CN114958275A - PU adhesive for fabric bonding and preparation method thereof - Google Patents
PU adhesive for fabric bonding and preparation method thereof Download PDFInfo
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- CN114958275A CN114958275A CN202210750103.4A CN202210750103A CN114958275A CN 114958275 A CN114958275 A CN 114958275A CN 202210750103 A CN202210750103 A CN 202210750103A CN 114958275 A CN114958275 A CN 114958275A
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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
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether 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
- 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
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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
- C08G18/61—Polysiloxanes
Abstract
The invention belongs to the field of adhesives, and particularly relates to a PU adhesive for fabric bonding and a preparation method thereof. The PU adhesive for fabric bonding comprises polyether ester polyol, polyether modified hydroxyl-terminated silicone oil and an isocyanate compound in a mass ratio of (3-15): (1-6): 0.05-2): 1, wherein a polyether ester chain segment in the polyether ester polyol has a structure shown in a formula (I), and the polyether modified hydroxyl-terminated silicone oil has a structure shown in a formula (II). The PU adhesive for adhering the fabrics provided by the invention has good moisture absorption, ventilation, flexibility, water resistance, aging resistance and resilience. Meanwhile, the glue is uniformly dispensed, the glue dispensing smoothness is good, the phenomena of unsmooth glue dispensing and glue breaking in the glue dispensing process can be well avoided, the glue can be compounded with fabrics such as knitted fabrics, plain woven fabrics and non-woven fabrics to be made into various fabrics or linings, the appearance of a fabric laminated product is not influenced after curing, and the glue dispensing device has an industrial application prospect.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a PU adhesive for fabric bonding and a preparation method thereof.
Background
In the 70 s of the 20 th century, the adhesive is applied to industries such as European and American printing, clothing, shoemaking, furniture and the like. The adhesive for fabric attachment is researched from the 20 th century and the 70 th century in China, and after the development of 30 years, the adhesive for fabric attachment which is industrially produced at present mainly comprises hot melt adhesives (such as polyethylenes, ethylene-vinyl acetate copolymers, copolyesters, polyamides and polyurethanes), solvent adhesives, emulsion adhesives and the like, and is mainly used in the aspect of lining cloth of clothes and various functional after-finishing and printing processes of clothes fabrics.
Along with the improvement of the daily living standard of people, the requirements of people on various properties of clothes are higher and higher, the application of the adhesive on the clothes is wider and wider, and even the adhesive is generally used on the original occasions without the adhesive. Because the fabric is mostly in direct contact with human body, the environmental protection and high-quality performance (including moisture absorption, air permeability, softness, hanging property, rigidity, resilience, wrinkle resistance and the like) of the adhesive for adhering the fabric are attracting more and more attention. The prior adhesives for textiles comprise solvent adhesives, emulsion adhesives, polyethylene hot melt adhesives, ethylene-vinyl acetate copolymer hot melt adhesives, copolyester hot melt adhesives, copolyamide hot melt adhesives and polyurethane hot melt adhesives. Wherein, the VOC content of the solvent glue and the emulsion glue is higher, and the environmental protection is poor. Polyethylene hot melt adhesives are relatively hard and have poor hand feel. Ethylene-vinyl acetate copolymer hot melt adhesives and copolyamide hot melt adhesives are poor in water washing resistance and dry cleaning resistance. Copolyester hot melt adhesives have high melt viscosity and poor dry cleaning resistance. The traditional polyurethane hot melt adhesive has high bonding strength, but has poor water resistance, aging resistance, moisture absorption, ventilation and rebound resilience.
In order to endow polyurethane hot melt adhesives with better moisture absorption, ventilation, flexibility, water resistance, aging resistance and rebound elasticity, the polyurethane hot melt adhesives can be modified by organosilicon. For example, CN103755919A discloses a method for preparing silicone modified polyurethane microspheres, which comprises using isocyanate, hydroxy silicone oil, polyether polyol and dimethylol propionic acid as raw materials, reacting isocyanate and hydroxy silicone oil under the action of a catalyst, reacting the obtained reaction product with polyether polyol and isocyanate, continuing to react with dimethylol propionic acid, neutralizing with triethylamine after the reaction is finished to obtain polyurethane prepolymer, cooling the obtained polyurethane prepolymer, emulsifying with an emulsifier, press-filtering, dehydrating and drying to obtain the silicone modified polyurethane microspheres. Wherein, the polyether polyol adopts polytetrahydrofuran diol and/or polypropylene oxide diol. The hydroxyl silicone oil has a structure shown in a formula (IV), contains a large amount of hydroxyl, has high functionality, and has high crosslinking degree in the reaction process, and the molecular structure end of the finally obtained polyurethane microsphere is terminated with-OH. For another example, CN108822278A discloses a synthesis method of organosilicon modified polyurethane, wherein the adopted raw materials comprise 1 to 20 parts by weight of hydrogen-terminated silicone oil, 20 to 30 parts by weight of vinyl polyether, 30 to 70 parts by weight of isocyanate, 5 to 25 parts by weight of oligomeric diol, 1 to 10 parts by weight of dimethylolpropionic acid chain extender, 1 to 5 parts by weight of triethylamine neutralizer and 5 to 15 parts by weight of capping agent, and the method comprises the following steps: (1) adding hydrogen-terminated silicone oil and vinyl polyether into a reactor, uniformly stirring, heating to 50-90 ℃, adding a catalyst, and continuously stirring for 1-3 hours to obtain a first intermediate; (2) heating the first intermediate to 60-80 ℃, adding isocyanate, a dimethylolpropionic acid chain extender and a triethylamine neutralizer, and reacting for 2-6 hours to obtain a second intermediate; (3) and heating the second intermediate to 60-80 ℃, and dropwise adding an end-capping reagent for reacting for 3-7 h to obtain the organic silicon modified polyurethane. Wherein the structure of the terminal hydrogen-containing silicone oil is shown as a formula (V).
However, because of the poor compatibility of the silicone segment and the polyurethane segment, the addition amount of silicone in the polyurethane hot melt adhesive is generally not high. Although the flexibility, water resistance and aging resistance of the existing organic silicon modified polyurethane hot melt adhesive are improved due to the introduction of organic silicon, the thixotropy of the adhesive is high due to poor compatibility, and in addition, the viscosity of the fabric adhesive is very high (the phenomenon that the fabric is oozed out after the adhesive is dispensed is prevented), so that the adhesive breaking phenomenon is easily caused during the adhesive dispensing, and the adhesive dispensing smoothness and the appearance flatness after the adhesive is attached are influenced.
Disclosure of Invention
The polyether modified hydroxyl-terminated silicone oil modified PU adhesive overcomes the defects of poor ventilation, poor flexibility, poor water resistance, poor rebound resilience and the like of the existing polyurethane adhesive. Meanwhile, the defects that thixotropy and unsmooth dispensing are influenced due to poor compatibility of the organic silicon modified polyurethane hot melt adhesive are overcome by the independently designed polyether ester polyol, and the PU adhesive for fabric attachment and the preparation method thereof are provided, wherein the PU adhesive has the advantages of air permeability, good flexibility, aging resistance, good thixotropy and good dispensing smoothness.
After intensive and extensive research, the inventor of the invention finds that the polyether ester polyol with the structure shown in the following formula (I) has good compatibility with polyether polyol with high molecular weight, and also has excellent bonding performance, and the polyether modified hydroxyl-terminated silicone oil with the structure shown in the following formula (II) has very good compatibility with PU. Based on this, the present invention has been completed.
Specifically, the invention provides a PU adhesive for fabric bonding, wherein the PU adhesive for fabric bonding contains polyether ester polyol, polyether modified hydroxyl-terminated silicone oil and an isocyanate compound in a mass ratio of (3-15): (1-6): 0.05-2): 1, a polyether ester chain segment in the polyether ester polyol has a structure shown in a formula (I), and the polyether modified hydroxyl-terminated silicone oil has a structure shown in a formula (II):
in the formula (I), R 1 And R 2 Each independently is a hydrogen atom or a methyl group, n is a positive integer of 5 to 15, x is a positive integer of 1 to 8, y is a positive integer of 1 to 8, and z is a positive integer of 1 to 6;
in the formula (II), a and b are respectively and independently positive integers of 1-5, m is a positive integer more than 5, R is C 1 -C 12 Alkylene or C 1 -C 12 Alkoxy group of (2).
In a preferred embodiment, the polyetherester polyol is synthesized by polymerization of adipic acid, a small molecule polyol which is ethylene glycol and/or 1, 4-butanediol, and a short-chain polyether polyol having a structure represented by formula (iii):
in the formula (III), R 1 And R 2 Each independently is a hydrogen atom or a methyl group, and n is a positive integer of 5 to 15.
In a preferred embodiment, the polyether ester polyol is contained in an amount of 50 to 75 parts by weight, the polyether polyol is contained in an amount of 10 to 30 parts by weight, the polyether-modified hydroxyl-terminated silicone oil is contained in an amount of 1 to 10 parts by weight, and the isocyanate compound is contained in an amount of 5 to 15 parts by weight.
In a preferred embodiment, the polyetherester polyol has a number average molecular weight of 1000 to 3000 and a functionality of 2.
In a preferred embodiment, the number average molecular weight of the polyether modified hydroxyl-terminated silicone oil is 500-2000.
In a preferred embodiment, the polyether polyol is selected from at least one of a polyoxyethylene polyol, a polyoxypropylene-oxyethylene copolyether polyol, and polytetrahydrofuran.
In a preferred embodiment, the isocyanate compound is an aromatic cyanate ester compound and/or an aliphatic isocyanate compound.
In a preferred embodiment, the PU adhesive for fabric attachment further contains an antioxidant.
In a preferred embodiment, the antioxidant is contained in an amount of 0.01 to 1 part by weight.
The invention also provides a preparation method of the PU adhesive for fabric bonding, wherein the method comprises the step of preparing the polyether ester polyol, the polyether modified hydroxyl-terminated silicone oil, the isocyanate compound and the optional antioxidant through polymerization reaction.
In a preferred embodiment, the polymerization reaction is carried out by adding the polyether ester polyol, the polyether modified hydroxyl-terminated silicone oil and the optional antioxidant into a reaction kettle, heating to 110-130 ℃, stirring in vacuum for 2-3 hours, cooling to 70-90 ℃, adding the isocyanate compound, stirring in vacuum for 1-10 minutes, heating to 110-130 ℃, and continuing stirring in vacuum for 0.5-2 hours.
The key point of the invention is that polyether ester polyol with a specific structure and polyether modified hydroxyl-terminated silicone oil are introduced into the PU adhesive, so that the obtained PU adhesive for bonding the fabrics has very good thixotropic property, is in a milk white solid state at room temperature, can be coated and dispensed by heating and melting, is colorless and transparent after being cooled and solidified, is not sticky, has very good dispensing uniformity, can well avoid the phenomena of unsmooth and glue breaking in the dispensing process, can be compounded with fabrics such as knitted fabrics, plain woven fabrics, non-woven fabrics and the like to be made into various fabrics or linings, does not influence the appearance of the bonded fabrics after being solidified, and has great industrial application prospect.
Detailed Description
The PU adhesive for fabric bonding provided by the invention contains polyether ester polyol, polyether modified hydroxyl-terminated silicone oil, an isocyanate compound and an optional antioxidant. Wherein the mass ratio of the polyether ester polyol, the polyether modified hydroxyl-terminated silicone oil, the antioxidant and the isocyanate compound is (3-15): 1-6): 0.05-2): 0-0.2): 1. The polyether ester polyol is used in an amount of 3-15 parts by weight, such as 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by weight, based on 1 part by weight of isocyanate; the content of the polyether polyol is 1-6 parts by weight, such as 1, 2, 3, 4, 5, 6 parts by weight and the like; the content of the polyether modified hydroxyl-terminated silicone oil is 0.05-2 parts by weight, such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 parts by weight and the like; the content of the antioxidant is 0-0.2 weight parts, such as 0, 0.02, 0.05, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2 weight parts and the like. In a particularly preferred embodiment, the polyether ester polyol is contained in an amount of 50 to 75 parts by weight, the polyether polyol is contained in an amount of 10 to 30 parts by weight, the polyether modified hydroxyl-terminated silicone oil is contained in an amount of 1 to 10 parts by weight, the isocyanate compound is contained in an amount of 5 to 15 parts by weight, and the antioxidant is contained in an amount of 0 to 1 part by weight, and thus the PU adhesive for fabric attachment is more excellent in overall performance.
In the present invention, the polyether ester segment in the polyether ester polyol has a structure represented by formula (i):
in the formula (I), R 1 And R 2 Each independently is a hydrogen atom or a methyl group, n is a positive integer of 5 to 15, x is a positive integer of 1 to 8, y is a positive integer of 1 to 8, and z is a positive integer of 1 to 6.
In one specific embodiment, the polyether ester polyol is synthesized by polymerization reaction of adipic acid, small molecule polyol and short chain polyether polyol, wherein the small molecule polyol is ethylene glycol and/or 1,4 butanediol, and the short chain polyether polyol has a structure shown in a formula (III), R in the formula (III) 1 And R 2 Each independently is a hydrogen atom or a methyl group, and n is a positive integer of 5 to 15. Wherein the adipic acid, the small molecule polyol and the short chain polyether polyol are used in such amounts that the content of each structural unit is controlled within the range defined by the formula (I), for example, the weight ratio of the adipic acid, the small molecule polyol and the short chain polyether polyol may be1:(0.2-0.8):(0.2-0.8). In addition, the polymerization reaction generally needs to be carried out in the presence of a catalyst and under the protection of an inert gas. The catalyst may be tetrabutyl titanate, for example. The inert gas may be, for example, at least one of nitrogen, argon, and a group zero element gas. The polymerization reaction conditions include that the reaction temperature can be 90-150 ℃, and the reaction time can be 8-15 hours.
In addition, the number average molecular weight of the polyether ester polyol is preferably 1000-3000, and the functionality is preferably 2.
In the invention, the polyether modified hydroxyl-terminated silicone oil has a structure shown in a formula (II):
in the formula (II), a and b are respectively and independently positive integers of 1-5; n is a positive integer greater than 5; preferably a positive integer of 5 to 20; r is C 1 -C 12 Alkylene or C 1 -C 12 Alkoxy group of (2).
In the present invention, the polyether-modified hydroxyl-terminated silicone oil is commercially available, and specific examples thereof include, but are not limited to: at least one of the belief X-22-4952, X-22-4272 and KF 6123.
In addition, the number average molecular weight of the polyether modified hydroxyl-terminated silicone oil is preferably 500-2000, and more preferably 800-1600.
The PU adhesive for fabric bonding provided by the invention takes polyurethane as matrix resin, takes polyether modified hydroxyl-terminated silicone oil as a modifier, introduces an organic silicon chain segment into the polyurethane chain segment through polymerization, greatly improves the compatibility of a system by utilizing polyether ester polyol and the polyether modified hydroxyl-terminated silicone oil while not reducing the bonding strength of the adhesive, so that the obtained PU adhesive for fabric bonding has higher viscosity in a standing state, has smaller viscosity when being sheared, has good thixotropic property and very good dispensing uniformity, and can well avoid the phenomena of unsmooth and glue breaking in the dispensing process.
In the present invention, the polyether polyol is preferably a difunctional polyether polyol and/or a trifunctional polyether polyol, and is specifically obtained by ring-opening polymerization using a polyhydroxy small molecule compound (such as 1, 4-butanediol, bisphenol a, glycerin, etc.) as an initiator and an epoxy compound (such as ethylene oxide, propylene oxide, tetrahydrofuran compounds, etc.) as a polymerization monomer, and specific examples thereof include, but are not limited to: at least one of polyoxyethylene polyol, polyoxypropylene-oxyethylene copolyether polyol and polytetrahydrofuran. Further, the polyether polyol preferably has a number average molecular weight of 2000 to 4000, and specific examples thereof include, but are not limited to: voranol 2000LM, Voranol 2120, Voranol 4000LM and Voranol 4240 of Dow, USA.
In the present invention, the isocyanate compound is a compound having two or more isocyanate groups at the molecular chain terminal, and may be an aromatic cyanate compound and/or an aliphatic isocyanate compound, and specific examples thereof include, but are not limited to: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4 ' -diisocyanate, hydrogenated diphenylmethane-4, 4 ' -diisocyanate, polymeric diphenylmethane-4, 4 ' -diisocyanate, 1, 5-naphthalene diisocyanate, at least one of norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
In the present invention, the antioxidant may be at least one of an antioxidant commercially available from Ciba of Switzerland under the trademark Irganox 1520, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), 2, 6-di-tert-butyl-p-cresol, tert-butyl catechol, and 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol).
The preparation method of the PU adhesive for fabric attachment provided by the invention comprises the steps of preparing the polyether ester polyol, the polyether modified hydroxyl-terminated silicone oil, the isocyanate compound and the optional antioxidant through polymerization reaction. The polymerization reaction mode is not particularly limited, and preferably comprises the steps of adding polyether ester polyol, polyether modified hydroxyl-terminated silicone oil and an optional antioxidant into a reaction kettle, heating to 110-130 ℃, stirring in vacuum for 2-3 hours, cooling to 70-90 ℃, adding an isocyanate compound, stirring in vacuum for 1-10 minutes, heating to 110-130 ℃, and continuing stirring in vacuum for 0.5-2 hours. The polymerization reaction is carried out in the preferable mode, the whole process is carried out in a vacuum state, the influence of the external environment on the preparation process can be avoided, the active components are effectively protected, and the PU adhesive for bonding the finished fabrics has better storage stability.
The present invention will be described in detail below by way of examples. The examples of embodiments are intended to be illustrative of the invention and are not to be construed as limiting the invention. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Preparation example 1 preparation of polyether ester polyol
Adipic acid, ethylene glycol, 1,4 butanediol and short-chain polyether polyol (with the structure shown in formula (III), R 1 Is a hydrogen atom, R 2 Is a hydrogen atom, n is a positive integer of 5 to 15) in a weight ratio of 1:0.28: 0.21: 0.65, adding tetrabutyl titanate as a catalyst, wherein the dosage of the catalyst is 0.01 percent of the total weight of the adipic acid, the ethylene glycol, the 1,4 butanediol and the short-chain polyether polyol, heating to 110 ℃ under the protection of inert gas, reacting for 13 hours, and cooling to room temperatureThe obtained polyether ester polyol has a structure shown as a formula (I), wherein x is a positive integer of 1-8, y is a positive integer of 1-8, z is a positive integer of 1-6, and the number average molecular weight is 1600.
Preparation example 2 preparation of polyether ester polyol
Adipic acid, ethylene glycol, 1,4 butanediol and short-chain polyether polyol (with the structure shown in formula (III), R 1 Is methyl, R 2 Methyl, n is a positive integer of 5-15) is added into a reaction kettle according to the weight ratio of 1:0.12:0.45:0.2, tetrabutyl titanate is added as a catalyst, the dosage of the catalyst is 0.01 percent of the total weight of adipic acid, ethylene glycol, 1,4 butanediol and short-chain polyether polyol, the temperature is raised to 130 ℃ under the protection of inert gas for reaction for 8 hours, and the reaction product is cooled to room temperature to obtain the polyether polyol, wherein the structure of the polyether polyol is shown as the formula (I), wherein x is a positive integer of 1-8, y is a positive integer of 1-8, z is a positive integer of 1-6, and the number average molecular weight is 2200.
Example 1
This example is intended to illustrate the PU adhesive for fabric attachment and the process for producing the same according to the present invention.
Adding 57 wt% of polyether ester polyol (prepared from preparation example 1), 23 wt% of polyether polyol (purchased from Voranol 4000LM of Dow, USA), 5 wt% of polyether modified hydroxyl-terminated silicone oil (purchased from X-22-4952 of Yuetui) and 0.3 wt% of antioxidant (1010) into a reaction kettle, heating to 110 ℃, stirring in vacuum for 3 hours, cooling to 90 ℃, adding 14.7 wt% of diphenylmethane-4, 4' -diisocyanate, stirring for 1 minute, heating to 110 ℃, stirring in vacuum for 2 hours, discharging to obtain the PU adhesive for fabric bonding, marking as PU-1, and showing a milky white solid state at room temperature.
Example 2
This example is intended to illustrate the PU adhesive for fabric attachment and the process for producing the same according to the present invention.
Adding 70.5 wt% of polyether ester polyol (prepared by preparation example 2), 10 wt% of polyether polyol (Voranol 2000LM from Dow company, USA), 5 wt% of polyether modified hydroxyl terminated silicone oil (KF 6123 from Xinyue) and 0.3 wt% of antioxidant (168) into a reaction kettle, heating to 120 ℃, stirring in vacuum for 2.5 hours, cooling to 80 ℃, adding 14.2 wt% of diphenylmethane-4, 4' -diisocyanate, stirring for 5 minutes, heating to 120 ℃, continuing stirring in vacuum for 1 hour, discharging, and obtaining the PU adhesive for fabric attachment, which is marked as PU-2 and is in a milky white solid state at room temperature.
Comparative example 1
A PU adhesive for fabric attachment was prepared as in example 1, except that the polyetherester polyol was replaced with the same weight part of polyester polyol (HDPOL-2320 available from yokoku technologies) and the conditions were the same as in example 1, to obtain a reference PU adhesive for fabric attachment, designated as DPU-1.
Comparative example 2
A PU adhesive for fabric attachment was prepared as in example 1, except that the polyether-modified hydroxyl-terminated silicone oil was replaced with the same weight part of hydroxyl silicone oil (purchased from believes, having a structure shown in formula (vi)) under the same conditions as in example 1, to obtain a reference PU adhesive for fabric attachment, which was designated as DPU-2.
Test example
(1) Thixotropic property:
the thixotropic properties of the PU adhesives PU-1 and PU-2 for textile bonding obtained in the examples and the PU adhesives DPU-1 and DPU-2 for reference textile bonding obtained in each comparison were measured with a BROOKFIELD viscometer, specifically, the viscosity at 5rpm and 10rpm was measured at 150 ℃ using the same No. 29 rotor (5rpm) /η (10rpm) Wherein η (5rpm) Expressing the viscosity,. eta.at 5rpm (10rpm) The viscosity at 10rpm is shown and the results are shown in Table 1.
(2) Viscosity:
the viscosities of the PU adhesives PU-1 and PU-2 for bonding fabrics obtained in each example and the PU adhesives DPU-1 and DPU-2 for bonding reference fabrics obtained in each comparative example were measured by a BROOKFIELD viscometer, specifically, viscosity data at 5rpm after 30min rotation of a 29# rotor at 150 ℃ were measured, and the results are shown in Table 1.
(3) And (3) glue dispensing fluency:
the glue dispensing fluency of the PU adhesives PU-1 and PU-2 for bonding fabrics obtained in each example and the PU adhesives DPU-1 and DPU-2 for bonding reference fabrics obtained in each proportion is tested by a hot melt glue dispenser, specifically, a glue line with the diameter of 20mm is continuously dispensed by a nozzle with the diameter of 2mm at the glue dispensing temperature of 150 ℃ and the air pressure of 0.5MPa, and the glue line is observed whether the glue line has the glue breaking phenomenon after the glue is dispensed for 5min, and the obtained results are shown in Table 1.
(4) Hardness:
the PU adhesives PU-1 and PU-2 for fabric bonding obtained in each example and the PU adhesives DPU-1 and DPU-2 for reference fabric bonding obtained in each proportion were poured into a mold having a thickness of 6mm, cured at room temperature for 7 days, and the rubber mass was taken out and tested for hardness by a Shore A hardness tester in accordance with ASTM D-2240, and the results are shown in Table 1.
(5) The rebound ratio is as follows:
the PU adhesives PU-1 and PU-2 for bonding fabrics obtained in each example and the PU adhesives DPU-1 and DPU-2 for bonding reference fabrics obtained in each comparative example were scraped to form a 0.3mm adhesive film by a film scraper, cured for 3 days, cut into dumbbell-shaped samples, and the initial length L0 of the samples was recorded. And a universal mechanical testing machine is adopted for tensile test, and the fixed tensile rate is 300%. The stretched sample was then removed and its length L measured after 3 min. 1- (L-L0)/L0 is the rebound ratio. The results are shown in Table 1.
TABLE 1
| Item | Thixotropic property | Viscosity (mPa. s) | Fluency of dispensing | Hardness Shore A | Rebound resilience |
| Example 1 | 1.1 | 63750 | The glue line is uniform and continuous | 41 | 0.98 |
| Example 2 | 1.3 | 56800 | The glue line is uniform and continuous | 47 | 0.82 |
| Comparative example 1 | 1.7 | 24860 | Uneven glue line and broken glue | 63 | 0.70 |
| Comparative example 2 | 1.5 | 52600 | Uneven glue lines and broken glue | 52 | 0.75 |
The results in table 1 show that the PU adhesive for fabric bonding provided by the invention has good flexibility and resilience, good system compatibility, low thixotropy and good glue dispensing smoothness, can well avoid the phenomena of uneven glue lines and glue breaking in the glue dispensing process, can not cause the problems of unevenness of fabric bonding and the like due to uneven glue lines, glue breaking and the like when being compounded with fabrics such as knitted fabrics, plain fabrics, non-woven fabrics and the like to be made into various fabrics or linings, further influences the appearance of cured fabric bonding products, and has great industrial application prospects.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. The PU adhesive for fabric bonding is characterized by comprising polyether ester polyol, polyether modified hydroxyl-terminated silicone oil and an isocyanate compound in a mass ratio of (3-15): (1-6): 0.05-2): 1, wherein a polyether ester chain segment in the polyether ester polyol has a structure shown in a formula (I), and the polyether modified hydroxyl-terminated silicone oil has a structure shown in a formula (II):
in the formula (I), R 1 And R 2 Each independently is a hydrogen atom or a methyl group, n is a positive integer of 5 to 15, x is a positive integer of 1 to 8, y is a positive integer of 1 to 8, and z is a positive integer of 1 to 6;
in the formula (II), a and b are respectively and independently a positive integer of 1-5, m is a positive integer larger than 5, R is C 1 -C 12 Alkylene or C 1 -C 12 Alkoxy group of (2).
2. The PU adhesive for fabric attachment according to claim 1, wherein the polyetherester polyol is synthesized by polymerization of adipic acid, a small molecule polyol which is ethylene glycol and/or 1, 4-butanediol, and a short chain polyether polyol having a structure represented by formula (III):
in the formula (III), R 1 And R 2 Each independently is a hydrogen atom or a methyl group, and n is a positive integer of 5 to 15.
3. The PU adhesive for fabric attachment according to claim 1, wherein the polyether polyol is contained in an amount of 50 to 75 parts by weight, the polyether polyol is contained in an amount of 10 to 30 parts by weight, the polyether-modified hydroxyl-terminated silicone oil is contained in an amount of 1 to 10 parts by weight, and the isocyanate compound is contained in an amount of 5 to 15 parts by weight.
4. The PU adhesive for fabric attachment according to claim 1, wherein the polyetherester polyol has a number average molecular weight of 1000 to 3000 and a functionality of 2.
5. The PU adhesive for fabric attachment according to claim 1, wherein the polyether-modified hydroxyl-terminated silicone oil has a number average molecular weight of 500 to 2000.
6. The PU adhesive for fabric attachment according to any one of claims 1 to 5, wherein the polyether polyol is at least one selected from the group consisting of a polyoxyethylene polyol, a polyoxypropylene-oxyethylene copolyether polyol and polytetrahydrofuran.
7. The PU adhesive for fabric bonding according to any one of claims 1 to 5, wherein the isocyanate compound is an aromatic cyanate ester compound and/or an aliphatic isocyanate compound.
8. The PU adhesive for fabric bonding according to any one of claims 1 to 5, further comprising an antioxidant; the content of the antioxidant is 0.01-1 part by weight.
9. The method for preparing the PU adhesive for fabric attachment according to any one of claims 1 to 8, wherein the method comprises the step of preparing the polyether ester polyol, the polyether modified hydroxyl-terminated silicone oil, the isocyanate compound and the optional antioxidant through polymerization.
10. The preparation method of the PU adhesive for fabric attachment according to claim 9, wherein the polymerization reaction is carried out by adding polyether ester polyol, polyether modified hydroxyl-terminated silicone oil and optional antioxidant into a reaction kettle, heating to 110-130 ℃, vacuum stirring for 2-3 hours, cooling to 70-90 ℃, adding isocyanate compound, vacuum stirring for 1-10 minutes, heating to 110-130 ℃, and continuing vacuum stirring for 0.5-2 hours.
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| CN115772714A (en) * | 2022-12-07 | 2023-03-10 | 华峰化学股份有限公司 | High-strength high-heat-resistance spandex and preparation method thereof |
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