CN114045147B - Single-component polyurethane foaming adhesive and preparation method and application thereof - Google Patents

Single-component polyurethane foaming adhesive and preparation method and application thereof Download PDF

Info

Publication number
CN114045147B
CN114045147B CN202111445965.8A CN202111445965A CN114045147B CN 114045147 B CN114045147 B CN 114045147B CN 202111445965 A CN202111445965 A CN 202111445965A CN 114045147 B CN114045147 B CN 114045147B
Authority
CN
China
Prior art keywords
polyol
component polyurethane
adhesive
parts
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111445965.8A
Other languages
Chinese (zh)
Other versions
CN114045147A (en
Inventor
王青
谢东
李发勇
刘海露
李辰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Biological and Medical Engineering of Guangdong Academy of Sciences
Original Assignee
Institute of Biological and Medical Engineering of Guangdong Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Biological and Medical Engineering of Guangdong Academy of Sciences filed Critical Institute of Biological and Medical Engineering of Guangdong Academy of Sciences
Priority to CN202111445965.8A priority Critical patent/CN114045147B/en
Publication of CN114045147A publication Critical patent/CN114045147A/en
Application granted granted Critical
Publication of CN114045147B publication Critical patent/CN114045147B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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

Abstract

The invention discloses a single-component polyurethane foaming adhesive and a preparation method and application thereof. The single-component polyurethane foaming adhesive comprises the following components in parts by mass: 31.1-55.3 parts of vegetable oil polyol, 15.0-53.4 parts of polyether polyol, 30-106 parts of polyester polyol, 100 parts of isocyanate and 0.176-1.570 parts of catalyst. The single-component polyurethane foaming adhesive provided by the invention has no organic solvent, has a good micro-cell structure and cohesiveness after solidification, is simple in preparation process, adjustable in solidification rate and foaming multiple, and is simple and convenient to use and suitable for binding of the foamed ceramic tile gap base surface material.

Description

Single-component polyurethane foaming adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite adhesives, and relates to a single-component polyurethane foaming adhesive, a preparation method and application thereof.
Background
Compared with the traditional wall building material, the foamed ceramic has the advantages of quick construction, dry construction, no waterproof treatment and labor saving, but the product belongs to porcelain, is completely vitrified, has small shrinkage deformation rate, and is very strict in construction, especially the problem of bonding wall plates. The traditional ceramic tile pavement is that cement and sand are prepared into mortar to be smeared on the back of the tile, the construction process has high technological requirements and high construction difficulty, the cement mortar forms hard connection, and the expansion caused by climate change and contraction easily lead to unstable adhesion, hollowing and water seepage of the wall tile, even mildew and falling. At present, the novel light partition board for building adopts special adhesive, and forms the novel wallboard with light weight, high density and high strength by bonding cement and EPS materials. The polyurethane filler is a relatively common adhesive, and can enable the wall body and each part to be connected to form elastic soft connection, and a sealed elastic connecting band is formed at a gap, so that cracking and water seepage caused by thermal expansion and contraction are effectively prevented. The two-component polyurethane filler is mainly divided into two types, namely a two-component polyurethane filler and a single-component polyurethane filler, when the two-component polyurethane filler is used, the two-component polyurethane filler is prepared according to a certain proportion and cured at room temperature, the two-component polyurethane filler is inconvenient to use, the mixing and the metering are labor-consuming and time-consuming, errors are easy to occur when a user mixes and meters, the process needs to be matched along with the use, and waste is easy to cause. The single-component filler avoids the defects, takes water as a cross-linking agent, releases gas through chemical reaction to form foam, extrudes and diffuses to the periphery to form elastic solidification matters to realize the bonding of gap base materials.
Patent CN 102341421a discloses a polyurethane foam comprising an ester-based polyol, which polyurethane foam is prepared from an isocyanate-modified polyol and a foam-forming mixture, wherein the foam is at least one polyfunctional isocyanate and a blowing agent, preferably water. Mixing the isocyanate modified polyol with the ester based polyol prior to or simultaneously with foaming and having a foam density of 5 to 100kg/m 3 . That is, the technology provides a double-component or multi-component polyurethane foam, the construction process is increased to a certain extent, and the foaming density does not meet the requirement of the foaming ceramic tile on the foaming density of the polyurethane adhesive for bonding. Patent CN 101676356a discloses a one-component polyurethane foaming adhesive, wherein the isocyanate in the adhesive component is diphenylmethane diisocyanate (MDI type), but the aromatic isocyanate generates aromatic amine with potential carcinogenic effect after hydrolysis of unreacted monomer or "fragments" generated by thermal cracking, so the selection of isocyanate is developed to aliphatic type. In addition, some single-component polyurethane adhesives are also selected to be added withThe organic solvent can reduce the viscosity of the system, can be used as a foaming agent to help the adjustment of the curing density, but has the problem of VOC emission. As soon as possible, single-component polyurethane foaming adhesives are reported, but most polyurethane adhesives cannot meet the use requirements of foaming ceramic tiles on foaming times, curing time, waterproof performance and the like of adhesives, and a polyurethane adhesive is needed to solve the problems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a single-component polyurethane foaming adhesive, a preparation method and application thereof, and the single-component polyurethane foaming adhesive provided by the invention has no organic solvent, has good micro-cell structure and cohesiveness after solidification, is simple in preparation process, adjustable in solidification rate and expansion multiple, is simple and convenient to use, and is suitable for bonding of foamed ceramic tile slit basal plane materials.
The technical scheme adopted by the invention is as follows: the single-component polyurethane foaming adhesive comprises the following components in parts by mass: 31.1-55.3 parts of vegetable oil polyol, 15.0-53.4 parts of polyether polyol, 30-106 parts of polyester polyol, 100 parts of isocyanate and 0.176-1.570 parts of catalyst.
Preferably, the single-component polyurethane foaming adhesive comprises the following components in parts by mass: 34.6-51.8 parts of vegetable oil polyol, 16.7-33.0 parts of polyether polyol, 33-66 parts of polyester polyol, 100 parts of isocyanate and 0.65-1.14 parts of catalyst.
The density of the single-component polyurethane foaming adhesive after curing is 100-175kg/m 3 The surface drying time is 0.5-1 hour.
Preferably, the vegetable oil polyol is castor oil polyol.
The castor oil polyol is the triglyceride of fatty acid, the average functionality of hydroxyl in the molecular structure is 2.7, and the castor oil molecular structure also contains three long side chains of 12 carbon atoms, so that the castor oil can prepare crosslinked network polyurethane from the aspect of the castor oil molecular chain structure, and the body type crosslinked structure endows the material with better water resistance and can effectively resist water erosion. In addition, polyester polyol can endow polyurethane with higher heat resistance, bonding strength, oil resistance and oxidation resistance, but has poorer hydrolysis resistance stability; the polyether polyol can endow the material with better flexibility, low temperature resistance and water resistance, but has poorer strength and ageing resistance. Furthermore, isophorone diisocyanate (IPDI) is relatively low in toxicity compared to MDI and TDI, and we prefer IPDI as the isocyanate component from the standpoint of environmental protection and low toxicity. Therefore, in order to achieve better performance, from the aspects of environmental protection and low cost, the castor oil polyol, the polyester polyol and the polyether polyol are prepared into mixed polyol, and then the mixed polyol is reacted with IPDI type isocyanate to prepare the single-component polyurethane foaming adhesive.
Preferably, the polyether polyol is propylene glycol polyether and/or polytetrahydrofuran glycol, and the molecular weight of the polyether polyol is between 1000 and 2000.
Preferably, the polyester polyol is poly (1, 4-butylene glycol) adipate, and the molecular weight of the polyester polyol is between 1000 and 2000.
Preferably, the isocyanate is isophorone diisocyanate (IPDI).
Preferably, the catalyst comprises an organotin catalyst and an alcohol compound catalyst, wherein the organotin catalyst is dibutyltin dilaurate or dibutyltin diacetate, and the alcohol compound catalyst is triethanolamine or dimethylethanolamine; the mass ratio of the organotin catalyst to the alcohol compound catalyst is 1:2-1:1.
Preferably, the catalyst is added in an amount of 0.1 to 0.5wt% based on the total mass of the system.
The invention also provides a preparation method of the single-component polyurethane foaming adhesive, which comprises the following steps:
(1) Mixing vegetable oil polyol, polyether polyol and polyester polyol, heating to 105-110 ℃ and drying to obtain mixed polyol;
(2) Mixing the mixed polyol obtained in the step (1) with isocyanate, heating to 50-60 ℃, reacting for 30-120min under nitrogen atmosphere protection, cooling to 40-50 ℃ when the isocyanate content in the reaction system reaches 6-18%, adding a catalyst, stirring for 5-10min, and cooling to room temperature to obtain the single-component polyurethane foaming adhesive. The isocyanate content refers to the mass fraction of isocyanate to the total mass of the reaction system.
The invention also protects the application of the single-component polyurethane foaming adhesive as the foaming ceramic tile adhesive. The single-component polyurethane foaming adhesive prepared by the invention has the advantages of no organic solvent, adjustable viscosity, adjustable foaming multiplying power, adjustable mechanical property and the like, and can be subjected to targeted performance fine adjustment according to the actual application requirements of the foaming ceramic tile in different scenes.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the vegetable oil polyol, the polyester polyol and the polyether polyol are prepared into the mixed polyol, the performance advantages of the vegetable oil polyol, the polyester polyol and the polyether polyol are fully exerted, and the polyurethane adhesive material is endowed with good waterproof performance while the bonding strength is not influenced through molecular structure regulation and control under the condition that the organic silicon resin or the fluorine-containing resin is not additionally adopted.
(2) The single-component polyurethane foaming adhesive prepared by the invention has the advantages of no organic solvent, adjustable viscosity, adjustable foaming multiplying power, adjustable mechanical property and the like, and can be subjected to targeted performance fine adjustment according to the actual application requirements of the foaming ceramic tile in different scenes.
(3) The vegetable oil polyol castor oil in the system of the single-component polyurethane foaming adhesive prepared by the invention can effectively replace up to 50% of petroleum polyol, can save energy sources and reduce the production cost of the single-component polyurethane foaming adhesive.
Drawings
FIG. 1 is a graph showing the viscosity of the adhesives obtained in example 5 and comparative examples 1 to 4, wherein PBA/PTMG represents the adhesive obtained in comparative example 1, PBA represents the adhesive obtained in comparative example 2, CO represents the adhesive obtained in comparative example 3, CO/PTMG represents the adhesive obtained in comparative example 4, and PBA/PTMG/CO represents the adhesive obtained in example 5.
FIG. 2 is a graph showing the static contact angle with water of the adhesives obtained in example 5 and comparative examples 1 to 4, wherein PBA/PTMG represents the adhesive obtained in comparative example 1, PBA represents the adhesive obtained in comparative example 2, CO represents the adhesive obtained in comparative example 3, CO/PTMG represents the adhesive obtained in comparative example 4, and PBA/PTMG/CO represents the adhesive obtained in example 5;
FIG. 3 is a graph showing the water absorption ratio of the adhesives obtained in example 5 and comparative examples 1 to 4, wherein PBA/PTMG represents the adhesive obtained in comparative example 1, PBA represents the adhesive obtained in comparative example 2, CO represents the adhesive obtained in comparative example 3, CO/PTMG represents the adhesive obtained in comparative example 4, and PBA/PTMG/CO represents the adhesive obtained in example 5;
FIG. 4 shows the foaming effect of a commercial polyurethane adhesive at 2h and 24 h;
FIG. 5 shows the foaming effect of the polyurethane adhesive prepared in example 5 in the range of 0 to 20 hours.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof. The reagents proposed in the present invention are all commercially available, unless otherwise specified.
Example 1
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, propylene glycol polyether and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours, so that a small amount of water in the system is removed, and the mixed polyol is obtained. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 7% -8%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:2) into the reaction system, continuously stirring for 5 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 30min, the real drying time of 110min and the curing density of 160kg/m 3 。
Example 2
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 10% -11%, adding dibutyl tin dilaurate and dimethylethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1.5) into the reaction system, continuously stirring for 5 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 50min, the real drying time of 130min and the curing density of 140kg/m 3 。
Example 3
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 8% -9%, adding dibutyl tin dilaurate and dimethylethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1.5) into the reaction system, continuously stirring for 6 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 40min, the real drying time of 120min and the curing density of 150kg/m 3 。
Example 4
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 9% -10%, adding dibutyl tin dilaurate and dimethylethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:2) into the reaction system, continuously stirring for 6 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 45min, the real drying time of 150min and the curing density of 150kg/m 3 。
Example 5
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 17% -18%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:2) into the reaction system, continuously stirring for 10 minutes, cooling to room temperature, discharging, sealing and storing.
Surface of one-component polyurethane foam adhesive prepared by using the components in this exampleThe dry time is 60min, the real dry time is 120min, and the curing density is 100kg/m 3 。
Comparative example 1
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
the preparation procedure was as in example 5.
The one-component polyurethane foaming adhesive prepared by adopting the components in comparative example 1 has the surface drying time of 45min, the real drying time of 180min and the curing density of 120kg/m 3 。
Comparative example 2
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
the preparation procedure was as in example 5.
The one-component polyurethane foaming adhesive prepared by adopting the components in comparative example 2 has the surface drying time of 45min, the real drying time of 120min and the curing density of 130kg/m 3 。
Comparative example 3
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
the preparation procedure was as in example 5.
The one-component polyurethane foaming adhesive prepared by adopting the components in comparative example 1 has the surface drying time of 100min, the real drying time of 180min and the curing density of 130kg/m 3 。
Comparative example 4
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
the preparation procedure was as in example 5.
The one-component polyurethane foaming adhesive prepared by adopting the components in comparative example 1 has the surface drying time of 90min, the real drying time of 150min and the curing density of 120kg/m 3 。
Example 6
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polypropylene glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours, so that a small amount of water in the system is removed, and the mixed polyol is obtained. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 15% -16%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:2) into the reaction system, continuously stirring for 10 minutes, cooling to room temperature, discharging, sealing and storing.
The surface drying time of the single-component polyurethane foaming adhesive prepared by adopting the components in the embodiment is 50min, the real drying time is 130min, and the curing density is high120kg/m 3 。
Example 7
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 14% -15%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1.5) into the reaction system, continuously stirring for 5-10 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 45min, the real drying time of 110min and the curing density of 115kg/m 3 。
Example 8
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 11% -12%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1.5) into the reaction system, continuously stirring for 5 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 35min, the real drying time of 90min and the curing density of 110kg/m 3 。
Example 9
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 12% -13%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1) into the reaction system, continuously stirring for 5 minutes, cooling to room temperature, discharging, sealing and storing.
Single-component polyurethane foaming adhesive prepared by adopting components in the embodimentThe surface drying time is 40min, the real drying time is 80min, and the curing density is 105kg/m 3 。
Example 10
A preparation method of a single-component polyurethane foaming adhesive for foaming ceramic tiles comprises the following raw materials in formula:
according to the proportion, castor oil polyol, polytetrahydrofuran glycol and poly (1, 4-butanediol adipate) glycol are mixed and added into a three-neck flask with a stirrer with a thermometer, the temperature is raised to 110 ℃, and the mixture is vacuumized and dried for 2 hours to remove a small amount of water in the system, so as to obtain the mixed polyol. And then the dehydrated mixed polyol and IPDI are dosed according to the formula, the temperature is raised to 50 ℃, the stirring speed is increased, and nitrogen is introduced to start the reaction. And (3) sampling and measuring the content of isocyanate groups in the polymer every 10 minutes, cooling to 40 ℃ when the content of isocyanate reaches 12% -13%, adding dibutyl tin dilaurate and triethanolamine (the mass ratio of the dibutyl tin dilaurate to the triethanolamine is 1:1) into the reaction system, continuously stirring for 5 minutes, cooling to room temperature, discharging, sealing and storing.
The one-component polyurethane foaming adhesive prepared by adopting the components in the embodiment has the surface drying time of 35min, the real drying time of 100min and the curing density of 100kg/m 3 。
Experimental example 1
(1) Experimental materials: example 5, comparative examples 1-4 were prepared to give a one-component polyurethane adhesive, deionized water, beaker, forceps, absorbent paper, balance.
(2) The experimental treatment method comprises the following steps: after the polyurethane adhesives obtained in example 5, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were foamed and cured, a cuboid of 1cm×1cm×0.5cm was cut, the viscosity of the adhesives was measured by using a rotational viscometer, and the surface contact angle was measured by using a dataphysics OCA20 static contact angle meter; in addition, the mass of the product is m1, and the product is cooked in distilled water for three hours and taken out every one hourThe water on the surface of the sample was sucked by filter paper and then weighed to m2, and the water absorption S was calculated as follows: s= (m 2 -m 1 )/m 1
Wherein: s is water absorption,%; m is m 1 G is the weight of the adhesive film before cooking; m is m 2 G is the weight of the adhesive film after cooking.
The viscosities of the above adhesives at 60℃were measured using a rotational viscometer, respectively, to prepare a PBA type adhesive (comparative example 2), a PBA/PTMG type adhesive (comparative example 1), a CO type adhesive (comparative example 3), a CO/PTMG type adhesive (comparative example 4) and a PBA/PTMG/CO type adhesive (example 5), and the results are shown in FIG. 1. From the figure, the addition of a proper amount of polyether glycol and castor oil can greatly reduce the viscosity of the system and facilitate uniform sizing operation. However, if castor oil is used alone as the polyol component in the system, the castor oil has a functionality of 2.7 and reacts and crosslinks with isocyanate to form a three-dimensional network structure, so that the system fluidity is deteriorated and the system viscosity is increased. Meanwhile, the adhesive is cured for 1 day at room temperature to prepare a foaming adhesive film, and the smooth surface and the water static contact angle and the water absorption rate of boiling water for one hour, two hours and three hours are respectively tested. The results are shown in fig. 2 and 3. It can be seen from the figure that after the polyether polyol is added, the static contact angle of the adhesive and water is increased from 85 degrees to 89 degrees, and the water absorption of the adhesive is reduced to a certain extent. After castor oil polyalcohol is added into the system, the static contact angle of the castor oil polyalcohol and water is 101 degrees, and the water absorption rate of the adhesive can be greatly reduced. When the system only contains PTMG/CO, the static contact angle of the adhesive film and water is 104 DEG, and the static contact angle of the castor oil type adhesive and water reaches 109 deg. The body type crosslinking structure and the low surface energy of the castor oil polyol can effectively improve the water resistance of the adhesive, can obviously reduce the water absorption rate of the polyurethane adhesive and improve the water resistance, and can meet the use requirements of the foaming ceramic tile on the water resistance of the adhesive and the like. In addition, the early experiments prove that when the system only contains polyester polyol, the foaming of the adhesive after curing is hard and brittle, and the foaming is easy to be limited by skinning. When the system only contains castor oil or only contains castor oil/polyether polyol, the relative molecular mass of soft segments in polyurethane molecular chains is increased, the flexibility of the molecular chains is enhanced, and the cured product is softer and easy to form foam collapse. Therefore, the castor oil, the polyether polyol and the polyester polyol can exert the performance advantages of the castor oil, the polyether polyol and the polyester polyol to the maximum extent by adding the castor oil, the polyether polyol and the polyester polyol in a certain range, reduce the viscosity of the system and improve the foaming ratio and the water resistance of the system.
Experimental example 2
(1) Experimental materials: example 5 some commercially available one-part polyurethane adhesive.
(2) The experimental treatment method comprises the following steps: the commercial polyurethane adhesive and the self-made polyurethane adhesive were coated on the surface of a substrate (plastic film), and the curing time was observed, and the results are shown in fig. 4 and 5, respectively.
As can be seen from the figure, after a certain polyurethane adhesive is commercially available for 2 hours, the surface layer is cured, the deep layer is not cured, and the curing is complete after 24 hours. The polyurethane adhesive prepared by the invention is basically cured for 2 hours, and compared with 24 hours of curing, the foaming multiple is not obviously changed. Compared with the polyurethane adhesive sold in the market, the polyurethane adhesive prepared by the invention has better foaming multiple and curing effect.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (2)

1. The application of the single-component polyurethane foaming adhesive as the foaming ceramic tile adhesive is characterized in that the single-component polyurethane foaming adhesive comprises the following components in parts by mass: 34.6-51.8 parts of vegetable oil polyol, 16.7-33.0 parts of polyether polyol, 33-66 parts of polyester polyol, 100 parts of isocyanate and 0.65-1.14 parts of catalyst; the vegetable oil polyol is castor oil polyol; the polyether polyol is propylene glycol polyether and/or polytetrahydrofuran glycol, and the molecular weight of the polyether polyol is between 1000 and 2000; the polyester polyol is poly adipic acid-1, 4-butanediol ester diol, and the molecular weight of the polyester polyol is between 1000 and 2000; the isocyanate is isophorone diisocyanate; the catalyst comprises an organotin catalyst and an alcohol compound catalyst, wherein the organotin catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, the alcohol compound catalyst is triethanolamine or dimethylethanolamine, the mass ratio of the organotin catalyst to the alcohol compound catalyst is 1:2-1:1, and the adding amount of the catalyst is 0.1-0.5wt% of the total mass of the system.
2. The use according to claim 1, wherein the preparation method of the single-component polyurethane foaming adhesive comprises the following steps:
(1) Mixing vegetable oil polyol, polyether polyol and polyester polyol, heating to 105-110 ℃ and drying to obtain mixed polyol;
(2) Mixing the mixed polyol obtained in the step (1) with isocyanate, heating to 50-60 ℃, reacting for 30-120min under nitrogen atmosphere protection, cooling to 40-50 ℃ when the isocyanate content in the reaction system reaches 6-18%, adding a catalyst, stirring for 5-10min, and cooling to room temperature to obtain the single-component polyurethane foaming adhesive.
CN202111445965.8A 2021-11-30 2021-11-30 Single-component polyurethane foaming adhesive and preparation method and application thereof Active CN114045147B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111445965.8A CN114045147B (en) 2021-11-30 2021-11-30 Single-component polyurethane foaming adhesive and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111445965.8A CN114045147B (en) 2021-11-30 2021-11-30 Single-component polyurethane foaming adhesive and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114045147A CN114045147A (en) 2022-02-15
CN114045147B true CN114045147B (en) 2023-12-01

Family

ID=80211900

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111445965.8A Active CN114045147B (en) 2021-11-30 2021-11-30 Single-component polyurethane foaming adhesive and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114045147B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528801A (en) * 2003-09-28 2004-09-15 上海市合成树脂研究所 Method for preparing perfomed polymer for monocomponent polyurethane foam gule
CN1858082A (en) * 2005-04-13 2006-11-08 拜尔材料科学有限公司 Polyurethane foams made with vegetable oil hydroxylate, polymer polyol and aliphatic polyhydroxy alcohol
CN101676356A (en) * 2008-09-18 2010-03-24 上海昊海化工有限公司 Monocomponent polyurethane foaming type adhesive
CN103819649A (en) * 2012-11-19 2014-05-28 廊坊开发区斯科瑞聚氨酯有限公司 Production method for portable self-spraying bi-component foam caulking agent
CN106496517A (en) * 2016-10-09 2017-03-15 山东大学 A kind of macromolecule slip casting strengthening material
CN110467714A (en) * 2019-08-30 2019-11-19 浙江大众隔热科技有限公司 A kind of polyurethane rigid foam plastic and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528801A (en) * 2003-09-28 2004-09-15 上海市合成树脂研究所 Method for preparing perfomed polymer for monocomponent polyurethane foam gule
CN1858082A (en) * 2005-04-13 2006-11-08 拜尔材料科学有限公司 Polyurethane foams made with vegetable oil hydroxylate, polymer polyol and aliphatic polyhydroxy alcohol
CN101676356A (en) * 2008-09-18 2010-03-24 上海昊海化工有限公司 Monocomponent polyurethane foaming type adhesive
CN103819649A (en) * 2012-11-19 2014-05-28 廊坊开发区斯科瑞聚氨酯有限公司 Production method for portable self-spraying bi-component foam caulking agent
CN106496517A (en) * 2016-10-09 2017-03-15 山东大学 A kind of macromolecule slip casting strengthening material
CN110467714A (en) * 2019-08-30 2019-11-19 浙江大众隔热科技有限公司 A kind of polyurethane rigid foam plastic and preparation method thereof

Also Published As

Publication number Publication date
CN114045147A (en) 2022-02-15

Similar Documents

Publication Publication Date Title
JP6077932B2 (en) Non-bleed, high-strength, high-stretch hand-painted urethane coating waterproofing composition
TWI438243B (en) Processes for producing polyurethane foams containing alkoxysilane functional polymers and uses therefor
US5011902A (en) Co-catalyst system for preparing polyurethane based plywood-patch compositions
CN108949090B (en) Solvent-free two-component polyurethane sealant and preparation method thereof
CN114045147B (en) Single-component polyurethane foaming adhesive and preparation method and application thereof
US4902736A (en) One-part curing composition
CN105238256A (en) Allyl ether modified single-component polyurethane waterproof paint and preparation method thereof
JPS6244784B2 (en)
CN112225878B (en) High-alkali-resistance aqueous bi-component isocyanate curing agent and preparation method thereof
CN110527482A (en) Railway ballastless track special dual-component filleting waterproof gasket cement and preparation method thereof
CN112375530B (en) Polyurethane composition with reduced foaming and matte effect
CN113603881A (en) Fluorinated polytetrahydrofuran diol and preparation method thereof, fluorinated polyurethane waterproof coating and composition thereof, and preparation method and application of fluorinated polyurethane waterproof coating
CN114736596A (en) Quick-drying type single-component polyurethane waterproof coating and preparation method thereof
CN1737059A (en) Moisture-curable polyurethane resin composition
CN111057461A (en) Preparation method of novel single-component water-curing polyurethane waterproof coating
CN114276774A (en) Solvent-free bi-component foamed polyurethane adhesive and application thereof
CN116875175B (en) Polyurethane waterproof coating
JPH0788416B2 (en) Curable composition
BR112021009141A2 (en) moisture curing polyurethane composition containing oxazolidine
JPH0480224A (en) Water-curable polyurethane prepolymer composition
CN114213958B (en) Biomass oil-based single-component polyurethane waterproof paint and preparation method thereof
JP2001072894A (en) Putty material
CN117887346A (en) Preparation technology of polyether type moisture-cured polyurethane waterproof paint
JPS5978227A (en) Urethane prepolymer composition
EP4041793A1 (en) One-part polyurethane sealant for low temperature applications

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant