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CN-121991325-A - Flame-retardant water-repellent poly (epsilon-caprolactone) and preparation method and application thereof

CN121991325ACN 121991325 ACN121991325 ACN 121991325ACN-121991325-A

Abstract

The invention provides a flame-retardant water-repellent poly (epsilon-caprolactone) and a preparation method and application thereof. The structural formula of the flame-retardant water-repellent poly (epsilon-caprolactone) is shown as formula I: A formula I; wherein, R 1 is selected from any one of-Ph, -OC 2 H 5 、-O-C 3 H 6 ; R 2 is selected from any one of-O-Ph and-OC 2 H 5 、-O-C 3 H 6 , R F is selected from any one of- (CF 2 ) 7 CH 3 、-CF 2 -SiMe 3 、-C 2 F 5 ), and x and y are polymerization degrees, the flame-retardant-water-repellent poly (epsilon-caprolactone) provided by the invention has the advantages of realizing flame retardant and water-repellent functions by introducing a flame retardant network and water-repellent groups and modifying a molecular structure, improving flame retardant and water-repellent performance, improving LOI (loss of oxygen) more than or equal to 32%, enabling a water contact angle to be more than 150 degrees, and being good in toughness, and capable of rapidly and effectively finishing fabrics.

Inventors

  • WANG ZHUJUN
  • WANG GANG
  • CAI YI

Assignees

  • 玮博杰生物材料(浙江)有限公司

Dates

Publication Date
20260508
Application Date
20260204

Claims (10)

  1. 1. A flame-retardant and water-repellent poly (epsilon-caprolactone) is characterized in that the structural formula of the poly (epsilon-caprolactone) is shown as a formula I: A formula I; Wherein, R 1 is selected from any one of-Ph and-OC 2 H 5 、-O-C 3 H 6 ; r 2 is selected from any one of-O-Ph and-OC 2 H 5 、-O-C 3 H 6 ; r F is selected from any one of- (CF 2 ) 7 CH 3 、-CF 2 -SiMe 3 、-C 2 F 5 ); And x and y are the polymerization degree.
  2. 2. A method for preparing the flame retardant-water repellent poly (epsilon-caprolactone) according to claim 1, which is characterized by comprising the following steps: s1, mixing caprolactone, dienyl valerolactone and stannous octoate, and performing a first reaction in a nitrogen atmosphere to obtain high-activity polycaprolactone; s2, carrying out reflux reaction on the high-activity polycaprolactone, the organic phosphorus compound and the triethylamine in a dichloromethane solution to obtain flame-retardant polycaprolactone; And S3, adding the flame-retardant polycaprolactone and fluorine-containing bromoalkyl into a mixed solution containing methanol, chlorine (pyridine) bis (dimethylglyoxime) -cobalt and zinc powder under the atmosphere of nitrogen to perform a second reaction, so as to obtain the flame-retardant water-repellent poly (epsilon-caprolactone).
  3. 3. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S1, the molar ratio of caprolactone, dienyl valerolactone and stannous octoate is 200:10-30:1.
  4. 4. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S1, the parameters of the first reaction are that nitrogen is filled and vacuumized alternately, and then the temperature is raised to 80-90 ℃ to react at the rotating speed of 150-200 r/min for 10-12 h.
  5. 5. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S2, the molar ratio of the organic phosphorus compound to the triethylamine to the caprolactone is 11-33:11-33:200; the organic phosphide is at least one selected from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethyl phosphite, diphenyl phosphite and diisopropyl phosphite.
  6. 6. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S2, the temperature of the reflux reaction is 50-70 ℃ and the time is 1-2 h.
  7. 7. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S3, the molar ratio of the volume of methanol to the molar ratio of the chloro (pyridine) bis (dimethylglyoxime) -cobalt to the zinc powder is 10 mL:0.1-0.2 mmol and 10-20 mmol; the molar ratio of the mass of the flame-retardant polycaprolactone to the fluorine-containing bromoalkyl is 10 g:5-15 mmol.
  8. 8. The method for preparing flame retardant-water repellent poly (epsilon-caprolactone) according to claim 2, wherein in step S3, the fluorine-containing bromoalkyl group is at least one selected from perfluorobromooctane, difluoromethyl trimethylsilane, 1-bromoperfluorohexane and perfluorobromoethane.
  9. 9. The method for preparing the flame-retardant and water-repellent poly (epsilon-caprolactone) according to claim 2, wherein in the step S3, the second reaction time is 4-8 hours.
  10. 10. The flame-retardant water-repellent PCL emulsion is characterized by comprising, by mass, 25-35% of polycaprolactone, 1-2% of sodium dodecyl benzene sulfonate and 63-74% of deionized water; Wherein the polycaprolactone is selected from the group consisting of the flame retardant-water repellent poly (epsilon-caprolactone) of claim 1 or the flame retardant-water repellent poly (epsilon-caprolactone) obtained according to the preparation method of any one of claims 2 to 9.

Description

Flame-retardant water-repellent poly (epsilon-caprolactone) and preparation method and application thereof Technical Field The invention relates to the technical field of functional polymer materials, in particular to a flame-retardant water-repellent poly (epsilon-caprolactone) and a preparation method and application thereof. Background With the rapid development of industries such as aerospace, national defense and military industry, new energy automobiles, high-end clothing and the like, nylon fibers become an indispensable basic material in key fields by virtue of the high strength, wear resistance and light weight characteristics. The statistics show that the global chinlon fiber market of 2023 breaks through 1200 hundred million yuan, and the high-end application field accounts for more than 45 percent. However, nylon fiber has a Limiting Oxygen Index (LOI) of only 18% -20%, belongs to inflammable materials, has a combustion heat value as high as 35-40 MJ/kg, releases a large amount of toxic gases such as CO, HCN and the like (the concentration can reach more than 5000 ppm) during combustion, and is accompanied by a severe dripping phenomenon (the dripping temperature exceeds 240 ℃). The molten drop can cause secondary combustion and also cause skin deep burn, and in the fire accident caused by the textile in 2022 according to the fire statistics of the emergency management department, the casualties caused by the molten drop reach 37 percent, and the direct economic loss exceeds 28 hundred million yuan. Therefore, development of high-efficiency flame-retardant nylon-based textiles has become a significant need in the public safety field. Meanwhile, special scenes such as tents, firefighters, new energy automobile interiors and the like provide double functional requirements of flame retardance and water repellency for textiles. For example, fire-fighting clothes are required to have water repellency (water contact angle >130 DEG) while being flame-retardant (LOI is more than or equal to 35%), so as to prevent permeation of high-temperature steam, and new energy automobile interior materials are required to meet UL 94V-0 flame-retardant standards and resist rain and snow erosion. However, the traditional flame-retardant finishing technology (such as halogen flame retardant) has the defects of poor environmental protection, low washability (the flame retardance is reduced by more than 60% after 5 times of washing) and the like, and the fluorine-containing compound (PFAS) commonly used in water-repellent finishing is listed in a persistent organic pollutant list by the Stockholm convention due to bioaccumulation. Therefore, development of an environment-friendly multifunctional coating technology becomes a bottleneck to be broken through in the industry. In the field of coating materials, poly (epsilon-caprolactone) (PCL) has the remarkable advantages that the coating can still keep elasticity in an environment of 40 ℃ below zero due to the unique molecular structure (Tg is approximately equal to-60 ℃) and the impact resistance is improved by 40% compared with the traditional polyurethane coating, and meanwhile, the semi-crystalline property of PCL endows the fabric with good air permeability (the water vapor permeability reaches 5000 g/m2.24h) and wrinkle resistance (the wrinkle recovery angle is more than 280 ℃). However, unmodified PCL has two major fatal defects, namely, the limiting oxygen index is only 17%, the peak value of heat release rate (PHRR) during combustion is as high as 320 kW/m <2 >, and the ester group in the polyester main chain is easy to form a hydrogen bond with water molecules, so that the water absorption rate of the coating reaches 8% -10%, and the application of the coating in a humid environment is severely restricted. Although the prior art attempts to improve the performance by blending an inorganic flame retardant (such as aluminum hydroxide) or introducing a fluorinated hydrophobic chain segment, the problems that the flame retardant is easy to separate out, the durability of a hydrophobic layer is poor (the contact angle is reduced by 40% after 3 times of friction) and the like exist, and the requirement of the high-end field on long-acting flame retardance-lasting water repellency cannot be met. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a flame-retardant water-repellent poly (epsilon-caprolactone), and a preparation method and application thereof, and solves the problems in the prior art. In order to achieve the above purpose, the invention is realized by the following technical scheme: According to a first aspect of the present invention there is provided a flame retardant-water repellent poly (epsilon-caprolactone) of the formula I: A formula I; Wherein, R 1 is selected from any one of-Ph and-OC 2H5、-O-C3H6; r 2 is selected from any one of-O-Ph and-OC 2H5、-O-C3H6; r F is selected from any one of- (CF 2)7CH3、-CF2-SiMe3、-C2F