CN111218251A - Polyurethane adhesive for ETPU track molding and preparation method thereof - Google Patents
Polyurethane adhesive for ETPU track molding and preparation method thereof Download PDFInfo
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- CN111218251A CN111218251A CN202010199367.6A CN202010199367A CN111218251A CN 111218251 A CN111218251 A CN 111218251A CN 202010199367 A CN202010199367 A CN 202010199367A CN 111218251 A CN111218251 A CN 111218251A
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- diisocyanate
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Abstract
The invention discloses a polyurethane adhesive for ETPU runway molding, wherein the adhesive is a polyurethane prepolymer with 100% of solid content, which is prepared by reacting polyol with diisocyanate and adding an auxiliary agent; the auxiliary agent comprises an antioxidant, a catalyst, a hydrolysis resistance agent, a silane coupling agent and a flame retardant. The molar ratio of diisocyanate groups to polyol hydroxyl groups is 2.2-3.5: 1. The adhesive disclosed by the invention does not contain a solvent, has no solvent taste in the production process, and has no problems of safety and environmental protection. Aromatic diisocyanate and plasticizer are not used, and the problems of free TDI and free MDI aromatic toxic substance release are solved. The single-component polyurethane adhesive does not use a curing agent, does not need to be prepared with glue, and is simple and convenient in construction process. The TVOC is lower than the national standard, accords with the limit standard of harmful substances in non-solid raw materials of the synthetic material surface layer of the sports ground, and the runway processed by adopting the product mixed with ETPU particles has high rebound resilience, excellent mechanical property, good durability and good application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane adhesive for ETPU runway molding and a preparation method thereof.
Background
The TPU is named as a thermoplastic polyurethane elastomer, is mainly divided into a polyester type and a polyether type, has high mechanical property, hydrolysis resistance and microbial corrosion resistance, has a wide hardness range and high resilience, wear resistance and oil resistance, and is widely applied to the fields of daily necessities, sports goods, toys, decorative materials and the like. The novel TPU foaming material of high resilience foam particles obtained by changing the structural reorganization of TPU is named as ETPU (expanded thermoplastic polyurethane), is commonly called popcorn material, and is a novel polymer material formed by aggregating a plurality of TPU foaming small balls with enough elasticity and light weight. The environment-friendly high-wear-resistance wear-resistant cable has the characteristics of environmental protection, ultra-light density, difficult deformation, high wear resistance, temperature change resistance, yellowing resistance (the yellowing resistance grade can reach 4 grade), and the like. The rubber material is widely applied to shoe material industry, packaging materials, buffer gaskets, vibration damping materials, automobile interior materials, tires and the like.
The ETPU has high resilience, excellent mechanical property and good durability, can be applied to the bottom layer, the surface layer and the like of sports ground tracks and floors, not only has the properties of high elasticity, aging resistance, corrosion resistance and the like of the traditional EPDM granules, but also has the advantages of the ETPU, has the same chemical polarity with polyurethane glue, thereby leading to firm bonding capability, achieving the effect of preventing granules from falling off, providing the track buffer property by a special micro-foaming structure, reducing sports injury, having no vulcanized peculiar smell of the EPDM, being self-environment-friendly, having light density, reducing the use amount by the same area, and being the material of a new generation of environment-friendly tracks.
At present, common sports runways are generally formed by paving SBR rubber particles, EPDM rubber particles, polyurethane glue and other auxiliary materials on site. In recent years, toxic runway events occur in various places, which cause symptoms of cough, vomiting, asthma, skin allergy, nosebleed and the like of a plurality of students, and are mainly caused by materials used in the construction process. The main component of the sports track is polyurethane elastomer, and the basic raw materials of the sports track can be divided into polyether polyol, catalyst, polyisocyanate (mainly TDI) and other auxiliary materials. The traditional runway is paved by mainly using two components, wherein the materials mainly comprise Toluene Diisocyanate (TDI) and 3,3 dichloro-4, 4 diamino diphenylmethane (MOCA) curing type polyurethane runway, the TDI has high potential toxicity, and the MOCA belongs to chemical carcinogenic substances. The source of track odor is mainly from chlorides that may appear in Polyurethane (PU) glues, residual free Toluene Diisocyanate (TDI), residual toluene, xylene, etc., residual sulfides in EPDM particles, polycyclic aromatic hydrocarbons, plasticizers, etc., resulting in a track with an irritating odor.
The TDI residue problem promotes the athletic track to be improved from a TDI type to an MDI type with relatively small harm to human bodies, in addition, the waterborne PU with higher cost and the like are also used as an MDI-polyether-MOCA system, and the cost is low.
With the daily requirement of the country on environmental protection, the sports track gradually develops towards the directions of higher performance, lower cost, comfort, environmental protection, health and the like, and the improvement of the traditional track becomes a necessary trend. After a poisonous runway event, the environmental protection standard is more and more strict, the use of TDI type and lead series catalysts is forbidden, free TDI, free MDI, VOC, benzene, polycyclic aromatic hydroxyl and the like are limited, the use of MOCA chain extender, short-chain chlorinated paraffin and phthalate plasticizer is forbidden, the requirement on odor is strict, and the like. The PU runway rubber on the market can not meet the environmental protection requirement.
Chinese patent CN104893645A discloses a polyurethane plastic runway adhesive and a preparation method thereof, wherein the method adopts micromolecular amine as a curing agent, and has the problems of high curing speed and high toxicity.
Chinese patent CN103627310A discloses a preparation method of a spray coating surface layer of an environment-friendly polyurethane plastic runway, the method adopts amines with high potential toxicity such as MOCA, diethyl diphenylamine and the like as chain extenders, and phthalic acid plasticizers are added in the formula, so that the problem of high toxicity exists.
Chinese patent CN105038684A discloses a preparation method of an environment-friendly polyurethane adhesive for plastic runways, which takes polyether polyol and aromatic diisocyanate as raw materials, chlorinated paraffin and dibutyl phthalate as additives, white carbon black as a filler and organic tin as a catalyst, and prepares the environment-friendly high-performance polyurethane adhesive for plastic runways by a prepolymer method, so that the environment-friendly adhesive with low volatility, no toxicity and no pungent smell is prepared, and has excellent service performance. However, the raw materials in the environment-friendly adhesive adopt a large amount of solvents and aromatic diisocyanate, and when the environment-friendly adhesive is exposed to hot weather or strong ultraviolet irradiation, the aromatic toxicants and the like can be quickly released, so that the environment-friendly adhesive is harmful to human bodies. In addition, a large amount of silicon dioxide is added into the adhesive, and the adhesive is easy to crack along with the increase of the content of the silicon dioxide.
Chinese patent CN10833494A discloses an environment-friendly single-component polyurethane plastic runway adhesive and a preparation method thereof, the polyurethane plastic runway adhesive is prepared by using polyether polyol, aromatic diisocyanate, plasticizer and the like, and the aromatic diisocyanate in the formula has the problems of free TDI and free MDI.
Chinese patent CN106431867B discloses an aqueous environment-friendly plastic runway adhesive and a preparation method thereof, wherein the adhesive comprises A, B components, the component A is aqueous acrylic emulsion, the component B uses amine curing agent to replace the adhesive prepared by aromatic diisocyanate in the prior art, the release problem of aromatic toxic substances is improved, and the aqueous adhesive has the problems of low-temperature freezing and difficult drying.
For the application field of runway adhesives, a substitute preparation process is urgently needed to solve various problems of processing of the adhesive for sports runways. Aiming at strict environmental protection requirements, the novel raw materials are added, the novel process is used for improving the product, so that the runway rubber with the novel formula meets the environmental protection requirements, the performance is improved to a certain extent, and the novel formula is used for the material of a new generation of ETPU environmental protection runways and has remarkable economic benefit.
Disclosure of Invention
The invention provides a polyurethane adhesive for ETPU runway molding and a preparation method thereof, and solves the problems of environmental protection and processing of the adhesive for the sports runway.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a polyurethane adhesive for ETPU runway molding is a polyurethane prepolymer with 100% of solid content, which is prepared by reacting polyol with diisocyanate and adding an auxiliary agent; the auxiliary agent comprises an antioxidant, a catalyst, a hydrolysis resistance agent, a silane coupling agent and a flame retardant.
Further, the adhesive comprises the following components in percentage by weight: 57-70 wt% of polyol, 25-35 wt% of diisocyanate, 0.2-0.5 wt% of antioxidant, 0.08-0.15 wt% of catalyst, 0.3-0.7 wt% of hydrolysis resistance agent, 0.5-1.5 wt% of silane coupling agent and 2.0-6.0 wt% of flame retardant.
Further, the polyalcohol is selected from one or more of poly neopentyl glycol phthalate, poly dipropylene glycol adipate, poly trimethylolpropane dipropylene glycol adipate, polypropylene oxide glycol and polypropylene oxide triol.
Further, the diisocyanate is selected from any one of hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated phenyl methane diisocyanate or a mixture of at least two of hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated phenyl methane diisocyanate.
Further, the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyol is 2.2-3.5: 1.
further, the antioxidant is any one of pentaerythritol β (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl β (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N' -bis [ β (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] -1, 6-hexanediamine, 1,3,5- (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) 1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, octyl β (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 6-di-t-butyl-4-methylphenol, or a mixture of at least two thereof.
Further, the hydrolysis resistant agent is carbodiimide; the silane coupling agent is any one or a mixture of at least two of a vinyl silane coupling agent, an amino silane coupling agent and an epoxy silane coupling agent; the catalyst is any one or a mixture of at least two of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, triethylene diamine, triethanolamine and dimorpholinyl diethyl ether; the flame retardant is one or a mixture of at least two of tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2, 3-dichloropropyl) phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate and antimony trioxide.
The invention also provides a preparation method of the polyurethane adhesive for ETPU runway molding, which comprises the following steps:
s1, adding the polyol and the antioxidant into a polymerization stirring reaction kettle after metering, wherein the polyol ester content is 57-70 wt% and the antioxidant addition amount is 0.2-0.5 wt% based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding diisocyanate for reaction, heating the reaction kettle, maintaining the reaction temperature to 90-100 ℃, and keeping the reaction time to be not less than 2 hours;
s4, detecting the weight percentage content of NCO% of isocyanate group in the reaction process of the step S3, when the NCO% reaches below a theoretical value, adding 0.08-0.15 wt% of catalyst, 0.3-0.7 wt% of hydrolysis resistance agent, 0.5-1.5 wt% of silane coupling agent and 2.0-6.0 wt% of flame retardant into a reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubble exists in the reaction kettle, and obtaining a viscous liquid product.
Further, in the step S3, the equivalent weight of the consumed diisocyanate calculated by the molecular weight of the polyol ester is calculated, and the excess diisocyanate is added in an amount of 2.2 to 3.5:1 times the equivalent weight of the polyol ester.
Further, in step S4, the calculation formula of the theoretical value of NCO% is: (weight of diisocyanate NCO addition-theoretical weight of NCO consumed by polyol plus chain extender)/total weight of the reactor contents.
The adhesive disclosed by the invention is single-component, does not use a curing agent, does not need to be prepared and is convenient to use, contains strongly polar active urethane groups (NHCOO) and isocyanate groups (NCO), can generate hydrogen bonds with an adhered material, and generates a high-molecular polymer with high polymerization force by reacting with moisture existing in air or attached to the surface of the adhered material and extending chain when in use, so that the adhesion force, the heat resistance and the like are obviously improved.
The adhesive is prepared by taking NCO end group prepolymer as a base material and adding additives such as an antioxidant, a catalyst, a hydrolysis resistance agent, a silane coupling agent, a flame retardant and the like which do not react with isocyanate groups. When in use, according to the ambient environment and the humidity of a base material, after sizing, the crosslinking reaction is carried out by moisture, and after curing, the rubber has good elasticity and excellent chemical resistance. The adhesive is liquid at normal temperature and has good operability. The adhesive is applied to ETPU plastic runways, is processed by directly paving or prefabricating a terrace, has firm bonding capability, and can achieve the purpose of preventing grains from falling.
The invention achieves the following beneficial effects:
(1) the adhesive disclosed by the invention is a single-component polyurethane adhesive, is simple and convenient in construction process, contains 100% of solid content and no solvent, is beneficial to environmental protection and safe production, and is suitable for composite processing of sports floor materials.
(2) The adhesive disclosed by the invention does not use aromatic diisocyanate, and has no problems of free TDI and free MDI aromatic toxic substance release.
(3) The adhesive disclosed by the invention does not contain chlorinated paraffin, plasticizer, formaldehyde and MOCA additive, and TVOC is lower than the national standard. After ETPU or EPDM particles are mixed with the product, the processed runway meets the requirements of national physical index GB/T18433.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
A polyurethane adhesive for forming an ETPU runway is a polyurethane prepolymer with 100% of solid content, which is prepared by reacting polyol with diisocyanate and adding an auxiliary agent. The auxiliary agent comprises an antioxidant, a catalyst, a hydrolysis resistance agent, a silane coupling agent and a flame retardant. The polyurethane adhesive for ETPU runway molding comprises the following components in percentage by weight: 57-70 wt% of polyol, 25-35 wt% of diisocyanate, 0.2-0.5 wt% of antioxidant, 0.08-0.15 wt% of catalyst, 0.3-0.7 wt% of hydrolysis resistance agent, 0.5-1.5 wt% of silane coupling agent and 2.0-6.0 wt% of flame retardant; the sum of the weight percentages of the components is 100 percent.
The polyol is selected from polyester polyol and/or polyether polyol. Preferably one or more of poly neopentyl glycol phthalate, poly dipropylene glycol adipate, poly trimethylolpropane dipropylene glycol adipate, polyoxypropylene glycol (PPG) and polyoxypropylene triol. The polyol is present in an amount of 57 to 70 wt%, based on the total weight of the polyurethane adhesive. The purity of polyoxypropylene diol and polyoxypropylene triol is required to be 99.5% or more, and the water content is required to be 300ppm or less. Neopentyl glycol phthalate has a molecular weight of 1000; the molecular weight of the poly (dipropylene glycol adipate) is 1000; the molecular weight of the poly (trimethylolpropane) dipropylene glycol adipate is 700, and the functionality is 2.6; the molecular weight of the polypropylene oxide glycol is 1000 and 2000; the molecular weight of the polyoxypropylene triol is 450 and 3000. The polyol ester has the following molecular weight and acid value AV meeting the requirements: the molecular weight is determined by the acetic anhydride-pyridine method, and the detection standard is established according to ASTM D6432. The acid number AV is determined by KOH titration and the standard of detection is established according to ASTM D4662.
The diisocyanate is aliphatic diisocyanate and is selected from any one or a mixture of at least two of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated phenyl methane diisocyanate (H12 MDI). In this embodiment, the diisocyanate is preferably isophorone diisocyanate (IPDI). The diisocyanate disclosed by the invention is free of yellowing, has excellent aging resistance, yellowing resistance, weather resistance and low viscosity, can be prepared into a non-yellowing adhesive product, is beneficial to improving the weather-resistant yellowing performance of an ETPU runway, and is free of the release problems of free TDI and free MDI aromatic toxic substances.
The molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyol is 2.2-3.5: 1; the diisocyanate content is 25 to 35 wt.%, based on the total weight of the polyurethane adhesive.
the antioxidant is any one or a mixture of at least two of pentaerythritol β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CHINOX 1010), octadecyl β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CHINOX 1076), N' -bis [ β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -1, 6-hexanediamine (CHINOX 1098), 1,3,5- (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) 1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (CHINOX 1790), octyl β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CHINOX 35), or 2, 6-di-tert-butyl-4-methylphenol (CHINOX BHT). in this embodiment, the antioxidant is preferably used in an amount of 0.2 to 0.5 wt% based on the total weight of the polyurethane adhesive.
The catalyst is any one of Dibutyl tin dilaurate (DBTDL), Dioctyl tin dilaurate (DOTDL), Stannous octoate (Stannous octoate), Triethylene diamine (Triethylene diamine), Triethanolamine (Trietholamine) or Dimorpholinodiethyl ether (DMDEE) or a mixture of at least two of them. In this example, the catalyst is preferably used in combination with dioctyltin dilaurate and dimorpholinyldiethylether. The catalyst is used for promoting the rapid reaction of isocyanate groups and hydroxyl groups and the crosslinking reaction of the processed isocyanate groups and moisture, and the use of the two catalysts has an addition effect on promoting the curing and curing speed of the adhesive. The total catalyst addition is 0.08-0.15 wt% based on the total weight of the polyurethane adhesive.
The hydrolysis resistance agent is carbodiimide, so that the adhesive has excellent hydrolysis resistance. The addition amount of the hydrolysis resistant agent is 0.3-0.7 wt% based on the total weight of the polyurethane adhesive.
The flame retardant is one or a mixture of at least two of tris (2-chloroethyl) phosphate (TCEP), tris (2-chloropropyl) phosphate (TCPP), tris (2, 3-dichloropropyl) phosphate (TDCPP), dimethyl methyl phosphate (DMMP), diethyl ethylphosphate (DEEP) and antimony trioxide. The amount of the polyurethane adhesive is 2.0 to 6.0 wt% based on the total weight of the polyurethane adhesive.
The silane coupling agent is any one or a mixture of at least two of a vinyl silane coupling agent, an amino silane coupling agent and an epoxy silane coupling agent. In this embodiment, the silane coupling agent is preferably an epoxy silane coupling agent. The amount added is 0.5 to 1.5 wt% based on the total weight of the polyurethane adhesive.
A preparation method of a polyurethane adhesive for ETPU runway molding comprises the following steps:
s1, adding the polyol and the antioxidant into a polymerization stirring reaction kettle after metering, wherein the polyol ester content is 57-70 wt% and the antioxidant addition amount is 0.2-0.5 wt% based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, calculating the equivalent of the consumed diisocyanate according to the molecular weight of the polyol ester, adding excessive diisocyanate in an amount which is 2.2-3.5:1 times of the equivalent of the polyol ester, heating the reaction kettle, maintaining the reaction temperature at 90-100 ℃, and keeping the reaction time not less than 2 hours;
s4, detecting the weight percentage content of NCO% of isocyanate group in the reaction process of the step S3, when the NCO% reaches below a theoretical value, adding 0.08-0.15% of catalyst, 0.3-0.7% of hydrolysis resistance agent, 0.5-1.5% of silane coupling agent and 2.0-6.0% of flame retardant based on the total weight of polyurethane adhesive into a reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubble exists in the reaction kettle, and obtaining the colorless to yellow sticky liquid of the product appearance. In the step, the theoretical value calculation formula of NCO% is as follows: (weight of diisocyanate NCO addition-theoretical weight of NCO consumed by polyol plus chain extender)/total weight of the reactor contents.
Example 1
A preparation method of a polyurethane adhesive for ETPU runway molding comprises the following steps:
s1, putting 61.88 wt% of polyoxypropylene diol 2000, 6.45 wt% of polyoxypropylene triol 3000 and 0.24 wt% of antioxidant into a polymerization stirring reaction kettle based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding 25.79 wt% of isophorone diisocyanate (IPDI) based on the total weight of the polyurethane adhesive, heating the reaction kettle, maintaining the reaction temperature at 90-100 ℃, and reacting for 3 hours;
s4, detecting the weight percentage content of NCO in the reaction process of the step S3, when the NCO% reaches a theoretical value below 6.88, adding 0.05 wt% of amine catalyst (DMDEE), 0.05 wt% of tin catalyst (DOTDL), 0.5 wt% of hydrolysis resistance agent, 1.0 wt% of silane coupling agent and 4.04 wt% of flame retardant into the reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubbles exist in the reaction kettle, and obtaining a viscous liquid product.
Examples 2,
A preparation method of a polyurethane adhesive for ETPU runway molding comprises the following steps:
s1, putting 2.73 wt% of neopentyl glycol phthalate, 54.67 wt% of polyoxypropylene glycol 1000, 2.73 wt% of polyoxypropylene triol 450 and 0.22 wt% of antioxidant into a polymerization stirring reaction kettle based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding 33.95 wt% of isophorone diisocyanate (IPDI) based on the total weight of the polyurethane adhesive, heating the reaction kettle, maintaining the reaction temperature to 90-100 ℃, and reacting for 2.5 hours;
s4, detecting the weight percentage content of NCO in the reaction process of the step S3, when the NCO% reaches a theoretical value below 7.26, adding 0.05 wt% of amine catalyst (DMDEE), 0.05 wt% of tin catalyst (DOTDL), 0.5 wt% of hydrolysis resistance agent, 1.0 wt% of silane coupling agent and 4.1 wt% of flame retardant into the reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubbles exist in the reaction kettle, and obtaining a viscous liquid product.
Example 3
A preparation method of a polyurethane adhesive for ETPU runway molding comprises the following steps:
s1, based on the total weight of the polyurethane adhesive, feeding 28.41 wt% of poly (dipropylene glycol adipate), 4.26 wt% of poly (trimethylolpropane dipropylene glycol adipate), 28.41 wt% of polypropylene oxide glycol 1000 and 0.25 wt% of antioxidant into a polymerization stirring reaction kettle;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding 33.05 wt% of isophorone diisocyanate (IPDI) based on the total weight of the polyurethane adhesive, heating the reaction kettle, maintaining the reaction temperature to 90-100 ℃, and reacting for 2.5 hours;
s4, detecting the weight percentage content of NCO in the reaction process of the step S3, when the NCO% reaches a theoretical value of below 7.06, adding 0.05 wt% of amine catalyst (DMDEE), 0.05 wt% of tin catalyst (DOTDL), 0.5 wt% of hydrolysis resistance agent, 1.0 wt% of silane coupling agent and 4.02 wt% of flame retardant into the reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubbles exist in the reaction kettle, and obtaining a viscous liquid product.
Example 4
A preparation method of a polyurethane adhesive for ETPU runway molding comprises the following steps:
s1, putting 2.75 wt% of neopentyl glycol phthalate, 55.02 wt% of dipropylene glycol adipate, 2.75 wt% of trimethylolpropane adipate and 0.25 wt% of antioxidant into a polymerization stirring reaction kettle based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding 33.5 wt% of isophorone diisocyanate (IPDI) based on the total weight of the polyurethane adhesive, heating the reaction kettle, maintaining the reaction temperature to 90-100 ℃, and reacting for 3 hours;
s4, detecting the weight percentage content of NCO in the reaction process of the step S3, when the NCO% reaches a theoretical value of below 7.39, adding 0.05 wt% of amine catalyst (DMDEE), 0.05 wt% of tin catalyst (DOTDL), 0.5 wt% of hydrolysis resistance agent, 1.0 wt% of silane coupling agent and 4.13 wt% of flame retardant into the reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubbles exist in the reaction kettle, and obtaining a viscous liquid product.
Table 1: EXAMPLES 1-4 product base recipe Table
Table 2: EXAMPLES 1-4 Adhesives Performance test Table
| Examples | 100％M | TS | EL | Softening point | Melting Point |
| kgf/cm2 | kgf/cm2 | ％ | ℃ | ℃ | |
| Example 1 | 54.65 | 512.76 | 858.48 | 180 | 216 |
| Example 2 | 82.04 | 471.84 | 523.08 | 180 | 225 |
| Example 3 | 96.67 | 553.03 | 621.45 | 185 | 223 |
| Example 4 | 114.04 | 516.67 | 492.20 | 175 | 215 |
The adhesive of the invention is tested for performance by reference to the standard ASTM D-412, the adhesive is coated on release paper to prepare a film, the film is placed at the room temperature of 23 ℃ and the relative humidity of 50% for curing for 96 hours, and the film cut pieces are tested by an electronic tensile testing machine at the tensile rate of 200mm/min, 100% M (modulus), TS (tensile strength) and EL (elongation). And using an oven method to cut the adhesive film into pieces, weighing corresponding weights according to the film thickness and a weight conversion table (45 grams per square centimeter load), clamping the weights below the test pieces, fixing the test pieces above the oven, starting heating, wherein the heating rate is 2 ℃/1min, and detecting the softening point and the melting point of the cured adhesive.
Table 2 shows the statistics of the physical analysis data of the products obtained in examples 1 to 4. As can be seen from Table 2, the tensile strength after curing can reach more than 400kgf/cm2, and the softening point ranges are all more than 170 ℃, which shows that the product has excellent physical adhesive strength and good heat resistance.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The polyurethane adhesive for ETPU runway molding is characterized in that the adhesive is a polyurethane prepolymer with 100% of solid content, which is prepared by reacting polyol with diisocyanate and adding an auxiliary agent; the auxiliary agent comprises an antioxidant, a catalyst, a hydrolysis resistance agent, a silane coupling agent and a flame retardant.
2. The polyurethane adhesive for ETPU runway molding according to claim 1, wherein the adhesive comprises the following components by weight percent: 57-70 wt% of polyol, 25-35 wt% of diisocyanate, 0.2-0.5 wt% of antioxidant, 0.08-0.15 wt% of catalyst, 0.3-0.7 wt% of hydrolysis resistance agent, 0.5-1.5 wt% of silane coupling agent and 2.0-6.0 wt% of flame retardant.
3. The polyurethane adhesive for ETPU runway molding according to claim 1, wherein the polyol is selected from one or more of poly neopentyl glycol phthalate, poly dipropylene glycol adipate, poly trimethylolpropane dipropylene glycol adipate, polypropylene oxide glycol and polypropylene oxide triol.
4. The polyurethane adhesive for ETPU runway molding according to claim 1, wherein the diisocyanate is selected from any one of hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated phenyl methane diisocyanate or a mixture of at least two thereof.
5. The polyurethane adhesive for ETPU runway molding according to claim 1, wherein the molar ratio of isocyanate group in the diisocyanate to hydroxyl group in the polyol is 2.2-3.5: 1.
6. the polyurethane adhesive for ETPU track formation according to claim 1, wherein the antioxidant is any one or a mixture of at least two of pentaerythritol β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -bis [ β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -1, 6-hexanediamine, 1,3,5- (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) 1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, octyl β (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2, 6-di-tert-butyl-4-methylphenol.
7. The polyurethane adhesive for ETPU runway molding according to claim 1, wherein the hydrolysis resistance agent is carbodiimide; the catalyst is any one or a mixture of at least two of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, triethylene diamine, triethanolamine and dimorpholinyl diethyl ether; the silane coupling agent is any one or a mixture of at least two of a vinyl silane coupling agent, an amino silane coupling agent and an epoxy silane coupling agent; the flame retardant is one or a mixture of at least two of tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2, 3-dichloropropyl) phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate and antimony trioxide.
8. A preparation method of a polyurethane adhesive for ETPU runway molding is characterized by comprising the following steps:
s1, adding the polyol and the antioxidant into a polymerization stirring reaction kettle after metering, wherein the polyol ester content is 57-70 wt% and the antioxidant addition amount is 0.2-0.5 wt% based on the total weight of the polyurethane adhesive;
s2, heating and melting the materials in the polymerization stirring reaction kettle, stirring and mixing uniformly, heating to ensure that the material temperature reaches 110-120 ℃, and then vacuumizing and dehydrating until the water content of the materials is lower than 300ppm (mg/kg);
s3, after dehydration is finished, reducing the temperature of the polymerization stirring reaction kettle to 60-70 ℃, introducing nitrogen to maintain the micro-positive pressure of the reaction kettle, adding diisocyanate for reaction, heating the reaction kettle, maintaining the reaction temperature to 90-100 ℃, and keeping the reaction time to be not less than 2 hours;
s4, detecting the weight percentage content of NCO% of isocyanate group in the reaction process of the step S3, when the NCO% reaches below a theoretical value, adding 0.08-0.15 wt% of catalyst, 0.3-0.7 wt% of hydrolysis resistance agent, 0.5-1.5 wt% of silane coupling agent and 2.0-6.0 wt% of flame retardant into a reaction kettle, uniformly stirring, carrying out negative pressure defoaming and continuous reaction until no bubble exists in the reaction kettle, and obtaining a viscous liquid product.
9. The method of claim 8, wherein in step S3, the equivalent weight of diisocyanate required to be consumed is calculated according to the molecular weight of polyol ester, and the excess diisocyanate is added in an amount of 2.2-3.5:1 times the equivalent weight of polyol ester.
10. The method of claim 8, wherein in step S4, the formula for calculating the theoretical value of NCO% is as follows: (weight of diisocyanate NCO addition-theoretical weight of NCO consumed by polyol plus chain extender)/total weight of the reactor contents.
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| CN114231241A (en) * | 2021-12-27 | 2022-03-25 | 河北巅峰体育设施有限公司 | Anti-yellowing adhesive and preparation method thereof |
| CN115044341A (en) * | 2022-08-15 | 2022-09-13 | 山东科力美实业有限公司 | Bi-component polyurethane adhesive for forming popcorn particles and preparation method thereof |
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