CN111217992A - Polyester polyol and moisture-curing polyurethane hot melt adhesive prepared from same - Google Patents
Polyester polyol and moisture-curing polyurethane hot melt adhesive prepared from same Download PDFInfo
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- CN111217992A CN111217992A CN201811431774.4A CN201811431774A CN111217992A CN 111217992 A CN111217992 A CN 111217992A CN 201811431774 A CN201811431774 A CN 201811431774A CN 111217992 A CN111217992 A CN 111217992A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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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
- C08G18/28—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
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
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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
- C08G18/28—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
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention provides polyester polyol and a moisture-curing polyurethane hot melt adhesive prepared by using the same. The polyester polyol provided by the invention is prepared by mixing and reacting the following components in parts by mass: A)100 parts by mass of one or more dicarboxylic acids and/or dicarboxylic acid esters; B) 1-90 parts by mass of dimer carboxylic acid; C) 10-500 parts by mass of one or more branched chain diols. Preferably, the component B is 5-60 parts by mass, and the component C is 30-300 parts by mass. The polyester provided by the invention can be used for preparing moisture-curing polyurethane hot melt adhesive for bonding low-surface-energy base materials, and the prepared hot melt adhesive can be applied to interlayer bonding of low-surface-energy base materials in wood and furniture industry, automobile manufacturing field, building industry, shoe manufacturing industry, packaging industry, textile industry and the like.
Description
Technical Field
The invention relates to the field of moisture-curing polyurethane hot melt adhesives, in particular to polyester polyol and a moisture-curing polyurethane hot melt adhesive prepared by using the same. The adhesive is suitable for bonding occasions with high requirements on low temperature resistance, flexibility and bonding force, in particular to bonding of low-surface-energy base materials.
Background
The moisture-curing polyurethane hot melt adhesive is prepared by taking a polyurethane prepolymer as a main material and adding various auxiliary agents (such as a catalyst, an antioxidant, a tackifier, a filler and the like). Because of containing isocyanate (-NCO) and carbamate (-NHCOO-) with strong polarity and high chemical activity, it has excellent chemical adhesive force with various materials. And the cohesion of the macromolecule can be increased by the hydrogen bond generated between the polyurethane and the bonded material, so that the bonding is firmer. The product can be widely applied to clothes, shoemaking, bags, handbags, clothing, medical treatment, military, toys, shoe material fabric lamination, silica gel breast pads, underwear auxiliary materials, waterproof zippers, trademark lamination, computer 3C products, water-filled bags, air-filled bags and foam composite products.
The dimer fatty acid is a product of natural oil and fat, and has the characteristics of low toxicity, wide source, renewability and the like. Because the dimer fatty acid contains two carboxyl groups and two larger nonpolar hydrocarbon groups, the high branching structure and the long carbon chain consisting of 36 carbon atoms ensure that the dimer fatty acid has non-crystallinity, high softness and super hydrophobicity. Can be used as an acid component in the preparation of polyester.
Although moisture-curing polyurethane hot melt adhesives have many advantages in performance, the adhesion between layers of low-surface-energy substrates is insufficient, and problems of poor wetting, poor bonding strength, even degumming and the like often occur. The defect causes the application of the moisture-curing polyurethane hot melt adhesive in the bonding of some low-surface-energy base materials, such as polyethylene, polypropylene, polyacrylate, silica gel and other materials, to be greatly limited.
In order to broaden the application effect of the moisture-curing polyurethane hot melt adhesive in low surface energy materials, technicians in the industry make various attempts and researches, and certain results are obtained.
Some very low surface tension materials, introduced into moisture-curing polyurethane hot melt adhesive systems by chemical or physical means, can improve wetting and increase adhesion of low surface energy substrates. CN104830222B introduces fluorine-containing monomer to improve the adhesion of the coating to low surface energy base material; CN102433062B introduces organosilicon modified acrylic resin, polydimethylsiloxane resin and nano silicon dioxide modified by fluorosilane to prepare the low surface energy antifouling paint; CN108251040A introduces hydroxyl-terminated organic silicone oil to react with isocyanate to prepare a moisture-curing polyurethane hot melt adhesive for bonding a low-surface-energy substrate; CN103059797B introduces dihydroxy silicone oil to prepare aqueous organosilicon modified polyurethane emulsion for adhering low surface energy base material; CN107207937A, a polyurethane adhesive for bonding low surface energy films is prepared by introducing polybutadiene structural polyol into a system; CN104830267B adopts water-based polybutadiene polyurethane emulsion to prepare an environment-friendly water-based adhesive suitable for a low surface tension film; CN104559814B prepares the light-cured adhesive by introducing a polybutadiene structure and a long aliphatic chain structure, and improves the affinity of the adhesive and a low-surface-energy substrate. The moisture-curing polyurethane adhesive prepared by introducing the structures of organic silicon, organic fluorine, polybutadiene and the like can be used for bonding low-surface-energy substrates, but the three substances have the limitation that the compatibility with polyester polyol, polyether polyol, isocyanate and the like is poor, so that the homogenization of the system becomes a difficult problem. In order to overcome the compatibility problem, technicians have to introduce efficient mixing equipment and compatible components, and meanwhile, the limited types of the three monomers also make the development of differential moisture-curing polyurethane hot melt adhesives difficult.
In order to solve the problem of bonding a low-surface-energy substrate and avoid the defects caused by pretreatment and introduction of organic silicon, organic fluorine and polybutadiene, a large number of exploration experiments are carried out, and the polyester polyol prepared by introducing a proper amount of dimer acid and selecting side-group-containing small-molecular polyol to carry out copolycondensation reaction is found to remarkably improve the bonding effect of the polyester polyol on the low-surface-energy substrate when the polyester polyol is used for a moisture-curing polyurethane hot melt adhesive. Both the incorporated dimerized fatty acid and the branched small molecule polyol are commercially available.
Disclosure of Invention
The object of the present invention is to develop a polyester polyol for moisture-curing polyurethane hotmelt adhesives, wherein low levels of dimer fatty acids and/or derivatives thereof are added to the polyester polyol, and the adhesion on low-surface-energy substrates is significantly increased by the moisture-curing polyurethane hotmelt adhesives prepared from the raw materials containing the polyester polyol.
Accordingly, in a first aspect, the present invention provides a polyester polyol for a moisture-curable polyurethane hot melt adhesive, prepared by reacting the following components: A)100 parts by mass of one or more dicarboxylic acids and/or dicarboxylic acid esters; B)1 to 90 parts by mass of a dimer carboxylic acid; C) 10-500 parts by mass of a polyol comprising one or more branched aliphatic diols; preferably, the component B) is 5-60 parts by mass, and the component C) is 30-300 parts by mass.
Further, the molar ratio of the polyhydric alcohol of component C) to the sum of components A) and B) is 1.01 to 2.00, preferably 1.05 to 1.6, and the weight proportion of the dimer carboxylic acid to the dibasic acid and/or the dicarboxylic ester is 1 to 90 wt%, preferably 5 to 25 wt%, more preferably 10 to 20 wt%.
The one or more dicarboxylic acids and/or dicarboxylic acid esters of component A) means that the carboxyl or ester group is located at the terminal carbon atom of the longest carbon chain, and is preferably a straight-chain aliphatic dicarboxylic acid.
Preferably, the component A dicarboxylic acid or dicarboxylic ester is a linear aliphatic carboxylic acid or carboxylic ester; the general structural formula is as follows: ROOC (CH)2)nCOOR, wherein n is an integer of 0-16, R is hydrogen, alkyl (preferably C1-C10 alkyl), phenyl. Preferably, n is 4, 8, 10, and R is hydrogen.
Specific examples of the dicarboxylic acid or dicarboxylic acid ester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof, further preferred are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof, particularly preferred are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, dodecanedioic acid, hexadecanedioic acid, dodecanedioic acid, and esters thereof, Pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof. Very particular preference is given to adipic acid, sebacic acid, dodecanedioic acid and esters thereof.
The structural general formula of the component B), namely dimer carboxylic acid is as follows:
wherein R is1、R2Is aliphatic alkane with 6-10 carbon atoms; r3、R4Is a fatty carbon chain of 6 to 18 carbon atoms and contains no more than 2 double bond functional groups (for example, 1 or 2 double bond functional groups). Preferably, the dimer carboxylic acid is unsaturated fatty acid with a cyclic structure formed by dimerizing oleic acid (9-octadecenoic acid) or linoleic acid (9, 12-octadecadienoic acid) and another molecule of unsaturated fatty acid, and can also be a hydrogenation product of dimer of oleic acid (9-octadecenoic acid) or linoleic acid (9, 12-octadecadienoic acid) and another molecule of unsaturated fatty acid; the unsaturated fatty acid can be one or more selected from oleic acid (9-octadecenoic acid), linoleic acid (9, 12-octadecenoic acid), conjugated linoleic acid (10, 12-octadecenoic acid), erucic acid (13-docosenoic acid), and nervonic acid (15-eicosatetraenoic acid). Namely R1Is C6H13、C7H15；R2Is C6H13、C7H13、C7H15、C8H17、C8H15；R3Is C7H14、C8H16；R4Is C8H14、C9H16、C11H22、C13H26. The weight proportion of the dimer carboxylic acid in the dibasic acid and/or the dibasic carboxylic ester is 1-90%. Further preferably, the dimer carboxylic acid is selected from hydrogenation products of bimolecular polymers of linoleic acid, and the weight proportion of the dimer carboxylic acid in the dibasic acid and/or the dibasic carboxylic acid ester is 5-25%.
In a further embodiment of the present invention, the dicarboxylic acid and/or dicarboxylic acid ester component may comprise, in part, one or more of cycloaliphatic diacids, aromatic diacids or anhydrides, heterocyclic diacids in addition to the linear aliphatic diacids. The content of one or more of alicyclic, aromatic dibasic acid or anhydride and heterocyclic dibasic acid is 0-50 wt%, preferably 0-30 wt%, and especially preferably 0-10 wt% of the dicarboxylic acid and/or dicarboxylic acid ester component. In a particularly preferred embodiment, no cycloaliphatic diacid, aromatic polyacid or anhydride, heterocyclic diacid is present.
An example of a cycloaliphatic diacid is 1, 4-cyclohexanedicarboxylic acid (CHDA). Examples of aromatic dibasic acids or anhydrides are terephthalic acid (TPA), isophthalic acid (IPA), Phthalic Anhydride (PA), naphthalene dicarboxylic acid. An example of a heterocyclic diacid is 2, 5-Furandicarboxylic Acid (FA).
The C) component one or more aliphatic diols with a branched chain structure have the following molecular structure:
wherein: m is an integer of 0 to 16;
R1、R2、R3、R4each independently hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl.
Examples of the dihydric alcohol having a branched structure of the present invention are 1, 2-propanediol, 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, dipropylene glycol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 3-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 2-pentanediol, neopentyl glycol hydroxypivalate, 2-ethyl-3-propyl-1, 3-propanediol, preferably 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 3-butanediol, 1, 2-pentanediol, further preferably 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, and most preferably 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol.
The hydroxyl value of the polyester prepared by the component A, B, C and/or some optional components is 10-225 mgKOH/g, preferably 10-110 mgKOH/g, and more preferably 10-60 mgKOH/g.
The melting point of the polyester is-30-35 ℃, and the preferable melting point is-20-18 ℃. Methods for the preparation of polyester polyols are well known in the art.
In a further embodiment according to the invention, component C) may comprise, in addition to the branched diols, unbranched aliphatic polyols, preferably diols. The proportion of unbranched polyols based on the total weight of component C) is from 0% to 90%, preferably from 0% to 50%, particularly preferably from 0% to 30%.
Examples of the unbranched aliphatic polyhydric alcohol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, and dodecanediol, and preferably ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and more preferably 1, 4-butanediol, and 1, 6-hexanediol.
In another embodiment according to the present invention, component C) may include cycloaliphatic diols and/or aromatic diols in addition to branched diols. The proportion of cycloaliphatic and/or aromatic diols based on the total weight of component C) is from 0% to 50%, preferably from 0% to 20%, particularly preferably from 0% to 10%.
Examples of the alicyclic diol include 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol and dodecanediol. Examples of the aromatic diols include hydroquinone dihydroxyethyl ether, resorcinol dihydroxypropyl ethyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether, 3-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether, dihydroxyethyl bisphenol A, and bisphenol A dihydroxypropyl ether.
The invention further provides a preparation method of the polyester. The polyesters of the present invention may be prepared by condensation reaction techniques well known in the art. The charging ratio of the polyhydric alcohol and polybasic acid and/or derivative thereof (including A) one or more dicarboxylic acid and/or dicarboxylic ester and B) dimer carboxylic acid) of the reaction is 1.01 to 2.00, preferably 1.05 to 1.6, by mole ratio. The condensation reaction is divided into two stages, the components A), B) and C) in the first stage react at 140-160 ℃ to distill a large amount of by-product water, and the temperature of the rectifying tower is kept not higher than 102 ℃ in the first stage, and the reaction time is 1-5 hours; in the second stage, the temperature is increased to 200-250 ℃ for continuous reaction for 2-20 h; starting a vacuum system (for example, increasing the vacuum degree to 0.09MPa within 1-3 h), and continuing to react for 3-30 h until the hydroxyl value and the acid value reach the design values. Cooling and discharging to obtain the polyester. Optionally, the catalyst for the reaction is organotin and/or organotitanium. Examples of the organotin catalysts include monobutyltin oxide, dibutyltin oxide, stannous octoate and dibutyltin dilaurate, and examples of the organotin catalysts include tetraisopropyl titanate and tetra-n-butyl titanate. The catalyst is generally added before the evacuation.
Another aspect of the present invention is a moisture-curable polyurethane hot melt adhesive prepared by further reacting the above-mentioned polyester polyol with an isocyanate and/or a polyisocyanate. The molar ratio of OH to NCO of the polyester polyol to the isocyanate and/or polyisocyanate in the moisture-curing polyurethane hotmelt is from 1:1.2 to 1:3, preferably from 1:2.2 to 1: 2.5.
The polyisocyanate may be one or more of a difunctional and/or polyfunctional aromatic, aliphatic and/or cycloaliphatic isocyanate. Aromatic polyisocyanates are particularly preferred. Examples of polyisocyanates are one or more of 1, 5-Naphthalene Diisocyanate (NDI), 4 '-diphenylmethane diisocyanate (MDI), 2, 4' -diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (HMDI), Toluene Diisocyanate Isomers (TDI), isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI). More particularly, the compounds are 4, 4 ' -diphenylmethane diisocyanate and mixtures of 4, 4 ' -diphenylmethane diisocyanate and 2, 4 ' -diphenylmethane diisocyanate.
In the moisture-curing polyurethane hot melt adhesive, the polyester content of the invention is 50 wt% to 99 wt%, preferably 60 wt% to 98 wt%, and more preferably 70 wt% to 95 wt%.
In a preferred embodiment, in addition to the polyester polyols of the invention, further polyols, including, for example, one or more of polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, are present in the moisture-curing polyurethane hotmelt adhesives, the mass ratio of the polyester polyols of the invention to the further polyols may be from 1: 0.5 to 2, preferably without further polyols.
The polyester polyols other than the polyester polyols according to the invention can be liquid and/or solid, amorphous and/or partially crystalline polyesters of any structure, having a molecular weight of from 1000g/mol to 20000g/mol, preferably from 2000g/mol to 10000g/mol, calculated from the hydroxyl number, acid number, functionality of the polyester, the preferred structure being linear. The polyether polyol is a polyether diol and/or polyether triol and the initiators are, for example, ethylene glycol, glycerol, trimethylolpropane, having a molecular weight of from 200g/mol to 8000g/mol, preferably from 400g/mol to 6000g/mol, calculated from the hydroxyl value, acid value, functionality of the polyether polyol. The polycaprolactone polyol can be any initiator, examples of which are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, trimethylolpropane, with a molecular weight calculated from the hydroxyl number, acid number, functionality of the polycaprolactone polyol, of 500g/mol to 10000g/mol, preferably 1000g/mol to 6000 g/mol. The polycarbonate polyols can be any starter, examples of which are 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, cyclohexanedimethanol or mixtures thereof, having a molecular weight of 1000 to 10000g/mol, preferably 1000 to 2000g/mol, calculated from the hydroxyl number, acid number of the polycarbonate polyol.
The moisture-curing polyurethane hotmelt adhesives of the invention may contain up to 50% by weight of further additives. These additives may be as follows: non-functionalized polymers serve as tackifying agents, such as Thermoplastic Polyurethanes (TPU) and/or polyacrylates and/or ethylene-vinyl acetate copolymers (EVA); pigments and/or fillers, such as talc, silica, titanium dioxide, barium sulfate, calcium carbonate, carbon black or colored pigments; tackifiers such as rosin, terpene resins and phenolic resins, and antioxidants and auxiliaries.
The acid number of the polyester polyol was determined according to HGT 2708-1995, and the sample was titrated to pink by potassium hydroxide after dissolution, calculated according to the following formula:
in the formula, Av: acid value, mg KOH/g
V1: titration sample consumed volume of KOH-ethanol standard titration solution, mL
V2: titration blank consumes volume, mL, of potassium hydroxide ethanol standard titration solution
c: concentration of potassium hydroxide ethanol standard titration solution, mol/L
m: quality of sample
56.10: molar mass of potassium hydroxide.
The hydroxyl value of polyester polyol is determined according to HG/T2709-1995 acetic anhydride-pyridine method, and the specific process is that a proper amount of sample is accurately weighed and placed in a conical flask, acetic anhydride pyridine solution is added to completely dissolve the sample, and the sample is placed in an oil bath for reflux reaction. Phenolphthalein was then added overnight and titrated to a pink color with a standard titration solution of potassium hydroxide in ethanol to remain fadeless for thirty seconds. And simultaneously, carrying out a blank experiment. Calculated as follows:
in the formula, OHV: hydroxyl value, mgKOH/g
And Av: acid value of sample, mg KOH/g
V1: amount of ethanol standard solution of potassium hydroxide in blank test, mL
V2: the amount of the standard solution of potassium hydroxide and ethanol in the titration of the sample is mL
c: concentration of potassium hydroxide ethanol standard titration solution, mol/L
m: quality of sample
56.10: molar mass of potassium hydroxide.
The hydroxyl number of the polyether polyol is determined according to GB/T12008.3-2009, the acid number of the polyether polyol is determined according to GB/T12008.5-2009, and the isocyanate (NCO) content is tested according to HG/T2409-1992.
Melting point was measured by Differential Scanning Calorimetry (DSC), temperature rise rate of 20K/min, and endothermic peak temperature of the second temperature rise.
The invention further provides a preparation method of the moisture-curing polyurethane hot melt adhesive, which comprises the following steps: the polyester polyol and optionally other polyols of the present invention are reacted with polyisocyanate under an inert atmosphere (e.g. under nitrogen protection) at a temperature of 120 to 140 ℃ to completion, and then vacuum defoamed. The reaction time may be 1 to 3 hours.
The invention also provides the application of the moisture-curing polyurethane hot melt adhesive for bonding low-surface-energy substrates.
The moisture-curing polyurethane hot melt adhesive is suitable for bonding various substrates and is particularly suitable for bonding low-surface-energy substrates, such as polyethylene, polypropylene, nylon and polyethylene terephthalate.
The low surface energy substrate has a surface energy of less than 38dyn/cm, preferably 28 to 38 dyn/cm.
The adhesive strength was determined by GBT 7122.
THE ADVANTAGES OF THE PRESENT INVENTION
The moisture-curing polyurethane hot melt adhesive for bonding the low-surface-energy base material prepared by using the polyester polyol can be applied to interlayer bonding containing the low-surface-energy base material in the wood and furniture industry, the automobile manufacturing field, the building industry, the shoe manufacturing industry, the packaging industry, the textile industry and the like.
The invention is further illustrated, but not limited, by the following examples.
Detailed Description
Detailed description of the preferred embodiment a
Adipic acid, dimer carboxylic acid, ethylene glycol, and 1, 2-propanediol were charged into a 5L stainless steel reactor equipped with a heating jacket, stirring, nitrogen stripping, a rectifying column, a vacuum gauge, and a recovered alcohol tank. Heating to 145 ℃ to melt, starting the reaction to distill the by-product water, and keeping the temperature for 1 hour. The temperature was further raised for 3 hours to 250 ℃. Keeping the temperature at 250 ℃ for 1 hour, gradually slowing the reaction water outlet, adding tetrabutyl titanate, increasing the vacuum degree to 0.09MPa within 1 hour, continuing the reaction, sampling, monitoring, and stopping the reaction when the acid value is lower than 1.5mgKOH/g and the hydroxyl value meets the requirement.
Preparation and testing of moisture-curing polyurethane Hot melt adhesive
Example PUR-1
Melting 50 parts by weight of the mixture in a 2L stainless steel reaction kettle
AD1204 (polyol available from Wawa chemical), 50 parts by weight of polyester OH-1, was dried at 120 ℃ under a vacuum of 0.09MPa for 3 hours. Subsequently, the NCO/OH molar ratio 2.2/1.0 is added4, 4' -diphenylmethane diisocyanate (MDI) preheated to 60 ℃ is added and stirred rapidly and uniformly. And continuously reacting for 1-3 h at 130 ℃ under the protection of nitrogen to reach the reaction end point. Finally, vacuumizing, defoaming, discharging and packaging. The moisture-curing polyurethane hot melt adhesive obtained had a melt viscosity (130 ℃) of 6 pas. The adhesive strength to polyethylene after curing at 25 ℃ and 65% relative humidity for seven days was 7N/mm2The adhesive strength to polypropylene was 8N/mm2The adhesive strength to polyamide was 6N/mm2。
Comparative example PUR-2
Melting 50 parts by weight of the mixture in a 2L stainless steel reaction kettle
AD1204 (a product of Wanhua Chemicals, commercially available), 50 parts by weight of polyester OH-a, dried at 120 ℃ under a vacuum of 0.09MPa for 3 hours. Subsequently, 4' -diphenylmethane diisocyanate (MDI, Vanhua Chemicals) preheated to 60 ℃ was added in an NCO/OH molar ratio of 2.2/1.0
MDI-100) and stirred rapidly. And continuously reacting for 1-3 h at 130 ℃ under the protection of nitrogen to reach the reaction end point. Finally, vacuumizing, defoaming, discharging and packaging. The moisture-curing polyurethane hot melt adhesive obtained had a melt viscosity (130 ℃) of 8 pas. The adhesive strength to polyethylene after curing at 25 ℃ and 65% relative humidity for seven days was 4N/mm2The adhesive strength to polypropylene was 3N/mm2The adhesive strength to polyamide was 4N/mm2。
The adhesion strength data of the two examples PUR-1, PUR-2 indicated that the adhesion of moisture-curing polyurethane hotmelts to low-surface-energy substrates (polyethylene, polypropylene, polyamide) was greatly improved when the polyesters according to the invention were used.
Examples PUR-3 to PUR-13
According to the composition shown in Table 2, the same procedure as that of inventive example 1 PUR-1 was conducted.
Claims (10)
1. The polyester polyol for the moisture-curing polyurethane hot melt adhesive is prepared by the following reaction components: A)100 parts by mass of one or more dicarboxylic acids and/or dicarboxylic acid esters; B)1 to 90 parts by mass of a dimer carboxylic acid; C) 10-500 parts by mass of a polyol comprising one or more branched aliphatic diols; preferably, the component B) is 5-60 parts by mass, and the component C) is 30-300 parts by mass.
2. The polyester polyol according to claim 1, wherein the molar ratio of the polyol of component C) to the sum of components A) and B) is from 1.01 to 2.00, preferably from 1.05 to 1.6, and the weight proportion of dimer carboxylic acid B) to the diacid and/or dicarboxylic ester A) is from 1 to 90 wt.%, preferably from 5 to 25 wt.%.
3. The polyester polyol according to claim 1 or 2, wherein the component dicarboxylic acid or dicarboxylic ester of a) is a linear aliphatic carboxylic acid or carboxylic ester; the general structural formula is as follows: ROOC (CH)2)nCOOR, wherein n is an integer of 0-16, R is hydrogen, alkyl (preferably C1-C10 alkyl) and phenyl, preferably, n is 4, 8 or 10, and R is hydrogen;
preferably, the component dicarboxylic acid or dicarboxylic acid ester of A) is selected from one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof, further preferably from one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof, particularly preferably from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and esters thereof, One or more of tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanedioic acid, octadecanedioic acid and esters thereof.
4. The polyester polyol according to claim 1 or 2, wherein the component B), dimer carboxylic acid, has the following general structural formula:
wherein R is1、R2Is aliphatic alkane with 6-10 carbon atoms; r3、R4A fatty carbon chain of 6 to 18 carbon atoms and containing no more than 2 double bond functional groups;
preferably, the dimer carboxylic acid is unsaturated fatty acid with a cyclic structure formed by dimerizing oleic acid (9-octadecenoic acid) or linoleic acid (9, 12-octadecadienoic acid) with another molecule of unsaturated fatty acid, or is a dimer hydrogenation product of oleic acid (9-octadecenoic acid) or linoleic acid (9, 12-octadecadienoic acid) with another molecule of unsaturated fatty acid; the other unsaturated fatty acid is one or more selected from oleic acid (9-octadecenoic acid), linoleic acid (9, 12-octadecenoic acid), conjugated linoleic acid (10, 12-octadecenoic acid), erucic acid (13-docosenoic acid), and nervonic acid (15-eicosatetraenoic acid).
5. The polyester polyol according to any one of claims 1 to 4, wherein the C) component one or more aliphatic diols having a branched structure have the following molecular structure:
wherein: m is an integer of 0 to 16;
R1、R2、R3、R4each independently hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl;
preferably, the aliphatic diol having a branched structure is one or more selected from the group consisting of 1, 2-propanediol, 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, dipropylene glycol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 3-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 2-pentanediol, neopentyl glycol hydroxypivalate, 2-ethyl-3-propyl-1, 3-propanediol, preferably 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, and the like, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 2, 3-butanediol, 1, 2-pentanediol, more preferably 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, and most preferably one or more of 2-methyl-propanediol, 3-methyl-1, 5-pentanediol, and neopentyl glycol.
6. The polyester polyol according to any one of claims 1 to 5, wherein the polyester polyol has a hydroxyl value of 10 to 225mg KOH/g and an acid value of 0 to 5mg KOH/g; preferably, the hydroxyl value is 10-110 mg KOH/g, and the acid value is 0-3 mg KOH/g; further preferably, the hydroxyl value is 10-60 mg KOH/g, and the acid value is 0.1-1 mg KOH/g; the melting point of the polyester is-30-35 ℃. Preferably, the melting point of the polyester is-20-18 ℃.
7. The method for preparing polyester polyol according to any one of claims 1 to 6, which is prepared by a two-stage condensation reaction, wherein the first stage components A), B) and C) react at 140 to 160 ℃ to largely distill off by-product water, and the temperature of a rectifying tower is kept at not higher than 102 ℃ for 1 to 5 hours; in the second stage, the temperature is increased to 200-250 ℃ for continuous reaction for 2-20 h; and starting a vacuum system, and continuing to react for 3-30 hours until the hydroxyl value and the acid value reach the design values.
8. Moisture-curing polyurethane hot melt adhesive prepared by further reacting the polyester polyol of any one of claims 1 to 7 with an isocyanate and/or a polyisocyanate, wherein the molar ratio of OH to NCO of the polyester polyol and the isocyanate and/or the polyisocyanate is 1:1.2 to 1:3, preferably 1:2.2 to 1: 2.5.
9. The moisture-curing polyurethane hot melt adhesive according to claim 8, wherein the polyisocyanate is one or more of difunctional and/or polyfunctional aromatic, aliphatic and/or cycloaliphatic isocyanates, preferably aromatic polyisocyanates, more preferably 1, 5-Naphthalene Diisocyanate (NDI), 4 ' -diphenylmethane diisocyanate (MDI), 2, 4 ' -diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (HMDI), Tolylene Diisocyanate Isomers (TDI), isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), particularly preferably 4, 4 ' -diphenylmethane diisocyanate and 4, a mixture of 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate.
10. Use of the moisture-curing polyurethane hotmelt adhesives as claimed in claim 8 or 9 for bonding low-surface-energy substrates.
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| CN111471165A (en) * | 2020-06-03 | 2020-07-31 | 星贝达（上海）化工材料有限公司 | Polyester polyol for polyester engineering plastics and preparation method thereof |
| CN112694860A (en) * | 2020-12-21 | 2021-04-23 | 广州市白云化工实业有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN113249079A (en) * | 2021-05-28 | 2021-08-13 | 广东盛业化学科技有限公司 | Moisture-curing polyurethane hot melt adhesive composition and preparation method thereof |
| CN114672275A (en) * | 2022-04-29 | 2022-06-28 | 福建奥翔体育塑胶科技股份有限公司 | Single-component moisture-curing polyurethane adhesive and preparation method and application thereof |
| CN115073715A (en) * | 2021-10-22 | 2022-09-20 | 上海联景高分子材料有限公司 | Polyester polyol for adhesive, and preparation method and application thereof |
| CN115851213A (en) * | 2022-12-26 | 2023-03-28 | 广州市白云化工实业有限公司 | Reactive polyurethane hot melt adhesive for nitrile rubber bonding and preparation method thereof |
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| CN115851213A (en) * | 2022-12-26 | 2023-03-28 | 广州市白云化工实业有限公司 | Reactive polyurethane hot melt adhesive for nitrile rubber bonding and preparation method thereof |
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