CN117584586A - Mould-resistant TPO thermoplastic polyolefin waterproof coiled material and preparation method thereof - Google Patents

Mould-resistant TPO thermoplastic polyolefin waterproof coiled material and preparation method thereof Download PDF

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CN117584586A
CN117584586A CN202410064918.6A CN202410064918A CN117584586A CN 117584586 A CN117584586 A CN 117584586A CN 202410064918 A CN202410064918 A CN 202410064918A CN 117584586 A CN117584586 A CN 117584586A
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thermoplastic polyolefin
modified
mildew
waterproof coiled
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王洪波
顾金佳
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Jiangsu Ouxidun Technology Co ltd
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Jiangsu Ouxidun Technology Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
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    • 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
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention discloses a mildew-resistant TPO thermoplastic polyolefin waterproof coiled material and a preparation method thereof, which belong to the technical field of waterproof coiled materials and sequentially comprise a modified isolating membrane, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base cloth, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolating membrane from top to bottom; the modified thermoplastic polyolefin material is prepared from the following raw materials: thermoplastic polyolefin resins, light stabilizers, lubricants, antioxidants, heat stabilizers, chemical coupling agents, antibacterial agents, and nano-active agents; the modified isolating film is prepared from the following raw materials: PP, modified plasticizer, emulsifier, light calcium carbonate, benzoyl peroxide and mold-resistant additive; the mould TPO thermoplastic polyolefin waterproof coiled materials prepared by the invention have excellent mould resistance, and the mould resistance effect reaches level 0.

Description

Mould-resistant TPO thermoplastic polyolefin waterproof coiled material and preparation method thereof
Technical Field
The invention relates to the technical field of waterproof coiled materials, in particular to a mildew-resistant TPO thermoplastic polyolefin waterproof coiled material and a preparation method thereof.
Background
As is well known, a building waterproof roll is a waterproof material widely used in basements, planted roofs, and kitchens and bathrooms of buildings, and has been widely used in the field of building waterproofing; when the existing building waterproof coiled material is used, the special use environment is very suitable for the growth of mould, the corrosion effect of the mould growth on the building waterproof coiled material is very obvious, if the waterproof coiled material laid in a kitchen or toilet or a basement is corroded by mould, the waterproof layer can be damaged on one hand, and on the other hand, great harm can be brought to people, and respiratory tract infection can be caused, so that symptoms such as nasal mucositis, anaphylactic reaction and the like can occur; if the waterproof coiled material in the planted roof is corroded by mould, the plant is killed, and the waterproof layer is damaged; the existing building waterproof coiled material is found to be mildew when laid indoors or outdoors, and the living quality of people is greatly affected.
Disclosure of Invention
The invention aims to provide a mildew-resistant TPO thermoplastic polyolefin waterproof coiled material and a preparation method thereof, so as to solve the problem that the waterproof coiled material in the prior art is easy to mildew.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides a mildew-resistant TPO thermoplastic polyolefin waterproof coiled material, which sequentially comprises a modified isolation film, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base fabric, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolation film from top to bottom; the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 5-8:8-12:4-7:6-9, wherein the weight of the modified thermoplastic polyolefin material and the weight of the modified isolation film are the weight of the two layers.
Further, the modified thermoplastic polyolefin material is prepared from the following raw materials in parts by weight: 30-50 parts of thermoplastic polyolefin resin, 3-5 parts of light stabilizer, 5-10 parts of lubricant, 1-3 parts of antioxidant, 1-5 parts of heat stabilizer, 1-10 parts of chemical coupling agent, 5-10 parts of antibacterial agent and 1-5 parts of nano active agent.
Further, the antibacterial agent is prepared from the following raw materials in parts by weight: 10-30 parts of allyl isothiocyanate, 30-50 parts of ethanol, 1-10 parts of chitosan-terephthaloborate, 1-5 parts of camphor extract and 1-10 parts of sunflower extract.
Further, the light stabilizer is o-hydroxybenzophenone or benzotriazole, and the heat stabilizer is one or a compound of hindered phenols or phosphates; the lubricant is lubricating oil or engine oil, the antioxidant is hydroquinone, thiobisphenol or p-phenylenediamine, the chemical coupling agent is silane coupling agent or titanate coupling agent, and the nano active agent is nano active zinc oxide or nano active titanium oxide.
Further, the modified isolation film is prepared from the following raw materials in parts by weight: 30-50 parts of PP, 5-10 parts of modified plasticizer, 1-3 parts of emulsifier, 1-5 parts of light calcium carbonate, 3-5 parts of benzoyl peroxide and 1-10 parts of mildew-resistant additive.
Further, the mildew-resistant additive is prepared from the following raw materials in parts by weight: 1-5 parts of garlic extract, 3-5 parts of citronella extract, 1-10 parts of antibacterial agent BM-102TG, 1-10 parts of nano-silver inorganic antibacterial agent JL-8001, 10-20 parts of bentonite, 1-5 parts of magnesium stearate and 10-30 parts of pentaerythritol.
Further, the modified plasticizer is prepared from the following raw materials in parts by weight: 10-30 parts of acetyl tributyl citrate, 10-30 parts of dioctyl terephthalate, 3-5 parts of 2, 2-dimethyl-3-hydroxy propionic acid, 1-5 parts of propylene glycol alginate, 1-5 parts of 1, 4-butylene glycol and 1-3 parts of sodium carboxymethyl cellulose; the emulsifier is polyoxyethylene ether, polyethylene glycol fatty acid ester or glycerol stearate.
Further, the composite bonding layer is prepared from the following raw materials in parts by weight: 10-30 parts of polyhydroxy polymer, 1-5 parts of tackifier, 20-30 parts of saturated styrene block copolymer, 5-10 parts of furfuryl alcohol extracted from natural plants and 1-3 parts of three-wire oil.
Further, the tackifier is lignin, xanthan gum, alginate or tapioca starch.
In a second aspect, the invention provides a preparation method of the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material, which comprises the following steps:
step 1: preparation of modified barrier film
Adding a mildew-resistant additive, benzoyl peroxide, a plasticizer and an emulsifier into a double-screw extruder for blending, melting at 180-200 ℃ for 10-15min, adding PP and light calcium carbonate, reacting for 10-20min, and extruding to obtain a modified isolating film;
step 2: preparation of composite tie layers
Adding polyhydroxy polymer, tackifier and furfuryl alcohol extracted from natural plant into a double screw extruder, mixing, melting at 150-180deg.C for 5-10min, adding saturated styrene block copolymer and three-wire oil, reacting for 10-15min, and extruding to obtain composite adhesive layer;
step 3: preparation of modified thermoplastic polyolefin materials
Adding a light stabilizer, a lubricant, an antioxidant, a heat stabilizer, an antibacterial agent and a nano active agent into a double-screw extruder for blending, melting for 3-5min at 200-210 ℃, adding a thermoplastic polyolefin resin and a chemical coupling agent, reacting for 20-30min, and extruding to obtain a modified thermoplastic polyolefin material;
step 4: mould-proof TPO thermoplastic polyolefin waterproof coiled material
And (3) performing hot press molding on the modified isolation film, the composite bonding layer, the modified thermoplastic polyolefin material, the polyester tire base cloth, the modified thermoplastic polyolefin material, the composite bonding layer and the modified isolation film from top to bottom by a three-roller mill, and then cooling, rectifying, trimming, cutting, rolling and packaging to obtain the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material.
Compared with the prior art, the invention has the beneficial effects that:
according to the waterproof coiled material, the antibacterial agent is added into the raw materials for preparing the modified thermoplastic polyolefin material, and is prepared from allyl isothiocyanate, ethanol, chitosan-terephthaloborate, camphor extract and sunflower extract, wherein the chitosan-terephthaloborate and the allyl isothiocyanate have strong sterilization effect, various bacteria can be effectively killed in an initial germination stage, microbial breeding is avoided, the camphor extract and the sunflower extract are matched with each other in a specific proportion, synergy is achieved, when bacteria and mold are in contact with or stay in the vicinity of the waterproof coiled material, the antibacterial agent immediately starts to act, the cell walls of the bacteria and mold are damaged, the functions of activity, growth and propagation of the bacteria and the mold are destroyed, the growth and propagation of the bacteria and the mold cannot be realized, the antibacterial effect is durable, and the putrefaction and mildew caused by environmental factors in the use process of the waterproof coiled material are delayed. The raw materials in the antibacterial agent are safe and nontoxic, and the antibacterial agent has the characteristics of high efficiency, environmental protection, good mildew resistance effect and the like.
The mildew-resistant additive is added into the raw materials for preparing the modified isolation film, and is prepared from garlic extract, citronella extract, antibacterial agent BM-102TG, nano silver inorganic antibacterial agent JL-8001, bentonite, magnesium stearate and pentaerythritol, wherein the antibacterial agent BM-102TG and the nano silver inorganic antibacterial agent JL-8001 have strong sterilization effect, various bacteria can be effectively killed in the initial germination stage, microbial breeding is avoided, the garlic extract and the citronella extract are mutually matched in a specific proportion, the synergism is realized, in addition, bentonite has strong adsorption performance, bacteria can be effectively killed by adsorption, the magnesium stearate can improve the stability of the mildew-resistant additive, the mildew-resistant additive can exert high antibacterial and mildew-resistant effects, the mildew-resistant coiled material is prevented from generating mildew, and the mildew time and mildew index level are greatly improved.
The invention well bonds the modified isolating film and the modified thermoplastic polyolefin material through the composite bonding layer, and provides a certain guarantee for the preparation of the waterproof coiled material.
The waterproof coiled material sequentially comprises a modified isolating film, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base cloth, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolating film from top to bottom, wherein a mildew-resistant additive and an antibacterial agent are respectively added into the modified isolating film and the modified thermoplastic polyolefin material, and the waterproof coiled material has excellent mildew resistance, and the mildew resistance effect reaches level 0.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The garlic extracts in the following examples and comparative examples are produced by Chongqing Rui ya Biotechnology Co., ltd; camphor extract is produced by volley biotechnology limited, langasite; sunflower extract is produced by Woltesi Biotechnology Co., ltd; the citronella extract is produced by Shanyang associated peak biotechnology, inc.; the antibacterial agent BM-102TG is produced by Guangzhou Jinao New Material technology Co., ltd; the nano silver inorganic antibacterial agent JL-8001 is produced by the chemical industry Co.Ltd.
Example 1: the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material sequentially comprises a modified isolation membrane, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base fabric, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolation membrane from top to bottom; the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 5:8:4:6.
The modified thermoplastic polyolefin material is prepared from the following raw materials in parts by weight: 30 parts of thermoplastic polyolefin resin, 3 parts of o-hydroxybenzophenone, 5 parts of lubricating oil, 1 part of hydroquinone, 1 part of hindered phenol, 1 part of silane coupling agent, 5 parts of antibacterial agent and 1 part of nano active zinc oxide. Wherein the o-hydroxybenzophenone is 2, 4-dihydroxybenzophenone, the hindered phenol is 2, 6-di-tert-butyl-4-methylphenol, and the silane coupling agent is 3-triethoxysilyl-1-propylamine.
The antibacterial agent is prepared from the following raw materials in parts by weight: 10 parts of allyl isothiocyanate, 30 parts of ethanol, 1 part of chitosan-terephthaloborate, 1 part of camphor extract and 1 part of sunflower extract.
The modified isolating film is prepared from the following raw materials in parts by weight: 30 parts of PP, 5 parts of modified plasticizer, 1 part of polyoxyethylene ether, 1 part of light calcium carbonate, 3 parts of benzoyl peroxide and 1 part of mildew-resistant additive.
The mildew-resistant additive is prepared from the following raw materials in parts by weight: 1 part of garlic extract, 3 parts of citronella extract, 1 part of antibacterial agent BM-102TG, 1 part of nano-silver inorganic antibacterial agent JL-8001 part, 10 parts of bentonite, 1 part of magnesium stearate and 10 parts of pentaerythritol.
The modified plasticizer is prepared from the following raw materials in parts by weight: 10 parts of acetyl tributyl citrate, 10 parts of dioctyl terephthalate, 3 parts of 2, 2-dimethyl-3-hydroxy propionic acid, 1 part of propylene glycol alginate, 1 part of 1, 4-butylene glycol and 1 part of sodium carboxymethyl cellulose.
The composite bonding layer is prepared from the following raw materials in parts by weight: 10 parts of polyhydroxy polymer, 1 part of lignin, 20 parts of saturated styrene block copolymer, 5 parts of furfuryl alcohol extracted from natural plants and 1 part of three-wire oil. Wherein the polyhydroxy polymer is hydroxypropyl methylcellulose.
The preparation method of the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material comprises the following steps:
step 1: preparation of modified barrier film
Adding 1 part of antibacterial agent BM-102TG, 1 part of nano silver inorganic antibacterial agent JL-8001 part, 10 parts of bentonite, 1 part of magnesium stearate and 10 parts of pentaerythritol into stirring equipment, starting stirring, controlling the temperature to be 50 ℃, adding 1 part of garlic extract and 3 parts of citronella extract, and stirring for 20min to obtain a mildew-resistant additive;
adding 10 parts of acetyl tributyl citrate, 10 parts of dioctyl terephthalate, 3 parts of 2, 2-dimethyl-3-hydroxy propionic acid and 1 part of propylene glycol alginate into stirring equipment, starting stirring, controlling the temperature to be 100 ℃, controlling the rotating speed to be 60rpm, stirring for 20min, adding 1 part of 1, 4-butylene glycol and 1 part of sodium carboxymethyl cellulose, and continuing stirring for 10min to obtain a modified plasticizer;
adding 1 part of mould-resistant additive, 3 parts of benzoyl peroxide, 5 parts of modified plasticizer and 1 part of polyoxyethylene ether into a double-screw extruder for blending, adding 30 parts of PP and 1 part of light calcium carbonate after melting for 10min at 180 ℃, reacting for 10min, and extruding to obtain a modified isolating film;
step 2: preparation of composite tie layers
Adding 10 parts of polyhydroxy polymer, 1 part of lignin and 5 parts of furfuryl alcohol extracted from natural plants into a double screw extruder for blending, melting at 150 ℃ for 5min, adding 20 parts of saturated styrene block copolymer and 1 part of three-wire oil for reaction for 10min, and extruding to obtain a composite bonding layer;
step 3: preparation of modified thermoplastic polyolefin materials
Adding 10 parts of allyl isothiocyanate, 30 parts of ethanol and 1 part of chitosan-terephthaloborate into stirring equipment, starting stirring, controlling the temperature to be 50 ℃, adding 1 part of camphor extract and 1 part of sunflower extract, and stirring for 20min to obtain an antibacterial agent;
3 parts of o-hydroxybenzophenone, 5 parts of lubricating oil, 1 part of hydroquinone, 1 part of hindered phenol, 5 parts of antibacterial agent and 1 part of nano active zinc oxide are added into a double-screw extruder to be blended, after being melted for 3min at 200 ℃, 30 parts of thermoplastic polyolefin resin and 1 part of silane coupling agent are added, and the reaction is carried out for 20min, and the modified thermoplastic polyolefin material is obtained by extrusion;
step 4: mould-proof TPO thermoplastic polyolefin waterproof coiled material
And (3) performing hot press molding on the modified isolation film, the composite bonding layer, the modified thermoplastic polyolefin material, the polyester tire base cloth, the modified thermoplastic polyolefin material, the composite bonding layer and the modified isolation film from top to bottom through a three-roller mill, wherein the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 5:8:4:6, and then cooling, rectifying, trimming, cutting, rolling and packaging to obtain the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material.
Example 2: the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material sequentially comprises a modified isolation membrane, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base fabric, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolation membrane from top to bottom; the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 7:10:5:7.
The modified thermoplastic polyolefin material is prepared from the following raw materials in parts by weight: 40 parts of thermoplastic polyolefin resin, 4 parts of o-hydroxybenzophenone, 7 parts of lubricating oil, 2 parts of thiobisphenol, 3 parts of hindered phenol, 6 parts of silane coupling agent, 7 parts of antibacterial agent and 3 parts of nano active zinc oxide. Wherein the o-hydroxybenzophenone is 2, 4-dihydroxybenzophenone, the hindered phenol is 2, 6-di-tert-butyl-4-methylphenol, and the silane coupling agent is 3-triethoxysilyl-1-propylamine.
The antibacterial agent is prepared from the following raw materials in parts by weight: 20 parts of allyl isothiocyanate, 40 parts of ethanol, 6 parts of chitosan-terephthaloborate, 3 parts of camphor extract and 6 parts of sunflower extract.
The modified isolating film is prepared from the following raw materials in parts by weight: 40 parts of PP, 7 parts of modified plasticizer, 2 parts of polyethylene glycol fatty acid ester, 3 parts of light calcium carbonate, 4 parts of benzoyl peroxide and 5 parts of mildew-resistant additive.
The mildew-resistant additive is prepared from the following raw materials in parts by weight: 3 parts of garlic extract, 4 parts of citronella extract, 6 parts of antibacterial agent BM-102TG, 1 part of nano-silver inorganic antibacterial agent JL-8001, 16 parts of bentonite, 3 parts of magnesium stearate and 20 parts of pentaerythritol.
The modified plasticizer is prepared from the following raw materials in parts by weight: 20 parts of acetyl tributyl citrate, 20 parts of dioctyl terephthalate, 4 parts of 2, 2-dimethyl-3-hydroxy propionic acid, 3 parts of propylene glycol alginate, 3 parts of 1, 4-butylene glycol and 2 parts of sodium carboxymethyl cellulose.
The composite bonding layer is prepared from the following raw materials in parts by weight: 20 parts of polyhydroxy polymer, 3 parts of alginate, 25 parts of saturated styrene block copolymer, 7 parts of furfuryl alcohol extracted from natural plants and 2 parts of three-wire oil. Wherein the polyhydroxy polymer is hydroxypropyl methylcellulose.
The preparation method of the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material comprises the following steps:
step 1: preparation of modified barrier film
Adding 6 parts of antibacterial agent BM-102TG, 1 part of nano silver inorganic antibacterial agent JL-8001, 16 parts of bentonite, 3 parts of magnesium stearate and 20 parts of pentaerythritol into stirring equipment, starting stirring, controlling the temperature to be 60 ℃, adding 3 parts of garlic extract and 4 parts of citronella extract, and stirring for 30min to obtain a mildew-resistant additive;
adding 20 parts of acetyl tributyl citrate, 20 parts of dioctyl terephthalate, 4 parts of 2, 2-dimethyl-3-hydroxy propionic acid and 3 parts of propylene glycol alginate into stirring equipment, starting stirring, controlling the temperature to be 110 ℃, controlling the rotating speed to be 90rpm, stirring for 25min, adding 3 parts of 1, 4-butylene glycol and 2 parts of sodium carboxymethyl cellulose, and continuing stirring for 13min to obtain a modified plasticizer;
5 parts of mould-resistant additive, 4 parts of benzoyl peroxide, 7 parts of modified plasticizer and 2 parts of polyethylene glycol fatty acid ester are added into a double-screw extruder to be blended, after being melted at 190 ℃ for 13min, 40 parts of PP and 3 parts of light calcium carbonate are added, and the mixture is reacted for 15min, and then the modified isolating film is obtained by extrusion;
step 2: preparation of composite tie layers
Adding 20 parts of polyhydroxy polymer, 3 parts of alginate and 7 parts of furfuryl alcohol extracted from natural plants into a double screw extruder for blending, melting for 7min at 160 ℃, adding 25 parts of saturated styrene block copolymer and 2 parts of three-wire oil for reaction for 13min, and extruding to obtain a composite bonding layer;
step 3: preparation of modified thermoplastic polyolefin materials
Adding 20 parts of allyl isothiocyanate, 40 parts of ethanol and 6 parts of chitosan-terephthaloborate into stirring equipment, starting stirring, controlling the temperature to be 60 ℃, adding 3 parts of camphor extract and 6 parts of sunflower extract, and stirring for 30min to obtain an antibacterial agent;
adding 4 parts of o-hydroxybenzophenone, 7 parts of lubricating oil, 2 parts of thiobisphenol, 3 parts of hindered phenol, 7 parts of antibacterial agent and 3 parts of nano active zinc oxide into a double-screw extruder for blending, melting for 4min at 205 ℃, adding 40 parts of thermoplastic polyolefin resin and 6 parts of silane coupling agent, reacting for 25min, and extruding to obtain a modified thermoplastic polyolefin material;
step 4: mould-proof TPO thermoplastic polyolefin waterproof coiled material
And (3) performing hot press molding on the modified isolation film, the composite bonding layer, the modified thermoplastic polyolefin material, the polyester tire base cloth, the modified thermoplastic polyolefin material, the composite bonding layer and the modified isolation film from top to bottom through a three-roller mill, wherein the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 7:10:5:7, and then cooling, rectifying, trimming, cutting, rolling and packaging to obtain the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material.
Example 3: the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material sequentially comprises a modified isolation membrane, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base fabric, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolation membrane from top to bottom; the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 8:12:7:9.
The modified thermoplastic polyolefin material is prepared from the following raw materials in parts by weight: 50 parts of thermoplastic polyolefin resin, 5 parts of benzotriazole, 10 parts of engine oil, 3 parts of p-phenylenediamine, 5 parts of phosphate, 10 parts of titanate coupling agent, 10 parts of antibacterial agent and 5 parts of nano active titanium oxide. Wherein, the benzotriazole is 2- (2-hydroxy-5-methylphenyl) benzotriazole, the phosphate is triphenyl phosphate, and the titanate coupling agent is isopropyl tri (dioctyl pyrophosphoryloxy) titanate.
The antibacterial agent is prepared from the following raw materials in parts by weight: 30 parts of allyl isothiocyanate, 50 parts of ethanol, 10 parts of chitosan-terephthaloborate, 5 parts of camphor extract and 10 parts of sunflower extract.
The modified isolating film is prepared from the following raw materials in parts by weight: 50 parts of PP, 10 parts of modified plasticizer, 3 parts of glycerol stearate, 5 parts of light calcium carbonate, 5 parts of benzoyl peroxide and 10 parts of mildew-resistant additive.
The mildew-resistant additive is prepared from the following raw materials in parts by weight: 5 parts of garlic extract, 5 parts of citronella extract, 10 parts of antibacterial agent BM-102TG, 5 parts of nano-silver inorganic antibacterial agent JL-8001 10 parts of bentonite, 5 parts of magnesium stearate and 30 parts of pentaerythritol.
The modified plasticizer is prepared from the following raw materials in parts by weight: 30 parts of acetyl tributyl citrate, 30 parts of dioctyl terephthalate, 5 parts of 2, 2-dimethyl-3-hydroxy propionic acid, 5 parts of propylene glycol alginate, 5 parts of 1, 4-butylene glycol and 3 parts of sodium carboxymethyl cellulose.
The composite bonding layer is prepared from the following raw materials in parts by weight: 30 parts of polyhydroxy polymer, 5 parts of tapioca starch, 30 parts of saturated styrene block copolymer, 10 parts of furfuryl alcohol extracted from natural plants and 3 parts of three-wire oil. Wherein the polyhydroxy polymer is hydroxypropyl methylcellulose.
The preparation method of the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material comprises the following steps:
step 1: preparation of modified barrier film
Adding 10 parts of antibacterial agent BM-102TG, 10 parts of nano silver inorganic antibacterial agent JL-8001 10 parts, 20 parts of bentonite, 5 parts of magnesium stearate and 30 parts of pentaerythritol into stirring equipment, starting stirring, controlling the temperature to 80 ℃, adding 5 parts of garlic extract and 5 parts of citronella extract, and stirring for 40min to obtain a mildew-resistant additive;
adding 30 parts of acetyl tributyl citrate, 30 parts of dioctyl terephthalate, 5 parts of 2, 2-dimethyl-3-hydroxy propionic acid and 5 parts of propylene glycol alginate into stirring equipment, starting stirring, controlling the temperature to 120 ℃, controlling the rotating speed to 120rpm, stirring for 30min, adding 5 parts of 1, 4-butylene glycol and 3 parts of sodium carboxymethyl cellulose, and continuing stirring for 15min to obtain a modified plasticizer;
adding 10 parts of mould-resistant additive, 5 parts of benzoyl peroxide, 10 parts of modified plasticizer and 3 parts of glycerol stearate into a double-screw extruder for blending, adding 50 parts of PP and 5 parts of light calcium carbonate after melting for 15min at 200 ℃, reacting for 20min, and extruding to obtain a modified isolating film;
step 2: preparation of composite tie layers
Adding 30 parts of polyhydroxy polymer, 5 parts of tapioca starch and 10 parts of furfuryl alcohol extracted from natural plants into a double screw extruder for blending, melting for 5-10min at 180 ℃, adding 30 parts of saturated styrene block copolymer and 3 parts of three-wire oil for reaction for 15min, and extruding to obtain a composite bonding layer;
step 3: preparation of modified thermoplastic polyolefin materials
Adding 30 parts of allyl isothiocyanate, 50 parts of ethanol and 10 parts of chitosan-terephthaloborate into stirring equipment, starting stirring, controlling the temperature to 80 ℃, adding 5 parts of camphor extract and 10 parts of sunflower extract, and stirring for 40min to obtain an antibacterial agent;
adding 5 parts of benzotriazole, 10 parts of engine oil, 3 parts of p-phenylenediamine, 5 parts of phosphate, 10 parts of antibacterial agent and 5 parts of nano active titanium oxide into a double-screw extruder for blending, adding 50 parts of thermoplastic polyolefin resin and 10 parts of titanate coupling agent after melting for 5min at 210 ℃, reacting for 30min, and extruding to obtain a modified thermoplastic polyolefin material;
step 4: mould-proof TPO thermoplastic polyolefin waterproof coiled material
And (3) performing hot press molding on the modified isolation film, the composite bonding layer, the modified thermoplastic polyolefin material, the polyester tire base cloth, the modified thermoplastic polyolefin material, the composite bonding layer and the modified isolation film from top to bottom through a three-roller mill, wherein the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 8:12:7:9, and then cooling, rectifying, trimming, cutting, rolling and packaging to obtain the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material.
Comparative example 1
Unlike example 1, the following is: the raw materials for preparing the modified isolating film do not comprise mould-resistant additives.
Comparative example 2
Unlike example 1, the following is: the raw materials for preparing the modified thermoplastic polyolefin material do not comprise antibacterial agents.
Comparative example 3
Unlike example 1, the following is: the raw materials for preparing the mildew-resistant additive do not comprise nano silver inorganic antibacterial agent JL-8001 and garlic extract; the antibacterial agent is prepared from materials excluding allyl isothiocyanate and sunflower extract.
Mold resistance ratings were made on the mold resistant TPO thermoplastic polyolefin waterproofing membrane of examples 1-3 and comparative examples 1-3 according to the GB/T35468 root penetration resistant waterproofing membrane evaluation method. The results are shown in Table 1.
Table 1 test results of mold resistance of the mold-resistant waterproof rolls of examples 1 to 3 and comparative examples 1 to 3
As can be seen from table 1: since the modified barrier film in comparative example 1 does not have an antifungal effect, only the modified thermoplastic polyolefin material has an antifungal effect, whereas the modified thermoplastic polyolefin material in comparative example 2 does not have an antifungal effect, only the modified barrier film has an antifungal effect, the mildew-resistant grades of the mildew TPO thermoplastic polyolefin waterproof rolls prepared in comparative example 1 and comparative example 2 are both low, and the mildew-resistant effects are both general; since the raw materials for preparing the mildew-resistant additive in comparative example 3 do not comprise nano silver inorganic antibacterial agent JL-8001 and garlic extract, and the raw materials for preparing the antibacterial agent do not comprise allyl isothiocyanate and sunflower extract, the mildew TPO thermoplastic polyolefin waterproof coiled material prepared in comparative example 3 has a certain mildew-resistant effect, but the mildew-resistant effect does not reach an ideal effect; the mould TPO thermoplastic polyolefin waterproof coiled materials prepared in the examples 1-3 have excellent mould resistance, and the mould resistance effect reaches 0 grade because the mould-resistant additive and the antibacterial agent are respectively added into the modified isolation film and the modified thermoplastic polyolefin material in the examples 1-3.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material is characterized by sequentially comprising a modified isolation membrane, a composite bonding layer, a modified thermoplastic polyolefin material, a polyester base fabric, a modified thermoplastic polyolefin material, a composite bonding layer and a modified isolation membrane from top to bottom; the mass ratio of the polyester tire base cloth to the modified thermoplastic polyolefin material to the composite bonding layer to the modified isolation film is 5-8:8-12:4-7:6-9.
2. The mildew-resistant TPO thermoplastic polyolefin waterproof roll according to claim 1, wherein the modified thermoplastic polyolefin material is prepared from the following raw materials in parts by weight: 30-50 parts of thermoplastic polyolefin resin, 3-5 parts of light stabilizer, 5-10 parts of lubricant, 1-3 parts of antioxidant, 1-5 parts of heat stabilizer, 1-10 parts of chemical coupling agent, 5-10 parts of antibacterial agent and 1-5 parts of nano active agent.
3. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material according to claim 2, wherein the antibacterial agent is prepared from the following raw materials in parts by weight: 10-30 parts of allyl isothiocyanate, 30-50 parts of ethanol, 1-10 parts of chitosan-terephthaloborate, 1-5 parts of camphor extract and 1-10 parts of sunflower extract.
4. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material according to claim 2, wherein the light stabilizer is o-hydroxybenzophenone or benzotriazole, and the heat stabilizer is one or a compound of hindered phenols or phosphates; the lubricant is lubricating oil or engine oil, the antioxidant is hydroquinone, thiobisphenol or p-phenylenediamine, the chemical coupling agent is silane coupling agent or titanate coupling agent, and the nano active agent is nano active zinc oxide or nano active titanium oxide.
5. The mildew-resistant TPO thermoplastic polyolefin waterproof roll according to claim 2, wherein the modified isolation film is prepared from the following raw materials in parts by weight: 30-50 parts of PP, 5-10 parts of modified plasticizer, 1-3 parts of emulsifier, 1-5 parts of light calcium carbonate, 3-5 parts of benzoyl peroxide and 1-10 parts of mildew-resistant additive.
6. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material according to claim 5, wherein the mildew-resistant additive is prepared from the following raw materials in parts by weight: 1-5 parts of garlic extract, 3-5 parts of citronella extract, 1-10 parts of antibacterial agent BM-102TG, 1-10 parts of nano-silver inorganic antibacterial agent JL-8001, 10-20 parts of bentonite, 1-5 parts of magnesium stearate and 10-30 parts of pentaerythritol.
7. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material according to claim 5, wherein the modified plasticizer is prepared from the following raw materials in parts by weight: 10-30 parts of acetyl tributyl citrate, 10-30 parts of dioctyl terephthalate, 3-5 parts of 2, 2-dimethyl-3-hydroxy propionic acid, 1-5 parts of propylene glycol alginate, 1-5 parts of 1, 4-butylene glycol and 1-3 parts of sodium carboxymethyl cellulose; the emulsifier is polyoxyethylene ether, polyethylene glycol fatty acid ester or glycerol stearate.
8. The mildew-resistant TPO thermoplastic polyolefin waterproof coiled material according to claim 5, wherein the composite adhesive layer is prepared from the following raw materials in parts by weight: 10-30 parts of polyhydroxy polymer, 1-5 parts of tackifier, 20-30 parts of saturated styrene block copolymer, 5-10 parts of furfuryl alcohol extracted from natural plants and 1-3 parts of three-wire oil.
9. The mold resistant TPO thermoplastic polyolefin waterproofing membrane according to claim 8, wherein the tackifier is lignin, xanthan gum, alginate or tapioca starch.
10. The method for preparing the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material as claimed in claim 8, which is characterized by comprising the following steps:
step 1: preparation of modified barrier film
Adding a mildew-resistant additive, benzoyl peroxide, a modified plasticizer and an emulsifier into a double-screw extruder for blending, melting at 180-200 ℃ for 10-15min, adding PP and light calcium carbonate, reacting for 10-20min, and extruding to obtain a modified isolating film;
step 2: preparation of composite tie layers
Adding polyhydroxy polymer, tackifier and furfuryl alcohol extracted from natural plant into a double screw extruder, mixing, melting at 150-180deg.C for 5-10min, adding saturated styrene block copolymer and three-wire oil, reacting for 10-15min, and extruding to obtain composite adhesive layer;
step 3: preparation of modified thermoplastic polyolefin materials
Adding a light stabilizer, a lubricant, an antioxidant, a heat stabilizer, an antibacterial agent and a nano active agent into a double-screw extruder for blending, melting for 3-5min at 200-210 ℃, adding a thermoplastic polyolefin resin and a chemical coupling agent, reacting for 20-30min, and extruding to obtain a modified thermoplastic polyolefin material;
step 4: mould-proof TPO thermoplastic polyolefin waterproof coiled material
And (3) performing hot press molding on the modified isolation film, the composite bonding layer, the modified thermoplastic polyolefin material, the polyester tire base cloth, the modified thermoplastic polyolefin material, the composite bonding layer and the modified isolation film from top to bottom by a three-roller mill, and then cooling, rectifying, trimming, cutting, rolling and packaging to obtain the mildew-resistant TPO thermoplastic polyolefin waterproof coiled material.
CN202410064918.6A 2024-01-17 2024-01-17 Mould-resistant TPO thermoplastic polyolefin waterproof coiled material and preparation method thereof Pending CN117584586A (en)

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CN102505807A (en) * 2011-10-29 2012-06-20 唐山德生防水材料有限公司 TPO (thermoplastic polyolefin) modified asphalt root resistant waterproof roll and preparation method thereof
CN103924692A (en) * 2013-01-15 2014-07-16 江苏凯伦建材股份有限公司 Thermoplastic polyolefin wet laying water-resistant coiled material
CN107933034A (en) * 2017-11-21 2018-04-20 广西武宣金牌防水材料科技有限公司 Thermoplastic polyolefin TPO waterproof rolls and preparation method thereof
CN113388336A (en) * 2021-06-25 2021-09-14 广东禹能建材科技股份有限公司 TPO thermoplastic polyolefin polymer non-asphalt-based self-adhesive film waterproof coiled material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102505807A (en) * 2011-10-29 2012-06-20 唐山德生防水材料有限公司 TPO (thermoplastic polyolefin) modified asphalt root resistant waterproof roll and preparation method thereof
CN103924692A (en) * 2013-01-15 2014-07-16 江苏凯伦建材股份有限公司 Thermoplastic polyolefin wet laying water-resistant coiled material
CN107933034A (en) * 2017-11-21 2018-04-20 广西武宣金牌防水材料科技有限公司 Thermoplastic polyolefin TPO waterproof rolls and preparation method thereof
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