CN113789003B - Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof - Google Patents
Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof Download PDFInfo
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- CN113789003B CN113789003B CN202111359381.9A CN202111359381A CN113789003B CN 113789003 B CN113789003 B CN 113789003B CN 202111359381 A CN202111359381 A CN 202111359381A CN 113789003 B CN113789003 B CN 113789003B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/66—Sealings
- E04B1/665—Sheets or foils impervious to water and water vapor
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/754—Self-cleaning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention relates to a self-cleaning anti-permeability waterproof sheet and a preparation method and application thereof, wherein the raw materials of the sheet comprise polypropylene resin, a high-molecular elastomer, a cyclic olefin copolymer and a high-molecular antistatic agent, wherein the cyclic olefin copolymer and the high-molecular antistatic agent account for 5-30% of the total mass of the raw materials of the sheet, and the mass ratio of the cyclic olefin copolymer to the high-molecular antistatic agent is 0.1-10: 1. According to the invention, the high-molecular antistatic agent and the cycloolefin copolymer are added into the sheet material which takes the polypropylene resin and the high-molecular elastomer as main raw materials, so that the surface resistance is reduced, the long-acting stain-resistant self-cleaning effect of the surface of the sheet material is achieved, the waterproof and anti-permeability of the whole material can be effectively improved, the better mechanical property is maintained, meanwhile, the high-molecular antistatic agent and the cycloolefin copolymer can achieve the synergistic effect, the rigidity of the surface of the sheet material is improved, and the surface self-cleaning effect is improved.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a self-cleaning anti-permeability waterproof sheet as well as a preparation method and application thereof.
Background
The TPO waterproof coiled material is exposed for use, and has good weather resistance and good aging resistance. However, TPO materials generally have a high surface resistance value, and are likely to generate static electricity on the surface and adsorb dust.
In order to improve the surface stain resistance of the TPO coil, a super-hydrophobic layer is usually formed on the surface of the TPO coil, but the super-hydrophobic surface is difficult to avoid having certain lipophilicity, easy to adsorb oil on the surface, further capable of attaching dust, small in water contact angle, difficult to take away the attached oil stain dust due to rain wash, and difficult to keep the purpose of long-term self-cleaning.
Usually, in order to improve the antistatic performance, an antistatic agent is added into a polyolefin waterproof roll, generally, the antistatic agent is a surfactant, the antistatic agent is added into polymer resin to be melted and blended, after the resin is solidified, the antistatic agent migrates to the surface, hydrophilic groups are arranged towards the air side to form a conductive layer, and the surface resistivity of the material is reduced to achieve the antistatic purpose so as to reduce dust adsorption. However, the mechanism depends on surface water absorption, and the influence of humidity is large, so that the waterproof performance of the coiled material is influenced, and the long-term retention is poor. On the other hand, the environment for the growth of microorganisms is provided, and the service life of the polyolefin waterproof roll is greatly shortened. Therefore, although the antistatic property can be improved to some extent, the long-term retention is poor.
For example, chinese patent CN109910414B discloses a waterproof roll of polymer, which comprises an outer waterproof layer, a base material layer, an isolation film layer, and an inner layer of polymer polyester, wherein the outer waterproof layer and the base material layer are laminated from outside to inside, and the isolation film layer and the inner layer of polymer polyester are laminated by pressure sensitive adhesive; the high-molecular polyester inner layer comprises the following raw materials in parts by weight: 110-135 parts of ethylene-vinyl acetate copolymer, 23-36 parts of thermoplastic polyester elastomer, 5-10 parts of stabilizer, 6-14 parts of heavy calcium powder, 0.5-2.6 parts of antistatic agent and 0.4-0.8 part of antioxidant graphene. The antistatic agent is one or more of polyethylene oxide, polyether amide imide and PEG-methyl methacrylate copolymer. However, in this patent, a polymeric antistatic agent is used in the inner layer of the waterproof roll, and the outer surface of the waterproof roll still cannot achieve long-lasting self-cleaning property.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a waterproof sheet with long-acting self-cleaning effect on the outer surface and excellent anti-permeability performance and a preparation method thereof.
A second object of the present invention is to provide an application of the waterproof sheet described above.
In order to achieve the purpose, the invention adopts the technical scheme that:
the waterproof sheet comprises raw materials of polypropylene resin, a high-molecular elastomer, a cyclic olefin copolymer and a high-molecular antistatic agent, wherein the cyclic olefin copolymer and the high-molecular antistatic agent account for 5-30% of the total mass of the raw materials of the sheet, and the mass ratio of the cyclic olefin copolymer to the high-molecular antistatic agent is 0.1-10: 1.
In some preferred embodiments of the present invention, the cycloolefin copolymer and the polymeric antistatic agent account for 5 to 25% of the total mass of the raw materials of the sheet, and more preferably, the cycloolefin copolymer and the polymeric antistatic agent account for 15 to 25% of the total mass of the raw materials of the sheet.
In some preferred embodiments of the present invention, the mass ratio of the cycloolefin copolymer to the polymeric antistatic agent is 0.5 to 5: 1. More preferably, the mass ratio of the cycloolefin copolymer to the polymeric antistatic agent is 0.5 to 2: 1. More preferably, the mass ratio of the cycloolefin copolymer to the polymeric antistatic agent is 0.5 to 0.9: 1.
The surface resistivity of the sheet is reduced by adding the macromolecular antistatic agent, and the surface hydrophilicity is improved, so that the surface self-cleaning effect is achieved.
The polymer antistatic agent is added into the waterproof sheet, and forms fine layered or ribbed distribution on the surface layer through the movement of molecules to form a conductive surface layer, and a spherical core-shell structure is formed in the center part to form a static charge channel for releasing static. On one hand, dust adsorption can be reduced, meanwhile, a small water contact angle can be formed on the surface of the sheet by rainwater, dust stained on the surface can be taken away, on the other hand, the reduction of antistatic performance caused by rainwater washing is not easy to occur, and the long-acting antistatic self-cleaning effect is achieved.
In some embodiments of the present invention, the polymeric antistatic agent is selected from the group consisting of polyethylene-b-polyethylene glycol block copolymers, polyethylene oxide-epichlorohydrin copolymers, polyetheresteramides, and polyetheresterimides. In some preferred embodiments of the present invention, the polyethylene-b-polyethylene glycol block copolymer has better compatibility with the polypropylene resin and the polymeric elastomer. The polymer antistatic agent is selected from Pelctron PVL of Sanyo chemical company.
In some embodiments of the invention, the Cyclic Olefin Copolymer (COC) is a thermoplastic amorphous cyclic olefin copolymer obtained by metallocene-catalyzed polymerization of norbornene and ethylene monomers. Preferably, the glass transition temperature (Tg value) of the cycloolefin copolymer is 60 to 160 ℃. For example, Topas series from Riben Baysian or Zeonex series from Riwenyo in Japan can be used. Specifically, 8007F-600 (Tg value: 78 ℃), Topas 6015S-04 (Tg value: 158 ℃).
The cycloolefin copolymer (COC) has higher glass transition temperature and stronger rigidity and water vapor barrier property, the COC slows down the crystallization rate of polypropylene resin/high-molecular elastomer (TPO) through melt blending to form a finer and more compact alpha-crystal form, and the amorphous area of the high-molecular elastomer (TPO) is filled to improve the surface compactness, so that the self-cleaning property of the sheet is improved. In addition, the macromolecular antistatic agent has certain hygroscopicity, so that the risk of reducing the waterproof and anti-permeability performance of the sheet material added into a macromolecular elastomer system is realized, and the addition of COC effectively blocks water vapor and improves the waterproof and anti-permeability performance of the sheet material. Therefore, the cycloolefin copolymer in the sheet not only has synergistic effect with the high-molecular antistatic agent to improve the self-cleaning property of the sheet, but also can play a role in water vapor barrier.
In some preferred embodiments of the present invention, the polymeric elastomer is an ethylene-based copolymerized thermoplastic elastomer.
In some preferred and specific embodiments of the present invention, the ethylene content in the polymeric elastomer is not less than 12% by mass. The elastomer with the ethylene mass content not lower than 12% is selected to ensure the compatibility between the high molecular elastomer and the cycloolefin copolymer. Preferably, the mass content of ethylene is not less than 12% and not more than 80%.
In the present invention, the polymer elastomer is a thermoplastic polyolefin elastomer (TPO).
In some preferred embodiments of the present invention, the polymeric elastomer is a combination of one or more of a propylene-ethylene copolymer, an ethylene-alpha-butene copolymer, and an ethylene-alpha-octene copolymer. The melt index (230 ℃, 2.16 kg) of the macromolecular elastomer is less than or equal to 8g/10 min.
The polymer elastomer can be selected from Vistamaxx 6102 (ethylene content is 16 wt%) of Exxon Mobil and Versify 2300 of Dow.
The polypropylene resin (PP) is selected from homo-polypropylene resin and co-polypropylene resin. In some preferred embodiments of the present invention, the polypropylene resin has a melt index (230 ℃, 2.16 kg) of 8g/10min or less.
In some preferred and specific embodiments, the mass ratio of the polypropylene resin to the polymeric elastomer is 1: 1-4. More preferably, the mass ratio of the polypropylene resin to the high molecular elastomer is 1: 1.5-3.
In some embodiments of the present invention, the raw material of the waterproof sheet further comprises a color master and/or an auxiliary agent. Further, the auxiliary agent is selected from one or more of an antibacterial agent, an antioxidant and a light stabilizer.
In some preferred and specific embodiments of the present invention, the raw materials of the waterproof sheet include the following components in parts by weight:
20-30 parts of polypropylene resin;
30-70 parts of a high-molecular elastomer;
2-20 parts of a cycloolefin copolymer;
2-20 parts of a high-molecular antistatic agent;
1-8 parts of color master batch;
0.1-1 part of an antibacterial agent;
0.1-1 part of antioxidant;
0.1-1 part of light stabilizer.
Preferably, the raw materials of the waterproof sheet comprise the following components in parts by weight:
20-30 parts of polypropylene resin;
40-60 parts of a high-molecular elastomer;
5-15 parts of a cycloolefin copolymer;
5-15 parts of a high-molecular antistatic agent;
1-8 parts of color master batch;
0.1-1 part of an antibacterial agent;
0.1-1 part of antioxidant;
0.1-1 part of light stabilizer.
Preferably, the color master batch is a titanium dioxide master batch taking TPO as a carrier. In the color master batch, the mass ratio of titanium dioxide to TPO is 5-9: 3, and the specific mass ratio is 7: 3.
The titanium dioxide is rutile titanium dioxide, and the average particle size is 200-400 mu m. Such as R100, R105, R960 from the company Kemu, USA.
The titanium dioxide master batch is selected to provide white color for the sheet, is dispersed in the sheet, can absorb certain ultraviolet light, can reflect most visible light, and has the functions of improving aging resistance and heat insulation.
The antimicrobial agent is capable of reducing bacterial growth caused by exposure of the sheet material for a prolonged period of time, and preferably the antimicrobial agent is an organic antimicrobial agent. The organic antibacterial agent includes, but is not limited to, one or more of quaternary ammonium salt, phenol, organic metal, pyridine, imidazole and thiophene antibacterial agent. The antibacterial agent is selected from J151 of Foshan Coprinus.
Preferably, the antioxidant is one or more of the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 264, antioxidant 246 and antioxidant 168. Preferably, the antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio is 1:1 in combination.
Preferably, the light stabilizer is a hindered amine light stabilizer, such as selected from Chimassorb 2020.
The second technical scheme adopted by the invention is as follows: the waterproof composite sheet comprises a base layer and a waterproof layer arranged on the base layer, wherein the waterproof layer comprises the waterproof sheet.
In some preferred and specific embodiments, the thickness ratio of the base layer to the waterproof layer is 4-8: 1. Further, the thickness of waterproof layer is 0.05~0.20mm, the thickness of basic unit is 0.6~1.3 mm.
In some preferred embodiments, the raw materials for preparing the base layer comprise a polypropylene resin and a high polymer elastomer, and the mass ratio of the polypropylene resin to the high polymer elastomer is 1: 1-4. Preferably, the mass ratio of the polypropylene resin to the high polymer elastomer is 1: 1-2.
In some preferred and specific embodiments, the raw materials for preparing the base layer further comprise a filler accounting for 10-15% of the total mass content of the raw material formula of the base layer.
Further preferably, the raw materials for preparing the base layer comprise the following components in parts by weight: 20-30 parts of polypropylene resin, 30-70 parts of high-molecular elastomer, 5-20 parts of filler, 0.1-1 part of auxiliary agent and 1-3 parts of color master batch.
Preferably, the color master batch in the base layer is a titanium dioxide master batch taking TPO as a carrier. More preferably, the color master in the base layer and the color master in the waterproof layer are the same color master.
Preferably, the filler is selected from calcium powder, further, the calcium powder is calcium carbonate powder. Such as Omyacab T1 from Omica.
Preferably, the adjuvant in the base layer is selected from antioxidants.
In some preferred and specific embodiments, the base layer and the waterproof layer are prepared by co-extrusion molding.
The third technical scheme adopted by the invention is as follows: the preparation method of the waterproof composite sheet comprises the steps of respectively melting the raw materials of the base layer and the waterproof layer, co-extruding, cooling and shaping to obtain the waterproof composite sheet.
In some preferred and specific embodiments, the raw materials of the base layer include polypropylene resin, high molecular elastomer, filler, auxiliary agent and color master, the raw materials of the waterproof layer include polypropylene resin, high molecular elastomer, cyclic olefin copolymer, high molecular antistatic agent, color master and auxiliary agent, and the preparation method includes the following steps:
(1) mixing the filler and the auxiliary agent in the base layer with part of the high-molecular elastomer respectively, extruding and granulating to obtain filler master batches and auxiliary agent master batches;
(2) mixing the auxiliary agent in the waterproof layer with part of the high polymer elastomer, extruding and granulating to prepare auxiliary agent master batches;
(3) adding the filler master batch, the auxiliary master batch, the resin polypropylene, the high-molecular elastomer and the color master batch of the base layer into a first double-screw extruder, adding the auxiliary master batch, the polypropylene resin, the high-molecular elastomer, the cyclic olefin copolymer, the high-molecular antistatic agent and the color master batch of the waterproof layer into a second double-screw extruder, respectively melting, then carrying out composite extrusion through a co-extrusion die head, cooling and shaping to obtain the waterproof composite sheet, wherein the temperature of a feeding section of the first double-screw extruder is 20-35 ℃, the temperature of a melting section is 130-190 ℃, the temperature of a metering section is 190-200 ℃, and the feeding speed is 55-80 rpm; the temperature of the feeding section of the second double-screw extruder is 20-35 ℃, the temperature of the melting section is 130-190 ℃, the temperature of the metering section is 190-200 ℃, and the feeding speed is 55-80 rpm; the die head temperature is 190-200 ℃.
Further, in the step (1), in the filler masterbatch, the high molecular elastomer accounts for 20-40% of the total mass of the filler masterbatch; in the auxiliary agent master batch, the high molecular elastomer accounts for 60-80% of the total mass of the auxiliary agent master batch; when preparing each master batch, the high-molecular elastomer is fed through a main feeding port at a feeding speed of 20-50 rpm, the filler or the auxiliary agent is fed through a side feeding port at a feeding speed of 20-50 rpm, the screw temperature of 140-190 ℃, the die head temperature of 180-200 ℃ and the underwater pelletizing temperature of 60-80 ℃.
Further, in the step (2), in the auxiliary agent master batch, the high molecular elastomer accounts for 60-80% of the total mass of the auxiliary agent master batch; when the auxiliary agent master batch is prepared, the high-molecular elastomer is fed through a main feeding port at a feeding speed of 20-50 rpm, the auxiliary agent is fed through a side feeding port at a feeding speed of 20-50 rpm, the screw temperature is 140-190 ℃, the die head temperature is 180-200 ℃, and the underwater pelletizing temperature is 60-80 ℃.
The fourth technical scheme adopted by the invention is as follows: the sheet or the composite sheet is used as a waterproof roll.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the high-molecular antistatic agent and the cycloolefin copolymer are added into the sheet taking the polypropylene resin and the high-molecular elastomer as main raw materials, so that the surface resistance is reduced, the surface crystal compactness is improved, the surface of the sheet achieves the long-acting stain-resistant self-cleaning effect, the waterproof permeability resistance of the whole material can be effectively improved, the better mechanical property can be maintained, meanwhile, the high-molecular antistatic agent and the cycloolefin copolymer can achieve the synergistic effect, the rigidity of the surface of the sheet is improved, and the surface self-cleaning effect is improved.
The sheet disclosed by the invention is exposed for use as a waterproof coiled material, so that a long-term antistatic self-cleaning effect is achieved.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to specific examples so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.
Example 1
The composition of the waterproof sheet of this example is shown in table 1, wherein,
the antioxidant is a combination of the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1:1.
The white masterbatch is obtained by granulating R105 and TPO (Vistamaxx 6202) according to the mass ratio of 7:3 by a double-screw extruder.
The antibacterial agent is J151.
The preparation method comprises the following steps:
(1) respectively mixing the antibacterial agent, the antioxidant and the light stabilizer with part of the high-molecular elastomer, and respectively extruding and granulating through a double-screw extruder to obtain the antibacterial agent master batch, the antioxidant master batch and the light stabilizer master batch, wherein in each master batch, the elastomer accounts for 70% of the mass of the master batch, the elastomer is fed through a main feeding port at a feeding speed of 30RPM, the antibacterial agent or the antioxidant or the light stabilizer is fed through a side feeding port with a screw length-diameter ratio of 32:1, the feeding speed is 30RPM, the screw temperature is 140-190 ℃, the die head temperature is 190 ℃, and the underwater pelletizing temperature is 60-80 ℃.
(2) Adding PP, the rest high-molecular elastomer, COC, the high-molecular antistatic agent, the white masterbatch, the antibacterial agent masterbatch, the antioxidant masterbatch and the light stabilizer masterbatch into a stirrer to be mixed for 20min, putting into a double-screw extruder, and controlling the temperature of each section of the extruder as follows: the feeding section is room temperature, the melting section is 130-190 ℃, the metering section is 190-200 ℃, the temperature of a die head distributor is 200 ℃, the feeding speed is controlled to be 75rpm, the rotating speed of a melting double-screw is 250rpm, and then the material is cooled and calendered by a first calendering roll and a second calendering roll, wherein the temperature of the first calendering roll is 60 ℃, and the temperature of the second calendering roll is 50 ℃; and cooling and calendering the calendered sheet by a second calendering roller and a third calendering roller, wherein the temperature of the third calendering roller is 40 ℃, and rolling to obtain the waterproof sheet with the thickness of 0.9 mm.
Comparative example 1
The composition of the raw materials of the waterproof sheet provided by the comparative example is shown in table 1, and the rest is basically the same as that of example 1.
Comparative example 2
The composition of the raw materials of the waterproof sheet provided by the comparative example is shown in table 1, and the rest is basically the same as that of example 1.
Table 1 shows the raw material compositions (in parts by mass) of the sheets of example 1 and comparative examples 1 to 2
Performance testing
The waterproof sheets of the embodiment 1 and the comparative examples 1-2 are subjected to permeability resistance test according to ASTM E960-2000, physical property test according to GB/T27789-.
Table 2 shows the index requirements of the impervious waterproof sheet
Table 3 shows the results of the performance test of the waterproof sheets of example 1 and comparative examples 1 to 2
Example 2
The waterproof composite sheet of this embodiment, including basic unit and the waterproof layer of setting on the basic unit, wherein, the raw materials of preparation basic unit comprises following component: 36 parts of PP, 54 parts of high polymer elastomer, 12 parts of calcium powder, 0.2 part of antioxidant and 1 part of white master batch, wherein the calcium powder is Omyacab T1, and the antioxidant is antioxidant 1010.
The raw materials for preparing the waterproof layer are shown in table 4, wherein the specific materials of the PP, the polymer elastomer, the COC, the polymer antistatic agent, the white masterbatch, the antibacterial agent, the antioxidant and the light stabilizer in the waterproof layer are the same as those in example 1, and the specific materials of the PP, the polymer elastomer and the white masterbatch in the base layer are the same as those in the waterproof layer.
The waterproof composite sheet of the example was prepared by the following method:
(1) respectively mixing the calcium powder and the antioxidant in the base layer with part of the high-molecular elastomer, and respectively extruding and granulating through a double-screw extruder to obtain calcium powder master batches and antioxidant master batches, wherein in each master batch, the elastomer accounts for 70% of the mass of the master batch, the elastomer is fed through a main feeding port at a feeding speed of 30rpm, the calcium powder or the antioxidant is fed through a side feeding port with a screw length-diameter ratio of 32:1, the feeding speed is 30rpm, the screw temperature is 140-190 ℃, the die head temperature is 190 ℃, and the underwater pelletizing temperature is 60-80 ℃.
(2) Respectively mixing the antibacterial agent, the antioxidant and the light stabilizer in the waterproof layer with part of the high-molecular elastomer, and respectively extruding and granulating through a double-screw extruder to obtain antibacterial agent master batch, antioxidant master batch and light stabilizer master batch, wherein in each master batch, the elastomer accounts for 70% of the mass of the master batch, the elastomer is fed through a main feeding port at a feeding speed of 30rpm, the antibacterial agent or the antioxidant or the light stabilizer is fed through a side feeding port with a length-diameter ratio of 32:1 of a screw rod, the feeding speed is 30rpm, the screw rod temperature is 140-.
(3) Adding PP, the residual high-molecular elastomer, the calcium powder master batch, the antioxidant master batch and the white master batch of a base layer into a first stirrer to be mixed for 20min, adding PP, the residual high-molecular elastomer, COC, the high-molecular antistatic agent, the white master batch, the antibacterial agent master batch, the antioxidant master batch and the light stabilizer master batch of a waterproof layer into a second stirrer to be mixed for 20min, then respectively putting the mixture into a first double-screw extruder and a second double-screw extruder, carrying out composite extrusion through a co-extrusion die head, and controlling the temperatures of the sections of the first double-screw extruder and the second double-screw extruder as follows: the temperature of a feeding section of the first twin-screw extruder is 20-35 ℃, the temperature of a melting section is 130-190 ℃, the temperature of a metering section is 190-200 ℃, and the feeding speed is 75 rpm; the temperature of a feeding section of the second double-screw extruder is 20-35 ℃, the temperature of a melting section is 130-190 ℃, the temperature of a metering section is 190-200 ℃, and the feeding speed is 75 rpm; the die distributor temperature was 200 ℃ and the melt twin screw speed was 250 rpm.
Cooling and calendering the fused composite sheet by a first calendering roller and a second calendering roller, wherein the temperature of the first calendering roller is 60 ℃, and the temperature of the second calendering roller is 50 ℃; and cooling and calendaring the calendered composite sheet by a second calendaring roller and a third calendaring roller, wherein the temperature of the third calendaring roller is 40 ℃, and the waterproof sheet with the thickness of 0.9mm is obtained by rolling, wherein the thickness of the base layer is 0.8mm, and the thickness of the waterproof layer is 0.1 mm.
Example 3
The structure of the waterproof composite sheet of this example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer are shown in table 4, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Example 4
The structure of the waterproof composite sheet of this example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer are shown in table 4, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Example 5
The structure of the waterproof composite sheet of this example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer are shown in table 4, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Example 6
The structure of the waterproof composite sheet of this example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer are shown in table 4, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Table 4 shows the raw material compositions (in parts by mass) of the waterproof layers of the waterproof composite sheets of examples 2 to 6
Comparative example 3
The structure of the waterproof composite sheet of this comparative example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer were as shown in table 5, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Comparative example 4
The structure of the waterproof composite sheet of this comparative example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer were as shown in table 5, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Comparative example 5
The structure of the waterproof composite sheet of this comparative example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer were as shown in table 5, and the preparation method of the waterproof composite sheet was the same as that of example 2.
Comparative example 6
The structure of the waterproof composite sheet of this comparative example was the same as that of example 2, the raw materials used for preparing the base layer were the same as those of example 2, the raw materials for preparing the waterproof layer were as shown in table 5, and the preparation method of the waterproof composite sheet was the same as that of example 2.
In this example, the small molecule antistatic agent is Atmer 129 from the company bluegrass.
Table 5 shows the raw material compositions (in parts by weight) of the waterproof composite sheets of comparative examples 3 to 6
The waterproof composite sheets of examples 2-6 and comparative examples 3-6 were subjected to permeability resistance test according to ASTM E960-2000, physical property test according to GB/T27789-.
Table 6 shows the results of the performance test of the waterproof composite sheets of examples 2 to 6
Table 7 shows the results of the performance test of the waterproof composite sheets of comparative examples 3 to 6
Note: the lap edge peel strength refers to the peel strength after the sheets are lapped by thermal welding.
As can be seen from examples 2 to 5 and comparative example 6, the addition of the polymeric antistatic agent can effectively control the surface resistance to 1013And the surface resistance after 5 times of water washing is very little influenced, which shows that the stain resistance can be maintained for a long time. As can be seen from examples 2 to 5 and comparative examples 3 to 5, both the polymeric antistatic agent and COC have synergyWith the effect of increasing efficiency, on the one hand can improve the impermeability to steam, and on the other hand can effectively improve the surface stain resistance, through reducing surface resistance, can reach the effect of surface automatically cleaning through the rainwash. Furthermore, after the composite sheet is prepared, the high impermeability and self-cleaning performance of the whole material can be improved, the mechanical property of the material can be effectively maintained, and the problems of overhigh tensile strength or small elongation at break of the material are avoided. The single-layer sheet and the composite sheet can be applied to different occasions.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (12)
1. A waterproof sheet for a waterproof roll, characterized in that: the sheet comprises raw materials including polypropylene resin, a high polymer elastomer, a cyclic olefin copolymer and a high polymer antistatic agent, wherein the cyclic olefin copolymer and the high polymer antistatic agent account for 5-25% of the total mass of the raw materials of the sheet, the mass ratio of the cyclic olefin copolymer to the high polymer antistatic agent is 0.5-2: 1, the high polymer elastomer is a thermoplastic polyolefin elastomer, and the mass ratio of the polypropylene resin to the high polymer elastomer is 1: 1-4;
the cycloolefin copolymer is a thermoplastic amorphous cycloolefin copolymer obtained by polymerizing norbornene and ethylene monomers under the catalysis of metallocene;
the polymer antistatic agent is one or a combination of polyethylene-b-polyethylene glycol block copolymer, polyoxyethylene-epichlorohydrin copolymer, polyether ester amide and polyether ester imide.
2. The waterproof sheet according to claim 1, characterized in that: the glass transition temperature of the cycloolefin copolymer is 60-160 ℃.
3. The waterproof sheet according to claim 1 or 2, characterized in that: the high polymer elastomer is an ethylene copolymerized thermoplastic elastomer; and/or the melt index of the polypropylene resin at 230 ℃ and 2.16kg is less than or equal to 8g/10 min.
4. The waterproof sheet according to claim 1 or 2, characterized in that: the high molecular elastomer is one or a combination of more of propylene-ethylene copolymer, ethylene-alpha-butene copolymer and ethylene-alpha-octene copolymer.
5. The waterproof sheet according to claim 1 or 2, characterized in that: the raw materials of the waterproof sheet also comprise color master and/or auxiliary agents.
6. The waterproof sheet according to claim 5, wherein the waterproof sheet comprises the following raw materials in parts by weight:
20-30 parts of polypropylene resin;
30-70 parts of a high-molecular elastomer;
2-20 parts of a cycloolefin copolymer;
2-20 parts of a high-molecular antistatic agent;
1-8 parts of color master batch;
0.1-1 part of an antibacterial agent;
0.1-1 part of antioxidant;
0.1-1 part of light stabilizer.
7. The utility model provides a waterproof composite sheet, includes the basic unit and sets up waterproof layer on the basic unit, its characterized in that: the waterproof layer comprises the waterproof sheet according to any one of claims 1 to 6.
8. The waterproof composite sheet according to claim 7, characterized in that: the thickness ratio of the base layer to the waterproof layer is 4-8: 1; and/or the raw materials of the base layer comprise polypropylene resin and a high polymer elastomer, and the mass ratio of the polypropylene resin to the high polymer elastomer is 1: 1-4.
9. The waterproof composite sheet according to claim 8, wherein the base layer is made of the following components in parts by weight: 20-30 parts of polypropylene resin, 30-70 parts of high-molecular elastomer, 5-20 parts of filler, 0.1-1 part of auxiliary agent and 1-3 parts of color master batch.
10. The waterproof composite sheet according to claim 7, characterized in that: the base layer and the waterproof layer are prepared through co-extrusion molding.
11. The method for producing the waterproof composite sheet according to any one of claims 7 to 10, characterized in that: the preparation method comprises the steps of respectively melting the raw materials of the base layer and the waterproof layer, co-extruding, cooling and shaping to obtain the waterproof composite sheet.
12. Use of the waterproof sheet according to any one of claims 1 to 6 or the waterproof composite sheet according to any one of claims 7 to 10 as a waterproof roll.
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| CN202111359381.9A CN113789003B (en) | 2021-11-17 | 2021-11-17 | Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof |
| PCT/CN2022/112020 WO2023087803A1 (en) | 2021-11-17 | 2022-08-12 | Self-cleaning impermeable waterproof sheet, preparation method therefor, and application thereof |
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| CN202111359381.9A CN113789003B (en) | 2021-11-17 | 2021-11-17 | Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof |
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| CN116515418B (en) * | 2023-07-03 | 2023-09-29 | 江苏凯伦建材股份有限公司 | Polymer pre-laid waterproof coiled material, preparation method thereof and hot melt adhesive film |
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| CN101166784A (en) * | 2005-03-29 | 2008-04-23 | 大科能树脂有限公司 | Antistatic resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film, and method for producing the same |
| JP2018095786A (en) * | 2016-12-15 | 2018-06-21 | 三井化学株式会社 | Resin composition and crosslinked body of the same |
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| CA2202403A1 (en) * | 1994-10-14 | 1996-04-25 | Anthony Jay Dias | Blends of polypropylene and elastic alpha-olefin/cycle olefin copolymers |
| JP2002249625A (en) * | 2001-02-27 | 2002-09-06 | Nippon Zeon Co Ltd | Polypropylene resin composition for thermoforming and polypropylene resin sheet |
| CN1233772C (en) * | 2002-12-31 | 2005-12-28 | 中国石油化工股份有限公司齐鲁分公司 | Durable anti-static agent for acrylic fiber |
| US8128842B2 (en) * | 2006-09-01 | 2012-03-06 | BASF SE Ludwigshafen | Process for the preparation of an antistatic composition |
| ES2912607T3 (en) * | 2012-12-10 | 2022-05-26 | Buergofol GmbH | Insertion Hose for Trenchless Sewer Rehabilitation |
| CN110964289A (en) * | 2019-11-05 | 2020-04-07 | 南通普力马弹性体技术有限公司 | Antistatic elastomer material and preparation method thereof |
| CN111087739A (en) * | 2019-12-03 | 2020-05-01 | 天津金发新材料有限公司 | Permanent antistatic high-toughness talcum powder filled polypropylene material and preparation method thereof |
| CN112831122A (en) * | 2020-12-31 | 2021-05-25 | 泉州市锦彩环保科技有限公司 | Antistatic color master batch for protective clothing and preparation method thereof |
| CN113637263B (en) * | 2021-04-21 | 2023-03-28 | 江苏凯伦建材股份有限公司 | Anti-sliding pre-paved waterproof coiled material |
| CN113789003B (en) * | 2021-11-17 | 2022-02-25 | 江苏凯伦建材股份有限公司 | Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101166784A (en) * | 2005-03-29 | 2008-04-23 | 大科能树脂有限公司 | Antistatic resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film, and method for producing the same |
| JP2018095786A (en) * | 2016-12-15 | 2018-06-21 | 三井化学株式会社 | Resin composition and crosslinked body of the same |
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