Flame-retardant waterproof coiled material and processing technology thereof

Abstract

The invention discloses a flame-retardant waterproof roll and a processing technology thereof. Belongs to the technical field of coiled materials, and the prepared coiled material comprises the following raw materials: 80-100 parts of polyolefin, 3-5 parts of a cross-linking agent, 9-11 parts of a modifier and 0.1-0.3 part of an initiator. Wherein the coiled material takes polyolefin as a matrix, so that the material is easy to process and has good acid and alkali corrosion resistance, water resistance and electrical insulating property. The modifier is added into the coiled material for modification, so that the prepared coiled material has good flame retardance and ultraviolet aging resistance; therefore, the prepared coiled material has good flame retardance, ultraviolet aging resistance and waterproof performance, and has important application value in the field of buildings.

Description

Technical Field

[0001] The invention belongs to the technical field of waterproof coiled materials, and in particular relates to a flame retardant waterproof coiled material and a processing technology thereof. Background Art

[0002] With the rapid development of my country's economy, various buildings have sprung up like mushrooms after a spring rain. People's requirements for moisture-proof, anti-seepage and anti-leakage of buildings, especially large buildings, are getting higher and higher. Traditional asphalt waterproofing membranes cannot meet people's requirements, so polymer waterproofing membranes have developed rapidly. The first to develop are EPDM waterproofing membranes and polyvinyl chloride (PVC) waterproofing membranes. However, EPDM waterproofing membranes have high processing requirements, and PVC waterproofing membranes contain plasticizers in the raw materials, which will cause a series of problems due to the migration of plasticizers. In addition, the existing PVC membranes have large smoke volume, poor thermal stability, and poor fluidity. Friction heat is easily generated during injection molding, resulting in degradation and yellowing, which seriously affects the product appearance, performance and safety. In the late 1990s, thermoplastic polyolefin waterproofing membranes began to enter the market in North America and Europe, and entered the Chinese market at the beginning of this century, and were used in some large-scale construction projects. Due to the good comprehensive performance and processability of thermoplastic polyolefins, thermoplastic polyolefin waterproofing membranes have developed rapidly. Thermoplastic polyolefin waterproofing membranes do not contain plasticizers, and there is no problem of becoming brittle due to plasticizer migration. They have comprehensive characteristics such as high tensile strength, good puncture resistance, smooth surface, high reflectivity and pollution resistance. In engineering applications, they are also easy to process, weldable, convenient to construct and completely recyclable. They are new green and environmentally friendly waterproof materials. However, polyolefins are also a type of highly flammable polymer material, and a large amount of harmful gases will be produced during the combustion process. The fire hazards caused by this have become the focus of global attention. At present, the halogen-free flame retardant of polyolefins mainly includes the following categories: the first category is inorganic flame retardants; the second category is phosphorus-containing flame retardants; the third category is silicon-containing flame retardants; and the fourth category is nano-carbon material flame retardants. In general, the halogen-free flame retardant system currently studied has the following main problems: first, it is difficult for polyolefins to achieve the desired flame retardant effect in the presence of a single flame retardant, so the addition amount is generally very high; second, since polyolefins are extremely flammable, a small amount of nano-scale fillers can only reduce their heat release rate, and it is difficult to meet the requirements for oxygen index and vertical combustion. Summary of the invention

[0003] The purpose of the present invention is to provide a flame retardant waterproof coiled material and a processing technology thereof.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A flame retardant waterproof coiled material comprises the following raw materials in parts by weight: 80-100 parts of polyolefin, 3-5 parts of cross-linking agent, 9-11 parts of modifier and 0.1-0.3 parts of initiator.

[0006] Furthermore, the polyolefin is obtained by copolymerization of ethylene and propylene (mass ratio 3:7).

[0007] Furthermore, the cross-linking agent is dicumyl peroxide.

[0008] Furthermore, the initiator is one of benzoyl peroxide and methyl ethyl ketone peroxide.

[0009] The prepared coil material is based on polyolefin, which gives the material easy processing, good acid and alkali corrosion resistance, water resistance and electrical insulation.

[0010] Furthermore, the modifier is prepared by the following steps:

[0011] S1. Allyl acetic acid, ethanol and EDC are placed in a three-necked flask equipped with a stirring device. 4-chloro-1-butylamine is dissolved in ethanol and dripped into the three-necked flask dropwise. The mixture is stirred evenly and heated to 75° C. for 3 hours. Toluene is added and azeotropic distillation is performed to obtain the intermediate 1, wherein the ratio of 4-chloro-1-butylamine to allyl acetic acid is 10.02 g:10.76 g. The specific reaction steps are as follows:

[0012]

[0013] S2. Add DMSO, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and intermediate 1 into a four-necked flask, stir, heat to 110°C, react for 3h, cool to room temperature, add excess sodium carbonate and filter, purify by column chromatography (eluent is a mixed solvent of ether / carbon tetrachloride, the volume ratio of the two is 1:3), remove the eluent by rotary evaporation to obtain intermediate 2, the ratio of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate to intermediate 1 is 24.01g:10.15g, and the specific reaction steps are as follows:

[0014]

[0015] S3. Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-chlorobutyraldehyde and toluene into a four-necked flask equipped with a stirrer, and stir and react at 100° C. for 6 h under the protection of nitrogen. After the reaction is completed, azeotropic distillation is first performed, and then recrystallization is performed to obtain intermediate 3. The ratio of DOPO to 4-chlorobutyraldehyde is 21.60 g:10.66 g. The specific reaction steps are as follows:

[0016]

[0017] S4, DMSO, intermediate 2 and intermediate 3 were added to a four-necked flask, stirred, heated to 110 ° C, reacted for 3h, cooled to room temperature, added excess sodium carbonate and filtered, purified by column chromatography (eluent using a mixed solvent of toluene / carbon tetrachloride, the volume ratio of the two is 2:5), the eluent was removed by rotary evaporation to obtain a modifier, the ratio of the amount of intermediate 2 and intermediate 3 is 31.68g:16.10g, and the specific reaction steps are as follows:

[0018]

[0019] The prepared modifier molecule contains a benzene ring, which is a rigid structure and can enhance the mechanical properties and heat resistance of the polyolefin matrix to a certain extent; the modifier molecule contains nitrogen and phosphorus elements, wherein the nitrogen and phosphorus elements belong to nitrogen-based and phosphorus-based flame retardant components respectively, forming NP synergistic flame retardant, which can work together with the benzene ring to greatly improve the flame retardant performance of the matrix; in addition, the modifier molecule also contains a hindered amine structure, which can be converted into nitroxide free radicals (NO·) after absorbing light energy, and these nitroxide free radicals can capture alkyl active free radicals generated in the photo-oxidative degradation of polymer materials, and have a regeneration function in the process of light stabilization, thereby improving the anti-ultraviolet aging performance of the matrix; the carbon-carbon double bond at one end of the modifier molecule can chemically react with the polyolefin molecular chain, be grafted onto the matrix molecular chain in a chemically bonded manner, enhance the interaction force between the modifier and the matrix, make the modifier and the matrix more closely connected, and improve the long-term stability of various properties of the matrix.

[0020] Another object of the present invention is to provide a processing technology for a flame retardant waterproof membrane, comprising the following steps:

[0021] The raw materials such as polyolefin, cross-linking agent, modifier and initiator are uniformly mixed in the above proportion to obtain a blend; the blend is melted, extruded, calendered and cooled to obtain a flame-retardant waterproof membrane.

[0022] Beneficial effects of the present invention:

[0023] 1. The coiled material prepared by the present invention is based on polyolefin, which gives the material good chemical resistance, water resistance, mechanical strength and electrical insulation;

[0024] 2. The present invention modifies polyolefin by using a modifier. The introduction of benzene rings, nitrogen-containing groups, phosphorus-containing groups and hindered amine chains in the modifier improves the flame retardant properties and anti-ultraviolet aging properties of the coiled material.

[0025] Therefore, the coiled material prepared by the present invention has high-efficiency flame retardancy, anti-ultraviolet aging performance and waterproof performance. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Embodiment 1

[0028] Preparation of modifier:

[0029] S1. Place 10.76 g of allyl acetic acid, 30 mL of ethanol and 3.64 g of EDC in a three-necked flask equipped with a stirring device. Dissolve 10.02 g of 4-chloro-1-butylamine in 30 mL of ethanol and add dropwise into the three-necked flask. Stir evenly and heat to 75 ° C. React for 3 h. Add toluene and obtain intermediate 1 by azeotropic distillation.

[0030] S2. Add 50 mL of DMSO, 24.01 g of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate and 10.15 g of intermediate 1 into a four-necked flask, stir, heat to 110°C, react for 3 h, cool to room temperature, add 0.75 g of sodium carbonate and filter, purify by column chromatography (the eluent is a mixed solvent of ether / carbon tetrachloride, the volume ratio of the two is 1:3), remove the eluent by rotary evaporation to obtain intermediate 2.

[0031] S3. Add 21.60 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10.66 g of 4-chlorobutyraldehyde and 100 mL of toluene into a four-necked flask equipped with a stirrer, and stir the reaction at 100 °C for 6 h under the protection of nitrogen. After the reaction is completed, perform azeotropic distillation and then recrystallize from toluene / ethanol (volume ratio of 2:1) to obtain intermediate 3.

[0032] S4. Add 70 mL DMSO, 31.68 g intermediate 2 and 16.10 g intermediate 3 into a four-necked flask, stir, heat to 110 ° C, react for 3 hours, cool to room temperature, add 1.12 g sodium carbonate and filter, purify by column chromatography (the eluent is a mixed solvent of toluene / carbon tetrachloride, the volume ratio of the two is 2:5), remove the eluent by rotary evaporation to obtain a modifier.

[0033] Embodiment 2

[0034] Preparation of modifier:

[0035] S1. Place 21.52 g of allyl acetic acid, 60 mL of ethanol and 7.28 g of EDC in a three-necked flask equipped with a stirring device, dissolve 20.04 g of 4-chloro-1-butylamine in 60 mL of ethanol, and add dropwise into the above three-necked flask, stir evenly and heat to 75 ° C., react for 3 h, add toluene, and obtain intermediate 1 by azeotropic distillation.

[0036] S2. Add 100 mL DMSO, 48.02 g bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate and 20.30 g intermediate 1 into a four-necked flask, stir, heat to 110°C, react for 3 h, cool to room temperature, add 1.50 g sodium carbonate and filter, purify by column chromatography (the eluent is a mixed solvent of ether / carbon tetrachloride, the volume ratio of the two is 1:3), remove the eluent by rotary evaporation to obtain intermediate 2.

[0037] S3. Add 43.20 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 21.32 g of 4-chlorobutyraldehyde and 200 mL of toluene into a four-necked flask equipped with a stirrer, and stir the reaction at 100 °C for 6 h under the protection of nitrogen. After the reaction is completed, azeotropic distillation is performed first, and then recrystallization is performed in toluene / ethanol (volume ratio of 2:1) to obtain intermediate 3.

[0038] S4. Add 140 mL DMSO, 63.36 g intermediate 2 and 32.2 g intermediate 3 into a four-necked flask, stir, heat to 110 ° C, react for 3 hours, cool to room temperature, add 2.24 g sodium carbonate and filter, purify by column chromatography (the eluent is a mixed solvent of toluene / carbon tetrachloride, the volume ratio of the two is 2:5), remove the eluent by rotary evaporation to obtain a modifier.

[0039] Embodiment 3

[0040] Preparation of flame retardant waterproof membrane:

[0041] 80.0 g of polyolefin (mass ratio of ethylene to propylene is 3:7), 3.0 g of dicumyl peroxide, 9.0 g of the modifier prepared in Example 1 and 0.1 g of benzoyl peroxide were uniformly mixed to obtain a blend; the blend was melted and then extruded, calendered and cooled to obtain a flame-retardant waterproof membrane.

[0042] Embodiment 4

[0043] Preparation of flame retardant waterproof membrane:

[0044] 90.0 g of polyolefin (mass ratio of ethylene to propylene 3:7), 4.0 g of dicumyl peroxide, 10.0 g of the modifier prepared in Example 2 and 0.2 g of methyl ethyl ketone peroxide were uniformly mixed to obtain a blend; the blend was melted and then extruded, calendered and cooled to obtain a flame-retardant waterproof membrane.

[0045] Embodiment 5

[0046] Preparation of flame retardant waterproof membrane:

[0047] 100.0 g of polyolefin (mass ratio of ethylene to propylene 3:7), 5.0 g of dicumyl peroxide, 11.0 g of the modifier prepared in Example 2 and 0.3 g of benzoyl peroxide were uniformly mixed to obtain a blend; the blend was melted and then extruded, calendered and cooled to obtain a flame-retardant waterproof membrane.

[0048] Comparative Example 1

[0049] The modifier in Example 5 was replaced by DOPO flame retardant, and the remaining steps were the same as those in Example 5 to prepare a flame retardant waterproof membrane.

[0050] Comparative Example 2

[0051] The modifier is removed, and the remaining steps are the same as those in Example 5 to obtain a flame retardant waterproof membrane.

[0052] The coils prepared in Examples 3 to 5 and Comparative Examples 1 to 2 were subjected to the following performance tests, and the results are shown in the following table:

[0053] Anti-aging performance test: The tensile performance test was carried out in accordance with GB / T 1040.2-2022, with a tensile rate of 50 mm / min and a clamping distance of 6 cm; after 72 hours of ultraviolet irradiation treatment, the tensile performance test was carried out again.

[0054]

[0055] It can be seen from the above table that the coiled material prepared by the present invention has good flame retardancy, anti-ultraviolet aging performance and waterproof performance, and has important application value in the field of construction.

[0056] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0057] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A processing technology for flame retardant waterproof coiled material, characterized in that: The following steps are involved: The polyolefin, the crosslinking agent, the modifier and the initiator raw materials are uniformly mixed in a mass ratio of 80-100:3-5:9-11:0.1-0.3 to obtain a blend; the blend is melted, extruded, calendered and cooled to obtain a flame-retardant waterproof membrane.

2. The processing technology of a flame retardant waterproof coiled material according to claim 1, characterized in that: The polyolefin is obtained by copolymerization of ethylene and propylene.

3. The processing technology of a flame retardant waterproof coiled material according to claim 1, characterized in that: The cross-linking agent is dicumyl peroxide.

4. The processing technology of a flame retardant waterproof coiled material according to claim 1, characterized in that: The initiator is one of benzoyl peroxide and methyl ethyl ketone peroxide.

5. The processing technology of a flame retardant waterproof coiled material according to claim 1, characterized in that: The specific preparation process of the modifier is as follows: S1. Allyl acetic acid, ethanol and EDC are placed in a three-necked flask, 4-chloro-1-butylamine is dissolved in ethanol, and the mixture is added dropwise into the three-necked flask, the mixture is stirred evenly and the temperature is raised to 75° C. The reaction is carried out for 3 h, and toluene is added. Intermediate 1 is obtained by azeotropic distillation. S2, DMSO, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and intermediate 1 were added to a four-necked flask, stirred, heated to 110°C, reacted for 3 hours, cooled to room temperature, added with excess sodium carbonate, filtered, purified by column chromatography, and rotary evaporated to obtain intermediate 2; S3, adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4-chlorobutyraldehyde and toluene into a four-necked flask, stirring and reacting at 100° C. for 6 h under the protection of nitrogen, after the reaction is completed, azeotropic distillation is first performed, and then recrystallization is performed to obtain intermediate 3; S4. Add DMSO, intermediate 2 and intermediate 3 into a four-necked flask, stir, heat to 110°C, react for 3 hours, cool to room temperature, add excess sodium carbonate, filter, purify by column chromatography, and rotary evaporation to obtain a modifier.

6. The processing technology of a flame retardant waterproof coiled material according to claim 5, characterized in that: In step S1, the ratio of allyl acetic acid to 4-chloro-1-butylamine is 10.76 g:10.02 g.

7. The processing technology of a flame retardant waterproof coiled material according to claim 5, characterized in that: In step S2, the ratio of the amount of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate to the amount of intermediate 1 is 24.01 g:10.15 g.

8. The processing technology of a flame retardant waterproof coiled material according to claim 5, characterized in that: In step S3, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 4-chlorobutyraldehyde is 21.60 g:10.66 g.

9. The processing technology of a flame retardant waterproof coiled material according to claim 5, characterized in that: The ratio of the amount of intermediate 2 to that of intermediate 3 in step S4 is 31.68 g:16.10 g.

10. A flame retardant waterproofing membrane, characterized in that: Obtained according to the processing technology described in any one of claims 1 to 9.

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