Antistatic polyolefin waterproof coiled material and preparation method thereof

Abstract

The invention provides an antistatic polyolefin waterproof coiled material and a preparation method thereof, and relates to the technical field of waterproof coiled materials. The antistatic polyolefin waterproof coiled material is prepared from the following raw material components in parts by weight: 35 to 65 parts of polyolefin resin, 15 to 26 parts of a toughening agent, 0.2 to 0.5 part of a dispersing agent, 5 to 15 parts of inorganic filler, 0.2 to 0.6 part of an anti-aging agent, 0.1 to 0.5 part of an ultraviolet absorbent, 2 to 4 parts of a compatilizer and 11 to 15 parts of an antistatic agent, the antistatic agent is composed of an antistatic agent A and an antistatic agent B in a weight ratio of 10: (1-5); the antistatic agent A is alkyl polyoxyethylene ether sulfonate; the antistatic agent B is prepared from ethoxylated alkylamine and a glyceride compound. The polyolefin waterproof coiled material disclosed by the invention has relatively good antistatic durability and physical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of waterproof coiled materials, and relates to an antistatic polyolefin waterproof coiled material and a preparation method thereof. Background Art

[0002] Polyolefin (TPO) waterproofing membrane is a thermoplastic waterproofing membrane mixed with ethylene propylene elastomer and polypropylene. It has excellent performance and no migration of plasticizers during later use, which causes catalysis of the material. It is a green and environmentally friendly waterproofing material. In recent years, it has been widely recognized and applied in photovoltaic roofs. Antistatic performance has gradually become an important requirement for polyolefin waterproofing membranes. Existing waterproofing membranes mostly use ionic antistatic agents, which will gradually migrate to the surface of the waterproofing membrane to eliminate the static charge generated by itself or neutralize the free charge in the environment. It has the characteristics of small addition amount and small effect on the physical properties of the waterproofing membrane. However, this antistatic method gradually loses its antistatic effect due to friction, water washing, etc., and generally maintains for 3-5 years. Therefore, it is necessary to use a permanent antistatic agent, but due to the large amount of permanent antistatic agent added, it has a greater impact on the physical properties of the waterproofing membrane, such as poor toughness.

[0003] Therefore, it is necessary to conduct further research on permanent antistatic waterproof membranes, which can give waterproof membranes lasting antistatic properties while having a lower impact on the physical properties of the waterproof membranes. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antistatic polyolefin waterproof coiled material and a preparation method thereof.

[0005] The technical solution of the present invention is as follows:

[0006] An antistatic polyolefin waterproof coiled material, wherein the raw material components, by weight, comprise 35-65 parts of a polyolefin resin, 15-26 parts of a toughening agent, 0.2-0.5 parts of a dispersant, 5-15 parts of an inorganic filler, 0.2-0.6 parts of an antioxidant, 0.1-0.5 parts of an ultraviolet absorber, 2-4 parts of a compatibilizer, and 11-15 parts of an antistatic agent;

[0007] The antistatic agent is composed of antistatic agent A and antistatic agent B in a weight ratio of 10:1-5;

[0008] The antistatic agent A is an alkyl polyoxyethylene ether sulfonate;

[0009] The antistatic agent B consists of ethoxylated alkylamine and glyceride compound.

[0010] Preferably, the structure of the alkyl polyoxyethylene ether sulfonate is as shown in the following formula (1):

[0011] Cn H 2n+1 (OCH2CH2) m SO3M(1)

[0012] Wherein, n=8-36, m=6-30, and M is a monovalent metal ion.

[0013] More preferably, n=12-36, m=9-20.

[0014] Preferably, the glyceride compound is selected from glyceryl monostearate and / or glyceryl monopalmitate.

[0015] Preferably, the weight ratio of the ethoxylated alkylamine to the glyceride compound is 1:2-2:1.

[0016] Preferably, the toughening agent is selected from one or a combination of two or more of polyolefin elastomers, EPDM rubber elastomers, natural rubber elastomers and ethylene-vinyl acetate copolymer elastomers.

[0017] Preferably, the dispersant is selected from one or a combination of two or more of polyethylene wax, zinc stearate, magnesium stearate, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.

[0018] Preferably, the inorganic filler is selected from one or a combination of two or more of talc, metakaolin, heavy calcium carbonate, light calcium carbonate, wollastonite, glass microspheres and mica powder.

[0019] Preferably, the compatibilizer is selected from maleic anhydride grafted polymer or glycidyl methacrylate grafted polymer.

[0020] The method for preparing the antistatic polyolefin waterproof membrane described in any of the above technical solutions comprises mixing the raw material components uniformly, performing melt extrusion and forming through a three-roller machine, and then trimming and rolling.

[0021] The beneficial effects of the present invention are:

[0022] (1) The polyolefin waterproof membrane of the present invention is added with an antistatic agent prepared by mixing antistatic agent A and antistatic agent B, and the added amount is relatively high, which can give the waterproof membrane a lasting antistatic property. A relatively large amount of toughening agent and a certain amount of compatibilizer are then added. The waterproof membrane of the present invention will not have a significant adverse effect on its physical properties due to the addition of a relatively large amount of antistatic agent.

[0023] (2) The antistatic agent of the present invention is compounded by antistatic agent A and antistatic agent B, and antistatic agent B is composed of ethoxylated alkylamine and glyceride compound, which can provide a long-lasting antistatic effect and realize permanent antistatic performance of the waterproof membrane. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0025] In order to make the waterproof membrane have permanent antistatic properties and have little effect on the physical properties of the waterproof membrane, on the one hand, the present invention provides an antistatic polyolefin waterproof membrane, the raw material components, by weight, include 35-65 parts of polyolefin resin, 15-26 parts of toughening agent, 0.2-0.5 parts of dispersant, 5-15 parts of inorganic filler, 0.2-0.6 parts of antioxidant, 0.1-0.5 parts of ultraviolet absorber, 2-4 parts of compatibilizer and 11-15 parts of antistatic agent;

[0026] The antistatic agent is composed of antistatic agent A and antistatic agent B in a weight ratio of 10:1-5, for example, the weight ratio can be any value of 10:1, 10:2, 10:3, 10:4, 10:5 or any value in between, without special restrictions;

[0027] Antistatic agent A is alkyl polyoxyethylene ether sulfonate;

[0028] Antistatic agent B is composed of ethoxylated alkylamine and glyceride compounds.

[0029] In the present invention, in order to make the polyolefin waterproofing coiled material have permanent antistatic properties, a combination of antistatic agent A and antistatic agent B is used, and the amount of antistatic agent A is relatively large. Antistatic agent B is a small molecule antistatic agent, which will gradually migrate to the surface of the waterproofing coiled material to provide an antistatic effect, but there is also a problem of insufficient persistence. In the present invention, a relatively large amount of antistatic agent A is added, and the molecular weight of antistatic agent A is relatively large. In addition to playing an antistatic role by itself, it can also interact with antistatic agent B, thereby improving the stability of the antistatic agent in the waterproofing coiled material, avoiding the gradual loss and failure of the antistatic agent, and playing an antistatic persistence role.

[0030] Since a large amount of antistatic agent is added, it will have a negative impact on the physical properties of the polyolefin waterproof membrane, especially the toughness. A large amount of toughening agent and a certain amount of compatibilizer are added to the polyolefin waterproof membrane of the present invention, so that the waterproof membrane has permanent antistatic properties and good physical properties.

[0031] In a preferred embodiment of the present invention, the structure of the alkyl polyoxyethylene ether sulfonate is shown in the following formula (1): n H 2n+1 (OCH2CH2) m SO3M(1)

[0032] Wherein, n=8-36, m=6-30, and M is a monovalent metal ion, such as a sodium ion.

[0033] The alkyl polyoxyethylene ether sulfonate of the present invention has a relatively high molecular weight, and when added to the waterproof coiled material, it can interact with the antistatic agent B to play a relatively lasting antistatic effect, further improve the durability of the antistatic effect, and achieve a permanent antistatic effect.

[0034] In a more preferred embodiment of the present invention, n=12-36, m=9-20. For example, n can be 12, such as lauryl, n can be 18, such as stearyl, n can be 16, such as cetyl, or tetracosyl, etc. For example, n=18, m=12, alkyl polyoxyethylene ether sodium sulfonate can be recorded as stearyl polyoxyethylene ether (12) sodium sulfonate, and so on.

[0035] In a preferred embodiment of the present invention, the glyceride compound is selected from glyceryl monostearate and / or glyceryl monopalmitate. Both glyceryl monostearate and glyceryl monopalmitate have hydrophilic and lipophilic groups in their molecular structures, and have a certain incompatibility in the waterproofing membrane, and can gradually migrate and precipitate to the surface of the waterproofing membrane, playing an antistatic role.

[0036] In a preferred embodiment of the present invention, the weight ratio of the ethoxylated alkylamine to the glyceride compound is 1:2-2:1. For example, the weight ratio of the ethoxylated alkylamine to the glyceride compound can be any value of 2:1, 3:2, 4:3, 1:1, 3:4, 2:3, 1:2 or any value therebetween, without particular limitation.

[0037] In a preferred embodiment of the present invention, the toughening agent is selected from one or a combination of two or more of polyolefin elastomer POE, ethylene propylene diene monomer rubber elastomer EPDM, natural rubber elastomer NR and ethylene-vinyl acetate copolymer elastomer EVA. In the present invention, in order to solve the problem of deterioration of physical properties such as impact toughness and tensile strength caused by adding a large amount of antistatic agent, a large amount of toughening agent is added in the present invention, and it is found that the physical properties can be better restored.

[0038] In a preferred embodiment of the present invention, the dispersant is not particularly limited and can be selected from one or a combination of two or more of polyethylene wax, zinc stearate, magnesium stearate, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.

[0039] In a preferred embodiment of the present invention, the inorganic filler is not particularly limited and can be selected from one or a combination of two or more of talc, metakaolin, heavy calcium carbonate, light calcium carbonate, wollastonite, glass microspheres and mica powder.

[0040] The compatibilizer can well improve the compatibility of inorganic fillers with polyolefin resins, toughening agents and other polymers. In a preferred embodiment of the present invention, the compatibilizer is selected from maleic anhydride grafted polymers or glycidyl methacrylate grafted polymers. The maleic anhydride grafted polymer can be maleic anhydride grafted PE, maleic anhydride grafted PP, maleic anhydride grafted EPDM, maleic anhydride grafted EVA, etc., and the glycidyl methacrylate grafted polymer can be GMA grafted POE, GMA grafted PE, GMA grafted PP, etc. The grafting rate of maleic anhydride in the maleic anhydride grafted polymer and the grafting rate of GMT in the glycidyl methacrylate grafted polymer can be 0.5-2%, respectively.

[0041] On the other hand, the present invention provides a method for preparing the antistatic polyolefin waterproofing membrane described in any of the above technical solutions, wherein the raw material components are mixed evenly, melt-extruded, formed by a three-roller machine, and rolled up by trimming. The specific preparation method can be as follows:

[0042] 1) Add the measured raw material components into the mixer, start stirring, stirring speed of 150 rpm, stirring time of 30 min, and pour into the storage hopper of the twin-screw extruder for standby use.

[0043] 2) Set the extruder temperature, the first zone is room temperature, the second zone is 175°C, and the temperature of the remaining zones is 175-190°C.

[0044] 3) Set the screen changer temperature to 180-200℃, the melt pump temperature to 175-190℃, and the flow channel temperature to 175-190℃.

[0045] 4) Set the die temperature to 170-190°C.

[0046] 5) Set the temperature of the three-roll mill to 20-30℃ for the upper roll, 30-50℃ for the middle roll, 30-50℃ for the lower roll, and 20-30℃ for the other cooling rolls.

[0047] 6) After the temperature reaches the set requirement and is kept warm for 1 hour, start the twin-screw extruder.

[0048] 7) Adjust the speed of the twin-screw extruder and the three-roller machine to make the product reach the required thickness.

[0049] 8) The speed of the cooling roller and the traction roller shall not be higher than the speed of the three-roller machine.

[0050] 9) Cut the edges and roll up neatly.

[0051] The technical solution of the present invention is further described and illustrated according to various embodiments below. Unless otherwise specified, the parts described in the following embodiments are parts by weight.

[0052] Example 1

[0053] Antistatic polyolefin waterproofing membrane, the raw material components, by weight, include 50 parts of polyethylene (2.16 kg load, 190° C., melt index 3 g / 10 min), 20 parts of toughening agent POE, 0.4 parts of zinc stearate, 10 parts of talc, 2 parts of metakaolin, 0.4 parts of antioxidant 1076, 0.2 parts of ultraviolet absorber UV-329, 3 parts of maleic anhydride grafted PE (grafting rate 1%) and 12 parts of antistatic agent;

[0054] The antistatic agent is composed of antistatic agent A and antistatic agent B in a weight ratio of 10:2, and the antistatic agent A is sodium stearyl polyoxyethylene ether (12) sulfonate;

[0055] Antistatic agent B is composed of ethoxylated alkylamine and glyceryl monostearate in a weight ratio of 1:1.

[0056] Example 2

[0057] The difference between this embodiment and embodiment 1 is that the weight ratio of the antistatic agent A to the antistatic agent B in embodiment 1 is adjusted from 10:2 to 10:1. The other steps remain unchanged.

[0058] Example 3

[0059] The difference between this embodiment and embodiment 1 is that the weight ratio of the antistatic agent A to the antistatic agent B in embodiment 1 is adjusted from 10:2 to 10:5. The other steps remain unchanged.

[0060] Example 4

[0061] The difference between this embodiment and embodiment 1 is that the weight ratio of ethoxylated alkylamine to glyceryl monostearate in embodiment 1 is adjusted from 1:1 to 2:1. The other steps remain unchanged.

[0062] Example 5

[0063] The difference between this embodiment and embodiment 1 is that the weight ratio of ethoxylated alkylamine to glyceryl monostearate in embodiment 1 is adjusted from 1:1 to 1:2. The other steps remain unchanged.

[0064] Comparative Example 1

[0065] The difference between this comparative example and Example 1 is that the antistatic agent in Example 1 is adjusted from 12 parts to 2 parts, and the antistatic agent is composed of ethoxylated alkylamine and glyceryl monostearate in a weight ratio of 1:1. The other steps remain unchanged.

[0066] Comparative Example 2

[0067] The difference between this comparative example and Example 1 is that the weight fraction of the antistatic agent in Example 1 remains unchanged, and the antistatic agent is composed of ethoxylated alkylamine and glyceryl monostearate in a weight ratio of 1:1. The remaining steps remain unchanged.

[0068] Comparative Example 3

[0069] The difference between this comparative example and Example 1 is that the antistatic agent in Example 1 is adjusted to consist of 12 parts of sodium stearyl polyoxyethylene ether (12) sulfonate. The other steps remain unchanged.

[0070] Comparative Example 4

[0071] The difference between this comparative example and Example 1 is that the antistatic agent B in Example 1 is adjusted to be composed of glyceryl monostearate in an equal weight. The other steps remain unchanged.

[0072] Comparative Example 5

[0073] The difference between this comparative example and Example 1 is that the antistatic agent B in Example 1 is adjusted to be composed of ethoxylated alkylamine in an equal weight. The other steps remain unchanged.

[0074] Example 6

[0075] The antistatic polyolefin waterproofing membrane comprises, by weight, 45 parts of polyethylene (2.16 kg load, 190° C., melt index 5 g / 10 min), 15 parts of toughening agent POE, 0.5 parts of zinc stearate, 8 parts of talc, 3 parts of metakaolin, 0.4 parts of antioxidant 1076, 0.2 parts of ultraviolet absorber UV-329, 2 parts of maleic anhydride grafted PE (grafting rate 1%) and 13 parts of antistatic agent;

[0076] The antistatic agent is composed of antistatic agent A and antistatic agent B in a weight ratio of 10:3, wherein the antistatic agent A is sodium stearyl polyoxyethylene ether (9) sulfonate;

[0077] The antistatic agent B is composed of ethoxylated alkylamine and glyceride compound in a weight ratio of 1:1.

[0078] Example 7

[0079] The difference between this embodiment and embodiment 6 is that the toughening agent POE in embodiment 6 is adjusted from 15 parts to 21 parts. The other steps remain unchanged.

[0080] Example 8

[0081] The difference between this embodiment and embodiment 6 is that the toughening agent POE in embodiment 6 is adjusted from 15 parts to 26 parts. The other steps remain unchanged.

[0082] Example 9

[0083] The difference between this example and Example 6 is that in Example 6, sodium stearyl polyoxyethylene ether (9) sulfonate is replaced by sodium lignoceryl polyoxyethylene ether (15) sulfonate of equal weight. The other steps remain unchanged.

[0084] Comparative Example 6

[0085] The difference between this comparative example and Example 6 is that the toughening agent POE in Example 6 is adjusted from 15 parts to 5 parts. The other steps remain unchanged.

[0086] Comparative Example 7

[0087] The difference between this comparative example and Example 6 is that the toughening agent POE in Example 6 is adjusted from 15 parts to 10 parts. The other steps remain unchanged.

[0088] Performance Testing

[0089] The properties of the waterproof membranes of Examples 1-9 and Comparative Examples 1-7 are shown in Table 1 below.

[0090] The tensile strength, elongation at break, tear strength, low-temperature bendability, dimensional change rate after heat treatment, retention rate of tensile strength after heat aging and seam peel strength are tested according to the method of standard GB 27789-2011 "Thermoplastic Polyolefin (TPO) Waterproof Membrane".

[0091] The surface resistivity is tested according to the method of standard GB1410-2006 "Determination method of surface resistivity and volume resistivity".

[0092] Antistatic durability test: The sample to be tested is placed at 85°C and 85% humidity for 3 months, taken out, the surface is wiped dry and placed at room temperature for 24 hours, and then the surface resistivity is tested.

[0093] Table 1

[0094]

[0095]

[0096] It can be seen from the data results in Table 1 that the polyolefin waterproof membrane of the present invention not only has good antistatic durability and achieves permanent antistatic properties, but also has good physical properties.

[0097] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. An antistatic polyolefin waterproofing membrane, characterized in that: The raw material components include, by weight, 35-65 parts of polyolefin resin, 15-26 parts of toughening agent, 0.2-0.5 parts of dispersant, 5-15 parts of inorganic filler, 0.2-0.6 parts of antioxidant, 0.1-0.5 parts of ultraviolet absorber, 2-4 parts of compatibilizer and 11-15 parts of antistatic agent; The antistatic agent is composed of antistatic agent A and antistatic agent B in a weight ratio of 10:1-5; The antistatic agent A is an alkyl polyoxyethylene ether sulfonate; The antistatic agent B consists of ethoxylated alkylamine and glyceride compound.

2. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The structure of the alkyl polyoxyethylene ether sulfonate is shown in the following formula (1): C n H 2n+1 (OCH2CH2) m SO3M(1) Wherein, n=8-36, m=6-30, and M is a monovalent metal ion.

3. The antistatic polyolefin waterproofing membrane according to claim 2, characterized in that: Said n=12-36, m=9-20.

4. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The glyceride compound is selected from glyceryl monostearate and / or glyceryl monopalmitate.

5. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The weight ratio of the ethoxylated alkylamine to the glyceride compound is 1:2-2:

1.

6. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The toughening agent is selected from one or a combination of two or more of polyolefin elastomers, EPDM rubber elastomers, natural rubber elastomers and ethylene-vinyl acetate copolymer elastomers.

7. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The dispersant is selected from one or a combination of two or more of polyethylene wax, zinc stearate, magnesium stearate, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.

8. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The inorganic filler is selected from one or a combination of two or more of talc, metakaolin, heavy calcium carbonate, light calcium carbonate, wollastonite, glass microspheres and mica powder.

9. The antistatic polyolefin waterproofing membrane according to claim 1, characterized in that: The compatibilizer is selected from maleic anhydride grafted polymer or glycidyl methacrylate grafted polymer.

10. The method for preparing the antistatic polyolefin waterproofing membrane according to any one of claims 1 to 9, characterized in that: The raw material components are mixed uniformly, melt-extruded, formed by a three-roller machine, and wound up by trimming.

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