CN115466587A - Heat activated reactive adhesive and preparation method thereof - Google Patents
Heat activated reactive adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN115466587A CN115466587A CN202210784984.1A CN202210784984A CN115466587A CN 115466587 A CN115466587 A CN 115466587A CN 202210784984 A CN202210784984 A CN 202210784984A CN 115466587 A CN115466587 A CN 115466587A
- Authority
- CN
- China
- Prior art keywords
- acid
- heat
- polyether polyol
- adhesive
- polyol
- 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.)
- Pending
Links
Images
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
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic 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
- C08G18/42—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
Abstract
The invention discloses a heat-activated reactive adhesive, which is a single-component reactive hot melt adhesive with the solid content of 100 percent, is suitable for the lamination of various substrates, has softer hand feeling and higher initial strength at the same time by adding polyether polyol, polyester polyol, isocyanate, a hydroxyl compound, a plasticizer, a catalyst and a filler and reacting with moisture in the air for crosslinking. The adhesive strength of the adhesive to the plastic base material is excellent and can reach 100N/25mm. In addition, the obtained adhesive is a heat-activated adhesive, has long opening time, high final strength and good elasticity in a wide temperature range, has good humidity resistance, good chemical resistance, good peel strength and a wide bonding range.
Description
Technical Field
The invention relates to the field of preparation of adhesives, C09J175/06, in particular to a heat-activated reactive adhesive and a preparation method thereof.
Background
In the dust collector roller industry, the double-sided adhesive tape is widely applied to a bonding roller and a felt due to the advantages of convenient operation and instant use after bonding. With the technology of the dust collector being updated, the rotating speed of the roller is faster and faster, and the requirement on the bonding strength of the roller of the dust collector is higher and higher. When the rotating speed of the dust collector is more than 2000 rpm, the bonding strength of the double-sided adhesive tape can not meet the requirement, and the felt can be peeled off along with the quick rotation of the dust collector roller. The invention aims to solve the technical problem of providing the adhesive which can meet the bonding strength of a roller body and felt of a high-speed dust collector and meet the roller production process.
The patent CN202010184715.2 discloses a water-based polyurethane adhesive with high heat activation temperature and a preparation method thereof, wherein polyester polyol obtained from recycled PET products is mixed with polyether polyol, isocyanate, a hydrophilic chain extender, a catalyst, a low-boiling-point organic solvent, a neutralizer and aminoethane sodium sulfonate to obtain the adhesive, and the adhesive has high heat activation temperature, good high temperature resistance, good mechanical property and adhesive capacity, but poor humidity and heat resistance. Patent CN202010656086.9 discloses a solvent-free single-component moisture-curing polyurethane adhesive suitable for wood and a preparation method thereof, wherein a polyurethane prepolymer is obtained by reacting polyether polyol, polyester polyol and isocyanate, and then a catalyst and an auxiliary agent are added, so that the adhesive is high in pressure shear strength after being attached, can be used at room temperature, and is used for bonding wood and wood. But its bonding strength needs to be further improved.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a heat-activated reactive adhesive, which is prepared from raw materials including, by mass:
polyester polyol: 55-65%, polyether polyol: 25 to 35%, isocyanate: 10 to 20%, hydroxyl compound: 0.5 to 2%, plasticizer: 3-10%, catalyst: 0.2-2%, filler: 0.5 to 1.5 percent.
In some preferred embodiments, the polyester polyol is selected from at least one or more of polyethylene adipate glycol, polyhexamic acid-1,4-butanediol glycol, polydiethylene adipate glycol diethylene glycol, polydiethylene adipate glycol butanediol, sebacic acid/isophthalic acid/hexanediol/neopentyl glycol polyester polyol, adipic acid/isophthalic acid/terephthalic acid/neopentyl glycol/ethylene glycol polyester polyol, phthalic acid/octapentanediol condensed polyester polyol, adipic acid/hexanediol/neopentyl glycol polyester polyol; preferably, the polyester polyol is a polyester polyol of polyhexamic acid-1,4-butanediol ester diol and phthalic acid/octapentanediol condensation.
In some preferred embodiments, the weight ratio of the polyadipic acid-1,4-butanediol ester diol and the phthalic acid/octapentanediol condensed polyester polyol is 1: (0.75-2); preferably, the weight ratio of the polyadipic acid-1,4-butanediol ester diol to the phthalic acid/octapentanediol condensed polyester polyol is 1:1.45.
in some preferred embodiments, the poly adipic acid-1,4-butanediol ester diol has an average molecular weight of 600 to 4000g/mol, a viscosity of 200 to 1000cps at 75 ℃, and a hydroxyl number in the range of 35 to 200mgKOH/g; preferably, the polyadipic acid-1,4-butanediol ester diol has an average molecular weight of 1000g/mol, a viscosity of 450cps at 75 ℃ and a hydroxyl value in the range of 106 to 108mgKOH/g.
In some preferred embodiments, the phthalic acid/octapentanediol condensed polyester polyol has a molecular weight of 500 to 2000g/mol, a hydroxyl value of 75 to 150mgKOH/g, and an acid value of 3mgKOH/g or less; preferably, the molecular weight of the phthalic acid/octapentanediol condensed polyester polyol is 1000-1200 g/mol, the hydroxyl value is 100-116 mgKOH/g, and the acid value is less than or equal to 2mgKOH/g; further preferably, the molecular weight of the phthalic acid/octanethylene glycol condensed polyester polyol is 1061g/mol, the hydroxyl value is 104mgKOH/g, and the acid value is 1.7mgKOH/g.
In some preferred embodiments, the polyether polyol is selected from one or more of polypropylene oxide ether polyol, propylene oxide ethylene oxide co-polyether polyol, polytetrahydrofuran ether polyol, polytetramethylene ether glycol, modified silane polyether polyol, aliphatic polyether polyol; preferably, the polyether polyol is selected from the group consisting of polytetrahydrofuran ether polyols and modified silane polyether polyols.
In some preferred embodiments, the weight ratio of the polytetrahydrofuran polyether polyol to the modified silane polyether polyol is 1: (1-3); preferably, the weight ratio of the polytetrahydrofuran polyether polyol to the modified silane polyether polyol is 1:1.7.
in some preferred embodiments, the polytetrahydrofuran ether polyol has an average molecular weight of from 1000 to 4000g/mol, a hydroxyl number of from 30 to 118mgKOH/g, and a viscosity of from 260 to 1500cps at 40 ℃; preferably, the polytetrahydrofuran ether polyol has an average molecular weight of 3000g/mol, a hydroxyl value of 36.8-38 mgKOH/g and a viscosity of 1340cp at 40 ℃.
In some preferred embodiments, the modified silane polyether polyol has a functionality of from 0.1 to 2 and a viscosity of from 10000 to 30000mPa · s at 25 ℃; preferably, the modified silane polyether polyol has a functionality of 0.14 to 0.21 and a viscosity of 21000 mPas at 25 ℃.
The polyurethane adhesive formed by polyether polyol and polyester polyol under the action of isocyanate has better strength, particularly, polyester polyol obtained by condensation of poly adipic acid-1,4-butanediol ester diol and phthalic acid/octapentanediol is selected as the polyester polyol, and polytetrahydrofuran polyether polyol and modified silane polyether polyol are selected as the polyether polyol, so that the initial adhesive strength of the material can be enhanced. The probable reason is presumed to be that the introduction of the aromatic structure in the polyol can increase the rigidity of the system, and the introduction of other hydrophilic active groups can increase the reactivity during the curing reaction, promote the generation of high crosslinking degree, further increase the bonding strength and the high temperature resistance of the obtained reactive adhesive, and simultaneously promote the dispersion of other components such as fillers in the system, further improve the mechanical property of the system.
In some preferred embodiments, the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, p-toluene sulfonyl isocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate; preferably, the isocyanate is diphenylmethane diisocyanate.
In some preferred embodiments, the hydroxy compound is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, N-methyldiethanolamine, N-butyldiethanolamine, ethylenediamine ethanesulfonic acid, dimethylolbutyric acid, tartaric acid; preferably, the hydroxy compounds are dimethylolbutanoic acid and N-methyldiethanolamine.
In some preferred embodiments, the weight ratio of dimethylolbutyric acid to N-methyldiethanolamine is 1: (1-1.8); preferably, the mass ratio of the dimethylolbutyric acid to the N-methyldiethanolamine is 1:1.6.
in some preferred embodiments, the toughening agent is selected from one or more of epoxidized soybean oil, phenyl alkyl sulfonate, dioctyl phthalate, dipropylene glycol dibenzoate, diisononyl phthalate, butylbenzyl phthalate, diisodecyl phthalate; preferably, the toughening agent is diisononyl phthalate.
In some preferred embodiments, the catalyst is selected from one or more of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, diazabicyclo, triethylamine, triethylenediamine, dimorpholinodiethyl ether; preferably, the catalyst is dibutyltin dichloride.
In some preferred embodiments, the filler is selected from one or more of mica powder, calcium carbonate, silica, talc, white carbon, bentonite, kaolin; preferably, the filler is calcium carbonate, kaolin.
In some preferred embodiments, the mass ratio of calcium carbonate to kaolin is 1: (0.3 to 0.9); preferably, the mass ratio of the calcium carbonate to the kaolin is 1:0.7.
in some preferred embodiments, the calcium carbonate is selected from light calcium carbonate and/or heavy calcium carbonate; preferably, the calcium carbonate is ground calcium carbonate; further preferably, the average particle size of the heavy calcium carbonate is 500 to 1500 meshes; still more preferably, the ground calcium carbonate has an average particle size of 800 mesh.
In some preferred embodiments, the kaolin is selected from calcined kaolin and/or water washed kaolin; preferably, the kaolin is calcined kaolin; further preferably, the calcined kaolin has an average particle size of 0.5 to 5 μm; still more preferably, the calcined kaolin has an average particle size of 1.4 μm.
In a second aspect, the present invention provides a method for preparing a heat-activated reactive adhesive, comprising the steps of:
(1) Mixing polyester polyol and polyether polyol, and vacuumizing and dehydrating for 1-3 h at 110-130 ℃;
(2) Cooling to 35-50 ℃, adding isocyanate, hydroxyl compound, plasticizer, toughening agent and catalyst, and reacting for 2-5 h at 65-85 ℃ to obtain polyurethane prepolymer;
(3) Cooling to below 55 ℃, adding a plasticizer and a filler, and reacting for 1-3 h;
(4) Vacuum is relieved by dry nitrogen, and catalyst is added to obtain the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method, polyether polyol, polyester polyol, isocyanate, a hydroxyl compound, a plasticizer, a catalyst and a filler are added to react with moisture in the air to carry out crosslinking, so that the prepared reactive adhesive is a single-component reactive hot melt adhesive with the solid content of 100%, is suitable for the lamination of various substrates, has a softer hand feeling and has high initial strength. The adhesive strength of the adhesive to the plastic base material is excellent and can reach 100N/25mm. And the obtained adhesive has good flexibility and excellent high-temperature resistance.
(2) The adhesive obtained by the invention is a heat-activated adhesive, has long opening time, high final strength and good elasticity in a wide temperature range, has good damp-heat resistance and chemical resistance, is resistant to water, weak acid and caustic alkali solution, resists fuel oil, solvent and mineral oil in a short time, and also has good peel strength.
(3) The reactive adhesive obtained by the application has a wide bonding range, and is suitable for permanent bonding of polar materials such as ABS, PC, SMC, PVC, wood, foam, fabric, painted steel plates and the like. The non-polar materials such as PP, PE and the like can be bonded after special pretreatment, and the bonding method is particularly suitable for the dust collector roller of the dust collector roller.
Drawings
FIG. 1 is a graph of the curing time at 20 ℃ versus humidity for 0.5mm of the sample obtained in example 1.
Detailed Description
Example 1
1. A heat-activated reactive adhesive is prepared from the following raw materials in percentage by mass:
polyester polyol 57%, polyether polyol: 26%, isocyanate: 12%, hydroxy compound: 0.6%, plasticizer: 3.5%, catalyst: 0.4%, filler: 0.5 percent.
The polyester polyol is polyester polyol obtained by condensation of poly adipic acid-1,4-butanediol ester diol and phthalic acid/octapentanediol.
The weight ratio of the poly adipic acid-1,4-butanediol ester diol to the phthalic acid/octapentanediol condensed polyester polyol is 1:1.45.
the average molecular weight of the poly adipic acid-1,4-butanediol ester diol is 1000g/mol, the viscosity at 75 ℃ is 450cps, and the hydroxyl value range is 106-108 mgKOH/g (JinningBiao chemical Co., ltd., type HY-1022).
The molecular weight of the phthalic acid/octapentanediol condensed polyester polyol is 1061g/mol, the hydroxyl value is 104mgKOH/g, and the acid value is 1.7mgKOH/g (Shanghai Yu chemical Co., ltd., model A3030).
The polyether polyol is selected from polytetrahydrofuran polyether polyol and modified silane polyether polyol.
The weight ratio of the polytetrahydrofuran polyether polyol to the modified silane polyether polyol is 1:1.7.
the average molecular weight of the polytetrahydrofuran ether polyol is 3000g/mol, the hydroxyl value is 36.8-38 mgKOH/g, and the viscosity at 40 ℃ is 1340cps (purchased from Shandong Jiaying chemical technology Co., ltd.).
The functionality of the modified silane polyether polyol is 0.14-0.21, and the viscosity is 21000mPa & s (Dow, VORASIL 602) at 25 ℃.
The isocyanate is diphenylmethane diisocyanate.
The hydroxyl compound is dimethylolbutyric acid and N-methyldiethanolamine.
The mass ratio of the dimethylolbutyric acid to the N-methyldiethanolamine is 1:1.6.
the toughening agent is diisononyl phthalate.
The catalyst is dibutyltin dichloride.
The filler is calcium carbonate and kaolin.
The mass ratio of the calcium carbonate to the kaolin is 1:0.7.
the calcium carbonate is heavy calcium carbonate; the average particle size of the heavy calcium carbonate is 800 meshes (Guangxi Zhejiang chemical Co., ltd.).
The kaolin is calcined kaolin; the calcined kaolin had an average particle size of 1.4 μm (Burgers, burgers OPTIWHITE).
2. A method of preparing a heat-activated reactive adhesive comprising the steps of:
(1) Mixing polyester polyol and polyether polyol, and vacuumizing and dehydrating for 2.5h at 120 ℃;
(2) Cooling to 45 ℃, adding isocyanate, a hydroxyl compound, a plasticizer, a toughening agent and a catalyst, and reacting for 3.5 hours at 80 ℃ to obtain a polyurethane prepolymer;
(3) Cooling to 50 ℃, adding a plasticizer and a filler, and reacting for 1.5h;
(4) Vacuum is relieved by dry nitrogen, and catalyst is added to obtain the catalyst.
Example 2
1. A heat-activated reactive adhesive which is different from example 1 in that:
the weight ratio of the poly adipic acid-1,4-butanediol ester diol to the phthalic acid/octapentanediol condensed polyester polyol is 1:1.
2. a heat-activated reactive adhesive was prepared as in example 1.
Comparative example 1
1. A heat-activated reactive adhesive which is different from that of example 1 in that:
the weight ratio of the poly adipic acid-1,4-butanediol ester diol to the phthalic acid/octapentanediol condensed polyester polyol is 1:3.
2. a heat-activated reactive adhesive was prepared as in example 1.
Comparative example 2
1. A heat-activated reactive adhesive which is different from that of example 1 in that:
the weight ratio of the polytetrahydrofuran polyether polyol to the modified silane polyether polyol is 1:4.
2. a heat-activated reactive adhesive was prepared as in example 1.
Comparative example 3
1. A heat-activated reactive adhesive which is different from that of example 1 in that:
the filler is calcium carbonate.
2. A heat-activated reactive adhesive was prepared as in example 1.
Performance testing
1. The samples obtained in example 1 were tested and the results are shown in Table 1.
Table 1 test results of samples obtained in example 1
2. The curing time-humidity relationship was measured at 20 ℃ for a sample of 0.5mm obtained in example 1, and the results are shown in FIG. 1.
As can be illustrated by fig. 1, curing depends not only on the adhesive film thickness, but also on the moisture content in air, temperature, moisture content of the substrate, and permeability.
3. The samples obtained in the examples and comparative examples were tested, and the test results are shown in Table 2.
TABLE 2 test results of samples obtained in examples and comparative examples
Claims (10)
1. A heat-activated reactive adhesive is characterized by being prepared from the following raw materials in percentage by mass:
polyester polyol: 55-65%, polyether polyol: 25 to 35%, diphenylmethane diisocyanate: 10 to 20%, hydroxyl compound: 0.5 to 2%, plasticizer: 3-10%, catalyst: 0.2-2%, filler: 0.5 to 1.5 percent.
2. A heat-activated reactive adhesive as defined in claim 1, wherein said polyester polyol is at least one or more selected from the group consisting of polyethylene adipate glycol, polyethylene-1,4-butanediol, polyethylene adipate glycol, polyethylene glycol adipate glycol butanediol, polyethylene glycol adipate glycol butanediol, sebacic acid/isophthalic acid/hexanediol/neopentyl glycol polyester polyol, adipic acid/isophthalic acid/terephthalic acid/neopentyl glycol polyester polyol, phthalic acid/octapentanediol condensed polyester polyol, adipic acid/hexanediol/neopentyl glycol polyester polyol.
3. A heat-activated reactive adhesive as claimed in claim 1 or 2, wherein the polyester polyol is a polyester polyol obtained by condensation of a polyester of adipic acid-1,4-butanediol diol and phthalic acid/octapentanediol;
the weight ratio of the poly adipic acid-1,4-butanediol ester diol to the phthalic acid/octapentanediol condensed polyester polyol is 1: (0.75-2).
4. A heat-activated reactive adhesive as defined in claim 1, wherein said polyether polyol is selected from one or more of polypropylene oxide polyether polyol, propylene oxide ethylene oxide copolymer polyether polyol, polytetrahydrofuran polyether polyol, polytetramethylene ether glycol, modified silane polyether polyol, aliphatic polyether polyol.
5. A heat-activated reactive adhesive as claimed in claim 1 or 4, wherein said polyether polyol is selected from polytetrahydrofuran ether polyols and modified silane polyether polyols;
the weight ratio of the polytetrahydrofuran polyether polyol to the modified silane polyether polyol is 1: (1-3).
6. A heat-activated reactive adhesive according to claim 1, wherein the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, p-toluenesulfonyl isocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate.
7. A heat-activated reactive adhesive as claimed in claim 1, wherein said hydroxy compound is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, N-methyldiethanolamine, N-butyldiethanolamine, ethylenediamine ethanesulfonic acid, dihydroxymethylbutyric acid and tartaric acid.
8. A heat-activated reactive adhesive as claimed in claim 1, wherein the catalyst is selected from one or more of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, diazabicyclo, triethylamine, triethylenediamine, dimorpholinodiethyl ether.
9. A heat-activated reactive adhesive as claimed in claim 1, wherein said filler is selected from one or more of mica powder, calcium carbonate, silica, talc, white carbon, bentonite and kaolin.
10. A method of preparing a heat-activatable adhesive according to any one of claims 1 to 9, comprising the steps of:
(1) Mixing polyester polyol and polyether polyol, and vacuumizing and dehydrating for 1-3 h at 110-130 ℃;
(2) Cooling to 35-50 ℃, adding isocyanate, hydroxyl compound, plasticizer, toughening agent and catalyst, and reacting for 2-5 h at 65-85 ℃ to obtain polyurethane prepolymer;
(3) Cooling to below 55 ℃, adding a plasticizer and a filler, and reacting for 1-3 h;
(4) Vacuum is relieved by dry nitrogen, and catalyst is added to obtain the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210784984.1A CN115466587A (en) | 2022-06-28 | 2022-06-28 | Heat activated reactive adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210784984.1A CN115466587A (en) | 2022-06-28 | 2022-06-28 | Heat activated reactive adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115466587A true CN115466587A (en) | 2022-12-13 |
Family
ID=84367509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210784984.1A Pending CN115466587A (en) | 2022-06-28 | 2022-06-28 | Heat activated reactive adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115466587A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173031A (en) * | 2006-11-01 | 2008-05-07 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN101613448A (en) * | 2009-07-10 | 2009-12-30 | 烟台道成化学有限公司 | The preparation method of a kind of waterborne polyurethane resin and dipping sizing agent for synthetic leather base material |
| CN103881640A (en) * | 2014-03-27 | 2014-06-25 | 山东华诚高科胶粘剂有限公司 | Preparation method of single-component water-based polyurethane adhesive for use in flexible package compounding |
| CN105001776A (en) * | 2015-09-06 | 2015-10-28 | 北京东方雨虹防水技术股份有限公司 | Self-emulsifying type water curing environment-friendly polyurethane waterproof paint |
| CN110330937A (en) * | 2019-07-17 | 2019-10-15 | 上海应用技术大学 | A kind of Environment-friendlyadhesive adhesive and preparation method of high intensity |
| CN111334238A (en) * | 2020-03-17 | 2020-06-26 | 北京华腾新材料股份有限公司 | Waterborne polyurethane adhesive with high thermal activation temperature and preparation method thereof |
-
2022
- 2022-06-28 CN CN202210784984.1A patent/CN115466587A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173031A (en) * | 2006-11-01 | 2008-05-07 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN101613448A (en) * | 2009-07-10 | 2009-12-30 | 烟台道成化学有限公司 | The preparation method of a kind of waterborne polyurethane resin and dipping sizing agent for synthetic leather base material |
| CN103881640A (en) * | 2014-03-27 | 2014-06-25 | 山东华诚高科胶粘剂有限公司 | Preparation method of single-component water-based polyurethane adhesive for use in flexible package compounding |
| CN105001776A (en) * | 2015-09-06 | 2015-10-28 | 北京东方雨虹防水技术股份有限公司 | Self-emulsifying type water curing environment-friendly polyurethane waterproof paint |
| CN110330937A (en) * | 2019-07-17 | 2019-10-15 | 上海应用技术大学 | A kind of Environment-friendlyadhesive adhesive and preparation method of high intensity |
| CN111334238A (en) * | 2020-03-17 | 2020-06-26 | 北京华腾新材料股份有限公司 | Waterborne polyurethane adhesive with high thermal activation temperature and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109777336B (en) | Reactive polyurethane hot melt adhesive for PVC and preparation method thereof | |
| US5155180A (en) | Moisture-curing hot-melt adhesive | |
| CN107922562B (en) | Moisture-curable hot-melt polyurethane composition, method for producing foamed cured product thereof, synthetic leather, and method for producing same | |
| CN107459960B (en) | Bi-component polyurethane adhesive and preparation and application thereof | |
| CN110229645B (en) | High initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| KR20180126735A (en) | Eco-friendly artificial leather for interior of automobile and manufacturing method thereof | |
| CN111378413B (en) | Primer-free single-component polyurethane sealant and preparation method thereof | |
| CN108949090B (en) | Solvent-free two-component polyurethane sealant and preparation method thereof | |
| KR102086474B1 (en) | Reactive polyurethane hotmelt adhesives adapted an aerogel and producing method of coating textile using the same | |
| CN114044868B (en) | Heating detachable polyurethane hot melt adhesive, preparation raw materials, preparation method and bonding method thereof | |
| CN114085366B (en) | Polylactic alcohol ester diol, biodegradable polyurethane hot melt adhesive and preparation method thereof | |
| CN111320960A (en) | Low-viscosity high-temperature-resistant single-component solvent-free polyurethane adhesive and preparation method thereof | |
| CN110484190B (en) | Solvent-free single-component moisture-curing polyurethane adhesive for caravan bodies and preparation method thereof | |
| CN112812727B (en) | Long-holding-viscosity aqueous polyurethane adhesive and preparation method thereof | |
| CN112341983B (en) | Waterborne polyurethane adhesive and preparation method thereof | |
| CN113061227B (en) | Waterproof and moisture permeable waterborne polyurethane resin, and preparation method and application thereof | |
| CN111117549B (en) | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) | |
| CN115466587A (en) | Heat activated reactive adhesive and preparation method thereof | |
| CN113897165B (en) | Detachable polyurethane hot melt adhesive, preparation raw materials, preparation method and bonding method thereof | |
| CN115232591B (en) | Reactive polyurethane hot melt adhesive and preparation method thereof | |
| CN111978909B (en) | Reactive polyurethane hot melt adhesive for low-temperature coating and preparation method thereof | |
| KR100965469B1 (en) | Solvent-free moisture-curable hot melt urethane resin composition | |
| JP3881083B2 (en) | Method for producing moisture-curing one-component urethane sealant composition and composition thereof | |
| CN110885660A (en) | Polyurethane hot melt adhesive for low surface energy material and preparation method thereof | |
| CN112694860B (en) | Reactive polyurethane hot melt adhesive and preparation method thereof |
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 |