CN111139004B - Long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for non-asphalt-based high-polymer waterproof coiled material and preparation method thereof - Google Patents
Long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for non-asphalt-based high-polymer waterproof coiled material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of waterproof coiled materials, in particular to a long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for a non-asphalt-based high-molecular waterproof coiled material and a preparation method thereof, wherein the pressure-sensitive adhesive comprises the following raw materials: SEPS, naphthenic oil, first polyisobutene, second polyisobutene, terpene resin, hydrogenated carbon penta petroleum resin, nano zinc oxide, an antioxidant, an ultraviolet absorbent and a light stabilizer; the preparation method comprises the following steps: adding naphthenic oil, first polyisobutene, second polyisobutene, an antioxidant, an ultraviolet absorbent and a light stabilizer into production equipment, charging nitrogen, starting heating, stirring and heating, adding SEPS, stirring at a constant temperature, adding terpene resin and hydrogenated carbon penta petroleum resin, stirring at a constant temperature, adding nano zinc oxide, controlling the vacuum degree, stirring at a constant temperature. The pressure-sensitive adhesive meets the national standard requirements, has low cost, longer-acting weather resistance and low-temperature bending performance, simple and easy preparation process, does not need special equipment and process, and is non-toxic and harmless.
Description
Technical Field
The invention relates to the technical field of waterproof coiled materials, in particular to a long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for a non-asphalt-based high-polymer waterproof coiled material and a preparation method thereof.
Background
The non-asphalt-based polymer waterproof coiled material was invented by GRACE waterproof company in the United states at the earliest and brought into the China market. Subsequently, the state releases relevant standards in 2008, popularizes the pre-paved waterproof coiled material system and the construction technology, and at the present stage, China has many cities to develop underground comprehensive pipe gallery construction and tunnel engineering construction, thereby providing a wide application field for non-asphalt-based polymer waterproof coiled materials.
After the non-asphalt-based high-polymer waterproof coiled material is laid and fixed, reinforcing steel bars need to be bound, or the construction period is delayed and concrete cannot be poured immediately, so that the non-asphalt-based high-polymer waterproof coiled material is likely to face the condition of being one month or even longerIntermittent solar irradiation. Therefore, GB/T23457-2017 Pre-paved waterproof coiled material clearly stipulates that the coiled material passes through 60W/m2(300 nm-400 nm) the stripping strength requirement of the treated xenon-arc lamp with post-pouring cement mortar. However, after the non-asphalt-based polymer waterproof roll material in the market is irradiated by sunlight for one or two months, even if all the detection items are qualified, the bonding surface of the non-asphalt-based polymer waterproof roll material has cracks of different degrees, the low-temperature flexibility and the peeling strength of the roll material are generally reduced to be below 40% of the original value, even lower, and the skin type waterproof effect of the roll material is greatly influenced or even completely destroyed.
Disclosure of Invention
Aiming at the problems that after the existing non-asphalt-based high polymer waterproof coiled material on the market is irradiated by sunlight for one or two months, the bonding surface has cracks, the low-temperature flexibility and the peeling strength of the coiled material are reduced, and the skin type waterproof effect is influenced, the invention provides the long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for the non-asphalt-based high polymer waterproof coiled material and the preparation method thereof, the invention adopts hydrogenated polystyrene-polyisoprene-polystyrene thermoplastic rubber (Styrene Ethylene Propylene block copolymer, SEPS for short) as a basic framework material, and adopts naphthenic oil, two kinds of polyisobutylene, terpene resin, hydrogenated carbon penta petroleum resin and other auxiliary agents as auxiliary materials, the obtained hot-melt pressure-sensitive adhesive can meet the national standard requirements, simultaneously has low cost, has longer-acting weather resistance and low-temperature bending performance compared with other hot-melt pressure-sensitive adhesives on the market, and the production process is simple and easy, no need of special equipment and special process, and no toxicity and harm in the preparation process.
In a first aspect, the invention provides a long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for a non-asphalt-based high-molecular waterproof coiled material, which comprises the following raw materials:
SEPS, naphthenic oil, first polyisobutene, second polyisobutene, terpene resin, hydrogenated carbon penta petroleum resin, nano zinc oxide, an antioxidant, an ultraviolet absorbent and a light stabilizer.
Further, the pressure-sensitive adhesive comprises the following raw materials in percentage by weight:
further, the SEPS had a polystyrene content of 13%, a diblock content of 30%, and a melt index of 22g/10min (230 ℃ C., load of 5 kg).
Further, the molecular weight of the first polyisobutene is not more than 1300, the molecular weight of the second polyisobutene is a medium molecular polyisobutene, and the molecular weight distribution index is 3.0;
the terpene resin is light-colored aliphatic nonpolar resin;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent.
Further, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1-2: 1,
the hindered phenol antioxidant is preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ],
the phosphite antioxidant is preferably tris [2, 4-di-tert-butylphenyl ] phosphite.
Further, the ultraviolet absorbent is one or a combination of more of 2- (5-chloro (2H) -benzotriazole-2-yl) -4- (methyl) -6- (tert-butyl) phenol, 2- (2H-benzotriazole-2-yl) -4-tert-butyl-6-sec-butyl phenol, 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazole-2-yl) phenol and 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol.
Further, the light stabilizer is a hindered amine light stabilizer,
preferably, the compound is one or a combination of more of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, polysuccinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol) ester, and poly- { [6- [ (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) ] -imino ] }.
In a second aspect, the invention provides a preparation method of a hot-melt pressure-sensitive adhesive for a non-asphalt-based polymer waterproof coiled material, which comprises the following steps:
(1) adding naphthenic oil, first polyisobutene, second polyisobutene, an antioxidant, an ultraviolet absorbent and a light stabilizer into production equipment, charging nitrogen, stirring to uniformly mix materials, and heating to 165-175 ℃;
(2) adding SEPS, and stirring at a constant temperature until the rubber is completely melted;
(3) adding terpene resin and hydrogenated carbon five petroleum resin, keeping the temperature and stirring until the terpene resin and the hydrogenated carbon five petroleum resin are melted uniformly;
(4) adding nano zinc oxide, controlling the vacuum degree to be-0.06 MPa to-0.1 MPa, and stirring while keeping the temperature.
Further, the preparation method comprises the following steps:
(1) adding 10-20% of naphthenic oil, 13-26% of first polyisobutylene, 3-10% of second polyisobutylene, 0.3-0.5% of antioxidant, 0.3-0.5% of ultraviolet absorbent and 0.5-1% of light stabilizer into production equipment, charging nitrogen, stirring at the rotating speed of 30-40 r/min to uniformly mix materials, and heating to 165-175 ℃;
(2) adding 15-30% SEPS, and stirring for 30-40 min under heat preservation until the rubber is completely melted;
(3) adding 20-35% of terpene resin and 10-25% of hydrogenated carbon penta petroleum resin, keeping the temperature and stirring for 30-40 min, and dissolving the mixture evenly;
(4) adding 0.5-3% of nano zinc oxide, controlling the vacuum degree to be-0.06 MPa-0.1 MPa, and stirring for 30-60 min under the condition of heat preservation.
Further, the preparation method also comprises the following steps:
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
The beneficial effect of the invention is that,
the invention accurately finds the technical problem that the performance of the bonding surface of the non-asphalt-based high-polymer waterproof coiled material is damaged after long-term irradiation of sunlight, and provides the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material, which contains the light stabilizer, the ultraviolet absorbent, the nano zinc oxide and other auxiliaries in raw materials. The pressure-sensitive adhesive adopts SEPS as a base material, the SEPS is a hydrogenated material, the saturation degree of a rubber section of the pressure-sensitive adhesive is high, no crystallization exists, and the pressure-sensitive adhesive can have better heat resistance and ultraviolet aging resistance in a molecular structure; the nano zinc oxide has the ultraviolet absorptivity of more than 95 percent, particularly has the strongest absorption effect on ultraviolet rays in medium-long wave band, and can weaken the radiation intensity of ultraviolet rays received by SEPS molecular chain segments in the hot-melt pressure-sensitive adhesive, thereby protecting the hot-melt pressure-sensitive adhesive; the hindered amine light stabilizer can effectively trap free radicals generated by SEPS molecular chain segments caused by ultraviolet light, and prevent chain reactions which cause the aging of the molecular chain segments; the ultraviolet absorbent can strongly absorb high-energy ultraviolet rays (280 nm-400 nm) to perform energy conversion, and emit energy in the form of heat energy or harmless light with longer wavelength, thereby further protecting the SEPS from being damaged by the ultraviolet rays. The auxiliary agents act together to obviously improve the long-term ultraviolet resistance of the hot-melt pressure-sensitive adhesive, so that the bonding surface of the non-asphalt-based high-polymer waterproof coiled material can still keep excellent adhesive force and peel strength after being exposed to the sun for a long time, thereby ensuring the low-temperature bending performance of the coiled material and the stability of skin type waterproof effect.
The hot-melt pressure-sensitive adhesive for the non-asphalt-based high-molecular waterproof coiled material has a two-phase structure which is incompatible in the SEPS, namely polystyrene PS and hydrogenated polyisoprene PI, wherein the PS is dispersed in a PI continuous phase to play roles in vulcanization and reinforcement, and has good cohesive force and adhesive property, low modulus, good elasticity, small melt viscosity and easy coating due to the influence of a side chain methyl group of the polyisoprene in the middle block; the glass transition temperature of the PI phase is-60 ℃, the glass transition temperature of the PS phase is 95 ℃, and the PI phase has lower glass transition temperature, so that the finally prepared pressure-sensitive adhesive has better low-temperature performance and certain elasticity.
The hot-melt pressure-sensitive adhesive for the non-asphalt-based high-molecular waterproof coiled material adopts the compounding of the naphthenic oil (naphthenic rubber oil) and the first polyisobutylene as the plasticizer, the molecular weight of the naphthenic oil is small, and a part of the naphthenic oil is migrated and volatilized in the long-term storage and use processes of the non-asphalt-based high-molecular waterproof coiled material, especially in a high-temperature environment, so that the initial viscosity of the pressure-sensitive adhesive layer is easily deteriorated, hardened and even lost; the first polyisobutylene has a relatively large molecular weight, is compounded with naphthenic oil (the mass ratio of the naphthenic oil to the first polyisobutylene is 10-20: 13-26), and not only can the coiled material be ensured to have long-acting initial viscosity, but also the adhesive force between the pressure-sensitive adhesive and a high polymer base material can be improved. Meanwhile, the two substances have poor compatibility with the PS phase in the SEPS phase and good compatibility with the PI phase, so that the volume of the PI phase is increased, and the sensitivity to pressure is increased; on the other hand, the effect between molecules in the PI phase is reduced, so that creep deformation is easily generated between the pressure-sensitive adhesive and the adhered material, and the adhesive force is improved.
The hot-melt pressure-sensitive adhesive for the non-asphalt-based high-molecular waterproof coiled material is characterized in that tackifying resins (hydrogenated carbon penta petroleum resin and terpene resin) compatible with rubber in an SEPS molecular structure are selected to increase the initial adhesion and the peel strength of the pressure-sensitive adhesive, and the initial adhesion and the peel strength are increased along with the increase of the using amount of the tackifying resins in a certain range. On one hand, the tackifying resin reduces the cohesive force and modulus of the pressure-sensitive adhesive, on the other hand, the glass transition temperature of the rubber phase is increased, in order to ensure good low-temperature performance of the pressure-sensitive adhesive or the coiled material, the reduction of the low-temperature performance is compensated by a method of compounding the second polyisobutylene and the tackifying resin according to a certain proportion (the mass ratio of the second polyisobutylene to the tackifying resin is 3-10: 30-60), and meanwhile, the viscous base force of the pressure-sensitive adhesive is enhanced.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
20kg of SEPS, 17.5kg of naphthenic oil, 20.2kg of first polyisobutene, 8kg of second polyisobutene, 25.1kg of terpene resin, 20kg of hydrogenated carbon penta petroleum resin, 1kg of nano zinc oxide, 0.5kg of antioxidant, 0.5kg of ultraviolet absorbent and 0.75kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is prepared from the following components in percentage by weight of 1: a complex of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester of 1 and tris [2, 4-di-tert-butylphenyl ] phosphite;
the ultraviolet absorbent is 2- (5-chloro (2H) -benzotriazole-2-yl) -4- (methyl) -6- (tert-butyl) phenol;
the light stabilizer is bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 17.5kg of naphthenic oil, 20.2kg of first polyisobutene, 8kg of second polyisobutene, 0.5kg of antioxidant, 0.5kg of ultraviolet absorbent and 0.75kg of light stabilizer into a reaction kettle, introducing nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 20kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 25.1kg of terpene resin and 20kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 1kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Example 2
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
33kg of SEPS, 19.1kg of naphthenic oil, 32.2kg of first polyisobutene, 5kg of second polyisobutene, 28.5kg of terpene resin, 14kg of hydrogenated carbon penta petroleum resin, 3kg of nano zinc oxide, 0.6kg of antioxidant, 0.5kg of ultraviolet absorbent and 1kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is prepared from the following components in percentage by weight: a complex of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester of 1 and tris [2, 4-di-tert-butylphenyl ] phosphite;
the ultraviolet absorbent is 2- (2H-benzotriazole-2-yl) -4-tert-butyl-6-sec-butyl phenol;
the light stabilizer is poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 19.1kg of naphthenic oil, 32.2kg of first polyisobutene, 5kg of second polyisobutene, 0.6kg of antioxidant, 0.5kg of ultraviolet absorbent and 1kg of light stabilizer into a reaction kettle, charging nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 33kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 28.5kg of terpene resin and 14kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 3kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Example 3
The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material comprises the following raw materials:
40kg of SEPS, 31kg of naphthenic oil, 24.5kg of first polyisobutene, 5.5kg of second polyisobutene, 36.5kg of terpene resin, 28kg of hydrogenated carbon penta petroleum resin, 5kg of nano zinc oxide, 0.75kg of antioxidant, 0.7kg of ultraviolet absorbent and 1.5kg of light stabilizer;
wherein, the SEPS contains 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index (230 ℃, 5kg of load);
the naphthenic oil is water white, clear and transparent viscous liquid without peculiar smell, and the kinematic viscosity at 40 ℃ is less than 154mm2(ii)/s, pour point less than-21 ℃;
the molecular weight of the first polyisobutene is not more than 1300, the viscosity at 100 ℃ is 590 Cst-690 Cst, and the pour point is-10 ℃;
the second polyisobutene is a medium molecular polyisobutene having a molecular weight distribution index of 3.0, a Staudinger index of 24.9, a penetration (150 g.multidot.5 sec) at 25 ℃ of 1581/10 mm, and a kinematic viscosity index of 23500 mPa.multidot.s at 200 ℃;
the terpene resin is light-colored aliphatic nonpolar resin, the softening point is 100-109 ℃, the color number is not more than # 3, and the acid value is less than 1.0mg KOH/g;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin, the softening point is 90-110 ℃, and the color number is not more than # 3;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent;
the antioxidant is prepared from the following components in percentage by weight of 1.5: a complex of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester of 1 and tris [2, 4-di-tert-butylphenyl ] phosphite;
the weight ratio of the ultraviolet absorbent is 1: 1 of a complex of 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol;
the light stabilizer is poly- { [6- [ (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) ] -imino ] }.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) adding 31kg of naphthenic oil, 24.5kg of first polyisobutene, 5.5kg of second polyisobutene, 0.75kg of antioxidant, 0.7kg of ultraviolet absorbent and 1.5kg of light stabilizer into a reaction kettle, charging nitrogen, starting heating, stirring at the rotating speed of 30-40 r/min, and heating to 170 ℃;
(2) adding 40kg of SEPS thermoplastic rubber, and stirring for 40min at the constant temperature to ensure that the rubber is completely melted;
(3) adding 36.5kg of terpene resin and 28kg of hydrogenated carbon penta petroleum resin, and stirring for 40min under heat preservation to uniformly melt;
(4) adding 5kg of nano zinc oxide, controlling the vacuum degree to be-0.07 MPa, and stirring for 60min under the condition of heat preservation;
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
Comparative example 1
Comparative example 1 is a hot melt pressure sensitive adhesive for a non-asphalt-based polymer waterproof coiled material produced by a domestic brand manufacturer.
Comparative example 2
Comparative example 2 is a non-asphalt-based polymer waterproof roll manufactured by domestic famous brand manufacturers.
Comparative example 3
Comparative example 3 is different from example 1 in that an ultraviolet absorber is used, and the ultraviolet absorber used in comparative example 3 is UV-531([ 2-hydroxy-4- (octyloxy) phenyl ] phenyl ketone);
comparative example 4
Comparative example 4 is different from example 1 in the amounts of the ultraviolet absorber and the light stabilizer, and in comparative example 4, the amount of the ultraviolet absorber was 0kg and the amount of the light stabilizer was 1.25 kg.
Comparative example 5
Comparative example 5 is different from example 1 in the amount of the ultraviolet absorber and the light stabilizer, and comparative example 4 is 0.25kg of the ultraviolet absorber and 1.0kg of the light stabilizer.
Test example 1
The pressure-sensitive adhesives of examples 1-3 and comparative examples 1, 3-5 are respectively coated on HDPE sheets to prepare non-asphalt-based polymer waterproof rolls, and the specific preparation method is as follows:
(1) adding the hot-melt pressure-sensitive adhesive block into a melt adhesive box and heating to a molten state;
(2) starting the auxiliary heating equipment to coat the HDPE sheet;
(3) and (4) starting a sanding device, uniformly covering the isolation sand on the adhesive layer, compacting by adopting a composite compression roller, and rolling to obtain the coiled material.
The performance of the non-asphalt-based polymer waterproof roll and the non-asphalt-based polymer waterproof roll of the comparative example 2 were tested, and the test results are shown in table 1 below.
TABLE 1 waterproofing membranes Performance test results
As can be seen from Table 1, the ultraviolet-resistant hot-melt pressure-sensitive adhesive for the non-asphalt-based polymer waterproof roll has excellent performances. Compared with comparative examples 1-5, the pressure-sensitive adhesive has stronger and longer-acting ultraviolet resistance, particularly, the peeling strength of the coiled material after being irradiated by sunlight for 2 months in summer with post-poured cement mortar can still be kept above 70%, and no crack appears on the bonding surface.
The pressure-sensitive adhesive has various physical and chemical indexes meeting the specified requirements of GB/T23457-2017 Pre-laid waterproof coiled material, and has the advantages of low cost, simple production process and wide application prospect.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The long-acting anti-ultraviolet hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material is characterized by comprising the following raw materials in percentage by weight:
15 to 30 percent of SEPS, 10 to 20 percent of naphthenic oil, 13 to 26 percent of first polyisobutene, 3 to 10 percent of second polyisobutene, 20 to 35 percent of terpene resin, 10 to 25 percent of hydrogenated carbon five petroleum resin, 0.5 to 3 percent of nano zinc oxide, 0.3 to 0.5 percent of antioxidant, 0.3 to 0.5 percent of ultraviolet absorbent and 0.5 to 1 percent of light stabilizer;
the SEPS comprises 13 percent of polystyrene, 30 percent of diblock and 22g/10min of melt index;
the molecular weight of the first polyisobutene is not more than 1300, the second polyisobutene is a medium molecular polyisobutene, and the molecular weight distribution index is 3.0.
2. The pressure-sensitive adhesive of claim 1, wherein the terpene resin is a light colored aliphatic nonpolar resin;
the hydrogenated carbon five petroleum resin is light-colored hydrogenated petroleum resin;
the nano zinc oxide has the particle size distribution of 20-50 nm, the average particle size of 30nm, the purity of not less than 99.5 percent and the ultraviolet absorption rate of more than 95 percent.
3. The pressure-sensitive adhesive according to claim 1, wherein the antioxidant is a complex of a hindered phenol antioxidant and a phosphite antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1-2: 1,
the hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester,
the phosphite ester antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.
4. The pressure-sensitive adhesive of claim 1, wherein the ultraviolet absorber is one or more of 2- (5-chloro (2H) -benzotriazol-2-yl) -4- (methyl) -6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4-tert-butyl-6-sec-butyl phenol, 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol, and 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol.
5. The pressure-sensitive adhesive of claim 1, wherein the light stabilizer is a hindered amine light stabilizer,
the hindered amine light stabilizer is bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate or bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, poly succinic acid (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester, poly- { [6- [ (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) ] -imino ] }.
6. The preparation method of the long-acting ultraviolet-resistant hot-melt pressure-sensitive adhesive for the non-asphalt-based polymer waterproof roll according to claim 1, wherein the preparation method comprises the following steps:
(1) adding 10-20% of naphthenic oil, 13-26% of first polyisobutylene, 3-10% of second polyisobutylene, 0.3-0.5% of antioxidant, 0.3-0.5% of ultraviolet absorbent and 0.5-1% of light stabilizer into production equipment, charging nitrogen, stirring at the rotating speed of 30-40 r/min to uniformly mix materials, and heating to 165-175 ℃;
(2) adding 15-30% SEPS, and stirring for 30-40 min under heat preservation until the rubber is completely melted;
(3) adding 20-35% of terpene resin and 10-25% of hydrogenated carbon penta petroleum resin, keeping the temperature and stirring for 30-40 min, and dissolving the mixture evenly;
(4) adding 0.5-3% of nano zinc oxide, controlling the vacuum degree to be-0.06 MPa-0.1 MPa, and stirring for 30-60 min under the condition of heat preservation.
7. The method of claim 6, further comprising the steps of:
(5) and (3) completely and uniformly mixing, discharging, filtering, preparing into a prefabricated block, and packaging to obtain the hot-melt pressure-sensitive adhesive for the non-asphalt-based high-polymer waterproof coiled material.
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| CN104293255A (en) * | 2013-07-19 | 2015-01-21 | 北京东方雨虹防水技术股份有限公司 | Hot melt pressure-sensitive adhesive for high adhesive strength HDPE self-adhesive coiled materials, and preparation method thereof |
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