CN116790202A - Self-adhesive waterproof coiled material based on palm oil-based polyurethane - Google Patents

Abstract

The invention discloses a self-adhesive waterproofing membrane based on palm oil-based polyurethane, which belongs to the field of building waterproofing materials. The invention uses palm oil as raw material to synthesize palm oil diethanolamide, and then mixes it with glycol and hexamethylene diisocyanate as a binder, and uses PET fiber felt as a reinforcing material, and obtains it through a hot pressing molding process. Described self-adhesive waterproof membrane. The raw materials of the palm oil-based waterproofing membrane prepared by the present invention are derived from bio-based and solid waste resources, and all its properties meet the standards described in the national standard GB/T 35467-2017 for H and E-type wet-lay waterproofing membranes, so it has Good market prospects.

Description

A self-adhesive waterproofing membrane based on palm oil-based polyurethane

Technical field

The invention belongs to the field of building waterproofing materials, and specifically relates to a self-adhesive waterproofing membrane based on palm oil-based polyurethane.

Background technique

As an engineering composite material, waterproof membrane is made of a series of waterproof materials. It is characterized by high waterproof performance and can effectively prevent water penetration and erosion. Therefore, it is usually used in buildings. Waterproofing projects on roofs, walls, basements, etc. to extend the service life of buildings. In addition, it also has the advantages of weather resistance, corrosion resistance, heat resistance, etc. As a leak-free connection between the project foundation and the building, it is the first barrier for waterproofing of the entire project and plays a vital role in the entire project. effect. According to the composition of waterproofing membranes, it can be divided into the following categories: (1) Asphalt waterproofing membranes: Using asphalt as the main raw material, by adding reinforcing fibers (glass fiber felt, polyester felt, etc.), fillers and modifiers Made of other materials, it has good corrosiveness, mechanical strength and plasticity, and is easy to construct; (2) Polymer waterproof membrane: using polymers as the main raw materials, such as polyvinyl chloride (PVC), thermoplastic polyolefin waterproof membrane (TPO), butyl rubber (EPDM), etc., have excellent weather resistance, chemical stability and mechanical properties, and have a wide range of applications; (3) Composite waterproofing membrane: composed of two or more materials, Such as self-adhesive polymer waterproofing membranes, asphalt polymer waterproofing membranes, etc., have different characteristics and are suitable for different waterproof environments.

Polyethylene glycol terephthalate (PET), commonly known as polyester, is the main product among thermoplastic polyesters. PET is widely used in the preparation of chemical fibers (polyester) and is a raw material supplied to polyester fiber companies for processing fibers and related products. PET fiber has the advantages of high modulus, high strength, high elasticity, good shape retention and heat resistance. It has become the most widely used and most consumed fiber variety. However, during the processing and production process, PET fiber is chemically modified Afterwards, it cannot be melted and spun for utilization, resulting in the production of a large amount of waste PET fiber. Since PET fiber has stable chemical properties and poor biodegradability, random discarding will have a great impact on the environment. Therefore, how to effectively reuse PET waste fiber has become an urgent problem to be solved. At present, the recycling of PET fiber mainly includes the following types: mechanical (physical) recycling, chemical recycling, melt recycling and biodegradation. Mechanical recycling processes PET waste fibers into recycled fibers or particles after grinding, screening, etc., which are used to produce packaging materials, fiber felts, clothes, etc.; due to its simple production process, low cost, and wide range of applications, , has become the main recycling method in industry.

The invention uses biomass palm oil as raw material, renewable palm oil glycol POEA, commercial glycol and hexamethylene diisocyanate (HDI) as adhesive, and mechanically recycled polyethylene terephthalate (PET) fiber felt as the base material; a hot pressing molding process is used to prepare a self-adhesive waterproofing membrane based on palm oil-based polyurethane and waste PET fiber felt to realize the secondary utilization of PET waste fiber and biomass palm oil in building waterproofing materials The application of vegetable oil will open up a new path in the field of building materials and contribute to my country's "double carbon" plan.

Contents of the invention

The purpose of the present invention is to provide a self-adhesive waterproofing membrane prepared from palm oil-based polyurethane and PET fiber felt as raw materials, which solves the problem of recycling PET waste fibers, fills the gap in the application of vegetable oil in the field of building materials, and The waterproof membrane produced is environmentally friendly, and all properties can meet the standards of H and E wet-lay waterproof membranes in the national standard GB/T 35467-2017.

In order to achieve the above objects, the present invention adopts the following technical solutions:

A self-adhesive waterproofing membrane based on palm oil-based polyurethane is prepared through a hot pressing molding process using palm oil-based polyurethane prepolymer solution and PET fiber felt as raw materials.

Further, in terms of parts by mass, the amount of palm oil-based polyurethane prepolymer solution is 56 parts, and the amount of PET fiber felt is 10 parts.

Further, the palm oil-based polyurethane prepolymer solution is composed of 60 to 66 parts by mass of palm oil diethanolamide, 0 to 8 parts of glycol and 34 parts of hexamethylene diisocyanate at room temperature. And stir evenly for 5 minutes.

Furthermore, the palm oil diethanolamide is prepared from palm oil and diethanolamide as raw materials, using sodium methoxide as a catalyst, and its chemical structural formula is: (where R ₁ , R ₂ , and R ₃ are saturated or unsaturated fatty acids); specifically, nitrogen is introduced into a three-necked flask placed in an oil bath, and then diethanolamine and sodium methoxide are added to the flask, and the mixture is heated at 80°C. After mechanical stirring (150 r/min) for 10 minutes, add palm oil and raise the temperature to 120°C, and react for 4 hours; after the product is cooled to room temperature, it is miscible in ethyl acetate and purified repeatedly with saturated NaCl solution for 3~5 After several times, it was purified by rotary evaporation for 3 hours to obtain the palm oil diethanolamide; the molar ratio of palm oil, diethanolamine and sodium methoxide used was 1:6.6:0.17.

Furthermore, the glycol is 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol or 1,10-decanediol.

The preparation method of the self-adhesive waterproofing membrane is to evenly coat the palm oil-based polyurethane prepolymer solution on the PET fiber felt, place it in a mold after being fully infiltrated, and mold and cure at 4 MPa and 140°C for 30 minutes. After curing is completed, wait for the mold to cool to room temperature and demold.

The beneficial effects of the present invention are:

(1) The self-adhesive waterproofing membrane prepared by the present invention is a new type of material using biomass resources and solid waste resources as raw materials, and has the characteristics of being free of toxic solvents and environmentally friendly. It uses low-price, large-yield, green and harmless palm oil as raw material, opening up new applications of palm oil preparation in the field of building waterproof materials, and at the same time solving the problem of difficulty in secondary use of recycled PET fiber.

(2) The palm oil-based waterproofing membrane prepared by the present invention has good tensile strength, peel strength and water resistance, and its various properties meet the national standard GB/T 35467-2017 H and E wet-lay waterproofing membranes. The above standards therefore have good market prospects.

Detailed ways

A self-adhesive waterproofing membrane based on palm oil-based polyurethane. In terms of parts by mass, 56 parts of palm oil-based polyurethane prepolymer solution are evenly coated on 10 parts of PET fiber felt. After being fully infiltrated, it is placed in the mold. , mold it at 4 MPa and 140°C for 30 minutes, and wait until the mold is cooled to room temperature after solidification is completed.

Wherein, the palm oil-based polyurethane prepolymer solution is composed of 60 to 66 parts of palm oil diethanolamide, 0 to 8 parts of glycol and 34 parts of hexamethylene diisocyanate in parts by mass at room temperature. Stir evenly for 5 minutes.

In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.

Raw materials: Palm oil (melting point: 18°C; acid value: 0.16 mg KOH/g) purchased from Shanghai Dingfen Chemical Technology Co., Ltd., China; hexamethylene diisocyanate, 1,4-butanediol, 1,6 hexanediol Alcohol, 1,8-octanediol, 1,10-decanediol and diethanolamine were purchased from Shanghai Jingchun (Aladdin) Industrial Co., Ltd.; sodium chloride, ethyl acetate, and sodium methoxide were purchased from Shanghai Sinopharm Chemical Reagent Co., Ltd.; PET fiber felt cloth was purchased from China Energy Conservation Haidongqing New Materials Group Co., Ltd.

Synthesis process of palm oil diethanolamide:

Place a 1000 mL three-necked flask equipped with mechanical stirring in an oil bath and pass in N ₂ ; then add diethanolamine (124.9 g, 1.19 mol) and sodium methoxide (1.62 g, 0.03 mol), and stir at 80°C ( 150r/min) for 10 minutes, add palm oil (200 g, 0.18 mol) and raise the temperature to 120°C to react for 4 hours; after the reactant is cooled, it is miscible in ethyl acetate and purified repeatedly with saturated NaCl solution After 3 to 5 times, rotary evaporate for 3 hours to obtain palm oil diethanolamide.

Example 1 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 37.2 g of palm oil diethanolamide and 19.1 g of hexamethylene diisocyanate into a 500 mL beaker, and stir at room temperature for 5 minutes until mixed evenly to obtain a mixed solution POEA; evenly coat 56 g of the mixed solution POEA on 10 g PET fiber felt cloth, place it in a mold after being fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof membrane PET/POEA (wherein, palm oil diethanolamide and hexamethylene diethylene glycol The mass ratio of isocyanate is 66:34).

Example 2 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 35.9 g of palm oil diethanolamide, 19.1 g of hexamethylene diisocyanate and 1.1g of 1,4-butanediol into a 500 mL beaker, stir at room temperature for 5 min until evenly mixed, and obtain a mixed solution POEA-BDO0. 5; Evenly apply 56 g of the mixed solution POEA-BDO0.5 on 10 g of PET fiber felt, place it in the mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof roll Material PET/POEA-BDO0.5 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,4-butanediol is 64:34:2).

Example 3 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 34.8 g of palm oil diethanolamide, 19.1 g of hexamethylene diisocyanate and 2.3g of 1,4-butanediol into a 500 mL beaker, stir at room temperature for 5 minutes until evenly mixed, and obtain a mixed solution POEA-BDO1; Coat 56 g of the mixed solution POEA-BDO1 evenly on 10 g of PET fiber felt, place it in a mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof membrane PET/POEA. -BDO1 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,4-butanediol is 62:34:4).

Example 4 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 33.7g of palm oil diethanolamide, 19.1g of hexamethylene diisocyanate and 3.4g of 1,4-butanediol into a 500 mL beaker, stir at room temperature for 5 minutes until evenly mixed, and obtain a mixed solution POEA-BDO1. 5; Evenly apply 56 g of the mixed solution POEA-BDO1.5 on 10 g of PET fiber felt, place it in the mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof roll Material PET/POEA-BDO1.5 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,4-butanediol is 60:34:6).

Example 5 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 35.7 g of palm oil diethanolamide, 19.1 g of hexamethylene diisocyanate and 1.4g of 1,6-hexanediol into a 500 mL beaker, stir at room temperature for 5 min until evenly mixed, and obtain a mixed solution POEA-HDO0. 5; Evenly apply 56 g of the mixed solution POEA-HDO0.5 on 10 g of PET fiber felt, place it in the mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof roll Material PET/POEA-HDO0.5 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,6-hexanediol is 63.5:34:2.5).

Example 6 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 35.4 g of palm oil diethanolamide, 19.1 g of hexamethylene diisocyanate and 1.7g of 1,8-octanediol into a 500 mL beaker, stir at room temperature for 5 min until evenly mixed, and obtain a mixed solution POEA-ODO0. 5; Evenly apply 56 g of the mixed solution POEA-ODO0.5 on 10 g of PET fiber felt, place it in the mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof roll Material PET/POEA-ODO0.5 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,8-octanediol is 63:34:3).

Example 7 Preparation of PET fiber felt/palm oil-based polyurethane self-adhesive waterproof membrane:

Add 35.1 g of palm oil diethanolamide, 19.1 g of hexamethylene diisocyanate and 2.0 g of 1,10-decanediol into a 500 mL beaker, stir at room temperature for 5 min until evenly mixed, and obtain a mixed solution POEA-DDO0. 5; Evenly apply 56 g of the mixed solution POEA-DDO0.5 on 10 g of PET fiber felt, place it in the mold after it is fully soaked, and mold it at 4 MPa and 140°C for 30 minutes to prepare a self-adhesive waterproof roll Material PET/POEA-DDO0.5 (the mass ratio of palm oil diethanolamide, hexamethylene diisocyanate and 1,10-decanediol is 62.5:34:3.5).

1. Tensile property test:

According to the national standard GB/T 328.9-2007, prepare a rectangular coiled sample (200 mm × 50 mm); conduct a tensile test on an Instron 3365 universal testing machine at room temperature, with a tensile rate of 100 mm/min; record the tensile test. For tensile stress and tensile strain, each group of samples should be measured at least 5 times, and the mean and variance should be calculated (during the stretching process, the adhesive layer of the membrane should not be separated from the polymer film or base tire). The results are shown in Table 1.

Table 1 Tensile properties of waterproof membrane

It can be seen from Table 1 that the maximum tensile force of waterproof membranes PET/POEA, PET/POEA-BDO0.5, PET/POEA-BDO1 and PET/POEA-BDO1.5 increases with the increase of 1,4-butanediol content. and increases; but the elongation at the maximum tensile force shows a trend of first increasing and then decreasing, among which PET/POEA-BDO0.5 has the largest elongation, and its performance is better than that of waterproof membrane PET/POEA- HDO0.5, PET/POEA-ODO0.5 and PET/POEA-DDO0.5.

2. Tear strength test:

According to the national standard GB/T 529-2008, uncut right-angle splines were prepared to test the tear resistance of POEA-PET membranes. Conduct a tensile test on an Instron 3365 universal testing machine at room temperature, with a tensile rate of 250 mm/min; read the maximum tensile force value directly, and the results are expressed as force values. Each group of samples is measured at least 5 times, and the mean and variance are calculated. .

Table 2 Tear strength of waterproof membrane

It can be seen from Table 2 that the maximum tear strength of waterproof membranes PET/POEA, PET/POEA-BDO0.5, PET/POEA-BDO1 and PET/POEA-BDO1.5 increases with the 1,4-butanediol content. increase by increasing. At the same time, under the same dosage conditions, the maximum tearing force of the waterproof membrane increases first and then decreases as the number of carbon atoms in the glycol main chain increases. Among them, the maximum tearing force of the PET/POEA-ODO0.5 membrane increases. Maximum cracking strength.

3. Seam peel strength test:

According to the national standard GB/T 328.21-2007, the joint peel strength of POEA-PET waterproof membrane without treatment and water immersion treatment was tested. Untreated sample: prepare a rectangular spline (200 mm × 50 mm), and take 2 splines for bonding and overlapping. The overlapping area is 70 mm long and 50 mm wide; after overlapping, the sample is rolled repeatedly with a roller 3 times. , test after being placed at room temperature for 24 hours; the test rate of the sample is 100 mm/min, the results are expressed in force values (N/mm), and the average peel strength is calculated.

Table 3 Seam peeling performance of waterproof membrane

It can be seen from Table 3 that the joint peeling force of waterproof membranes PET/POEA, PET/POEA-BDO0.5, PET/POEA-BDO1 and PET/POEA-BDO1.5 increases with the increase of 1,4-butanediol content. And decrease. At the same time, under the same dosage conditions, the seam peeling force of the waterproof membrane increases with the increase in the number of carbon atoms in the glycol main chain.

The above are only preferred embodiments of the present invention, and all equivalent changes and modifications made in accordance with the patentable scope of the present invention shall fall within the scope of the present invention.

Claims (7)

1. A self-adhesive waterproofing membrane based on palm oil-based polyurethane, characterized in that: the self-adhesive waterproofing membrane is prepared by a hot pressing molding process using palm oil-based polyurethane prepolymer solution and PET fiber felt as raw materials. owned. 2. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 1, characterized in that: in terms of parts by mass, the amount of palm oil-based polyurethane prepolymer solution is 56 parts, and the amount of PET fiber felt is 56 parts. 10 servings. 3. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 1 or 2, characterized in that: the palm oil-based polyurethane prepolymer solution is composed of 60 parts by mass of palm oil diethanolamide. ~66 parts, 0~8 parts of glycol and 34 parts of hexamethylene diisocyanate were mixed and stirred for 5 minutes. 4. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 3, characterized in that: the glycol is 1,4-butanediol, 1,6-hexanediol, 1,8 - Octanediol or 1,10-decanediol. 5. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 3, characterized in that: the palm oil diethanolamide is made of palm oil and diethanolamide as raw materials, and sodium methoxide is used as a catalyst. It was prepared by reacting at 120°C for 4 hours in a nitrogen environment. 6. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 5, characterized in that: the molar ratio of palm oil, diethanolamine and sodium methoxide used is 1:6.6:0.17. 7. The self-adhesive waterproofing membrane based on palm oil-based polyurethane according to claim 1, characterized in that: its preparation method is to evenly coat the palm oil-based polyurethane prepolymer solution on the PET fiber felt, and wait until it is fully infiltrated. Then place it in the mold and press and solidify it at 4 MPa and 140°C for 30 minutes. After the curing is completed, wait for the mold to cool to room temperature and demould.