Preparation method of low-temperature-resistant waterproof moisture-permeable polyurethane adhesive as well as product and application thereof
By constructing a polyurethane structure with a dense region of hydrophobic hard segments and a hydrophilic region of soft segments, the problems of insufficient adhesion and poor waterproof and breathable properties of polyurethane adhesives in low-temperature environments are solved, achieving low-temperature resistant, waterproof, and breathable effects, and improving the performance of textiles such as ski suits.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- KANGDA NEW MATERIALS (GRP) CO LTD
- Filing Date
- 2026-03-03
- Publication Date
- 2026-05-12
AI Technical Summary
Existing polyurethane adhesives struggle to balance low-temperature resistance, waterproofing and breathability, and high adhesion. In particular, their adhesion to nylon fabrics is insufficient in low-temperature environments, affecting the performance of outdoor sports equipment such as ski suits.
Through precise molecular structure design, a polyurethane structure with a hydrophobic hard segment dense region and a soft segment hydrophilic region is constructed. Utilizing the principle of microphase separation, polycarbonate, amino silicone oil and polyether segments are combined to form an adhesive with excellent waterproof and breathable properties.
It achieves excellent bonding strength, prevents water penetration, and allows moisture to pass through in low-temperature environments, thus improving the waterproof and breathable properties and adhesion of textiles such as ski suits.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polyurethane adhesive technology, specifically to a method for preparing a low-temperature resistant, waterproof, and breathable polyurethane adhesive, its product, and its applications. Background Technology
[0002] Patent CN 104945594 A discloses a hydrolysis-resistant and low-temperature-resistant polyurethane adhesive, which uses polyether segments to replace part of the polyester segments, improving the flexibility of the segments and reducing the polarity of the molecular chains, thereby improving its hydrolysis resistance and low-temperature resistance, but with low adhesion. Patent CN 121406285 A discloses a furan-based polyurethane adhesive and its synthesis method, which introduces furanamide groups with rigid structures and hydrogen bond interactions into the hard segments of polyurethane to construct a microphase separation structure, and uses polyether polyols as segments to soften the segments and reduce the glass transition temperature of the segments. The adhesive has good low-temperature resistance, but poor adhesion and moisture permeability.
[0003] Therefore, developing a polyurethane adhesive that achieves synergistic effects of low-temperature resistance, water resistance, moisture permeability, and high adhesion through molecular structure design has become an urgent need in the field of low-temperature resistant, waterproof, and breathable bonding, such as for bonding skiwear fabrics.
[0004] As high-performance outdoor sports equipment, ski suits have extremely stringent requirements for their fabric bonding adhesives. The outer layer of ski suits is usually made of functional nylon fabric, which needs to be firmly bonded to a waterproof and breathable membrane. In cold environments, the adhesives must have excellent bonding strength and low-temperature resistance, while preventing snow water penetration and allowing sweat generated by the body during exercise to be released to maintain wearing comfort.
[0005] Existing polyurethane adhesives often struggle to balance low-temperature resistance and waterproof / breathable properties. Polyester-type segments have high glass transition temperatures, making them prone to hardening and cracking at low temperatures, and the ester groups are not resistant to hydrolysis. Polyether-type segments offer excellent flexibility and good low-temperature resistance, but their low polarity results in poor adhesion. Organosilane-modified polyurethanes exhibit good low-temperature resistance, but at higher concentrations, microphase separation is more pronounced, and their low polarity leads to poor moisture permeability. Furthermore, the adhesion of existing adhesives to nylon fabrics is easily affected by low-temperature environments; improper crosslinking control can lead to insufficient adhesion or an overly stiff adhesive layer, thus affecting the fabric's flexibility. Summary of the Invention
[0006] The purpose of this invention is to overcome the shortcomings of existing polyurethane adhesives, such as poor low-temperature resistance, water hydrolysis, poor moisture permeability, and low low-temperature adhesion, and to provide a method for preparing a low-temperature resistant, waterproof, and breathable polyurethane adhesive, as well as its products and applications.
[0007] To achieve the above objectives, this invention utilizes the principle of microphase separation through precise molecular structure design to construct a polyurethane structure with a dense, hydrophobic hard segment and a hydrophilic soft segment. The specific method is as follows:
[0008] A method for preparing a low-temperature resistant, waterproof, and breathable polyurethane adhesive includes the following steps:
[0009] Step 1: Mix diisocyanate and polycarbonate polyol in a solvent and react, then add amino silicone oil to react, to obtain a first amino-terminated prepolymer for later use. The first amino-terminated prepolymer is shown in the following structural formula 1:
[0010]
[0011] Structural formula 1, wherein R' is a molecular chain connecting two -NCO groups, R1 is a segment of poly(1,6-hexanediol diphenyl carbonate), and R2 is a segment of polydimethylsiloxane.
[0012] Step 2: Mix diisocyanate and polyether polyol in a solvent to obtain an isocyanate-terminated prepolymer for later use. The isocyanate-terminated prepolymer is shown in structural formula 2 below:
[0013]
[0014] Structural Formula 2;
[0015] Step 3: Mix the first amino-terminated prepolymer and the isocyanate-terminated prepolymer in a solvent to obtain a second amino-terminated prepolymer solution;
[0016] Step 4: Mix the second amino-terminated prepolymer solution with the polyisocyanate curing agent to obtain a low-temperature resistant, waterproof, and breathable polyurethane adhesive.
[0017] In a preferred embodiment of the present invention, the diisocyanate is 4,4-diphenylmethane diisocyanate (MDI).
[0018] The solvent is dimethylacetamide (DMAc);
[0019] The polycarbonate polyol is poly(1,6-hexanediol) diphenyl carbonate with a relative molecular weight of 1000-2000, and the molar ratio of polycarbonate polyol to 4,4-diphenylmethane diisocyanate (MDI) is 1:1.5-1:2.
[0020] The first amino-terminated prepolymer is in solution form with a concentration of 50-60 wt.%.
[0021] In a preferred embodiment of the present invention, the amino silicone oil is aminopropyl polydimethylsiloxane with a relative molecular weight of 1000-1800, and the molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) is 1:1.5-1:1.
[0022] In a preferred embodiment of the present invention, the reaction temperature in step one is 80-90 °C, and the total reaction time is 120-240 min.
[0023] In a preferred embodiment of the present invention, the polyether polyol in step two is polyethylene glycol with a relative molecular weight of 400-1000;
[0024] The diisocyanate in step two is 4,4-diphenylmethane diisocyanate (MDI).
[0025] The molar ratio of polyethylene glycol to 4,4-diphenylmethane diisocyanate (MDI) is 1:1.1-1:1.3;
[0026] The solvent is dimethylacetamide (DMAc);
[0027] The isocyanate-terminated prepolymer is in solution form with a concentration of 50-60 wt.%.
[0028] In a preferred embodiment of the present invention, the reaction temperature in step two is 80-90 °C, and the total reaction time is 120-240 min.
[0029] In a preferred embodiment of the present invention, the order of step one and step two can be replaced.
[0030] In a preferred embodiment of the present invention, the molar ratio of the amino-terminated prepolymer to the isocyanate-terminated prepolymer in step three is 1.2:1-1.5:1;
[0031] The solvent is dimethylacetamide (DMAc);
[0032] The concentration of the amino-terminated prepolymer solution is 50-60 wt.
[0033] In a preferred embodiment of the present invention, the reaction temperature in step three is 80-90 °C, and the total reaction time is 120-240 min.
[0034] In a preferred embodiment of the present invention, the polyisocyanate curing agent in step four is polyisocyanate curing agent TDI-TMP;
[0035] The mixing molar ratio of the second amino-terminated prepolymer solution to the polyisocyanate curing agent is 0.5:1 to 1:1;
[0036] The curing temperature is 40-60 ℃, and the curing time is 24-36 h.
[0037] A low-temperature resistant, waterproof, and breathable polyurethane adhesive is obtained by the above preparation method. In one molecular backbone of the low-temperature resistant, waterproof, and breathable polyurethane adhesive, the mass fraction of hard segment structure is 20-35 wt.%, the mass fraction of organosiloxane is 5-10 wt.%, and the mass fraction of soft segment structure is 55-75 wt.%.
[0038] An application of a low-temperature resistant, waterproof, and breathable polyurethane adhesive is disclosed. The application is for bonding textiles in the field of low-temperature resistant, waterproof, and breathable materials. The low-temperature resistant, waterproof, and breathable polyurethane adhesive cures on the bonding surface of the textile to form a polyurethane film structure. The glass transition temperature of the polyurethane film structure is -30 to -10 ℃. At 38 ℃ and 50% relative humidity, the water vapor transmission rate of the formed film is 210-300 g / (m²). 2 h).
[0039] The textiles mentioned in the low-temperature resistant, waterproof, and breathable field are ski suits or other textiles that require low-temperature resistant, waterproof, and breathable properties.
[0040] Beneficial effects:
[0041] Existing technologies cannot simultaneously achieve both waterproofing and breathability. This invention, through precise molecular chain structure design and aggregated state structure control, effectively prevents liquid water penetration while not affecting the transfer of gaseous water molecules through the soft segments, resulting in superior waterproofing and breathability compared to traditional coatings. Existing technologies use polyether or organosiloxane-modified polyurethane, offering limited functionality. This invention organically combines polycarbonate, amino silicone oil, and hydrophilic polyether. The polycarbonate hard segments provide high strength and waterproofing; the amino silicone oil imparts excellent low-temperature resistance and hydrophobic protection; and the hydrophilic polyether provides breathable channels, truly achieving a triple effect of waterproofing, breathability, and low-temperature resistance. Detailed Implementation
[0042] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0043] The working principle of this invention is as follows:
[0044] In step one, the high polarity of polycarbonate segments reacts with MDI to form physically aggregated hard segment microregions, constructing a dense physical barrier that prevents water molecules from entering. Simultaneously, organosiloxane segments are introduced into the polymer backbone. These segments possess extremely low surface energy and extremely low glass transition temperature, which not only protect the hard segment microregions but also endow the soft segments with excellent low-temperature resistance.
[0045] In step two, the polyether segment, as part of the soft segment, forms an adsorption-desorption channel for water vapor molecules with its hydrophilic groups, ensuring moisture permeability.
[0046] This invention is based on the molecular and aggregated structure design of polyurethane. In terms of molecular chain structure, since ester groups are susceptible to hydrolysis, this invention employs organosiloxane end-capping to protect the hard segments from hydrolysis. Simultaneously, to enhance intermolecular hydrogen bonding in the hard segments, polycarbonate is reacted with MDI, and the amino groups can form urea bonds with MDI. The organosiloxane and polyether molecular chains exhibit excellent flexibility, which can lower the glass transition temperature of the chain segments. In terms of aggregated structure, hydrophilic channels are constructed through microphase separation of the polyurethane soft and hard segments, thereby achieving a moisture-permeable effect; at the same time, the degree of crosslinking of the polyurethane is controlled to improve the adhesion of the adhesive.
[0047] The waterproof and breathable properties in the various embodiments of this invention refer to GB / T 12704.2-2009 "Textiles - Test methods for moisture permeability of fabrics - Part 2: Evaporation method"
[0048] Example 1
[0049] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1000 and 4,4-diphenylmethane diisocyanate (MDI) were mixed in a DMAc solution and reacted at a molar ratio of 1:1.5 at a temperature of 85 °C for 180 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 1:1.5 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 60 wt.%.
[0050] (2) Polyethylene glycol with a relative molecular weight of 400 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.1 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 60 wt.%.
[0051] (3) The first amino-terminated prepolymer and the isocyanate-terminated prepolymer were reacted in DMAc solution at a molar ratio of 1.2:1 at 85 °C for 180 min to obtain a second amino-terminated prepolymer solution with a concentration of 60 wt.%.
[0052] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.5:1, and applied to ski clothing fabric for curing to form a film at a temperature of 40 ℃ for 36 h.
[0053] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 1 was prepared. In one molecular backbone, the mass fraction of hard segments was 20 wt.%, the mass fraction of organosiloxane was 5 wt.%, and the mass fraction of soft segments was 75 wt.%. The glass transition temperature of the polyurethane film was -30 ℃. At 38 ℃ and 50% relative humidity, the water vapor permeability of the formed film was 300 g / (m²). 2 h).
[0054] Example 2
[0055] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1000 and 4,4-diphenylmethane diisocyanate (MDI) were mixed in a DMAc solution and reacted at a molar ratio of 1:1.8 at a temperature of 85 °C for 240 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 8:9 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 60 wt.%.
[0056] (2) Polyethylene glycol with a relative molecular weight of 400 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.2 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 60 wt.%.
[0057] (3) The first amino-terminated prepolymer and the isocyanate-terminated prepolymer were reacted in DMAc solution at a molar ratio of 1.2:1 at 85 °C for 180 min to obtain a second amino-terminated prepolymer solution with a concentration of 60 wt.%.
[0058] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.8:1, and applied to ski clothing fabric for curing to form a film at a temperature of 40 ℃ for 36 h.
[0059] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 2, prepared in this way, has a main chain with a hard segment mass fraction of 22 wt.%, an organosiloxane mass fraction of 7 wt.%, and a soft segment mass fraction of 71 wt.%. The polyurethane film has a glass transition temperature of -28 °C and 38 °C at 50% relative humidity, and a water vapor permeability of 280 g / (m²). 2 h).
[0060] Example 3
[0061] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1000 was mixed with 4,4-diphenylmethane diisocyanate (MDI) in DMAc solution and reacted at a molar ratio of 1:2 at a temperature of 85 °C for 240 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 1:1 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 55 wt.%.
[0062] (2) Polyethylene glycol with a relative molecular weight of 400 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.3 in DMAc solution at a temperature of 90 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 55 wt.%.
[0063] (3) The first amino-terminated prepolymer and the isocyanate-terminated prepolymer were reacted in DMAc solution at a molar ratio of 1.3:1 at 90 °C for 180 min to obtain a second amino-terminated prepolymer solution with a concentration of 55 wt.%.
[0064] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 1:1, and applied to ski clothing fabric for curing to form a film at a temperature of 50 ℃ for 36 h.
[0065] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 3, prepared in this manner, has a main chain with a hard segment mass fraction of 25 wt.%, an organosiloxane mass fraction of 9 wt.%, and a soft segment mass fraction of 66 wt.%. The polyurethane film exhibits a glass transition temperature of -25 °C, and at 38 °C and 50% relative humidity, the water vapor permeability of the formed film is 260 g / (m²). 2 h).
[0066] Example 4
[0067] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1500 and 4,4-diphenylmethane diisocyanate (MDI) were mixed in a DMAc solution and reacted at a molar ratio of 1:1.5 at a temperature of 85 °C for 180 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1400 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 1:1.5 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 60 wt.%.
[0068] (2) Polyethylene glycol with a relative molecular weight of 1000 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.1 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 60 wt.%.
[0069] (3) The first amino-terminated prepolymer and the isocyanate-terminated prepolymer were reacted in DMAc solution at a molar ratio of 1.2:1 at 85 °C for 180 min to obtain a second amino-terminated prepolymer solution with a concentration of 60 wt.%.
[0070] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.5:1, and applied to ski clothing fabric for curing to form a film at a temperature of 40 ℃ for 36 h.
[0071] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 4, prepared in this way, has a main chain with a hard segment mass fraction of 24 wt.%, an organosiloxane mass fraction of 7 wt.%, and a soft segment mass fraction of 69 wt.%. The polyurethane film has a glass transition temperature of -27 °C and 38 °C at 50% relative humidity, and a water vapor permeability of 280 g / (m²). 2 h).
[0072] Example 5
[0073] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1500 and 4,4-diphenylmethane diisocyanate (MDI) were mixed in DMAc solution and reacted at a molar ratio of 1:1.8 at a temperature of 85 °C for 180 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 8:9 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 55 wt.%.
[0074] (2) Polyethylene glycol with a relative molecular weight of 1000 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.2 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 55 wt.%.
[0075] (3) Prepolymer 1 and prepolymer 2 were reacted in DMAc solution at a molar ratio of 1.2:1 at a temperature of 85 °C for 180 min to obtain a prepolymer solution with a second amino terminator and a solution concentration of 55 wt.%.
[0076] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.8:1, and applied to ski clothing fabric for curing to form a film at a temperature of 40 ℃ for 36 h.
[0077] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 5, prepared in this way, has a main chain with a hard segment mass fraction of 27 wt.%, an organosiloxane mass fraction of 10 wt.%, and a soft segment mass fraction of 63 wt.%. The polyurethane film has a glass transition temperature of -20 °C. At 38 °C and a relative humidity of 50%, the water vapor permeability of the formed film is 240 g / (m²). 2 h).
[0078] Example 6
[0079] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 1500 was mixed with 4,4-diphenylmethane diisocyanate (MDI) in DMAc solution and reacted at a molar ratio of 1:2 at a temperature of 85 °C for 240 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 8:9 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 55 wt.%.
[0080] (2) Polyethylene glycol with a relative molecular weight of 1000 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.3 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 55 wt.%.
[0081] (3) Prepolymer 1 and prepolymer 2 were reacted in DMAc solution at a molar ratio of 1.3:1 at a temperature of 85 °C for 180 min to obtain a prepolymer solution with a second amino terminator and a solution concentration of 55 wt.%.
[0082] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.8:1, and applied to ski clothing fabric for curing to form a film at a temperature of 40 ℃ for 36 h.
[0083] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 6, prepared in this way, has a main chain with a hard segment mass fraction of 28 wt.%, an organosiloxane mass fraction of 10 wt.%, and a soft segment mass fraction of 62 wt.%. The polyurethane film has a glass transition temperature of -20 °C. At 38 °C and a relative humidity of 50%, the water vapor permeability of the formed film is 220 g / (m²). 2 h).
[0084] Example 7
[0085] (1) Poly(1,6-hexanediol diphenyl carbonate) with a relative molecular weight of 2000 and 4,4-diphenylmethane diisocyanate (MDI) were mixed in DMAc solution and reacted at a molar ratio of 1:2 at a temperature of 85 °C for 240 min. Then, aminopropyl polydimethylsiloxane with a relative molecular weight of 1000 was added. The molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate (MDI) was 8:9 to obtain a prepolymer solution with the first amino end-capped structure and a solution concentration of 55 wt.%.
[0086] (2) Polyethylene glycol with a relative molecular weight of 1000 was reacted with 4,4-diphenylmethane diisocyanate (MDI) at a molar ratio of 1:1.3 in DMAc solution at a temperature of 85 °C for 180 min to obtain an isocyanate-terminated prepolymer solution with a concentration of 55 wt.%.
[0087] (3) Prepolymer 1 and prepolymer 2 were reacted in DMAc solution at a molar ratio of 1.3:1 at a temperature of 85 °C for 180 min to obtain a prepolymer solution with a second amino terminator and a solution concentration of 55 wt.%.
[0088] (4) The prepolymer solution with second amino end capping is mixed with polyisocyanate curing agent TDI-TMP at a molar ratio of 0.8:1, and then applied to the fabric for curing at 40 ℃ for 36 h.
[0089] The final skiwear low-temperature resistant, waterproof, and breathable polyurethane adhesive of Example 7, prepared in this manner, has a main chain with a hard segment mass fraction of 35 wt.%, an organosiloxane mass fraction of 10 wt.%, and a soft segment mass fraction of 55 wt.%. The polyurethane film has a glass transition temperature of -10 °C. At 38 °C and a relative humidity of 50%, the water vapor permeability of the formed film is 210 g / (m²). 2 h).
[0090] The inventors of this invention, in conjunction with standards, tested the reference documents, including CN 120645359 B, which discloses a waterproof and breathable polyurethane glove with a breathability of 62.5-83.3 g / (m²). 2 h); CN 112625211 A prepared a waterproof and breathable polyurethane film with environmental responsive function, the moisture permeability of which is 125-250 g / (m). 2 h).
Claims
1. A method for preparing a low-temperature resistant, waterproof, and breathable polyurethane adhesive, characterized in that, Includes the following steps: Step 1: Mix diisocyanate and polycarbonate polyol in a solvent and react, then add amino silicone oil to react, to obtain a first amino-terminated prepolymer for later use. The first amino-terminated prepolymer is shown in the following structural formula 1: Structural formula 1, wherein R' is a molecular chain connecting two -NCO groups, R1 is a segment of poly(1,6-hexanediol diphenyl carbonate), and R2 is a segment of polydimethylsiloxane. Step 2: Mix diisocyanate and polyether polyol in a solvent to obtain an isocyanate-terminated prepolymer for later use. The isocyanate-terminated prepolymer is shown in structural formula 2 below: Structural Formula 2; Step 3: Mix the first amino-terminated prepolymer and the isocyanate-terminated prepolymer in a solvent to obtain a second amino-terminated prepolymer solution; Step 4: Mix the second amino-terminated prepolymer solution with the polyisocyanate curing agent to obtain a low-temperature resistant, waterproof, and breathable polyurethane adhesive.
2. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, The diisocyanate is 4,4-diphenylmethane diisocyanate; The solvent is dimethylacetamide; The polycarbonate polyol is poly(1,6-hexanediol) diphenyl carbonate with a relative molecular weight of 1000-2000, and the molar ratio of polycarbonate polyol to 4,4-diphenylmethane diisocyanate is 1:1.5-1:
2. The first amino-terminated prepolymer is in solution form with a concentration of 50-60 wt.%.
3. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 2, characterized in that, The amino silicone oil is aminopropyl polydimethylsiloxane with a relative molecular weight of 1000-1800, and the molar ratio of amino silicone oil to 4,4-diphenylmethane diisocyanate is 1:1.5-1:
1.
4. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, The reaction temperature in step one is 80-90 ℃, and the total reaction time is 120-240 min.
5. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, The polyether polyol in step two is polyethylene glycol, with a relative molecular weight of 400-1000; The diisocyanate in step two is 4,4-diphenylmethane diisocyanate (MDI). The molar ratio of polyethylene glycol to 4,4-diphenylmethane diisocyanate (MDI) is 1:1.1-1:1.3; The solvent is dimethylacetamide (DMAc); The isocyanate-terminated prepolymer is in solution form with a concentration of 50-60 wt.%; the reaction temperature in step two is 80-90 ℃, and the total reaction time is 120-240 min.
6. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, The order of step one and step two can be substituted.
7. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, In step three, the molar ratio of the amino-terminated prepolymer to the isocyanate-terminated prepolymer is 1.2:1-1.5:1; The solvent is dimethylacetamide (DMAc); The concentration of the amino-terminated prepolymer solution is 50-60 wt.%. The reaction temperature in step three is 80-90 ℃, and the total reaction time is 120-240 min.
8. The preparation method of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 1, characterized in that, The polyisocyanate curing agent in step four is polyisocyanate curing agent TDI-TMP; The mixing molar ratio of the second amino-terminated prepolymer solution to the polyisocyanate curing agent is 0.5:1 to 1:1; The curing temperature is 40-60 ℃, and the curing time is 24-36 h.
9. A low-temperature resistant, waterproof, and breathable polyurethane adhesive, wherein the low-temperature resistant, waterproof, and breathable polyurethane adhesive is obtained by the preparation method according to any one of claims 1-8, characterized in that, In the main molecular chain of the low-temperature resistant, waterproof, and breathable polyurethane adhesive, the mass fraction of hard segment structure is 20-35 wt.%, the mass fraction of organosiloxane is 5-10 wt.%, and the mass fraction of soft segment structure is 55-75 wt.%.
10. An application of the low-temperature resistant, waterproof, and breathable polyurethane adhesive as described in claim 9, characterized in that, The application is for bonding textiles in the field of low-temperature resistant, waterproof, and breathable applications. The low-temperature resistant, waterproof, and breathable polyurethane adhesive cures on the bonding surface of the textile to form a polyurethane film structure. The glass transition temperature of the polyurethane film structure is -30 to -10 ℃. At 38 ℃ and 50% relative humidity, the water vapor transmission rate of the formed film is 210-300 g / (m²). 2 h).