CN115782327B - Upper surface layer, double-layer composite ethylene propylene diene monomer rubber waterproof coiled material and preparation method and application thereof - Google Patents
Upper surface layer, double-layer composite ethylene propylene diene monomer rubber waterproof coiled material and preparation method and application thereof Download PDFInfo
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- CN115782327B CN115782327B CN202211512070.6A CN202211512070A CN115782327B CN 115782327 B CN115782327 B CN 115782327B CN 202211512070 A CN202211512070 A CN 202211512070A CN 115782327 B CN115782327 B CN 115782327B
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000002344 surface layer Substances 0.000 title claims abstract description 61
- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 56
- 239000010410 layer Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 57
- -1 polypropylene Polymers 0.000 claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 41
- 239000000806 elastomer Substances 0.000 claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000004611 light stabiliser Substances 0.000 claims abstract description 25
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 23
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- 238000004078 waterproofing Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 17
- 238000003490 calendering Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 10
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010690 paraffinic oil Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 241000607598 Vibrio Species 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 description 15
- 238000010276 construction Methods 0.000 description 9
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of building waterproofing, and discloses an upper surface layer and double-layer composite ethylene propylene diene monomer waterproof coiled material, a preparation method and application thereof. The upper surface layer is formed by an ethylene propylene diene monomer waterproof layer, and the ethylene propylene diene monomer waterproof layer contains the following components: ethylene propylene diene monomer rubber, polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, reinforcing filler, vulcanizing agent, accelerator, anti-aging agent and light stabilizer. The waterproof coiled material provided by the invention can be welded, has a simple process, excellent physical properties, compact adhesion of a double-layer structure, good toughness, high strength and good weather resistance, and is suitable for the waterproof field of buildings.
Description
Technical Field
The invention relates to the field of building waterproofing, in particular to an upper surface layer and double-layer composite ethylene propylene diene monomer waterproof coiled material, and a preparation method and application thereof.
Background
The Ethylene Propylene Diene Monomer (EPDM) rubber waterproof coiled material is prepared by adding proper amount of butyl rubber, vulcanizing agent, accelerator, softener, reinforcing agent and the like into ethylene propylene diene monomer rubber, and performing the procedures of banburying, pulling-on piece filtering, extrusion molding and the like.
Ethylene propylene diene monomer is a high molecular polymer synthesized by copolymerizing ethylene, propylene and non-conjugated diene, and has high chemical stability due to the characteristic of a saturated structure of a main chain.
The ethylene propylene diene monomer waterproof coiled material has good ageing resistance and long service life. Because the main chain in the ethylene propylene diene monomer molecular structure has no double bond, when the ethylene propylene diene monomer waterproof coiled material is subjected to the actions of ozone, ultraviolet rays and damp and heat, the main chain is not easy to break, so that the ethylene propylene diene monomer waterproof coiled material has excellent weather resistance and ageing resistance, and the service life can reach more than 50 years.
However, the existing ethylene propylene diene monomer waterproof coiled material body cannot be welded, the general joint edge adopts a construction mode of solvent glue bonding, the construction time is long, the construction process is complex, the reliability of bonding parts is not high, the bonding parts fail after long-term use, water seepage and water leakage occur, and the like.
Therefore, the weldability and the seepage-proofing performance of the bonding part of the ethylene propylene diene monomer rubber waterproof coiled material are improved, the construction process is simplified, the construction time is shortened, and the method has important significance.
Disclosure of Invention
The invention aims to solve the problems of unweldable ethylene propylene diene monomer waterproof coiled materials, long construction time, complex construction process, easy failure of bonding parts and water seepage and water leakage in the prior art.
In order to achieve the above object, a first aspect of the present invention provides an upper surface layer applied to a waterproof roll, the upper surface layer being formed of an ethylene propylene diene monomer waterproof layer, the ethylene propylene diene monomer waterproof layer comprising the following components: ethylene propylene diene monomer rubber, polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, reinforcing filler, vulcanizing agent, accelerator, anti-aging agent and light stabilizer;
in the upper surface layer, based on 100 parts by weight of the total weight of the ethylene propylene diene monomer waterproof layer, the ethylene propylene diene monomer is 30-70 parts by weight, the polypropylene-based elastomer is 40-80 parts by weight, the TPO-g- (GMA-co-St) is 1-10 parts by weight, the softening oil is 2-10 parts by weight, the reinforcing filler is 10-20 parts by weight, the vulcanizing agent is 0.1-1 part by weight, the accelerator is 0.1-1 part by weight, the anti-aging agent is 1-4.5 parts by weight, and the light stabilizer is 1-5 parts by weight.
The second aspect of the invention provides a double-layer composite ethylene propylene diene monomer rubber waterproof roll, which comprises an upper surface layer and a lower surface layer which are sequentially laminated;
the upper surface layer is the upper surface layer of the first aspect, and
the lower surface layer is formed by a waterproof layer of thermoplastic polyolefin elastomer, and
the ratio of the thickness of the thinnest part of the upper surface layer to the thickness of the thinnest part of the lower surface layer is 1:1-1.8.
The third aspect of the invention provides a method for preparing the double-layer composite ethylene propylene diene monomer waterproof coiled material of the second aspect, which is carried out by applying the components of the waterproof coiled material of the second aspect, and comprises the following steps:
(1) Mixing and contacting: mixing ethylene propylene diene monomer, a polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, a filler, an anti-aging agent and a light stabilizer for contacting I to obtain a premix 1;
mixing and contacting a polypropylene-based elastomer, TPO-g- (GMA-co-St), metallocene polyethylene, a filler, an antioxidant and a pigment to obtain a premix 2;
(2) Granulating: granulating the premix 1 to obtain granules 1;
(3) Plasticizing and calendaring: extruding and plasticizing the pelleting material 1 and the premix 2, and introducing the pelleting material and the premix into a three-roll calender for calendering to obtain the double-layer composite ethylene propylene diene monomer waterproof coiled material.
The fourth aspect of the invention provides an application of the double-layer composite ethylene propylene diene monomer rubber waterproof coiled material in the waterproof field of buildings.
The double-layer composite ethylene propylene diene monomer waterproof coiled material provided by the invention has the advantages of reliable welding performance, tight adhesion, good waterproof performance and simple production process and construction process.
Drawings
Fig. 1 is a schematic structural view of a double-layer composite ethylene propylene diene monomer waterproof coiled material.
Description of the reference numerals
1: upper surface layer 2: lower surface layer
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
It should be noted that, in the aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components or terms in the aspects, and those skilled in the art should not understand the limitation of the present invention.
As described above, the first aspect of the present invention provides an upper surface layer applied to a waterproof roll, the upper surface layer is formed by an ethylene propylene diene monomer waterproof layer, and the ethylene propylene diene monomer waterproof layer contains the following components: ethylene propylene diene monomer rubber, polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, reinforcing filler, vulcanizing agent, accelerator, anti-aging agent and light stabilizer;
in the upper surface layer, based on 100 parts by weight of the total weight of the ethylene propylene diene monomer waterproof layer, the ethylene propylene diene monomer is 30-70 parts by weight, the polypropylene-based elastomer is 40-80 parts by weight, the TPO-g- (GMA-co-St) is 1-10 parts by weight, the softening oil is 2-10 parts by weight, the reinforcing filler is 10-20 parts by weight, the vulcanizing agent is 0.1-1 part by weight, the accelerator is 0.1-1 part by weight, the anti-aging agent is 1-4.5 parts by weight, and the light stabilizer is 1-5 parts by weight.
According to a preferred embodiment, in the ethylene propylene diene monomer waterproof layer, the softening oil is at least one selected from naphthenic oil, paraffinic oil and aromatic oil.
Preferably, the vulcanizing agent is at least one selected from sulfur and dicumyl peroxide.
Preferably, the accelerator is at least one selected from the group consisting of accelerator DM, accelerator TMTD, and accelerator BZ.
Preferably, the antioxidant is at least one selected from the group consisting of antioxidant 4010NA, antioxidant 4010, and antioxidant RD.
Preferably, the polypropylene-based elastomer is comprised of Liandbarsel CA10A, liandbarsel CA60A, and Violet VERSIFY 2300.
Preferably, the reinforcing filler is at least one selected from carbon black, white carbon black and calcium carbonate.
Preferably, the light stabilizer is at least one selected from the group consisting of light stabilizer UV-2020, ultraviolet absorber UV-326, ultraviolet absorber UV-531.
According to a preferred embodiment, the TPO-g- (GMA-co-St) is a product obtained by the following process:
s1, mixing raw materials for preparing TPO-g- (GMA-co-St) to obtain a mixture I;
s2, carrying out melt grafting on the mixture I at 180-230 ℃ to obtain TPO-g- (GMA-co-St), wherein the time of melt grafting is 8-15min;
wherein, the raw materials for preparing TPO-g- (GMA-co-St) comprise: polypropylene elastomer, glycidyl methacrylate, styrene, dicumyl peroxide and antioxidant 1010.
According to a preferred embodiment, the method further comprises: the mixing at least satisfies: the stirring is carried out under the condition of 300-800r/min, 70-90 ℃ and 8-15min.
The mixing apparatus of the present invention is not particularly limited, and may be carried out by conventional apparatus and means, such as a high-speed mixer.
In the present invention, the melt grafting apparatus is not particularly limited, and may be carried out by the conventional apparatus and means, for example, by a twin-screw extruder granulator.
Preferably, in the raw material for preparing TPO-g- (GMA-co-St), the glycidyl methacrylate is used in an amount of 1 to 5 parts by weight relative to 100 parts by weight of the polypropylene-based elastomer; the usage amount of the styrene is 0.5-4 parts by weight; the dosage of the dicumyl peroxide is 0.1-0.8 weight part; the antioxidant 1010 is used in an amount of 0.1 to 1 part by weight, wherein the polypropylene-based elastomer is the same as the polypropylene-based elastomer in the upper surface layer.
As described above, the second aspect of the present invention provides a double-layer composite ethylene propylene diene monomer waterproof roll comprising an upper surface layer and a lower surface layer laminated in this order;
the upper surface layer is the upper surface layer of the first aspect, and
the lower surface layer is formed by a waterproof layer of thermoplastic polyolefin elastomer, and
the ratio of the thickness of the thinnest part of the upper surface layer to the thickness of the thinnest part of the lower surface layer is 1:1-1.8.
According to a preferred embodiment, in the following, with reference to fig. 1, a double-layer structure of the double-layer composite ethylene propylene diene monomer rubber waterproof coiled material is provided, specifically:
the lower surface layer 2 has a groove structure, and the upper surface layer 1 is located in the groove structure of the lower surface layer 2; the double layer structure has a welded edge therein, which is formed by the thermoplastic polyolefin elastomer waterproof layer in the lower surface layer 2. The inventor finds that the physical properties of the waterproof coiled material prepared under the preferred condition are better.
According to a preferred embodiment, the thermoplastic polyolefin elastomer waterproof layer comprises the following components: TPO-g- (GMA-co-St), polypropylene-based elastomer, metallocene polyethylene, reinforcing filler, antioxidant, light stabilizer, pigment, wherein in the lower surface layer, the TPO-g- (GMA-co-St) is the same as the TPO-g- (GMA-co-St) in the upper surface layer described in the first aspect.
Preferably, in the thermoplastic polyolefin elastomer waterproof layer, the content of the TPO-g- (GMA-co-St) is 1 to 10 parts by weight, the content of the metallocene polyethylene is 10 to 40 parts by weight, the content of the reinforcing filler is 10 to 30 parts by weight, the content of the antioxidant is 0.1 to 1 part by weight, the content of the light stabilizer is 1 to 5 parts by weight, and the content of the pigment is 0.5 to 2 parts by weight, relative to 100 parts by weight of the polypropylene-based elastomer, wherein the polypropylene-based elastomer, the reinforcing filler and the light stabilizer are the same as the polypropylene-based elastomer, the reinforcing filler and the light stabilizer of the first aspect, respectively.
Preferably, in the thermoplastic polyolefin elastomer waterproof layer, the antioxidant is at least one selected from the group consisting of antioxidant 1010, antioxidant 168 and antioxidant 1076.
Preferably, the pigment is selected from at least one of titanium dioxide, carbon black and a colorant.
Preferably, the metallocene polyethylene is selected from at least one of metallocene high-density polyethylene and metallocene low-density polyethylene.
As described above, the third aspect of the present invention provides a method for preparing the double-layer composite ethylene propylene diene monomer rubber waterproof roll material according to the second aspect, the method is performed by using the components of the waterproof roll material according to the second aspect, and the method comprises the following steps:
(1) Mixing and contacting: mixing ethylene propylene diene monomer, a polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, a filler, an anti-aging agent and a light stabilizer for contacting I to obtain a premix 1;
mixing and contacting a polypropylene-based elastomer, TPO-g- (GMA-co-St), metallocene polyethylene, a filler, an antioxidant and a pigment to obtain a premix 2;
(2) Granulating: granulating the premix 1 to obtain granules 1;
(3) Plasticizing and calendaring: extruding and plasticizing the pelleting material 1 and the premix 2, and introducing the pelleting material and the premix into a three-roll calender for calendering to obtain the double-layer composite ethylene propylene diene monomer waterproof coiled material.
In the present invention, the apparatus for carrying out the mixing contact I is not particularly limited, and may be carried out by using a device commonly used in the art, for example, a high-speed kneader.
According to a preferred embodiment, in the process of the invention, the granulation in step (2) is carried out in a screw extruder.
According to a preferred embodiment, the method of the invention further comprises: before the granules are introduced into a three-roll calender, extruding and plasticizing by adopting two extruders, specifically, introducing the granules 1 into the extruder 1 for extruding and plasticizing to obtain a material I; introducing the premix 2 into an extruder 2 for extrusion plasticization to obtain a material II; and co-extruding the material I and the material II into a double-layer co-extrusion die for discharging to obtain a co-extrusion material to be applied to the three-roller calender for calendering.
According to a preferred embodiment, the method of the invention further comprises: and (3) before extruding and plasticizing the pelletization material 1 obtained in the step (2), dynamically vulcanizing the pelletization material 1 by adopting a vulcanizing agent and an accelerator to obtain vulcanized pelletization material 1 to be applied to extruding and plasticizing.
The present invention is not limited to the above-mentioned granulation, extrusion plasticizing, dynamic vulcanization and calendering, and may be carried out by technical means and parameters commonly used in the art, and the following exemplary provides an operation condition including:
the conditions of granulation and dynamic vulcanization are as follows: under the condition of stirring, the rotating speed is 400-600rpm, and the temperature is 180-230 ℃;
the extrusion plasticizing conditions are as follows: under the condition of stirring, the temperature is 180-230 ℃ and the rotating speed is 200-500rpm;
the calendaring conditions are as follows: the temperature is 30-70 ℃;
wherein, the temperature of granulation and dynamic vulcanization refers to the temperature of the die of the screw extruder.
According to a preferred embodiment, the mixed contact I at least satisfies: the stirring is carried out under the condition of 300-800r/min, 70-90 ℃ and 5-10min.
Preferably, the mixed contact II at least satisfies: the stirring is carried out under the condition of 300-800r/min, 70-90 ℃ and 5-10min.
As described above, the fourth aspect of the present invention provides the use of the double-layer composite ethylene propylene diene monomer rubber waterproof roll material according to the third aspect in the waterproof field of buildings.
Compared with the prior art, the waterproof coiled material provided by the invention has at least the following advantages:
(1) The waterproof coiled material provided by the invention has the characteristics of simple production process, high production efficiency, excellent physical properties and simple and quick construction.
(2) The waterproof coiled material provided by the invention has the characteristics of compact adhesion of a double-layer structure, good waterproof property, low oil charge, good toughness, high strength, good weather resistance and weldability.
The invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used are commercially available.
Some of the raw materials and sources used in the following examples are shown in table 1 below:
TABLE 1
High speed mixer: model SHR-800A, available from Zhengxing mechanical Co., ltd;
twin screw extrusion granulator: model JWE-75, available from Jin Wei machine manufacturing company, inc;
extruder 1: model CJWH75-44D, available from Jin Wei mechanical manufacturing Co., ltd;
extruder 2: model CJWH95-44D, available from Jin Wei mechanical manufacturing Co., ltd;
three-roll calender: model 600 x 2400 available from Jin Wei machine manufacturing company, inc;
physical property test of waterproof coiled material: testing according to GB/T18173.1-2012J L1 of the part 1 sheet of the high polymer waterproof material;
the seam peel strength of the waterproof roll was set to 6.11 in GB 27789-2011.
Unless otherwise specified, 10g is shown per part by weight in the examples below.
Preparation example A-1
The raw material formulation used for preparing TPO-g- (GMA-co-St) in this preparation example is:
this preparation is used to demonstrate that TPO-g- (GMA-co-St) was prepared as follows:
s1, mixing raw materials for preparing TPO-g- (GMA-co-St) to obtain a mixture I;
in the step S1, the mixing is carried out under the condition of stirring, the rotating speed is 500r/min, the temperature is 85 ℃, and the time is 8min;
s2, carrying out melt grafting on the mixture I in a double-screw extrusion granulator at the temperature of 200 ℃ to obtain TPO-g- (GMA-co-St), wherein the time of melt grafting is 10min;
TPO-g- (GMA-co-St) was obtained and designated as T1.
PREPARATION EXAMPLE A-2
The raw material formulation for preparing TPO-g- (GMA-co-St) in this preparation example was the same as that in preparation example A-1.
This preparation was carried out in a similar manner to preparation A-1, except that: in the preparation example, the preparation method comprises the following steps,
the mixing time in the step S1 is 14min;
the temperature of the melt grafting in the step S2 is 220 ℃, and the time of the melt grafting is 15min;
TPO-g- (GMA-co-St) was obtained and designated as T2.
Preparation example B-1
This preparation example is used to illustrate the preparation method of premix 1 (i.e., the upper surface layer according to the present invention).
Specifically, ethylene propylene diene monomer, polypropylene-based elastomer, TPO-g- (GMA-co-St) (T1), softening oil I, reinforcing filler, anti-aging agent and light stabilizer were mixed in a high-speed mixer to contact I, see Table 2 specifically.
Wherein, the mixing contact I is carried out under stirring, and the conditions of the mixing contact I are as follows: the rotation speed was 500rpm, the temperature was 85℃and the time was 8min.
Premix 1 was obtained and designated premix 1-a.
PREPARATION EXAMPLE B-2
Premix 1 was prepared in a similar manner to preparation B-1, except that:
in this preparation, the same parts by weight of softening oil II was used in place of softening oil I in preparation B-1 for mixed contact I, and TPO-g- (GMA-co-St) was used as T2, see Table 2 in particular;
premix 1 was obtained and designated premix 1-b.
Preparation example B-3
Premix 1 was prepared in a similar manner to preparation B-1, except that:
in this preparation, the same parts by weight of PP-g-MAH was used in place of TPO-g- (GMA-co-St) in preparation B-1 for mixed contact I, see in particular Table 2;
premix 1 was obtained and designated premix 1-c.
PREPARATION EXAMPLE B-4
Premix 1 was prepared in a similar manner to preparation B-1, except that: mixed contact I was performed using PEg-MAH instead of TPO-g- (GMA-co-St), see in particular Table 2;
premix 1 was obtained and designated premix 1-d.
PREPARATION EXAMPLE B-5
Premix 1 was prepared in a similar manner to preparation B-1, except that: mixing contact I was performed without the addition of TPO-g- (GMA-co-St), see in particular Table 2;
premix 1 was obtained and designated premix 1-e.
TABLE 2
PREPARATION EXAMPLE C-1
This preparation example is used to illustrate the preparation method of premix 2 (i.e., the lower surface layer according to the present invention).
Specifically, the preparation method comprises the following steps: polypropylene-based elastomer, TPO-g- (GMA-co-St) (T1), metallocene polyethylene, reinforcing filler, antioxidant and pigment are mixed and contacted with II, specifically referring to Table 3, wherein the conditions of the mixed and contacted II are as follows: the stirring is carried out under the condition of 500r/min of rotating speed, 85 ℃ of temperature and 8min of time;
premix 2 was obtained and designated premix 2-a.
PREPARATION EXAMPLE C-2
This preparation was carried out in a similar manner to preparation C-1, except that: the mixing contact II was performed using metallocene polyethylene II instead of metallocene polyethylene I and TPO-g- (GMA-co-St) was used as T2, see in particular Table 3;
premix 2 was obtained and designated premix 2-b.
PREPARATION EXAMPLE C-3
This preparation was carried out in a similar manner to preparation C-1, except that: mixed contact II was performed using PP-g-MAH instead of TPO-g- (GMA-co-St), see in particular Table 3;
premix 2 was obtained and designated premix 2-c.
PREPARATION EXAMPLE C-4
This preparation was carried out in a similar manner to preparation C-1, except that: mixed contact II was performed using PE-g-MAH instead of TPO-g- (GMA-co-St), see in particular Table 3;
premix 2 was obtained and designated premix 2-d.
PREPARATION EXAMPLE C-5
This preparation was carried out in a similar manner to preparation C-1, except that: mixing contact II was performed without addition of TPO-g- (GMA-co-St), see in particular Table 3;
premix 2 was obtained and designated premix 2-e.
TABLE 3 Table 3
Example 1
The embodiment is used for explaining the preparation of the double-layer composite ethylene propylene diene monomer rubber waterproof coiled material provided by the invention, and the preparation is carried out according to the following parameters, and comprises the following steps:
SS1, granulating:
adding the premix 1 into a screw extruder for granulation to obtain granules 1;
SS2, dynamic vulcanization:
before extrusion plasticizing the pelletization material 1, dynamically vulcanizing the pelletization material 1 by adopting a vulcanizing agent and a promoter to obtain vulcanized pelletization material 1 to be applied to extrusion plasticizing;
SS3, extrusion plasticization:
extruding and plasticizing by adopting two extruders, specifically, introducing the granules 1 into the extruder 1 for extruding and plasticizing to obtain a material I; introducing the premix 2 into an extruder 2 for extrusion plasticization to obtain a material II; coextruding the material I and the material II into a double-layer coextruding die for discharging to obtain a coextruding material to be applied to the three-roller calender for calendering;
SS4, calendering:
introducing the co-extrusion material into a three-roller calender for calendering to obtain a double-layer composite ethylene propylene diene monomer waterproof coiled material;
wherein premix 1 used was premix 1-a of all parts by weight obtained by the method in preparation example B-1, and premix 2 was premix 2-a of all parts by weight obtained by the method in preparation example C-1;
the conditions of granulation and dynamic vulcanization are as follows: under the condition of stirring, the rotating speed is 500rpm, and the temperature of a die of the screw extruder is 225 ℃;
the extrusion plasticizing conditions are as follows: under the condition of stirring, the temperature is 225 ℃ and the rotating speed is 365rpm;
the calendaring conditions are as follows: the temperature is 45 ℃ of the upper roller, 45 ℃ of the middle roller and 45 ℃ of the lower roller;
the waterproof coiled material is named as P1, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.7cm.
Example 1-a
This example was conducted in a similar manner to example 1, with the same operating conditions, except that: the addition amount of the raw materials is changed:
wherein, in the process of preparing the premix 1-a, the addition amount of the polypropylene-based elastomer is 50 parts by weight;
in the preparation of premix 2-a, the polypropylene-based elastomer was added in an amount of 80 parts by weight.
The waterproof coiled material is named as P1-a, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.5cm.
Example 1-b
This example was carried out in a similar manner to example 1, except that: the addition amount and the operation condition of the raw materials are changed:
wherein, in the process of preparing the premix 1-a, the addition amount of the polypropylene-based elastomer is 60 parts by weight, the addition amount of TPO-g- (GMA-co-St) is 5 parts by weight, the addition amount of the reinforcing filler is 15 parts by weight, and the addition amount of the light stabilizer is 2 parts by weight;
in the process of preparing the premix 2-a, the addition amount of the polypropylene-based elastomer is 80 parts by weight, the addition amount of the polypropylene-based elastomer is 5 parts by weight, and the addition amount of the reinforcing filler is 15 parts by weight;
in the process of preparing the waterproof coiled material, the conditions of granulation and dynamic vulcanization in the steps SS1 and SS2 are as follows: under the condition of stirring, the rotating speed is 500rpm, and the temperature of a die of the screw extruder is 200 ℃;
in step SS3, the extrusion plasticizing conditions are: under the condition of stirring, the temperature is 200 ℃ and the rotating speed is 450rpm;
in step SS4, the conditions of the calendering are: the temperature is 55 ℃ of the upper roller, 55 ℃ of the middle roller and 55 ℃ of the lower roller;
the waterproof coiled material is named as P1-b, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.8cm.
Example 1-c
This example was carried out in a similar manner to example 1, except that: the addition amount of the raw materials is changed:
wherein, in the process of preparing the premix 1-a, the addition amount of the polypropylene-based elastomer is 70 parts by weight, the addition amount of TPO-g- (GMA-co-St) is 5 parts by weight, the addition amount of the reinforcing filler is 15 parts by weight, and the addition amount of the light stabilizer is 2 parts by weight;
in the preparation of premix 2-a, the polypropylene-based elastomer was added in an amount of 100 parts by weight, the polypropylene-based elastomer was added in an amount of 5 parts by weight, and the reinforcing filler was added in an amount of 15 parts by weight.
The waterproof coiled material is named as P1-c, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.6cm.
Example 2
This example was carried out in a similar manner to example 1, except that: premix 1 is premix 1-b, premix 2 is premix 2-b;
the waterproof coiled material is named as P2, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.9cm.
Comparative example 1
This comparative example was conducted in a similar manner to example 1 except that: premix 1 used was all parts by weight of premix 1-C obtained by the method in preparation example B-3, and premix 2 was all parts by weight of premix 2-C obtained by the method in preparation example C-3;
the waterproof coiled material is named as DP1, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.7cm.
Comparative example 2
This comparative example was conducted in a similar manner to example 1 except that: premix 1 used was all parts by weight of premix 1-d obtained by the method in preparation example B-4, and premix 2 was all parts by weight of premix 2-d obtained by the method in preparation example C-4;
the waterproof coiled material is named as DP2, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.7cm.
Comparative example 3
This comparative example was conducted in a similar manner to example 1 except that: premix 1 used was all parts by weight of premix 1-e obtained by the method in preparation example B-5, and premix 2 was all parts by weight of premix 2-e obtained by the method in preparation example C-5;
the waterproof coiled material is named as DP3, the thinnest part of the upper surface layer is 0.5cm, and the thinnest part of the lower surface layer is 0.7cm.
Test example 1
The waterproof coiled materials prepared above were welded and lapped, and physical properties and seam peel strength were tested, and the results are shown in table 4.
TABLE 4 Table 4
Table 4 continuous table
From the results, the waterproof coiled material provided by the invention can be welded, has a simple process, excellent physical properties, compact adhesion of a double-layer structure, good toughness, high strength and good weather resistance, and is suitable for the waterproof field of buildings.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (7)
1. The double-layer composite ethylene propylene diene monomer waterproof coiled material is characterized by comprising an upper surface layer and a lower surface layer which are sequentially laminated; the upper surface layer is formed by an ethylene propylene diene monomer waterproof layer, the lower surface layer is formed by a thermoplastic polyolefin elastomer waterproof layer, and the ratio of the thickness of the thinnest part of the upper surface layer to the thickness of the thinnest part of the lower surface layer is 1:1 to 1.8;
the ethylene propylene diene monomer waterproof layer comprises the following components: ethylene propylene diene monomer rubber, polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, reinforcing filler, vulcanizing agent, accelerator, anti-aging agent and light stabilizer;
in the upper surface layer, based on 100 parts by weight of the total weight of the ethylene propylene diene monomer waterproof layer, the ethylene propylene diene monomer is 30-70 parts by weight, the polypropylene-based elastomer is 40-80 parts by weight, the TPO-g- (GMA-co-St) is 1-10 parts by weight, the softening oil is 2-10 parts by weight, the reinforcing filler is 10-20 parts by weight, the vulcanizing agent is 0.1-1 part by weight, the accelerator is 0.1-1 part by weight, the anti-aging agent is 1-4.5 parts by weight, and the light stabilizer is 1-5 parts by weight;
the thermoplastic polyolefin elastomer waterproof layer comprises the following components: TPO-g- (GMA-co-St), polypropylene-based elastomer, metallocene polyethylene, reinforcing filler, antioxidant, light stabilizer and pigment; the TPO-g- (GMA-co-St) is the same as the TPO-g- (GMA-co-St) in the upper surface layer;
the TPO-g- (GMA-co-St) is a product prepared by the following method:
s1, mixing raw materials for preparing TPO-g- (GMA-co-St) to obtain a mixture I;
s2, carrying out melt grafting on the mixture I at 180-230 ℃ to obtain TPO-g- (GMA-co-St), wherein the time of melt grafting is 8-15min;
wherein, the raw materials for preparing TPO-g- (GMA-co-St) comprise: polypropylene elastomer, glycidyl methacrylate, styrene, dicumyl peroxide and antioxidant 1010;
in the raw material for preparing TPO-g- (GMA-co-St), the glycidyl methacrylate is used in an amount of 1 to 5 parts by weight relative to 100 parts by weight of the polypropylene-based elastomer; the usage amount of the styrene is 0.5-4 parts by weight; the dosage of the dicumyl peroxide is 0.1-0.8 weight part; the antioxidant 1010 is used in an amount of 0.1 to 1 part by weight, wherein the polypropylene-based elastomer is the same as the polypropylene-based elastomer in the upper surface layer.
2. The waterproof coiled material according to claim 1, wherein in the ethylene propylene diene monomer waterproof layer, the softening oil is at least one selected from naphthenic oil, paraffinic oil and aromatic oil; and/or
The vulcanizing agent is at least one selected from sulfur and dicumyl peroxide; and/or
The accelerator is at least one selected from accelerator DM, accelerator TMTD and accelerator BZ; and/or
The anti-aging agent is at least one selected from anti-aging agent 4010NA, anti-aging agent 4010 and anti-aging agent RD; and/or
The polypropylene-based elastomer is selected from the group consisting of Liandbarsel CA10A, liandbarsel CA60A, vibrio VERSIFY 2300; and/or
The reinforcing filler is at least one selected from carbon black and calcium carbonate; and/or
The light stabilizer is at least one selected from light stabilizer UV-2020, ultraviolet absorber UV-326 and ultraviolet absorber UV-531.
3. The waterproof roll according to claim 1 or 2, wherein the content of the TPO-g- (GMA-co-St) is 1 to 10 parts by weight, the content of the metallocene polyethylene is 10 to 40 parts by weight, the content of the reinforcing filler is 10 to 30 parts by weight, the content of the antioxidant is 0.1 to 1 part by weight, the content of the light stabilizer is 1 to 5 parts by weight, and the content of the pigment is 0.5 to 2 parts by weight, relative to 100 parts by weight of the polypropylene-based elastomer, wherein the polypropylene-based elastomer, the reinforcing filler, and the light stabilizer are the same as the polypropylene-based elastomer, the reinforcing filler, and the light stabilizer of claim 1 or 2, respectively.
4. The waterproof roll according to claim 1 or 2, wherein in the thermoplastic polyolefin elastomer waterproof layer, the antioxidant is selected from at least one of an antioxidant 1010, an antioxidant 168, an antioxidant 1076; and/or
The pigment is at least one selected from titanium dioxide, carbon black and a colorant; and/or
The metallocene polyethylene is selected from at least one of metallocene high-density polyethylene and metallocene low-density polyethylene.
5. A method for preparing the double-layer composite ethylene propylene diene monomer waterproof coiled material according to any one of claims 1 to 4, which is characterized by comprising the following steps of:
(1) Mixing and contacting: mixing ethylene propylene diene monomer, a polypropylene-based elastomer, TPO-g- (GMA-co-St), softening oil, a filler, an anti-aging agent and a light stabilizer for contacting I to obtain a premix 1;
mixing and contacting a polypropylene-based elastomer, TPO-g- (GMA-co-St), metallocene polyethylene, a filler, an antioxidant and a pigment to obtain a premix 2;
(2) Granulating: granulating the premix 1 to obtain granules 1;
(3) Plasticizing and calendaring: extruding and plasticizing the pelleting material 1 and the premix 2, and introducing the pelleting material and the premix into a three-roll calender for calendering to obtain the double-layer composite ethylene propylene diene monomer waterproof coiled material.
6. The method of claim 5, wherein the mixed contact I satisfies at least: stirring at a rotation speed of 300-800r/min at 70-90deg.C for 5-10min; and/or
The mixed contact II satisfies at least: the stirring is carried out under the condition of 300-800r/min, 70-90 ℃ and 5-10min.
7. The use of the double-layer composite ethylene propylene diene monomer rubber waterproof coiled material as claimed in any one of claims 1 to 4 in the field of building waterproofing.
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