Thermoplastic polyolefin waterproof roll with barrier properties and preparation method thereof

Abstract

The invention provides a thermoplastic polyolefin waterproof coiled material with barrier properties and a preparation method thereof. The coiled material comprises, by weight, 20-100 parts of an olefin block copolymer, 20-80 parts of a thermoplastic polyolefin, 10-60 parts of a metallocene polyethylene, 1-33 parts of an ethylene and vinyl alcohol copolymer, 1-30 parts of an adhesive resin, 100-300 parts of magnesium hydroxide, 0.1-5 parts of an antioxidant, 0.1-5 parts of a light stabilizer, 1-30 parts of titanium dioxide, 0.1-5 parts of an ultraviolet absorber, 0.1-3 parts of an anti-copper agent, and 0.1-5 parts of a coupling agent. The present invention adopts olefin block copolymer OBC, thermoplastic polyolefin with high rubber content and metallocene polyethylene plastomer as main components, so that the anti-aging performance of the material itself is better than that of propylene-based elastomer; the formula system introduces a copolymer of ethylene and vinyl alcohol with excellent barrier properties, which can be integrated with vinyl olefin block copolymer and polyethylene, and can provide good oxygen and oil barrier capabilities.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof coiled material processing, and in particular to a thermoplastic polyolefin waterproof coiled material with barrier properties and a preparation method thereof. Background Art

[0002] Thermoplastic polyolefin (TPO) waterproofing membrane is a kind of rubber-plastic blended polymer waterproofing membrane with excellent anti-aging performance and very soft. With the development of technology, more and more thermoplastic polyolefin waterproofing membranes will be compounded with other waterproofing membranes with self-adhesive ability (modified asphalt, polymer hot melt pressure-sensitive adhesive or butyl adhesive) to form a membrane or used with coatings to form a "coated membrane" composite waterproofing system.

[0003] The rubber phase molecules in TPO coils are mostly amorphous, and the formulas of self-adhesive coils often contain small molecule oils. During the production or use of coils, the small molecule oils will diffuse into the TPO sheets, causing the performance of the TPO sheets and the self-adhesive layer to deteriorate at the same time. If not treated, this effect will intensify over time.

[0004] To solve the above problems, the common treatment method at present is to cover the surface of the coil with a barrier film. This treatment method has its advantages, that is, it is quick and convenient to produce. However, there are problems in the actual use process. That is, during the film thermal compounding process in the production process, high-temperature melt extrusion, mechanical traction and stretching or mechanical damage will cause the barrier layer of the material to break, thereby affecting the material's ability to block oil. Once the barrier layer is broken, the oil will diffuse into the material body, causing the material performance to deteriorate and reducing the material's service life. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present invention provides a thermoplastic polyolefin waterproof roll material with barrier properties, which solves the problems mentioned in the background technology.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0007] Thermoplastic polyolefin waterproof membrane with barrier properties, calculated by weight, has the following formula composition:

[0008] Olefin block copolymer: 20-100 parts;

[0009] Thermoplastic polyolefin: 20-80 parts;

[0010] Metallocene polyethylene: 10-60 parts;

[0011] Ethylene and vinyl alcohol copolymer: 1-33 parts;

[0012] Adhesive resin: 1-30 parts;

[0013] Magnesium hydroxide: 100-300 parts;

[0014] Antioxidant: 0.1-5 parts;

[0015] Light stabilizer: 0.1-5 parts;

[0016] Titanium dioxide: 1-30 parts;

[0017] Ultraviolet absorber: 0.1-5 parts;

[0018] Anti-copper agent: 0.1-3 parts;

[0019] Coupling agent: 0.1-5 parts.

[0020] Furthermore, the olefin block copolymer has a weight average molecular weight of 10,000-300,000, a comonomer of octene with a content of 11-33%, and a melt index of 0.2-3.0 g / 10 min.

[0021] Further, the thermoplastic polyolefin: a copolymer of thermoplastic ethylene and propylene, with a weight average molecular weight of 50,000-25,000, a rubber phase content of 55-85%, and a melt index of 0.4-4.0 g / 10 min;

[0022] Furthermore, the metallocene polyethylene has: a comonomer of hexene with a content of 5-25%; a molecular weight of 50,000-240,000; and a melt index of 0.3-3.0 g / 10 min.

[0023] Furthermore, the ethylene and vinyl alcohol copolymer has an ethylene comonomer content of 1-50%, a density of 1.00-1.20 g / cm3, a melt index of 0.5-4.0 g / 10 min, an oxygen permeability of 0.001-2.0 [mol / (㎡·s·Pa)], and a water vapor permeability of 10-300 g / ㎡ / day;

[0024] Furthermore, the adhesive resin is maleic anhydride grafted low-density polyethylene or maleic anhydride grafted polyolefin elastomer, with a grafting rate of 0.5-1.5%.

[0025] Furthermore, the magnesium hydroxide is a precipitated magnesium hydroxide with a d50 μm range of 1.10-1.80.

[0026] Furthermore, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant in a ratio of 2:1 or 1:1.

[0027] A method for preparing a thermoplastic polyolefin waterproof roll having barrier properties, the method comprising the following steps:

[0028] S1. Measure each raw material by loss-in-weight weighing;

[0029] S2, adding each raw material into a parallel co-rotating twin-screw extruder; maintaining the speed at 500-600RPM, setting the temperature at 190-230°C, and the extrusion melt pressure at 3-5MPa;

[0030] S3, each raw material is plasticized by high-speed shearing in a twin-screw extruder to obtain a uniform melt;

[0031] S4, the melt is rolled and cooled to shape by a three-roll calender;

[0032] S5. Control the thickness of the coil to 1.20±0.02mm.

[0033] Furthermore, the twin-screw extrusion temperature is set to 190-240° C., and the extrusion melt pressure is set to 2.0-5.0 MPa.

[0034] The present invention provides a thermoplastic polyolefin waterproof roll material with barrier properties. Compared with the prior art, it has the following beneficial effects:

[0035] 1. Using olefin block copolymer OBC, thermoplastic polyolefin with high rubber content and metallocene polyethylene plastomer as the main components, the material's anti-aging performance is better than that of propylene-based elastomer;

[0036] 2. The formula system introduces copolymers of ethylene and vinyl alcohol, which have excellent barrier properties. They can not only be integrated with vinyl olefin block copolymers and polyethylene, but also provide good oxygen and oil resistance. They can solve the problem of small molecule oil migration when TPO materials are compounded with self-adhesive coils containing small molecule oils or with other oil-containing coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0038] Figure 1 The schematic diagram of the preparation process of the thermoplastic polyolefin waterproof membrane with barrier properties of the present invention is shown. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are 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.

[0040] In order to solve the technical problems in the background technology, the following thermoplastic polyolefin waterproof membrane with barrier properties is provided:

[0041] The thermoplastic polyolefin waterproof coiled material with barrier properties provided by the present invention is prepared by blending and modifying the following materials: an olefin block copolymer; a second thermoplastic polyolefin; metallocene polyethylene; an ethylene and vinyl alcohol copolymer; an adhesive resin; magnesium hydroxide; an antioxidant; a light stabilizer; titanium dioxide; an ultraviolet absorber; an anti-copper agent; and a coupling agent. The formula is composed of olefin block copolymer: 20-100 parts; thermoplastic polyolefin: 20-80 parts; metallocene polyethylene: 10-60 parts; ethylene and vinyl alcohol copolymer: 1-33 parts; adhesive resin: 1-30 parts; magnesium hydroxide: 100-300 parts; antioxidant: 0.1-5 parts; light stabilizer: 0.1-5 parts; titanium dioxide: 1-30 parts; ultraviolet absorber: 0.1-5 parts; anti-copper agent: 0.1-3 parts; coupling agent (silane KH550-11 or aluminate coupling agent DL411): 0.1-5 parts.

[0042] As a preferred embodiment, the olefin block copolymer is a block copolymer of ethylene and 1-octene, and the ratio of the two is adjusted during the polymerization reaction production process to achieve the harmony of softness and hardness, thereby producing a new type of thermoplastic polyolefin. Its weight average molecular weight is 80000-300000, the content of comonomer 1-octene is 11-33%, and the melt index is 0.4-2.0g / 10min (190°C, 2.16kg).

[0043] Preferably, the thermoplastic polyolefin is a thermoplastic polyolefin produced by "reactor blending" of ethylene and propylene, wherein the weight average molecular weight is 50,000-25,000, the rubber phase content is 60-85%, and the melt index is 0.4-4.0 g / 10 min (230° C., 2.16 kg).

[0044] As a preferred metallocene polyethylene, its comonomer is hexene, the content is 5-25%; molecular weight is 50000-240000; melt index is 0.3-3.0g / 10min (190°C, 2.16kg);

[0045] Preferably, a copolymer of ethylene and vinyl alcohol, wherein the ethylene comonomer content is 1-50%; density: 1.00-1.20 g / cm3, melt index 0.5-4.0 g / 10 min (190°C 2.16 kg), oxygen permeability 0.001-2.0 [mol / (㎡·s·Pa)], water vapor permeability 10-300 g / ㎡ / day.

[0046] Preferably, the adhesive resin is maleic anhydride grafted low-density polyethylene or maleic anhydride grafted polyolefin elastomer, with a grafting rate of 0.5-1.5%;

[0047] Preferably, the magnesium hydroxide is a precipitated magnesium hydroxide with a d50 μm range of 1.10-1.80.

[0048] Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant in a ratio of 2:1 or 1:1;

[0049] Preferably, the light stabilizer is hindered amine light stabilizer C2020;

[0050] Preferably, the titanium dioxide is a chloride-process rutile titanium dioxide R105 or 2220 with a surface coated with silicon dioxide and aluminum oxide films;

[0051] Preferably, the ultraviolet absorber is: UV326, UV327 and UV329;

[0052] Preferably, the anti-copper agent is MD1024;

[0053] Preferably, the coupling agent is silane KH550 or kh570; or aluminate coupling agent DL411.

[0054] Thermoplastic polyolefin waterproof membrane with barrier properties, exemplarily, has the following embodiments:

[0055] Embodiment 1:

[0056] First, 52 parts of olefin block copolymer, 100 parts of second thermoplastic polyolefin; 15 parts of metallocene polyethylene, 20 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0057] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0058] Embodiment 2:

[0059] First, 60 parts of olefin block copolymer, 93 parts of second thermoplastic polyolefin; 25 parts of metallocene polyethylene, 22 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0060] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0061] Embodiment 3:

[0062] First, 70 parts of olefin block copolymer, 80 parts of second thermoplastic polyolefin; 35 parts of metallocene polyethylene, 24 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0063] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0064] Embodiment 4:

[0065] First, 80 parts of olefin block copolymer, 70 parts of second thermoplastic polyolefin; 45 parts of metallocene polyethylene, 26 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0066] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0067] Embodiment 5:

[0068] First, 90 parts of olefin block copolymer, 65 parts of second thermoplastic polyolefin; 55 parts of metallocene polyethylene, 28 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0069] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0070] Embodiment 6:

[0071] First, 100 parts of olefin block copolymer, 55 parts of second thermoplastic polyolefin; 55 parts of metallocene polyethylene, 30 parts of ethylene and vinyl alcohol copolymer; 10 parts of adhesive resin; 200 parts of magnesium hydroxide; 5 parts of antioxidant; 15 parts of light stabilizer C2020; rutile titanium dioxide R105; 64 parts of ultraviolet absorber UV32; 43 parts of anti-copper agent MD102; and 5 parts of silane coupling agent KH550.

[0072] The test formula is shown in Table 1 and the test results are shown in Table 2.

[0073] Table 1. Example formulation composition

[0074]

[0075] Table 2. Performance test results of the examples

[0076]

[0077] It can be seen from the test values ​​in Table 2 that the thermoplastic polyolefin waterproof membrane with barrier properties prepared by the present invention has basic mechanical properties that meet the requirements of GB 27789-2011, has a low oxygen permeability, and meets the requirements of ASTM D6878. The artificial climate accelerated aging performance can reach 10000h, which is at the leading performance level among similar products, and has oxygen barrier and oil isolation capabilities that ordinary materials do not have, and is a product with excellent performance.

[0078] In order to prepare the above-mentioned elastomer-modified thermoplastic polyolefin waterproof membrane with barrier properties, the following preparation method is provided:

[0079] S1. Measure each raw material by loss-in-weight weighing;

[0080] S2, adding each raw material into a parallel co-rotating twin-screw extruder; maintaining the speed at 500-600RPM, setting the temperature at 190-230°C, and the extrusion melt pressure at 3MPa;

[0081] S3, each raw material is subjected to high-speed shear mixing in a twin-screw extruder to obtain a plasticized mixture;

[0082] S4, the plasticized mixture is rolled by a three-roll calender to form a preliminary coil;

[0083] S5. The preliminary roll material is cooled and formed into a uniform thermoplastic polyolefin waterproof roll material by a forming machine, and the thickness is controlled at 1.20±0.02mm.

[0084] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0085] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. Thermoplastic polyolefin waterproof membrane with barrier properties, Features: In terms of mass fraction, its formula composition is: Olefin block copolymer: 20-100 parts; Thermoplastic polyolefin: 20-80 parts; Metallocene polyethylene: 10-60 parts; Ethylene and vinyl alcohol copolymer: 1-33 parts; Adhesive resin: 1-30 parts; Magnesium hydroxide: 100-300 parts; Antioxidant: 0.1-5 parts; Light stabilizer: 0.1-5 parts; Titanium dioxide: 1-30 parts; Ultraviolet absorber: 0.1-5 parts; Anti-copper agent: 0.1-3 parts; Coupling agent: 0.1-5 parts; The adhesive resin is maleic anhydride grafted low-density polyethylene or maleic anhydride grafted polyolefin elastomer, with a grafting rate of 0.5-1.5%; The olefin block copolymer has a weight average molecular weight of 10,000-300,000, a comonomer of octene and a content of 11-33%, a melt index of 0.2-3.0 g / 10 min, a test temperature of 190° C., and a test pressure of 2.16 kg; The thermoplastic polyolefin is a copolymer of thermoplastic ethylene and propylene, with a weight average molecular weight of 50,000-25,000, a rubber phase content of 55-85%, and a melt index of 0.4-4.0 g / 10 min; the test temperature is 230° C. and the test pressure is 2.16 kg; The metallocene polyethylene: the comonomer is hexene and the content is 5-25%; the molecular weight is 50000-240000; the melt index is 0.3-3.0g / 10min, the test temperature is: 190°C, and the test pressure is: 2.16kg; The ethylene and vinyl alcohol copolymer: the ethylene comonomer content is 1-50%; Density: 1.00-1.20g / cm³, melt index 0.5-4.0g / 10min, test temperature: 190℃, test pressure: 2.16kg; oxygen permeability: 0.001-2.0 [mol / (㎡·s·Pa)], water vapor permeability: 10-300g / ㎡ / day; The magnesium hydroxide is a precipitated magnesium hydroxide with a d50 range of 1.10-1.80 μm.

2. The thermoplastic polyolefin waterproof membrane with barrier properties according to claim 1, Features: The antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant in a ratio of 2:1 or 1:

1.

3. The method for preparing the thermoplastic polyolefin waterproof membrane with barrier properties according to claim 1, Features: The preparation method comprises the following steps: S1. Measure each raw material according to claim 1 by loss-in-weight weighing; S2, adding each raw material into a parallel co-rotating twin-screw extruder; maintaining the speed at 500-600RPM, setting the temperature at 190-230°C, and the extrusion melt pressure at 3-5MPa; S3, each raw material is plasticized by high-speed shearing in a twin-screw extruder to obtain a uniform melt; S4, the melt is rolled and cooled to shape by a three-roll calender; S5. Control the thickness of the coil to 1.20±0.02mm.

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