CN121136412A - A composite tube material for high-pressure air ribs and its preparation method - Google Patents
A composite tube material for high-pressure air ribs and its preparation methodInfo
- Publication number
- CN121136412A CN121136412A CN202511690634.9A CN202511690634A CN121136412A CN 121136412 A CN121136412 A CN 121136412A CN 202511690634 A CN202511690634 A CN 202511690634A CN 121136412 A CN121136412 A CN 121136412A
- Authority
- CN
- China
- Prior art keywords
- parts
- composite
- tube material
- pressure air
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及高分子化合物的组合物技术领域，具体公开了一种用于高压气肋的复合织管材料及其制备方法。所述复合织管材料按重量份计包括：脂环族异氰酸酯改性热塑性聚氨酯弹性体70‑85份、改性增强纤维18‑25份、界面相容剂4‑6份、复合抗老化体系2‑4份、纳米增强剂1‑3份、复合阻燃体系5‑15份、加工助剂1‑2份、溶剂10‑45份。所述制备方法包括纳米浆料预处理、纤维改性处理、原料预混、熔融共混造粒。本发明的复合织管材料兼具高力学强度、优异抗老化性能、环保高效阻燃及良好界面结合力，可满足高压气肋的使用要求，制备工艺简单可控，适合工业化生产。This invention relates to the field of polymer compound composition technology, specifically disclosing a composite tube material for high-pressure air ribs and its preparation method. The composite tube material comprises, by weight, 70-85 parts of alicyclic isocyanate-modified thermoplastic polyurethane elastomer, 18-25 parts of modified reinforcing fiber, 4-6 parts of interface compatibilizer, 2-4 parts of composite anti-aging system, 1-3 parts of nano-reinforcing agent, 5-15 parts of composite flame retardant system, 1-2 parts of processing aid, and 10-45 parts of solvent. The preparation method includes nano-slurry pretreatment, fiber modification treatment, raw material premixing, and melt blending granulation. The composite tube material of this invention possesses high mechanical strength, excellent anti-aging properties, environmentally friendly and efficient flame retardancy, and good interfacial bonding strength, meeting the requirements for high-pressure air ribs. The preparation process is simple and controllable, suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of compositions of high molecular compounds, in particular to a composite woven tube material for high-pressure air ribs and a preparation method thereof.
Background
The high-pressure air rib is used as a key inflatable load-carrying structure, and the application field of the high-pressure air rib is expanding from the fields of traditional military industry, aerospace, civil emergency, outdoor leisure and the like. This places more comprehensive demands on the fabric materials constituting the core thereof, not only that excellent mechanical properties and air tightness are required, but also that excellent weather resistance (particularly, resistance to ultraviolet yellowing), higher flame-retardant safety levels, and more stable long-term use properties have become indispensable characteristics for the new generation of products.
In the prior art, the conventional aromatic TPU is mostly adopted as a matrix, the appearance and long-term performance of the product are influenced by the characteristic of easy ultraviolet yellowing, the dispersion of the nano filler is mostly dependent on melt shearing, the effect is limited, and the flame-retardant system has the contradiction between efficiency and migration risk. Therefore, there is an urgent need to develop a new material system that comprehensively solves the above problems.
Disclosure of Invention
The invention aims to provide a composite woven tube material for high-pressure air ribs and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the aim, on the one hand, the invention provides a composite woven tube material for high-pressure air ribs, which comprises, by weight, 70-85 parts of alicyclic isocyanate modified thermoplastic polyurethane elastomer, 18-25 parts of modified reinforcing fibers, 4-6 parts of interfacial compatilizer, 2-4 parts of composite anti-aging system, 1-3 parts of nano reinforcing agent, 5-15 parts of composite flame retardant system, 1-2 parts of processing aid and 10-45 parts of solvent.
Preferably, the cycloaliphatic isocyanate modified thermoplastic polyurethane elastomer is a mixture of an HMDI-based polyester TPU and an HMDI-based polyether TPU in a weight ratio of (3-4): 1. A polyester type or polyether type TPU based on HMDI (hexamethylene diisocyanate) is selected, and preferably both are used in a mixture of (3-4): 1. The HMDI is of an alicyclic structure, has no benzene ring, has more excellent yellowing resistance and ageing resistance compared with aromatic isocyanate modified TPU, has high mechanical strength and good wear resistance, has good flexibility and excellent hydrolysis resistance, can cooperatively improve the comprehensive mechanical property of the material by compounding the two, has the elongation at break of more than or equal to 500 percent, and ensures the elastic recovery capability of the material under high pressure.
Preferably, the modified reinforced fiber is glass fiber or aramid fiber which is subjected to low-temperature plasma pretreatment and then is subjected to composite surface coating by an aminosilane coupling agent and part of the interfacial compatilizer, wherein the low-temperature plasma treatment power is 300-500W, and the treatment time is 2-5min. Glass fiber or aramid fiber is selected, and after being pretreated by low-temperature plasma, the glass fiber or the aramid fiber is compositely coated by an aminosilane coupling agent and a part of interfacial compatilizer. The low-temperature plasma treatment (300-500W, 2-5 min) can etch the surface of the fiber, increase the surface roughness and active groups, the amino group of the aminosilane coupling agent can react with the hydroxyl group on the surface of the fiber, the isocyanate group can react with the TPU matrix, the long flexible chain of the interfacial compatilizer can improve the interfacial binding force between the fiber and the matrix, reduce the interfacial defect, and obviously improve the tensile strength and tear resistance of the material.
The nano reinforcing agent is preferably nano silicon dioxide modified on the surface of stearic acid, and before the nano reinforcing agent is added, the nano reinforcing agent is prepared into pre-dispersed slurry with the solid content of 10-20% with partial processing auxiliary agent, and the pre-dispersed slurry is subjected to ultrasonic treatment with the power of 500-1000W for 10-30min, so that the agglomeration of nano particles can be effectively prevented, the size of the agglomeration is less than 80nm, and the nano silicon dioxide uniformly dispersed in a matrix can improve the tensile strength, the hardness and the wear resistance of the material through the nano reinforcing effect.
Preferably, the composite flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant and is formed by compounding an acid source, a carbon source and a gas source, wherein the weight ratio of the acid source to the carbon source to the gas source is (3-4) (1-1.5) (1).
Preferably, the acid source is ammonium polyphosphate (APP), the carbon source is Pentaerythritol (PER), and the gas source is Melamine (MEL). APP is an acid source, phosphoric acid is generated by thermal decomposition, PER is a carbon source, dehydration is carried out under the catalysis of phosphoric acid to form carbon, MEL is an air source, ammonia is released by heating, and the APP, the PER, the MEL and the MEL cooperate to form a compact expansion carbon layer, heat and oxygen transfer are blocked, high-efficiency flame retardance is realized, the limiting oxygen index is more than or equal to 30%, the mass loss rate is less than 5% after baking at 85 ℃ for 168 hours, the temperature-resistant stability is good, and the environment-friendly halogen-free performance is realized.
The processing aid is zinc stearate and polyethylene wax which are mixed according to the mass ratio of 1:1, so that the melt fluidity of the material can be improved, and the processing forming property can be improved.
Preferably, the composite anti-aging system is a compound of hindered phenol antioxidants, phosphite antioxidants and benzotriazole ultraviolet absorbers, and the weight ratio of the hindered phenol antioxidants to the phosphite antioxidants to the benzotriazole ultraviolet absorbers is 1 (1-1.5) (0.8-1.2). The hindered phenol antioxidant is selected from antioxidant 1010 as a main antioxidant and can capture free radicals, the phosphite antioxidant is selected from antioxidant 168 as an auxiliary antioxidant and can decompose hydroperoxide, the benzotriazole ultraviolet absorber is selected from UV-326 and can absorb ultraviolet light, and the three components are synergistic, so that the thermal oxidative aging resistance and the ultraviolet aging resistance of the material are obviously improved, and the service life of the material is prolonged.
Preferably, the interfacial compatibilizer is a polyurethane prepolymer having both isocyanate groups and long flexible chains. Polyurethane prepolymer with isocyanate groups and long flexible chains is selected, the isocyanate groups can react with amino groups and hydroxyl groups on the surface of the reinforced fiber and terminal hydroxyl groups of the TPU matrix, the long flexible chains can relieve interface stress concentration, the interface compatibility of the fiber and the matrix is further improved, and the fiber debonding is avoided.
On the other hand, the invention also provides a preparation method of the composite woven tube material for the high-pressure air rib, which comprises the following steps:
Mixing the nano reinforcing agent, part of processing aid and solvent in proportion, performing ultrasonic treatment for 10-30min with the power of 500-1000W to prepare nano pre-dispersion slurry, and then concentrating and drying to obtain nano composite master batch;
the preparation method comprises the steps of carrying out low-temperature plasma treatment on reinforced fibers with the treatment power of 300-500W and the treatment time of 2-5min, then immersing the reinforced fibers into a mixed solution consisting of an aminosilane coupling agent, an interfacial compatilizer accounting for 30-50% of the total weight of the interfacial compatilizer and an ethanol water solution, reacting for 2-4h at 70-85 ℃, centrifuging to obtain centrifugal precipitate, drying to obtain modified reinforced fibers, and carrying out two-step modification by low-temperature plasma etching, coupling agent and compatilizer composite coating to improve the interfacial binding force between the fibers and a matrix.
Placing the alicyclic isocyanate modified thermoplastic polyurethane elastomer, the nano composite master batch, the modified reinforced fiber, the composite flame retardant system, the composite anti-aging system, the rest processing aids and the rest interfacial compatilizer in a high-speed mixer according to the proportion, and mixing for 5-10min at the rotating speed of 2000-3000rpm to obtain uniform premix;
the premix is put into a parallel twin-screw extruder for melt blending, extrusion, cooling, traction and granulating, wherein the temperature range from a feed inlet to a machine head of the twin-screw extruder is 165 ℃, 175 ℃, 185 ℃, 195 ℃ and 190 ℃, the rotating speed of the screw is 250-350rpm, and the vacuum degree is controlled at-0.095 to-0.098 MPa. The rotating speed and the vacuum degree of the screw are controlled to ensure full melting and no bubble.
Preferably, the solvent is absolute ethanol. Absolute ethyl alcohol is selected as a pre-dispersing medium of the nano reinforcing agent, a uniformly dispersing environment is provided for the nano particles, agglomeration of the nano particles in a dry state is avoided, the nano particles are completely removed through vacuum drying in the preparation process, the nano particles are not remained in a final product, and core indexes such as mechanical property and flame retardant property of the material are not influenced.
The invention has the beneficial effects that:
According to the invention, an alicyclic TPU based on HMDI is adopted as a matrix, ultraviolet yellowing caused by benzene rings is eliminated from a molecular structure, the intrinsic improvement of weather resistance of a material is realized, and meanwhile, higher elongation at break (more than or equal to 500%) is given to the material, through an ultrasonic dispersion pretreatment process of introducing nano SiO 2, the size of an aggregate is controlled below 80nm at the initial stage of batching by utilizing cavitation effect, a perfect dispersion foundation is laid for subsequent melt blending, the effect of the nano SiO 2 serving as a heterogeneous nucleation point and a physical crosslinking point is maximized, the elastic modulus and the thermal deformation temperature of the material are obviously improved, a phosphorus-nitrogen synergistic expansion type flame retardant system is adopted, a compact porous expansion carbon layer is generated in a condensed phase during combustion, high-efficiency heat insulation and oxygen inhibition are realized, the Limiting Oxygen Index (LOI) is improved to a high flame retardant level of more than or equal to 30%, and the migration problem (mobility < 5%) of a small molecular flame retardant is fundamentally solved through a solidification carbon forming mechanism. The three core technologies cooperate to finally prepare the high-pressure air-rib composite woven tube material, which realizes the crossing progress in the aspects of yellowing resistance, mechanical toughness, modulus, thermal stability and flame retardance and overall length effectiveness, and the comprehensive performance is far superior to that of the prior art system.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
All reagents and raw materials in the present invention were commercially available, and the purity of the reagents was analytically pure.
HMDI-based polyester TPU is from Henschel polyurethane (Shanghai) Inc., model S6440.
HMDI-based polyether TPU is available from henmai polyurethane (Shanghai) limited under the model a92P4207.
The epoxy modified aromatic polyurethane is from complex high new material (Shanghai) limited company, and the model is EPU-105.
The interfacial compatilizer is derived from Kesi Innovative polymer (China) Co., ltd, and is model Desmodur MS-242.
The nanometer enhancer is from the company of the biological technology of the West An Jiyue, and the model is Q-0347854.
The isocyanate-siloxane difunctional crosslinking agent is from Nanjing Netherlands New Material technology Co., ltd, and the model is SCA-Y25M.
Example 1
The raw materials are prepared by the following components in parts by weight:
52.5 parts of HMDI-based polyester TPU, 17.5 parts of HMDI-based polyether TPU (weight ratio 3:1);
18 parts of glass fiber;
4 parts of interfacial compatilizer;
2 parts of a composite anti-aging system (antioxidant 1010: antioxidant 168: uv-326=1:1:0.8 (weight ratio));
1 part of nano reinforcing agent;
5 parts of a composite flame-retardant system (APP: PER: MEL=3:1:1 (weight ratio));
1 part of processing aid (zinc stearate: polyethylene wax=1:1 (weight ratio));
solvent (absolute ethanol) 10 parts.
The preparation method comprises the following steps:
(1) Pretreating nano slurry, namely mixing a nano reinforcing agent with part (0.3 part) of processing aid and absolute ethyl alcohol serving as a solvent, performing 500W ultrasonic treatment for 30min, concentrating under reduced pressure, and drying to obtain nano composite master batch;
(2) Fiber modification treatment, namely immersing glass fiber into a mixed solution consisting of 2.8 parts of KH-550 and part (2 parts) of interfacial compatilizer and ethanol water solution (ethanol: water=9:1, v/v, the dosage of which is 86.3 percent of that of the mixed solution) by low-temperature plasma treatment at 300W and 30 ℃ for 5min, sealing a reaction container, reacting for 4h at 70 ℃, centrifuging, taking out a centrifugal precipitate, and drying to obtain modified glass fiber;
(3) Premixing raw materials, namely placing the HMDI-based polyester TPU, the polyether TPU, the nano composite master batch, the modified glass fiber, the composite flame retardant system, the composite anti-aging system, the rest of processing aids and the rest of interfacial compatilizer in a high-speed mixer according to the proportion, and mixing for 10min at 2000rpm to obtain a premix;
(4) And (3) melt blending and granulating, namely putting the premix into a double-screw extruder for extrusion granulating, wherein the temperature range from a feed inlet to a machine head of the double-screw extruder is 165 ℃, 175 ℃, 185 ℃, 195 ℃ and 190 ℃, the screw rotation speed is 250rpm, and the vacuum degree is-0.095 MPa, so that the woven tube material is obtained.
Example 2
The raw materials are prepared by the following components in parts by weight:
60 parts of HMDI-based polyester TPU, 20 parts of HMDI-based polyether TPU (weight ratio 3:1);
21 parts of aramid fiber;
5 parts of interfacial compatilizer;
3 parts of a composite anti-aging system (antioxidant 1010: antioxidant 168: uv-326=1:1.2:1.0 (weight ratio));
2 parts of nano reinforcing agent;
10 parts of a composite flame-retardant system (APP: PER: MEL=3.5:1.2:1 (weight ratio));
1.5 parts of processing aid (zinc stearate: polyethylene wax=1:1 (weight ratio));
30 parts of solvent (absolute ethanol).
The preparation method comprises the following steps:
(1) Nanometer sizing agent pretreatment, namely mixing a nanometer reinforcing agent with part (0.5 part) of processing aid and absolute ethyl alcohol, performing 750W ultrasonic treatment for 20min, and then performing reduced pressure concentration and drying to obtain nanometer composite master batch;
(2) Fiber modification treatment, namely immersing aramid fiber into a mixed solution consisting of 4.0 parts of KH-550 and part (2 parts) of interfacial compatilizer and ethanol water solution (ethanol: water=9:1, v/v, the dosage of which is 85.0 percent of that of the mixed solution) through low-temperature plasma treatment at 400W and 40 ℃ for 3.5min, sealing a reaction vessel, reacting at 75 ℃ for 3h, and centrifuging to obtain a centrifugal precipitate, and drying to obtain modified aramid fiber;
(3) Premixing raw materials, namely placing the HMDI-based polyester TPU, the polyether TPU, the nano composite master batch, the modified aramid fiber, the composite flame retardant system, the composite anti-aging system, the rest of processing aids and the rest of interfacial compatilizer in a high-speed mixer according to the proportion, and mixing for 7min at 2500rpm to obtain a premix;
(4) And (3) melt blending and granulating, namely putting the premix into a double-screw extruder for extrusion granulating, wherein the temperature range from a feed inlet to a machine head of the double-screw extruder is 165 ℃, 175 ℃, 185 ℃, 195 ℃ and 190 ℃, the screw rotation speed is 300rpm, and the vacuum degree is-0.096 MPa, so that the woven tube material is obtained.
Example 3
The raw materials are prepared by the following components in parts by weight:
68 parts of HMDI-based polyester TPU, 17 parts of HMDI-based polyether TPU (weight ratio 4:1);
23 parts of glass fiber;
5 parts of interfacial compatilizer;
3 parts of a composite anti-aging system (antioxidant 1010: antioxidant 168: uv-326=1:1.5:1.2 (weight ratio));
2 parts of nano reinforcing agent;
12 parts of a composite flame-retardant system (APP: PER: MEL=4:1.5:1 (weight ratio));
1.8 parts of a processing aid (zinc stearate: polyethylene wax=1:1 (weight ratio));
solvent (absolute ethanol) 25 parts.
The preparation method comprises the following steps:
(1) Nano slurry pretreatment, namely mixing a nano reinforcing agent with part (0.6 part) of processing aid and absolute ethyl alcohol, performing 1000W ultrasonic treatment for 10min, and then performing reduced pressure concentration and drying to obtain nano composite master batch;
(2) Fiber modification treatment, namely immersing glass fiber into a mixed solution consisting of 5.4 parts of KH-550 and part (2.5 parts) of interfacial compatilizer and ethanol water solution (ethanol: water=9:1, v/v, the dosage of which is 82.4 percent of that of the mixed solution) through low-temperature plasma treatment at 500W and 45 ℃ for 2min, sealing a reaction container, reacting at 80 ℃ for 2.5h, and centrifuging to obtain a centrifugal precipitate, and drying to obtain modified glass fiber;
(3) Premixing raw materials, namely placing the HMDI-based polyester TPU, the polyether TPU, the nano composite master batch, the modified glass fiber, the composite flame retardant system, the composite anti-aging system, the rest processing aids and the rest interfacial compatilizer in a high-speed mixer according to the proportion, and mixing for 5min at 3000rpm to obtain a premix;
(4) And (3) melt blending and granulating, namely putting the premix into a double-screw extruder for extrusion granulating, wherein the temperature range from a feed inlet to a machine head of the double-screw extruder is 165 ℃, 175 ℃, 185 ℃, 195 ℃ and 190 ℃, the screw rotation speed is 350rpm, and the vacuum degree is-0.098 MPa, so that the woven tube material is obtained.
Example 4
The raw materials are prepared by the following components in parts by weight:
63 parts of HMDI-based polyester TPU, 18 parts of HMDI-based polyether TPU (weight ratio 3.5:1);
25 parts of aramid fiber;
6 parts of interfacial compatilizer;
4 parts of a composite anti-aging system (antioxidant 1010: antioxidant 168: uv-326=1:1.3:1.1 (weight ratio));
3 parts of nano reinforcing agent;
15 parts of a composite flame-retardant system (APP: PER: MEL=3.8:1.4:1 (weight ratio));
2 parts of processing aid (zinc stearate: polyethylene wax=1:1 (weight ratio));
45 parts of solvent (absolute ethanol).
The preparation method comprises the following steps:
(1) Nanometer sizing agent pretreatment, namely mixing a nanometer reinforcing agent with part (0.8 part) of processing aid and absolute ethyl alcohol, performing 800W ultrasonic treatment for 15min, concentrating and drying to obtain nanometer composite master batch;
(2) Fiber modification treatment, namely immersing aramid fiber into a mixed solution consisting of 5.5 parts of KH-550 and part (2.4 parts) of interfacial compatilizer and ethanol water solution (ethanol: water=9:1, v/v, accounting for 84.2 percent of the mixed solution) through low-temperature plasma treatment at 450W and 35 ℃ for 4min, sealing a reaction vessel, reacting for 2h at 85 ℃, and centrifuging to obtain a centrifugal precipitate, and drying to obtain modified aramid fiber;
(3) Premixing raw materials, namely placing the HMDI-based polyester TPU, the polyether TPU, the nano composite master batch, the modified aramid fiber, the composite flame retardant system, the composite anti-aging system, the rest of processing aids and the rest of interfacial compatilizer in a high-speed mixer according to the proportion, and mixing for 6min at 2800rpm to obtain premix;
(4) And (3) melt blending and granulating, namely putting the premix into a double-screw extruder for extrusion granulating, wherein the temperature range from a feed inlet to a machine head of the double-screw extruder is 165 ℃, 175 ℃, 185 ℃, 195 ℃ and 190 ℃, the screw rotation speed is 320rpm, and the vacuum degree is-0.097 MPa, so that the woven tube material is obtained.
Comparative example 1
Compared with the example 2, the reinforced fiber is not subjected to low-temperature plasma pretreatment and composite coating modification, and the rest components and the preparation process are the same.
Comparative example 2
Compared with example 2, the same amount of microencapsulated red phosphorus flame retardant (from Dongguan Hongtai-based flame retardant materials Co., ltd.) was used instead of the composite flame retardant system, and the rest of the components and the preparation process were the same.
Comparative example 3
Compared with example 2, the same amount of conventional MDI type aromatic TPU (kex, texin 250 DE) was used instead of the cycloaliphatic isocyanate modified thermoplastic polyurethane elastomer, the remaining components and the preparation process were the same.
Comparative example 4
Compared with example 2, the composite flame-retardant system only uses 12 parts of APP (without PER and MEL), and the rest components and the preparation process are the same.
Comparative example 5
Compared with example 2, the aramid fiber is only pretreated by low-temperature plasma (without KH-550 and interfacial compatilizer composite coating).
The composite woven tube materials prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance tests, and the test standards and methods are as follows.
1. Tensile Strength, elongation at Break
The detection standard is according to GB/T1040.2-2006, test conditions of plastic stretching property 2 nd part, molding and extrusion molding, the detection method is that a composite woven tube material is cut into dumbbell Type standard test pieces (Type 1A, total length 150mm, gauge length 50mm, width 10mm and thickness 2 mm), a universal material tester is adopted to carry out unidirectional stretching test at a stretching rate of 50mm/min, the maximum pulling force and the elongation of gauge length when the test pieces break are recorded, and the tensile strength (the maximum pulling force divided by the original cross section area of the test pieces) and the elongation at break (the percentage of the elongation of the gauge length to the original gauge length when the test pieces break) are calculated respectively.
2. Maximum bearing pressure
According to GB/T15560-1995 method for testing hydraulic instantaneous explosion and pressure resistance of plastic pipe for fluid transportation, the detection method comprises cutting a sample after pipe weaving molding into pipe sections with the length of 300mm, fixing two ends by adopting special sealing connectors, accessing a hydraulic test system, gradually boosting at the speed of 0.1MPa/min, monitoring the pressure change of the pipe section in real time until the pipe section breaks or obvious leakage occurs, and recording the maximum pressure value at the moment of breaking as the maximum bearing pressure.
3. Limiting Oxygen Index (LOI)
The detection standard is that according to GB/T2406.2-2009, the part 2 of the combustion behavior is room temperature test, the material is processed into a standard sample with the size of 80mm multiplied by 10mm multiplied by 4mm, the standard sample is vertically fixed in a combustion cylinder of an oxygen index tester, the flow rate of mixed gas of oxygen and nitrogen is regulated, the oxygen concentration is changed according to a certain gradient, the top end of the sample is ignited, the combustion condition of the sample is observed, and the lowest oxygen concentration when the combustion time of the sample is more than or equal to 3min or the combustion length of the sample is more than or equal to 50mm is recorded, namely the limiting oxygen index.
4. Retention of tensile Strength after aging and yellowing index after aging
According to the 2 nd part of a light source exposure test method of a plastic laboratory, the ageing resistance detection standard comprises the steps of placing a sample in a xenon lamp ageing test box, setting irradiance of 0.51W/(m2+nm) (340 nm), blackboard temperature of 65 ℃ and relative humidity of 50%, continuously ageing for 1000 hours, testing tensile strength according to GB/T1040.2-2006 after ageing, calculating the percentage of the tensile strength after ageing to the original tensile strength, namely the retention rate of the tensile strength, and simultaneously according to the GB/T2409-1980 plastic yellow index test method, measuring the yellowing index (delta YI) of the sample after ageing by adopting a color difference meter, and comparing the non-ageing sample as a reference.
5. Interfacial peel strength
The detection standard is that according to GB/T2790-1995 method for testing 180 DEG peel strength of adhesive for flexible materials, a fiber-matrix composite peel test sample (the width of the test sample is 25mm, the length of the test sample is 150mm, and the length of the exposed end of the fiber is 50 mm) is prepared from modified reinforced fibers and TPU matrix, a universal material testing machine is adopted to conduct 180 DEG peel test at the speed of 50mm/min, and the average peel force in the peel process is recorded and divided by the width of the test sample, namely the interfacial peel strength.
6. Mass loss rate
The detection standard refers to GB/T11997-2008 multipurpose plastic sample, and the detection method comprises the steps of taking a material sample (the mass is marked as m 0) dried to constant weight, placing the material sample in a blast drying oven at 85 ℃ for constant temperature baking for 168 hours, taking the material sample out, placing the material sample in a dryer for cooling to room temperature, weighing the mass (the mass is marked as m 1) of the cooled material sample, and calculating the mass loss rate according to a formula (m 0-m1）/m0 multiplied by 100 percent).
7. Combustion grade (UL 94)
The detection standard is based on UL94-2021"Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances", detection method, which comprises processing the material into standard sample of 127mm×12.7mm×3.2mm, vertically fixing in combustion test device, igniting sample top 10s with specified flame (height 20 mm), removing flame, recording flame burning time and flameless burning time of sample, observing whether dripping matter ignites absorbent cotton below, and determining combustion grade (V-0, V-1, V-2, etc.) according to combustion behavior, wherein the combustion grade determination index is shown in Table 1.
Table 1 combustion level determination index table
| Determination index | V-0 | V-1 | V-2 |
| Single flame burn time | After two ignition, the single flame burning time is less than or equal to 10s | After two ignition, the single flame burning time is less than or equal to 30s | After two ignition, the single flame burning time is less than or equal to 30s |
| Total time of two flame combustions | The sum of the two flame burning times is less than or equal to 50s | The sum of the two flame burning times is less than or equal to 250s | The sum of the two flame burning times is less than or equal to 250s |
| Flameless burn time | After two ignition, flameless combustion time is less than or equal to 30s | After two ignition, flameless combustion time is less than or equal to 60s | After two ignition, flameless combustion time is less than or equal to 60s |
| Ignition of drips | No drop or no ignition of absorbent cotton | No drop or no ignition of absorbent cotton | Has dripping matters which ignite absorbent cotton |
| Specimen burn limit | The combustion flame must not spread to the specimen holding end (marked line 100mm from the tip) | The combustion flame does not spread to the sample clamping end | The combustion flame does not spread to the sample clamping end |
8. Hydrolysis resistance (retention of tensile strength at 70 ℃ C. For 72h in water)
The detection standard is referred to GB/T15593-1995, section 3 of determination of tensile Properties of Plastic, test conditions of films and sheets, the detection method comprises the steps of placing a standard tensile sample in a constant-temperature water bath kettle at 70 ℃, boiling and soaking for 72h, taking out, absorbing surface moisture by filter paper, placing for 24h in a standard environment (23 ℃ and relative humidity of 50%), testing tensile strength according to GB/T1040.2-2006, and calculating the percentage of the tensile strength after hydrolysis to the original tensile strength, namely the retention rate of hydrolysis-resistant tensile strength.
The results of the performance tests on the woven tube materials of the examples and the comparative examples are shown in Table 2.
Table 2 results of performance test table
| Performance index | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Tensile Strength (MPa) | 42.3 | 48.6 | 51.2 | 53.8 | 34.2 | 46.8 | 45.4 | 38.5 | 47.2 |
| Elongation at break (%) | 580 | 620 | 605 | 630 | 490 | 585 | 540 | 520 | 605 |
| Maximum bearing pressure (MPa) | 3.8 | 4.5 | 4.8 | 5.0 | 2.9 | 4.1 | 3.7 | 3.5 | 4.3 |
| Limiting oxygen index (LOI,%) | 30.2 | 32.6 | 33.8 | 34.5 | 32.3 | 27.7 | 32.1 | 32.4 | 25.3 |
| Tensile Strength retention after aging (%) | 89.5 | 92.3 | 93.1 | 91.7 | 86.7 | 90.3 | 72.4 | 91.8 | 91.5 |
| Yellowing index after aging | 1.8 | 1.5 | 1.3 | 1.6 | 1.4 | 1.5 | 9.2 | 1.6 | 1.4 |
| Interfacial peel strength (N/mm) | 3.2 | 3.8 | 4.2 | 4.3 | 2.0 | 3.6 | 3.5 | 2.5 | 3.7 |
| Mass loss rate (%) | 3.4 | 2.9 | 2.5 | 2.6 | 2.8 | 3.5 | 3.1 | 3.0 | 3.1 |
| Combustion grade (UL 94) | V-0 | V-0 | V-0 | V-0 | V-0 | V-2 | V-0 | V-0 | V-2 |
| Hydrolysis resistance (retention of tensile strength at 70 ℃ C. For 72h,%) | 85.1 | 88.6 | 90.4 | 89.3 | 84.5 | 82.3 | 78.6 | 85.2 | 87.9 |
The interfacial bonding property and mechanical properties were significantly reduced in comparative example 1 as compared with example 2. The interfacial peel strength of comparative example 1 was only 2.0N/mm (example 2 was 3.8N/mm, 47.4% drop), the tensile strength was 34.2MPa (29.6% drop), and the maximum withstand pressure was 2.9MPa (35.6% drop). The main reasons are that the surface of the fiber is not subjected to low-temperature plasma pretreatment, the surface of the fiber is not subjected to micro etching, the specific surface area is small, active groups (hydroxyl and carboxyl) are absent, the fiber is not subjected to compound coating of an aminosilane coupling agent-KH-550, the chemical bond connection of a fiber-coupling agent-compatilizer-TPU matrix cannot be formed, the interface bonding is loose only by physical mixing, the fiber is easy to debond when being stressed, and the overall mechanical property and the high pressure resistance are further reduced.
Comparative example 2 is significantly deteriorated in flame retardant property and lowered in temperature resistance stability as compared with example 2. The LOI of comparative example 2 was only 27.7% (32.5% for example 2, 14.7% drop), the burn rating was reduced to V-2 rating, and the mass loss was 3.5% (25% rise). The microencapsulated red phosphorus flame retardant is added flame retardant, only depends on gas phase flame retardant (PO seed radical is released to capture combustion free radical), has no blocking effect of an expanded carbon layer, has low flame retardant efficiency, is easy to oxidize and decompose at high temperature (baking at 85 ℃) to cause mass loss increase, and forms a compact expanded carbon layer through the synergistic effect of APP (acid source), PER (carbon source) and MEL (air source), so that the flame retardant has the advantages of heat and oxygen blocking, excellent thermal stability, lasting flame retardant effect and environmental protection.
Comparative example 3 is inferior in anti-aging property and anti-yellowing property to example 2. The tensile strength retention after aging of comparative example 3 was only 72.4% (92.3% in example 2, 21.6% decrease), the yellowing index after aging was 9.2 (1.5 in example 2, 513.3% increase), and the hydrolysis resistance was also significantly reduced (78.6% vs88.6% retention of tensile strength). The main reason is that MDI is aromatic isocyanate, the molecular structure contains benzene ring, the benzene ring is easy to be oxidized and broken under the irradiation of ultraviolet light, so that the yellowing and the mechanical property attenuation of the material are caused, while HMDI is alicyclic isocyanate, has no benzene ring structure and higher chemical stability, and the polyester type and polyether type HMDI-TPU compound in the invention not only maintains the high strength of the polyester type, but also has the hydrolysis resistance of the polyether type, and the aging resistance and the structural stability of the far-super-aromatic TPU.
Comparative example 4 compared with example 2, the interfacial peel strength was reduced from 3.8N/mm to 2.5N/mm (34.2% reduction), and the maximum bearing pressure was reduced from 4.5MPa to 3.5MPa (22.2% reduction). The main reason is that only the plasma pretreatment can increase the surface activity of the fiber, but the chemical bond bridging between KH-550 and a compatilizer is lacking, a flexible transition layer cannot be formed, the interface stress concentration cannot be relieved, and the fiber is still easy to debond when being stressed. The effect of 1+1>2 is realized by the two-step modification (physical etching+chemical combination) of the embodiment 2, and the performance bottleneck of the pure physical modification is broken through.
Comparative example 5 compared to example 2, the LOI was reduced from 32.5% to 25.3% (22.2% reduction), the fire rating V-1, and the flame retardant failed. The main reason is that a single APP (acid source) cannot form an expanded carbon layer, flame retardation is realized only by acid gas, and the efficiency is extremely low. The APP/PER/MEL=3.5:1.2:1 of the embodiment 2 constructs a compact carbon layer to block heat/oxygen through the synergistic effect of acid catalytic carbonization and gas source expansion, realizes the basically lossless high flame retardance and mechanical property, and breaks through the technical bottleneck of the traditional additive flame retardant of flame retardance improving effect and mechanical property reducing.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention. In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The composite woven tube material for the high-pressure air ribs is characterized by comprising, by weight, 70-85 parts of alicyclic isocyanate modified thermoplastic polyurethane elastomer, 18-25 parts of modified reinforcing fibers, 4-6 parts of interfacial compatilizer, 2-4 parts of composite anti-aging system, 1-3 parts of nano reinforcing agent, 5-15 parts of composite flame retardant system, 1-2 parts of processing aid and 10-45 parts of solvent.
2. The composite woven tube material for high pressure air ribs as claimed in claim 1, wherein said alicyclic isocyanate modified thermoplastic polyurethane elastomer is a mixture of HMDI-based polyester TPU and HMDI-based polyether TPU in a weight ratio of (3-4): 1.
3. The composite woven tube material for the high-pressure air ribs according to claim 1, wherein the modified reinforced fiber is glass fiber or aramid fiber which is subjected to low-temperature plasma pretreatment and is subjected to composite surface coating by an aminosilane coupling agent and part of the interfacial compatilizer, and the low-temperature plasma treatment power is 300-500W and the treatment time is 2-5min.
4. The composite woven tube material for the high-pressure air ribs according to claim 1, wherein the nano reinforcing agent is nano silicon dioxide subjected to surface modification by stearic acid, and the nano reinforcing agent is prepared into pre-dispersed slurry with the solid content of 10-20% with part of processing aids before being added, and is subjected to ultrasonic treatment with the power of 500-1000W for 10-30min.
5. The composite woven tube material for the high-pressure air ribs according to claim 1, wherein the composite flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant and is formed by compounding an acid source, a carbon source and a gas source, and the weight ratio of the acid source to the carbon source to the gas source is (3-4) (1-1.5) 1.
6. The composite woven tube material for a high pressure air rib of claim 5, wherein the acid source is ammonium polyphosphate, the carbon source is pentaerythritol, and the air source is melamine.
7. The composite woven tube material for the high-pressure air ribs according to claim 1, wherein the composite anti-aging system is a compound of hindered phenol antioxidants, phosphite antioxidants and benzotriazole ultraviolet absorbers, and the weight ratio of the hindered phenol antioxidants, the phosphite antioxidants and the benzotriazole ultraviolet absorbers is 1 (1-1.5) (0.8-1.2).
8. The composite woven tube material for high pressure air ribs as claimed in claim 1, wherein said interfacial compatibilizer is a polyurethane prepolymer having both isocyanate groups and long flexible chains.
9. A method of producing a composite woven tube material for high pressure air ribs as claimed in any one of claims 1 to 8, comprising the steps of:
Mixing the nano reinforcing agent, part of processing aid and solvent in proportion, performing ultrasonic treatment to prepare nano pre-dispersion slurry, and then concentrating and drying to obtain nano composite master batch;
Firstly, carrying out low-temperature plasma treatment on reinforced fibers, then immersing the reinforced fibers into a mixed solution consisting of an aminosilane coupling agent, an interfacial compatilizer accounting for 30% -50% of the total weight of the interfacial compatilizer and an ethanol water solution, reacting for 2-4 hours at 70-85 ℃, and then centrifuging to obtain a centrifugal precipitate and drying to obtain modified reinforced fibers;
Placing the alicyclic isocyanate modified thermoplastic polyurethane elastomer, the nano composite master batch, the modified reinforced fiber, the composite flame-retardant system, the composite anti-aging system, the rest of processing aids and the rest of interfacial compatilizer into a high-speed mixer according to the proportion, and mixing to obtain uniform premix;
And (3) putting the premix into a co-directional parallel double-screw extruder, and carrying out melt blending, extrusion, cooling, traction and granulating.
10. The method for producing a composite woven tube material for high-pressure air ribs as claimed in claim 9, wherein the solvent is absolute ethyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511690634.9A CN121136412A (en) | 2025-11-18 | 2025-11-18 | A composite tube material for high-pressure air ribs and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511690634.9A CN121136412A (en) | 2025-11-18 | 2025-11-18 | A composite tube material for high-pressure air ribs and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN121136412A true CN121136412A (en) | 2025-12-16 |
Family
ID=98004792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202511690634.9A Pending CN121136412A (en) | 2025-11-18 | 2025-11-18 | A composite tube material for high-pressure air ribs and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN121136412A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201736503A (en) * | 2015-12-31 | 2017-10-16 | 盧伯利索先進材料有限公司 | Thermoplastic polyurethane composition |
| KR20180060715A (en) * | 2016-11-29 | 2018-06-07 | (주)유창하이텍 | Thermoplastic polyurethane composite comprising carbon nano tube, packing and diaphragm having thereof |
| CN111253731A (en) * | 2020-03-31 | 2020-06-09 | 浙江益弹新材料科技有限公司 | Halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN117681518A (en) * | 2023-12-27 | 2024-03-12 | 中国人民解放军海军特色医学中心 | Air column material and preparation method and application thereof |
| CN119409935A (en) * | 2024-11-19 | 2025-02-11 | 万华化学集团股份有限公司 | A dicyclohexylmethane diisocyanate composition and thermoplastic polyurethane elastomer |
| CN120682623A (en) * | 2025-07-17 | 2025-09-23 | 蒂优材料科技发展(上海)有限公司 | A glass fiber reinforced polyurethane composite material and its preparation process |
-
2025
- 2025-11-18 CN CN202511690634.9A patent/CN121136412A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201736503A (en) * | 2015-12-31 | 2017-10-16 | 盧伯利索先進材料有限公司 | Thermoplastic polyurethane composition |
| KR20180060715A (en) * | 2016-11-29 | 2018-06-07 | (주)유창하이텍 | Thermoplastic polyurethane composite comprising carbon nano tube, packing and diaphragm having thereof |
| CN111253731A (en) * | 2020-03-31 | 2020-06-09 | 浙江益弹新材料科技有限公司 | Halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN117681518A (en) * | 2023-12-27 | 2024-03-12 | 中国人民解放军海军特色医学中心 | Air column material and preparation method and application thereof |
| CN119409935A (en) * | 2024-11-19 | 2025-02-11 | 万华化学集团股份有限公司 | A dicyclohexylmethane diisocyanate composition and thermoplastic polyurethane elastomer |
| CN120682623A (en) * | 2025-07-17 | 2025-09-23 | 蒂优材料科技发展(上海)有限公司 | A glass fiber reinforced polyurethane composite material and its preparation process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102120849B (en) | Ethylene-propylene-diene monomer (EPDM) ablation-resistant composition containing high-regularity trapezoid polyphenyl silsesquioxane and preparation method thereof | |
| CN114350098A (en) | Heat-resistant environment-friendly cable material and preparation method thereof | |
| CN110791105A (en) | Low temperature flame retardant silicone outer sheath for cables and preparation method thereof | |
| CN119899460A (en) | A kind of outdoor aging-resistant PP board and preparation method thereof | |
| CN117511203A (en) | Flame-retardant protective sleeve material for special fire-resistant cable | |
| CN112159602A (en) | Self-repairing polyurethane fireproof insulating coating | |
| CN117050438A (en) | Flame-retardant PVC composite material and preparation method thereof | |
| CN119552433A (en) | Flame retardant rubber-plastic thermal insulation material and preparation method thereof | |
| CN115182158A (en) | Flame-retardant TPU (thermoplastic polyurethane) fiber membrane material and preparation method thereof | |
| CN111434701A (en) | A kind of nano-silica and phosphorus-based flame retardant compound modified water-based polyurethane and preparation method | |
| CN118027353A (en) | Production process of flame-retardant foaming sponge | |
| CN117024875A (en) | Biomass-based high-flame-retardance MPP pipe and preparation method thereof | |
| CN121136412A (en) | A composite tube material for high-pressure air ribs and its preparation method | |
| CN112457524B (en) | A kind of phosphorus flame retardant and preparation method thereof | |
| CN119463424B (en) | Anti-aging yellowing-resistant foamed polyester material and preparation method thereof | |
| CN111117046B (en) | Low-addition high-flame-retardance flame-retardant master batch and preparation method thereof | |
| CN117510993B (en) | Efficient flame retardant based on modified sepiolite and preparation method thereof | |
| CN113773416B (en) | Intrinsic flame-retardant modified natural rubber and preparation method thereof | |
| CN117362792A (en) | Flame-retardant PE drainage pipeline and preparation method thereof | |
| CN111073298A (en) | A kind of flame retardant plugging agent for substation and its preparation method and using method | |
| CN114836140A (en) | Waterborne polyurethane PE/POE composite waterproof coiled material, and preparation method and application thereof | |
| CN118440415B (en) | Preparation method of flame-retardant styrene-butadiene rubber | |
| CN116656296B (en) | A high temperature resistant packaging adhesive for electronic components and its manufacturing process | |
| CN116855008B (en) | A thermosetting sheath material for 80-year life cable for nuclear power plants and its preparation method | |
| CN116589686B (en) | Phosphorus-containing flame retardant, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |