: in step three, the flame-retardant and antibacterial reinforced prepreg tape was wound in the S direction on the outer wall of the silicon core pipe material body, and another flame-retardant and antibacterial reinforced prepreg tape was wound in the Z direction on the outer wall of the silicon core pipe material body, and then the flame-retardant and antibacterial reinforced prepreg tape wound silicon core pipe material was hot pressed, the die diameter was 40.4 mm, the mold pressure was 80 kg / m 2 , the temperature was 75°C, the hot pressing time was 25 s, and the semi-finished silicon core pipe material was obtained; the remaining steps were the same.

[0068] Example 5 differs from Example 1 in that: S2.1, the dispersion kettle is exhausted of air using nitrogen, then an accurately measured 80 g of hexafunctional polyurethane-modified acrylate resin-Songda SD7566, 60 g of difunctional polyurethane-modified acrylate resin-Songda SD6238, 120 g of flame-retardant modified polyurethane-modified acrylate resin in Preparation Example 1, 120 g of trimethylolpropane triacrylate, 250 g of tetrahydrofurfuryl methacrylate, 320 g of propoxylated neopentyl glycol diacrylate, 15 g of photoinitiator 184, 25 g of photoinitiator TPO, 3 g of leveling agent BYK-3500, 4 g of defoaming agent BYK-1788, 3 g of wetting agent EBECRYL 436 are placed in the dispersion kettle, mixed at a speed of 400 rpm for 15 min under nitrogen protection and a temperature of 4°C, vacuumed to a gauge pressure of 0.5 bar, vacuum defoaming for 5 min, vacuumed to a gauge pressure of 0.8 bar, vacuum defoaming for 10 min, nitrogen was filled to restore normal pressure, and the UV glue was obtained after discharging. The obtained UV glue needs to be stored in a low temperature and light shielding environment; S2.2, 10 g of KH-570, 40 g of sheet-shaped nano-molybdenum disulfide with an average particle size of 100 nm, 10 g of Likewei-antibacterial formaldehyde removal additive, 5.4 g of organically modified montmorillonite (BYK organically modified bentonite CLAYTONE 40), 36 g of ammonium polyphosphate APP 1000, and 48.6 g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture. Another dispersion kettle is selected, the air in the dispersion kettle is exhausted using nitrogen, 1000 g of the UV glue in S2.1 is weighed and added to the dispersion kettle, then the prepared mixture is added to the dispersion kettle in four times at a speed of 400 rpm, the interval time between the addition of the mixture is 5 min, after the addition is completed, the mixture is continuously mixed at a speed of 400 rpm for 10 min, vacuumed to a gauge pressure of 0.5 bar, vacuum defoaming for 5 min, vacuumed to a gauge pressure of 0.8 bar, vacuum defoaming for 10 min, nitrogen was filled to restore normal pressure, and the flame-retardant and antibacterial type prepreg was obtained after discharging; S2.3, the flame-retardant and antibacterial type prepreg prepared in S2.2 is scraped onto release paper and subjected to UV pre-curing treatment, the coating amount is 88.4 g / 2m 2 , the unit light energy is 20 mW / cm², the cumulative light exposure time is 8 s, the cumulative light exposure energy is 160 mJ / cm², and the width of the flexible flame-retardant and antibacterial type prepreg sheet is 12.0 mm after cutting and rolling. The remaining steps are the same.

[0069] Example 6 differs from Example 1 in that: S2.1, the dispersion kettle is exhausted of air using nitrogen, then an accurately measured 80 g of hexafunctional polyurethane-modified acrylate resin-Songda SD7566, 60 g of difunctional polyurethane-modified acrylate resin-Songda SD6238, 120 g of flame-retardant modified polyurethane-modified acrylate resin in Preparation Example 2, 120 g of trimethylolpropane triacrylate, 250 g of tetrahydrofurfuryl methacrylate, 320 g of propoxylated neopentyl glycol diacrylate, 15 g of photoinitiator 184, 25 g of photoinitiator TPO, 3 g of leveling agent BYK-3500, 4 g of defoaming agent BYK-1788, 3 g of wetting agent EBECRYL 436 are placed in the dispersion kettle, mixed at a speed of 400 rpm for 15 min under nitrogen protection and a temperature of 4°C, vacuumed to a gauge pressure of 0.5 bar, vacuum defoaming for 5 min, vacuumed to a gauge pressure of 0.8 bar, vacuum defoaming for 10 min, nitrogen was filled to restore normal pressure, and the UV glue was obtained after discharging. The obtained UV glue needs to be stored in a low temperature and light shielding environment; S2.2, 10 g of KH-570, 40 g of sheet-shaped nano-molybdenum disulfide with an average particle size of 100 nm, 10 g of Likewei-antibacterial formaldehyde removal additive, 6.3 g of organically modified montmorillonite (BYK organically modified bentonite CLAYTONE 40), 42 g of ammonium polyphosphate APP 1000, and 56.7 g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture. Another dispersion kettle is selected, the air in the dispersion kettle is exhausted using nitrogen, 1000 g of the UV glue in S2.1 is weighed and added to the dispersion kettle, then the prepared mixture is added to the dispersion kettle in four times at a speed of 400 rpm, the interval time between the addition of the mixture is 5 min, after the addition is completed, the mixture is continuously mixed at a speed of 400 rpm for 10 min, vacuumed to a gauge pressure of 0.5 bar, vacuum defoaming for 5 min, vacuumed to a gauge pressure of 0.8 bar, vacuum defoaming for 10 min, nitrogen was filled to restore normal pressure, and the flame-retardant and antibacterial type prepreg was obtained after discharging; S2.3, the flame-retardant and antibacterial type prepreg prepared in S2.2 is scraped onto release paper and subjected to UV pre-curing treatment, the coating amount is 88.9 g / 2m 2 , the unit light energy is 20 mW / cm², the cumulative light exposure time is 8 s, the cumulative light exposure energy is 160 mJ / cm², the width of the flexible flame-retardant and antibacterial type prepreg sheet is 12.0 mm after cutting and rolling; the remaining steps are the same.

[0070] The difference between Comparative Example 1 and Example 1 is that S2.1, the dispersion kettle is exhausted of air using nitrogen, then 80g of a hexafunctional polyurethane-modified acrylic ester resin-Songda SD7566, 60g of a difunctional polyurethane-modified acrylic ester resin-Songda SD6238, 120g of a difunctional polyurethane-modified acrylic ester resin-SD7541, 120g of trimethylolpropane triacrylate, 250g of tetrahydrofurfuryl methacrylate, 320g of propoxylated neopentyl glycol diacrylate, 15g of a photoinitiator 184, 25g of a photoinitiator TPO, 3g of a leveling agent BYK-3500, 4g of a defoaming agent BYK-1788, and 3g of a wetting agent EBECRYL 436 are weighed into the dispersion kettle, mixed at 4°C and 400rpm for 15min under nitrogen protection, vacuumed to 0.5bar gauge pressure, vacuum defoamed for 5min, vacuumed to 0.8bar gauge pressure, vacuum defoamed for 10min, nitrogen was filled to restore normal pressure, and the UV glue was obtained, which was stored in a low-temperature light-shielded environment; S2.2, 10g of KH-570, 40g of flaky nanometer molybdenum disulfide with an average particle size of 100nm, 10g of Lifeway-antibacterial formaldehyde removal additive, 9g of organically modified montmorillonite (BYK organobentonite CLAYTONE 40), 60g of ammonium polyphosphate APP 1000, and 81g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30min to obtain a mixture, another dispersion kettle is selected, the dispersion kettle is exhausted of air using nitrogen, 1000g of the UV glue in S2.1 is weighed into the dispersion kettle, and then the prepared mixture is added to the dispersion kettle in four portions at a speed of 400rpm, the interval time between the addition of the mixture is 5min, after the addition is completed, the mixture is continuously mixed at a speed of 400rpm for 10min, vacuumed to 0.5bar gauge pressure, vacuum defoamed for 5min, vacuumed to 0.8bar gauge pressure, vacuum defoamed for 10min, nitrogen was filled to restore normal pressure, and the flame-retardant antibacterial type pre-impregnated resin was obtained;

[0071] S2.3, the flame-retardant antibacterial type pre-impregnated resin prepared in S2.2 is coated on release paper and then subjected to UV pre-curing treatment, the coating amount is 55g / m 2 , the unit light energy is 20mW / cm², the cumulative light exposure time is 8s, the cumulative light energy is 160mJ / cm², and the width of the flexible flame-retardant antibacterial type pre-impregnated sheet material is 12mm after cutting and rolling;

[0072] S2.4, two pieces of the flexible flame-retardant antibacterial type pre-impregnated sheet material are laminated and then subjected to hot pressing: the hot pressing roller distance is 0.10mm, and the roller surface temperature is 80°C, cooling is performed after the hot pressing is completed: the cooling roller distance is 0.10mm, and the roller surface temperature is 10°C, and the flame-retardant antibacterial type pre-impregnated tape is obtained after rolling up;

[0073] Step three, the flame-retardant antibacterial type prepreg is seamlessly wound on the outer wall of the silicone core pipe body in the S direction, and then the silicone core pipe wound with the flame-retardant antibacterial type prepreg is hot-pressed, the die inner diameter is 40.2 mm, the die pressure is 65 kg / m 2 , the temperature is 75℃, the hot-pressing time is 20 s, and a semi-finished silicone core pipe is obtained;

[0074] Step four, the semi-finished silicone core pipe is subjected to UV curing treatment, the unit light energy is 80 mW / cm², the cumulative light time is 7 s, and the cumulative light energy is 560 mJ / cm², and a finished silicone core pipe is obtained.

[0075] The difference between the comparative example 2 and the comparative example 1 is that: in step three, the flame-retardant antibacterial type prepreg is seamlessly wound on the outer wall of the silicone core pipe body in the S direction, and another flame-retardant antibacterial reinforcing type prepreg is seamlessly wound on the outer wall of the silicone core pipe body in the Z direction, and then the silicone core pipe wound with the flame-retardant antibacterial reinforcing type prepreg is hot-pressed, the die inner diameter is 40.4 mm, the die pressure is 80 kg / m 2 , the temperature is 75℃, the hot-pressing time is 25 s, and a semi-finished silicone core pipe is obtained; the remaining steps are the same.

[0076] The difference between the comparative example 3 and the example 1 is that: 10 g of KH-570, 40 g of flaky nano-molybdenum disulfide with an average particle size of 100 nm, 10 g of Likewei-antibacterial formaldehyde removal additive, 5.4 g of organically modified montmorillonite (BYK organic bentonite CLAYTONE 40), 36 g of ammonium polyphosphate APP 1000, and 48.6 g of melamine phosphate are added into a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture, another dispersion kettle is selected, the air in the dispersion kettle is exhausted by nitrogen, 1000 g of the UV glue in S2.1 is weighed and added into the dispersion kettle, then the prepared mixture is added into the dispersion kettle in four times at a speed of 400 rpm, the interval time of the mixture addition is 5 min, after the addition is completed, the mixing is continued at a speed of 400 rpm for 10 min, the vacuum is extracted to a table pressure of 0.5 bar, the vacuum defoaming is performed for 5 min, the vacuum is extracted to a table pressure of 0.8 bar, the vacuum defoaming is performed for 10 min, the nitrogen is filled to restore the normal pressure, and the discharge is obtained to obtain the flame-retardant antibacterial type prepreg; S2.3, the flame-retardant antibacterial type prepreg prepared in S2.2 is scraped on release paper and subjected to UV pre-curing treatment, the coating amount is 88.4 g / 2 m 2 , the unit light energy is 20 mW / cm², the cumulative light time is 8 s, the cumulative light energy is 160 mJ / cm², the cutting and rolling are performed to obtain a flexible flame-retardant antibacterial type prepreg sheet with a width of 12.0 mm; the remaining steps are the same.

[0077] The difference between Comparative Example 4 and Example 1 is that: S2.2, 10 g of KH-570, 40 g of flaky nanometer molybdenum disulfide with an average particle size of 100 nm, 10 g of cuprous oxide (Kai Cheng, CAS: 1317-39-1), 9 g of organically modified montmorillonite (BYK organic bentonite CLAYTONE 40), 60 g of ammonium polyphosphate APP 1000, 81 g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture, another dispersion kettle is selected, the air in the dispersion kettle is exhausted by nitrogen, 1000 g of the UV glue in S2.1 is weighed and added to the dispersion kettle, then the prepared mixture is added to the dispersion kettle in four times at a speed of 400 rpm, the interval time of adding the mixture is 5 min, after the addition is completed, continue to mix at a speed of 400 rpm for 10 min, vacuum to 0.5 bar, vacuum defoaming for 5 min, vacuum to 0.8 bar, vacuum defoaming for 10 min, fill nitrogen to restore normal pressure, and the material can be discharged to obtain a flame-retardant antibacterial type pre-impregnated resin; the rest of the steps are the same.

[0078] The difference between Comparative Example 5 and Example 1 is that: S2.2, 10 g of KH-570, 40 g of flaky nanometer molybdenum disulfide with an average particle size of 100 nm, 9 g of organically modified montmorillonite (BYK organic bentonite CLAYTONE 40), 60 g of ammonium polyphosphate APP 1000, 81 g of melamine phosphate are added to a 5L laboratory stainless steel vacuum kneader for kneading treatment for 30 min to obtain a mixture, another dispersion kettle is selected, the air in the dispersion kettle is exhausted by nitrogen, 1000 g of the UV glue in S2.1 is weighed and added to the dispersion kettle, then the prepared mixture is added to the dispersion kettle in four times at a speed of 400 rpm, the interval time of adding the mixture is 5 min, after the addition is completed, continue to mix at a speed of 400 rpm for 10 min, vacuum to 0.5 bar, vacuum defoaming for 5 min, vacuum to 0.8 bar, vacuum defoaming for 10 min, fill nitrogen to restore normal pressure, and the material can be discharged to obtain a flame-retardant antibacterial type pre-impregnated resin; the rest of the steps are the same.

[0079] Performance test: The tensile strength, ring stiffness, and heat stress cracking resistance performance detection are carried out according to JTT 496-2018 “High-density polyethylene silicon core plastic pipe for highway underground communication pipeline”. The flame-retardant performance of the flame-retardant antibacterial reinforcing layer formed on the outer wall of the silicon core pipe is detected according to the vertical combustion test UL 94.

[0080] Table 1: Test parameter table of silicon core pipe in Examples 1-6 and Comparative Examples 1-3

[0081]

[0082] It can be seen from the combination of Example 1 and Comparative Example 1 and Table 1 that the reinforced mesh can improve the overall tensile strength, heat stress cracking resistance and ring stiffness of the silicon core pipe. It can be seen from the combination of Example 1, Example 4 and Comparative Examples 1-2 and Table 1 that the flame-retardant and antibacterial reinforcing layer formed by the double-layer flame-retardant and antibacterial reinforcing tape can more obviously improve the overall tensile strength, heat stress cracking resistance and ring stiffness of the silicon core pipe.

[0083] It can be seen from the combination of Example 5 and Comparative Example 3 and Table 1 that when the content of the flame-retardant filler composition is low, the flame-retardant and antibacterial reinforcing layer cannot achieve excellent fire-retardant effect. Therefore, the amount of the flame-retardant filler composition added in 100 parts of the UV glue matrix is preferably controlled to be 10-20 parts.

[0084] It can be seen from the combination of Examples 5-6 and Comparative Example 3 and Table 1 that the flame-retardant modified polyurethane modified acrylate resin in Preparation Example 1 can reduce the content of the flame-retardant filler composition under the premise of ensuring the flame-retardant performance, optimize the use cost of the flame-retardant filler and improve the overall bending toughness.

[0085] Table 2: Test antibacterial and mildew-resistant parameters of the silicon core pipe in Examples 1, 5-6 and Comparative Examples 3-5

[0086]

[0087] Note: The antibacterial performance is tested according to GB / T 31402-2023 “Determination of antibacterial activity on the surface of plastics and other non-porous materials”, and the antibacterial activity value = - , the number of bacteria on the surface of the material before treatment is N1, and the number of bacteria after treatment is N2, and the bacterial concentrations are Staphylococcus aureus ATCC 6538: 2.0 10 5 CFU / mL; Escherichia coli 8099: 2.0 10 5 CFU / mL.

[0088] The mildew resistance is tested according to GB / T 24128-2018 “Plastics Evaluation of Mildew Resistance of Mildew Resistance Agents for Plastics”, and the test strain is Aspergillus niger CICC 2487.

[0089] In summary, the flame-retardant and antibacterial reinforcing layer formed by the UV curing on the outer wall of the silicon core pipe body improves the overall flame retardance, antibacterial hygiene and tensile resistance, and the preparation method of the pre-impregnated tape-winding-UV curing has good environmental protection, high curing efficiency and is convenient for batch manufacturing.

[0090] It should be noted that the specific embodiments are only to explain and describe the technical solutions of the present application, and are not to limit the present application, and the person skilled in the art can make modifications to the embodiments without creative contribution according to the needs after reading the specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A silicon core tube, characterized in that: The device includes a silicon core tube body, the outer wall of which is formed with a flame-retardant and antibacterial reinforcing layer; the flame-retardant and antibacterial reinforcing layer is made of a flame-retardant and antibacterial reinforcing prepreg tape; the flame-retardant and antibacterial reinforcing prepreg tape includes a flame-retardant and antibacterial prepreg resin and a reinforcing mesh fabric; the thickness ratio of the silicon core tube body to the thickness of the flame-retardant and antibacterial reinforcing layer is 100:1 to 100:5; the mass ratio of the flame-retardant and antibacterial prepreg resin to the reinforcing mesh fabric in the flame-retardant and antibacterial reinforcing prepreg tape is 10:10 to 25:10; the flame-retardant and antibacterial prepreg resin is made from the following raw materials in parts by weight: 100 parts UV adhesive, 1-2 parts methacryloxysilane, 0.5-2 parts antibacterial nanofiller, 3 -6 parts of nano-molybdenum disulfide and 10-20 parts of flame-retardant filler composition; the UV adhesive is made from the following raw materials in parts by weight: 6-10 parts of hexafunctional polyurethane modified acrylate resin, 14-20 parts of difunctional polyurethane modified acrylate resin, 50-70 parts of UV reactive diluent, 2-5 parts of photoinitiator, 0.25-0.50 parts of leveling agent, 0.25-0.50 parts of defoamer, and 0.25-0.50 parts of wetting agent; the UV reactive diluent is composed of trimethylolpropane triacrylate, tetrahydrofuran methacrylate, and propoxylated neopentyl glycol diacrylate in a mass ratio of 5:10:10 to 10:10:

25.

2. The silicon core tube according to claim 1, characterized in that: The reinforcing mesh fabric is one of the following: fiberglass mesh fabric, aramid mesh fabric, carbon fiber mesh fabric, and UHMWPE mesh fabric.

3. The silicon core tube according to claim 1, characterized in that: The reinforcing mesh is a fiberglass mesh with a thickness of 50-150 μm and a basis weight of 45-166 g / m². 2 .

4. A silicon core tube according to claim 1, characterized in that: The flame-retardant filler composition consists of 4-8% organic modified montmorillonite, 36-42% ammonium polyphosphate, and 50-60% melamine phosphate.

5. A silicon core tube according to claim 1, characterized in that: The raw materials for synthesizing the difunctional polyurethane modified acrylate resin contain 4-8 wt% of phosphorus-containing polyol, which is tris(dipropylene glycol) phosphite.

6. A method for preparing a silicon core tube according to any one of claims 1-5, characterized in that: Includes the following steps: Step 1: Clean the surface of the silicon core tube body; Step 2: Preparation of flame-retardant and antibacterial reinforced prepreg tape; Step 3: Seamlessly wrap the flame-retardant and antibacterial reinforcing prepreg tape around the outer wall of the silicon core tube body. Then, hot-press the silicon core tube wrapped with the flame-retardant and antibacterial reinforcing prepreg tape, molding at 25-100 kg / m. 2 At a temperature of 60-80℃, the hot pressing time is 15-30s to obtain semi-finished silicon core tubes; Step four: Perform UV curing treatment on the semi-finished silicon core tube after hot pressing. The unit light energy is 50-100mW / cm², and the cumulative light energy is 500-600mJ / cm², to obtain the finished silicon core tube.

7. The method for preparing a silicon core tube according to claim 6, characterized in that: Step two, preparation of the flame-retardant and antibacterial reinforced prepreg: First, accurately measured hexafunctional polyurethane-modified acrylate resin, difunctional polyurethane-modified acrylate resin, UV reactive diluent, photoinitiator, leveling agent, defoamer, and wetting agent are mixed evenly and then vacuum defoamed to obtain UV adhesive; then, 100 parts of UV adhesive are weighed and mixed with 1-2 parts of methacryloxysilane, 0.5-2 parts of antibacterial nanofiller, 3-6 parts of nano molybdenum disulfide, and 10-20 parts of flame-retardant and antibacterial reinforced prepreg. The flame-retardant and antibacterial prepreg resin is obtained by uniformly mixing the flame-retardant and filler composition and vacuum defoaming. The flame-retardant and antibacterial prepreg resin is then coated onto release paper and subjected to UV pre-curing treatment with a unit light energy of 10-20 mW / cm² and a cumulative light energy of 150-200 mJ / cm², resulting in a flexible flame-retardant and antibacterial prepreg sheet. Finally, a reinforcing mesh is laid between two flexible flame-retardant and antibacterial prepreg sheets, followed by hot pressing, cooling, and winding to obtain a flame-retardant and antibacterial reinforced prepreg tape.

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