A high-pressure air rib outer layer material for inflatable floating bridges and its preparation method

Abstract

This invention relates to the field of composite material technology and discloses a high-pressure air rib outer layer material for inflatable floating bridges and its preparation method. The high-pressure air rib outer layer material of this invention has a layered structure, comprising an outer layer of woven tubing material, an intermediate layer of adhesive, and an inner layer of air-tight membrane. Polymer monomers and functional monomers are polymerized, and then a tackifier and amino resin are added to obtain the adhesive. The adhesive exhibits strong adhesion to both the polyester-based woven tubing and the polyurethane membrane, resulting in high peel strength and adhesion. The woven tubing material and the polyurethane air-tight membrane are tightly bonded and not easily separated or peeled off. Furthermore, the functional monomers contain multiple hydrophobic long carbon chains, which improves the water resistance and waterproof performance of the acrylic resin adhesive. The resulting high-pressure air rib outer layer material for inflatable floating bridges has high bonding strength, good waterproof performance, and high durability.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, specifically to an outer layer material for high-pressure air ribs of an inflatable pontoon bridge and its preparation method. Background Technology

[0002] Acrylic resin adhesives have advantages such as rapid curing, good flexibility, and excellent weather resistance, and are widely used in fiber textiles and metals. However, acrylic resin adhesives have poor water resistance, which is not conducive to their practical application in inflatable pontoon bridges, etc. Furthermore, acrylic resin adhesives have low affinity and interaction with substrates such as polyester textiles and polyurethane plastics, which affects the adhesive's bonding performance.

[0003] Adding functional monomers during the preparation of acrylic resins can endow adhesives with unique properties such as hydrophilicity and heat resistance. Examples include acrylic acid, N-hydroxymethylacrylamide, and fluorinated monomers. Patent CN109777308B discloses a low-odor acrylic adhesive for bonding spirit levels and its preparation method. Using monofunctional and difunctional acrylic monomers as raw materials, the prepared acrylic adhesive exhibits good peel strength to plastics and metals. However, this patent does not address the issue of the low waterproof performance of acrylic adhesives. Summary of the Invention

[0004] (I) Technical problem to be solved: In view of the shortcomings of the prior art, the present invention provides an outer layer material of high pressure air rib of inflatable floating bridge and its preparation method, which solves the problems of poor waterproof performance of acrylic resin adhesive and low adhesion between acrylic resin adhesive and polyester fiber woven material and polyurethane film.

[0005] (II) Technical solution: A high-pressure air rib outer layer material for an inflatable floating bridge, the outer layer material having a layered structure, including an outer layer of woven tube material, an intermediate layer of adhesive, and an inner layer of air-tight membrane.

[0006] The preparation method of the outer layer material of the high-pressure air rib of the inflatable floating bridge is as follows:

[0007] (1) Add allyl 3,5-dihydroxybenzoate, alkyl isocyanate, and dibutyltin dilaurate to dichloromethane, stir the reaction, distill under reduced pressure, wash the product with petroleum ether, and then recrystallize in dichloromethane to obtain the functional monomer. The reaction formula is:

[0008] .

[0009] (2) Add the polymerizing monomer and functional monomer to n-butanol, stir and then add the solution dropwise into the reaction vessel. Heat to the reaction temperature, add the solution containing the initiator dropwise, stir and react, cool and then add the tackifier and amino resin, stir and mix well to obtain the adhesive.

[0010] (3) Apply adhesive to the surface of the air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, dry and cure to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0011] Preferably, the woven tube material is obtained by weaving polyester fiber as the weft yarn and basalt fiber as the warp yarn.

[0012] Preferably, the airtight membrane is made of polyurethane membrane material.

[0013] Preferably, (1) the amount of allyl 3,5-dihydroxybenzoate is 100 parts by weight, the amount of alkyl isocyanate is 166-282 parts by weight, and the amount of dibutyltin dilaurate is 1.2-1.8 parts by weight.

[0014] Preferably, the isocyanate alkyl ester in (1) has the structural formula NCO-C a H 2a+1 , where a is 8-16.

[0015] Preferably, in (1), the reaction temperature is 35-40℃ and the reaction time is 4-5h.

[0016] Preferably, in (2), the amount of polymeric monomer is 92-97 parts by weight, the amount of functional monomer is 3-8 parts by weight, the amount of initiator is 1.8-2.6 parts by weight, the amount of tackifier is 10-25 parts by weight, and the amount of amino resin is 1.4-2.2 parts by weight.

[0017] Preferably, the monomers in (2) include methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

[0018] Preferably, the initiator in (2) includes diisopropylbenzene peroxide and azobisisobutyronitrile.

[0019] Preferably, the reaction temperature in (2) is 80-90℃ and the reaction time is 3-5h.

[0020] Preferably, the tackifier in (2) is rosin resin or terpene resin.

[0021] Preferably, the curing temperature in (3) is 80-100℃ and the curing time is 2-6h.

[0022] (III) Beneficial Technical Effects of the Invention: Methyl acrylate, hydroxyethyl acrylate, functional monomers, etc., are polymerized and then compounded with tackifiers and amino resins to obtain an adhesive. This adhesive is then used to bond a polyurethane air-sealing membrane and a polyester-based woven tube material to obtain the outer layer material of the high-pressure air ribs of the inflatable pontoon bridge. The functional monomer contains benzoate groups, which have a strong affinity for polyethylene terephthalate polyester fibers in the woven tube, thus improving the adhesion between the adhesive and the woven tube. Simultaneously, the functional monomer contains urethane groups, which form hydrogen bonds with the urethane groups in the polyurethane membrane, giving the acrylic resin adhesive a strong bond to the polyurethane membrane. This results in high peel strength and adhesion of the material. The adhesive tightly bonds the woven tube material and the polyurethane air-sealing membrane, making them difficult to separate and peel off. Furthermore, the functional monomer contains multiple hydrophobic long carbon chains, which improves the water resistance and waterproof performance of the acrylic resin adhesive. The resulting outer layer material of the high-pressure air ribs of the inflatable pontoon bridge exhibits high bonding strength, good waterproof performance, and high durability. Attached Figure Description

[0023] Figure 1 This is a cross-sectional view of the structure of the outer layer material of the high-pressure air ribs of the inflatable pontoon bridge.

[0024] Figure 2 This is the infrared spectrum of the functional monomer of Example 1. Detailed Implementation

[0025] The polyurethane airtight membrane described below is made by blowing polyurethane granules using a blown film machine. The woven tube material is made by weaving polyester fiber as the weft yarn and basalt fiber as the warp yarn. Rosin resin content is 99%, manufactured by Jinan Boao Chemical. Terpene resin CAS number 9003-74-1, manufactured by Shandong Wanhua Environmental New Materials. Amino resin, model Cytec 1130, manufactured by Weng Kai'er (Guangdong) Technology.

[0026] Allyl 3,5-dihydroxybenzoate was prepared according to the method described in the journal article J. Chem. Soc., Perkin Trans. 1, 1999, 501-508, "Dendronized polyacrylates with glucose units in the periphery". The structural formula is as follows: .

[0027] Example 1:

[0028] (1) Add 20g of allyl 3,5-dihydroxybenzoate, 44.6g of dodecyl isocyanate and 0.6g of dibutyltin dilaurate to 500mL of dichloromethane. Stir and reflux at 35℃ for 5h. Distill under reduced pressure, wash the product with petroleum ether, and then recrystallize in dichloromethane to obtain the functional monomer. Figure 12925 cm⁻¹ in the infrared spectrum -1 2855cm -1 It is the stretching vibration peak of -CH3 and -CH2-, 1724 cm⁻¹. -1 It is the stretching vibration peak of C=O in urethane and ester groups, 1601m. -1 It is the stretching vibration peak of the allyl C=C bond.

[0029] (2) Add 330g of methyl acrylate, 560g of butyl methacrylate, 80g of hydroxyethyl acrylate and 30g of functional monomer to 1.3L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 60mL of n-butanol solution containing 18g of dicumyl peroxide, stir and react for 4h, cool and add 150g of rosin resin and 18g of amino resin, stir and mix well to obtain the binder.

[0030] (3) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 90°C for 5 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0031] Example 2:

[0032] (1) Add 20g of allyl 3,5-dihydroxybenzoate, 56.4g of hexadecyl isocyanate and 0.9g of dibutyltin dilaurate to 600mL of dichloromethane. Stir and reflux at 40℃ for 4h. Distill under reduced pressure, wash the product with petroleum ether, and then recrystallize in dichloromethane to obtain the functional monomer.

[0033] (2) Add 390g of methyl methacrylate, 480g of butyl acrylate, 70g of hydroxyethyl acrylate and 60g of functional monomer to 1.5L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 80mL of n-butanol solution containing 21g of azobisisobutyronitrile, stir and react for 3h, cool and add 100g of rosin resin and 22g of amino resin, stir and mix well to obtain the adhesive.

[0034] (3) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 80°C for 6 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0035] Example 3:

[0036] (1) Add 20g of allyl 3,5-dihydroxybenzoate, 33.2g of octyl isocyanate and 0.7g of dibutyltin dilaurate to 500mL of dichloromethane. Stir and reflux at 40℃ for 4h. Distill under reduced pressure, wash the product with petroleum ether, and then recrystallize in dichloromethane to obtain the functional monomer.

[0037] (2) Add 253g of methyl acrylate, 610g of butyl methacrylate, 57g of hydroxyethyl acrylate and 80g of functional monomer to 1.5L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 80℃, add 60mL of n-butanol solution containing 26g of dicumyl peroxide, stir and react for 5h, cool and add 250g of terpene resin and 14g of amino resin, stir and mix well to obtain the binder.

[0038] (3) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 100°C for 2 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0039] Comparative Example 1:

[0040] (1) Add 330g of methyl acrylate, 560g of butyl methacrylate and 80g of hydroxyethyl acrylate to 1.3L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 60mL of n-butanol solution containing 18g of dicumyl peroxide, stir and react for 4h, cool and add 150g of rosin resin and 18g of amino resin, stir and mix well to obtain the adhesive.

[0041] (2) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 90°C for 5 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0042] Comparative Example 2:

[0043] (1) Add 330g of methyl acrylate, 560g of butyl methacrylate, 80g of hydroxyethyl acrylate and 30g of allyl benzoate (CAS No. 583-04-0) to 1.3L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 60mL of n-butanol solution containing 18g of dicumyl peroxide, stir and react for 4h, cool and add 150g of rosin resin and 18g of amino resin, stir and mix well to obtain the adhesive.

[0044] (2) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 90°C for 5 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0045] Comparative Example 3:

[0046] (1) Add 23.9 g of hydroxyethyl acrylate, 44.6 g of dodecyl isocyanate, and 0.6 g of dibutyltin dilaurate to 500 mL of dichloromethane. Stir and reflux at 35 °C for 5 h. Distill under reduced pressure. Add the product to petroleum ether. Filter and distill under reduced pressure to dry the filtrate to obtain the functional monomer, with the structural formula as follows: .

[0047] (2) Add 330g of methyl acrylate, 560g of butyl methacrylate, 80g of hydroxyethyl acrylate and 30g of functional monomer to 1.3L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 60mL of n-butanol solution containing 18g of dicumyl peroxide, stir and react for 4h, cool and add 150g of rosin resin and 18g of amino resin, stir and mix well to obtain the binder.

[0048] (3) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 90°C for 5 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0049] Comparative Example 4:

[0050] (1) Add 36.7 g of allyl 4-hydroxybenzoate, 44.6 g of dodecyl isocyanate, and 0.6 g of dibutyltin dilaurate to 500 mL of dichloromethane. Stir and reflux at 35 °C for 5 h. Distill under reduced pressure, wash the product with petroleum ether, and then recrystallize in dichloromethane to obtain the functional monomer with the following structural formula: .

[0051] (2) Add 330g of methyl acrylate, 560g of butyl methacrylate, 80g of hydroxyethyl acrylate and 30g of functional monomer to 1.3L of n-butanol. After stirring, add the solution dropwise into the reaction vessel, heat to 90℃, add 60mL of n-butanol solution containing 18g of dicumyl peroxide, stir and react for 4h, cool and add 150g of rosin resin and 18g of amino resin, stir and mix well to obtain the binder.

[0052] (3) Apply adhesive to the surface of polyurethane air-tight membrane, then put the woven tube material on the outer layer of the air-tight membrane, and dry and cure at 90°C for 5 hours to obtain the outer layer material of the high-pressure air rib of the inflatable floating bridge.

[0053] According to the method of standard GB / T 2791-1995, the T-peel strength of the adhesive in the outer layer material of the high-pressure air rib of the inflatable pontoon bridge between the woven tube material sleeve and the air-sealing membrane was tested.

[0054] The outer layer material of the high-pressure air rib of the inflatable pontoon bridge was immersed in water for 24 hours, then removed, dried, and the T-peel strength was tested.

[0055] Table 1 Peel strength test

[0056] Peel strength (kN / m) Peel strength after immersion in water (kN / m) Retention rate (%) Example 1 2.95 21.2 71.9 Example 2 3.76 29.0 77.1 Example 3 3.53 28.1 79.6 Comparative Example 1 2.27 14.6 64.3 Comparative Example 2 2.41 15.8 65.6 Comparative Example 3 2.54 17.3 68.1 Comparative Example 4 2.70 18.8 69.6

[0057] Compared with Comparative Example 1, Examples 1-4 incorporated functional monomers in the preparation of the acrylic resin adhesive. These monomers contained benzoate groups, which exhibited strong affinity for the polyethylene terephthalate polyester fibers in the woven tube, thus improving the adhesion between the adhesive and the woven tube. Simultaneously, the functional monomers contained urethane groups, which formed hydrogen bonds with the urethane groups in the polyurethane film, resulting in stronger adhesion between the acrylic resin adhesive and the polyurethane film. This led to higher peel strength, and the adhesive tightly bonded the woven tube material and the polyurethane airtight film, enhancing bonding strength and durability. The two materials were less prone to separation and peeling. Furthermore, the functional monomers contained multiple hydrophobic long carbon chains, which improved the adhesive's water resistance and waterproofing properties. Even after immersion in water, the samples maintained high peel strength and adhesion.

[0058] Compared with Example 1, the functional monomers of Comparative Example 2 do not contain urethane groups and hydrophobic long carbon chains. The acrylic resin adhesive has lower adhesion to the polyurethane airtight film, lower peel strength, and a greater decrease in peel strength after immersion in water.

[0059] The functional monomers in Comparative Example 3 do not contain benzoate groups, and the acrylic resin adhesive has low affinity and adhesion to the braided tube, resulting in low peel strength.

[0060] The functional monomers in Comparative Example 4 have fewer urethane groups and hydrophobic long carbon chains, resulting in lower adhesion to the polyurethane airtight film. The peel strength and the retention rate of peel strength after immersion in water are both lower than those in Example 1.

Claims

1. A high-pressure air rib outer layer material for an inflatable floating bridge, characterized in that, The outer layer material of the high-pressure air rib of the inflatable floating bridge has a layered structure, including an outer layer of woven tube material, an intermediate layer of adhesive, and an inner layer of air-tight membrane. The adhesive is prepared by the following method: adding polymeric monomers and functional monomers to n-butanol, stirring, adding the solution dropwise into a reaction vessel, heating to the reaction temperature, adding a solution containing an initiator dropwise, stirring to react, cooling, adding a tackifier and amino resin, stirring to mix, and obtaining the adhesive. The structural formula of the functional unit is: a is 8-16; The woven tube material is obtained by weaving polyester fiber as weft yarn and basalt fiber as warp yarn; the air-sealing membrane is a polyurethane membrane material. The amount of the polymeric monomer is 92-97 parts by weight, the amount of the functional monomer is 3-8 parts by weight, the amount of the initiator is 1.8-2.6 parts by weight, the amount of the tackifier is 10-25 parts by weight, and the amount of the amino resin is 1.4-2.2 parts by weight. The polymer monomers include one or more of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

2. The outer layer material of the high-pressure air rib of the inflatable pontoon bridge according to claim 1, characterized in that, The reaction temperature is 80-90℃, and the reaction time is 3-5h.

3. The outer layer material of the high-pressure air rib of the inflatable pontoon bridge according to claim 1, characterized in that, The initiator is dicumyl peroxide or azobisisobutyronitrile.

4. The outer layer material of the high-pressure air rib of the inflatable pontoon bridge according to claim 1, characterized in that, The tackifier is rosin resin or terpene resin.

5. The outer layer material of the high-pressure air rib of the inflatable pontoon bridge according to claim 1, characterized in that, The preparation method of the functional monomer is as follows: 100 parts by weight of allyl 3,5-dihydroxybenzoate, 166-282 parts by weight of alkyl isocyanate, and 1.2-1.8 parts by weight of dibutyltin dilaurate are added to dichloromethane, and the mixture is stirred and reacted at 35-40℃ for 4-5 hours. The product is then washed by vacuum distillation and recrystallized to obtain the functional monomer.

6. The outer layer material of the high-pressure air rib of the inflatable pontoon bridge according to claim 5, characterized in that, The isocyanate has the structural formula NCO-C. a H 2a+1 , where a is 8-16.

7. A method for preparing the outer layer material of the high-pressure air rib of an inflatable pontoon bridge as described in any one of claims 1-6, characterized in that, The preparation method includes: coating an adhesive on the surface of the airtight membrane, then covering the outer layer of the airtight membrane with woven tube material, and drying and curing it at 80-100℃ for 2-6 hours to obtain the outer layer material of the high-pressure air rib of the inflatable pontoon bridge.

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