CN111234765A - Glue for shoemaking and preparation method thereof - Google Patents
Glue for shoemaking and preparation method thereof Download PDFInfo
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- CN111234765A CN111234765A CN202010170462.3A CN202010170462A CN111234765A CN 111234765 A CN111234765 A CN 111234765A CN 202010170462 A CN202010170462 A CN 202010170462A CN 111234765 A CN111234765 A CN 111234765A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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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
- C08G18/4236—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
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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
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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
- C08G18/58—Epoxy resins
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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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a shoe-making glue which comprises the following components in parts by weight: 30-70 parts of polyurethane prepolymer, 20-70 parts of organic solvent and 0.1-1 part of inorganic micron powder; the polyurethane prepolymer comprises the following raw materials in parts by weight: 50-80 parts of mixed polyol, 5-10 parts of diisocyanate, 5-10 parts of epoxy resin, 1-3 parts of chain extender, 5-8 parts of cross-linking agent and 0.1-3 parts of inorganic nano powder. The invention discloses a shoe-making glue which still has higher adhesive force under lower viscosity, and also discloses a preparation method of the shoe-making glue.
Description
Technical Field
The invention relates to the field of adhesives, and particularly relates to a shoe-making glue and a preparation method thereof.
Background
Shoes are indispensable articles for daily use in life of people, and the production of the shoes is an important component of the knitting industry in China. Wherein in the production manufacturing process of shoes, vamp and sole need adopt glue often to carry out the veneer bonding to it, and traditional glue for shoemaking also need to guarantee higher viscosity when guaranteeing bonding strength, and mobility is relatively poor to also can increase in influencing its levelling nature and the glue quantity, overflow glue also appears easily moreover, consequently, a glue for shoemaking that viscosity is low while the bonding strength is high is the important subject of technical staff's research in the field.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a shoe-making glue and a preparation method thereof.
The technical solution of the invention is as follows:
the shoe-making glue comprises the following components in parts by weight: 30-70 parts of polyurethane prepolymer, 20-70 parts of organic solvent and 0.1-1 part of inorganic micron powder;
the polyurethane prepolymer comprises the following raw materials in parts by weight:
50-80 parts of mixed polyol, 5-10 parts of diisocyanate, 5-10 parts of epoxy resin, 1-3 parts of chain extender, 5-8 parts of cross-linking agent and 0.1-3 parts of inorganic nano powder.
Preferably, the mixed polyol comprises polyester polyol and polyether polyol in a weight ratio of 1-3: 2.
Preferably, the crosslinking agent is a metallic crosslinking agent.
Preferably, the particle size of the inorganic micron powder is 5-15 μm, and the particle size of the inorganic nano powder is 5-10 nm.
The invention also discloses a technical scheme that:
a preparation method of the glue for shoe making comprises the following steps:
step one, preparing a polyurethane prepolymer: reacting the mixed polyol with diiso-nitrile acid ester to obtain a first intermediate, and then reacting the first intermediate, inorganic nano-powder and a chain extender to obtain a polyurethane prepolymer;
step two, preparing a modified polyurethane prepolymer: reacting the polyurethane prepolymer in the step one with epoxy resin to obtain a second intermediate, and then reacting the second intermediate with a cross-linking agent to obtain a modified polyurethane prepolymer;
and step three, sequentially adding inorganic micron powder and an organic solvent into the modified polyurethane prepolymer in the step two, and uniformly stirring to obtain the glue.
Preferably, in the step one, before the reaction of the mixed polyol and the diisocyanate, an additional step one is further included, and the additional step one is specifically: vacuum drying the mixed polyol until the water content of the mixed polyol is 0.01-0.1%.
Preferably, in the first step, the reaction temperature of the mixed polyol and the diisocyanate is 60-85 ℃, and the reaction time is 1-2 h;
the reaction temperature of the first intermediate, the inorganic nano powder and the chain extender is 60-85 ℃, and the reaction time is 0.5-1 h.
Preferably, in the second step, the reaction temperature of the polyurethane prepolymer and the epoxy resin is 60-90 ℃, and the reaction time is 2-4 h.
Preferably, the third step is followed by a fourth step, and the fourth step is specifically: and distilling the glue, stopping distilling when the content of the organic solvent is lower than 0.05%, and adding deionized water until the solid content in the glue is 50-60%.
Preferably, in the fourth step, the distillation temperature is controlled to be 50-70 ℃.
The invention has the beneficial effects that:
(1) according to the glue for making shoes, chemical bonds on the particle surfaces of inorganic nano powder introduced into raw materials adopted in the polyurethane prepolymer interact with polar groups on an organic chain to form intramolecular cross-linking, so that the bonding strength is increased, and meanwhile, the inorganic nano powder reacts with a polyfunctional group on the polyurethane prepolymer under the action of external cross-linking of an introduced cross-linking agent to form a cross-linked network structure to a certain extent by the original linear polyurethane, so that the bonding strength of the glue can be improved;
the introduction of epoxy resin can change the form of the network structure formed by the linear structure of the molecular main chain of the polyurethane prepolymer, and further enhance the bonding strength of the glue.
(2) The preparation method of the glue for making shoes comprises the steps of firstly preparing a linear first intermediate by adopting mixed polyol and diisocyanate, then continuously adding inorganic nano powder and a chain extender for reaction, and preparing a process of lengthening the branched chain of the polyurethane prepolymer.
(3) When the glue is prepared, the added inorganic micron powder particles can increase the acting force of the glue and the surface of an adherend, so that the glue is combined more tightly, and the flowability of the glue can be improved.
(4) According to the invention, the organic solvent is distilled and water is added in the follow-up process, so that the environment-friendly property of the glue is greatly enhanced, the leveling property is also greatly increased, the glue overflow phenomenon is not easy to occur in the follow-up gluing process, and the gluing strength can also reach a higher value.
(5) The introduced metal cross-linking agent has bridging effect between the hydroxyl in the polyurethane prepolymer and the carbonyl in the metal cross-linking agent, so that the originally weak interaction becomes quite strong, the network structure is more stable, and the adhesive strength is improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention is further described below in conjunction with examples, which are to be understood as being illustrative only and in no way limiting.
Example 1
The shoe-making glue comprises the following components in parts by weight: 32 parts of polyurethane prepolymer, 55 parts of organic solvent and 0.1 part of inorganic micron powder;
the polyurethane prepolymer comprises the following raw materials in parts by weight:
53 parts of mixed polyol, 5 parts of diisocyanate, 5 parts of epoxy resin, 1 part of chain extender, 5 parts of cross-linking agent and 0.3 part of inorganic nano powder.
The mixed polyol comprises the following components in parts by weight: 2 and a polyether polyol.
In this example, the polyester polyol is polybutylene adipate glycol;
the polyether polyol is a product formed by ring-opening polymerization of sorbitol and glycerol as initiators and propylene oxide as a polymerization monomer;
in this example, the diisocyanate is selected from 1, 6-hexamethylene diisocyanate; the organic solvent adopts acetone;
in this embodiment, the crosslinking agent is a metal type crosslinking agent, specifically ammonium zirconium carbonate.
In this example, 1, 4-butanediol was used as the chain extender;
in this example, the particle size of the inorganic micro powder is 5 μm, the particle size of the inorganic nano powder is 7nm,
the inorganic micron powder and the inorganic nano powder are both silicon dioxide.
A preparation method of the glue for shoe making comprises the following steps:
the method comprises the following steps: preparing a polyurethane prepolymer;
reacting mixed polyol with diisocyanato at 60 ℃ for 1h to obtain a first intermediate, and reacting the first intermediate, inorganic nano powder and a chain extender at 75 ℃ for 0.5 h; preparing a polyurethane prepolymer;
step two: preparing a modified polyurethane prepolymer;
reacting the polyurethane prepolymer in the step one with epoxy resin at the reaction temperature of 65 ℃ for 2h to obtain a second intermediate, and then reacting the second intermediate with a crosslinking agent to obtain a modified polyurethane prepolymer;
step three: and D, sequentially adding inorganic micron powder and an organic solvent into the modified polyurethane prepolymer in the step two, and uniformly stirring to obtain the glue.
Example 2
The shoe-making glue comprises the following components in parts by weight: 67 parts of polyurethane prepolymer, 70 parts of organic solvent and 0.3 part of inorganic micron powder;
the polyurethane prepolymer comprises the following raw materials in parts by weight:
64 parts of mixed polyol, 7 parts of diisocyanate, 8 parts of epoxy resin, 2 parts of chain extender, 7 parts of cross-linking agent and 1.5 parts of inorganic nano powder.
The mixed polyol comprises the following components in parts by weight: 1 and a polyether polyol.
In this example, the polyester polyol is a polycarbonate diol.
The polyether polyol is prepared by ring-opening polymerization of sucrose and diethylene glycol as initiators and propylene oxide as a polymerization monomer; a hydroxyl number of 560mgKOH/g, a number average molecular weight of about 700;
in this example, the diisocyanate was isophorone diisocyanate.
In this example, acetone was used as the organic solvent;
in this embodiment, the crosslinking agent is a metal type crosslinking agent, specifically ammonium zirconium carbonate.
In this example, 1, 4-butanediol was used as the chain extender;
in this example, the particle size of the inorganic micro powder is 10 μm, and the particle size of the inorganic nano powder is 7 nm;
the inorganic micron powder and the inorganic nano powder are both titanium dioxide.
A preparation method of the glue for shoe making comprises the following steps:
the method comprises the following steps: preparing a polyurethane prepolymer;
reacting the mixed polyol with diisocyanato at 65 ℃ for 1.5h to obtain a first intermediate, and reacting the first intermediate, inorganic nano-powder and a chain extender at 78 ℃ for 1 h; preparing a polyurethane prepolymer;
step two: preparing a modified polyurethane prepolymer;
reacting the polyurethane prepolymer in the step one with epoxy resin at the reaction temperature of 85 ℃ for 3h to obtain a second intermediate, and then reacting the second intermediate with a crosslinking agent to obtain a modified polyurethane prepolymer;
step three: and D, sequentially adding inorganic micron powder and an organic solvent into the modified polyurethane prepolymer in the step two, and uniformly stirring to obtain the glue.
Example 3
The shoe-making glue comprises the following components in parts by weight: 70 parts of polyurethane prepolymer, 69 parts of organic solvent and 1 part of inorganic micron powder;
the polyurethane prepolymer comprises the following raw materials in parts by weight:
80 parts of mixed polyol, 8 parts of diisocyanate, 7 parts of epoxy resin, 3 parts of chain extender, 8 parts of cross-linking agent and 3 parts of inorganic nano powder.
The mixed polyol comprises the following components in parts by weight: 2 and a polyether polyol.
In this embodiment, the polyester polyol is polycaprolactone diol;
the polyether polyol takes glycerol as an initiator, propylene oxide is subjected to ring-opening polymerization, and ethylene oxide is subjected to end capping, so that the hydroxyl value is 311mgKOH/g, and the number average molecular weight is about 500.
In this example, the diisocyanate was dicyclohexylmethane diisocyanate.
In this example, acetone was used as the organic solvent;
in this embodiment, the crosslinking agent is a metal type crosslinking agent, specifically ammonium zirconium carbonate.
In this example, 1, 4-butanediol was used as the chain extender;
in this embodiment, the particle size of the inorganic micro powder is 15 μm, the particle size of the inorganic nano powder is 10nm, the inorganic micro powder is silicon dioxide, and the inorganic nano powder is titanium dioxide.
A preparation method of the glue for shoe making comprises the following steps:
the method comprises the following steps: preparing a polyurethane prepolymer;
reacting mixed polyol with diisocyanato at 85 ℃ for 2 hours to obtain a first intermediate, and reacting the first intermediate, inorganic nano powder and a chain extender at 85 ℃ for 1 hour; preparing a polyurethane prepolymer;
step two: preparing a modified polyurethane prepolymer;
reacting the polyurethane prepolymer in the step one with epoxy resin at the reaction temperature of 90 ℃ for 2h to obtain a second intermediate, and then reacting the second intermediate with a crosslinking agent to obtain a modified polyurethane prepolymer;
step three: and D, sequentially adding inorganic micron powder and an organic solvent into the modified polyurethane prepolymer in the step two, and uniformly stirring to obtain the glue.
Example 4
The embodiment is optimized on the basis of embodiment 2, specifically, epoxy resin is diamino modified epoxy resin, a specific modification method can adopt a reaction of epoxy resin and excessive aliphatic diamine to generate an amino-terminated epoxy resin ring-opening modifier, and epoxy resin is grafted into a polyurethane molecular chain by utilizing a reaction of amino and residual diisocyanato to obtain diamino modified epoxy resin; the rest is the same as example 2.
Example 5
This embodiment is a further variation on embodiment 4, and specifically includes, in the step one, an additional step one before the reaction of the mixed polyol and the diisocyanate, where the additional step one is specifically: the mixed polyol was vacuum-dried until the water content of the mixed polyol became 0.01%.
Example 6
This embodiment is a further variation on embodiment 4, and specifically includes, in the step one, an additional step one before the reaction of the mixed polyol and the diisocyanate, where the additional step one is specifically: the mixed polyol was vacuum-dried until the water content of the mixed polyol became 0.05%.
Example 7
This embodiment is a further variation on embodiment 4, and specifically includes, in the step one, an additional step one before the reaction of the mixed polyol and the diisocyanate, where the additional step one is specifically: the mixed polyol was vacuum-dried until the water content of the mixed polyol became 0.1%.
Example 8
The present embodiment is a variation made on the basis of embodiment 6, and specifically includes a fourth step after the third step, where the fourth step specifically is: and distilling the glue, controlling the distillation temperature at 65 ℃, stopping distillation when the content of the organic solvent is lower than 0.05%, and adding deionized water until the solid content in the glue is 55%.
Comparative example 1
The comparative example is a change made on the basis of example 2, and particularly relates to a shoe-making glue which comprises the following components in parts by weight: 67 parts of polyurethane prepolymer and 70 parts of organic solvent; the polyurethane prepolymer comprises the following raw materials in parts by weight: 64 parts of mixed polyol, 7 parts of diisocyanate, 2 parts of chain extender and 7 parts of crosslinking agent, the rest being the same as in example 2.
The above examples 1 to 8 and comparative example 1 were subjected to performance tests, and the test values are shown in table 1;
and (3) viscosity testing: the viscometer measurement was digitally displayed using Shanghai Instrument plant ND J28S.
And (3) testing water resistance: the water absorption rate can reflect the water resistance of the adhesive film. Preparing a glue film with the mass range of 0.1-0.5g, weighing the glue film and recording the glue film as W; then completely soaking the adhesive film in water for 24h, taking out, immediately sucking the water on the surface of the adhesive film by using filter paper, weighing the mass and recording the mass as W1Water absorption rate of (W)1-W)/W1×100％。
Measurement of peeling force: uniformly coating the prepared glue on the surface of a rubber bottom and PU leather, putting the rubber bottom and the PU leather into a blast oven, drying the rubber bottom and the PU leather for 10min at 60 ℃, taking out the glue, aligning and bonding the glue, carrying out hot pressing at a certain pressure for 3min, standing the glue at room temperature for 24h, and measuring the peeling force of the adhesive according to ISOISO-11644 at the peeling strength of 100mm/min by adopting a TS2000-S type multifunctional material tester of Taiwan high-speed railway science and technology, Inc.
TABLE 1 Performance test values for examples 1-8 and comparative example 1
As can be seen from Table 1, examples 1 to 8 are superior to comparative example 1, wherein the performance of example 8 is the best, namely when the viscosity of the glue is 1874mPa.s, the initial peeling rate reaches 141N, wherein the viscosity of comparative example 1 is 2389mPa.s, the peeling force is lower than that of example 2, and the water resistance is also poor, which shows that the glue of the present invention can still have higher peeling force under the condition of lower viscosity, mainly because of the addition of inorganic nano powder and inorganic micro powder, on one hand, the inorganic micro powder can improve the fluidity of the glue, namely, the viscosity of the glue, on the other hand, because the linear first intermediate is prepared by mixing polyol and diiso-nitrilate, and then the inorganic nano powder and the chain extender are continuously added for reaction to prepare the process of lengthening the branched chain of polyurethane, because of the polar action of the added inorganic nano powder particles, the internal crosslinking action is achieved, forming a part of network structure, and then preparing a modified polyurethane prepolymer; when the polyurethane prepolymer is prepared, the introduction of the epoxy resin enables active hydroxyl and epoxy groups on the epoxy resin to be grafted to the main chain of the polyurethane for block copolymerization to further form a network structure and the subsequent crosslinking reaction of a crosslinking agent to be added, so that the bonding strength of the modified polyurethane prepolymer is greatly enhanced, the viscosity suitability is ensured, the higher bonding strength is ensured, the glass transition temperature of the polyurethane is improved by the introduction of the inorganic powder, and the heat resistance is improved; in addition, compared with the embodiment 2, the embodiment 8 adds the subsequent optimization process of distilling the organic solvent and adding deionized water, so that the environment-friendly property of the glue is greatly enhanced, the leveling property is also improved, the glue overflow phenomenon is not easy to occur in the subsequent gluing process, and the adhesive strength can reach a higher value.
It can be further understood from table 1 that the performance of example 4 is better than that of example 2, mainly because the epoxy resin is diamine-modified epoxy resin, and the epoxy groups are all ring-opened, so that the epoxy groups are prevented from being attacked by nucleophiles such as hydroxyl and water to affect the storage stability of the glue, while the end group (primary amino group) in the structure of the diamino-modified epoxy resin and the secondary amino group in the chain structure of example 4 can form urea bonds with the diisonitrile ester, and the chain extension is performed while emulsifying in water, and because of the existence of a plurality of amino active sites, the obtained polyurethane has a network-like cross-linked structure, the molecular weight is increased, and the adhesive force of the adhesive is also improved to a certain extent. Meanwhile, mixed polyol is adopted, mainly because ether bonds in a polyether polyol molecular structure are easy to rotate and flexible, and have excellent hydrolysis resistance and low temperature resistance, but the ether bonds are easy to oxidize and degrade, the bonding strength of the ether bonds is relatively low, and the polyester polyol has relatively good bonding force, but the water resistance is poor, and the storage stability period of the emulsion is relatively short, so that the advantages of the polyether polyol and the polyester polyol can be combined by adopting the mixed alcohol of the polyether polyol and the polyester polyol, the bonding force of the prepared glue is higher, and the water resistance is strong.
In conclusion, the preparation method of the glue provided by the invention enables the linear polyurethane to be continuously branched and diffused, so that the linear structure is converted into the network structure, the compact network structure reduces the vacancy, namely, the solvent is difficult to permeate, and the water resistance of the glue after film forming is also enhanced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features. The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The glue for making shoes is characterized by comprising the following components in parts by weight: 30-70 parts of polyurethane prepolymer, 20-70 parts of organic solvent and 0.1-1 part of inorganic micron powder;
the polyurethane prepolymer comprises the following raw materials in parts by weight:
50-80 parts of mixed polyol, 5-10 parts of diisocyanate, 5-10 parts of epoxy resin, 1-3 parts of chain extender, 5-8 parts of cross-linking agent and 0.1-3 parts of inorganic nano powder.
2. The glue for shoemaking as claimed in claim 1, wherein said mixed polyol comprises polyester polyol and polyether polyol in a weight ratio of 1-3: 2.
3. The glue for shoemaking according to claim 1, wherein said cross-linking agent is a metallic cross-linking agent.
4. The glue for shoemaking according to claim 1, wherein the particle size of the inorganic micro powder is 5-15 μm, and the particle size of the inorganic nano powder is 5-10 nm.
5. The preparation method of the glue for shoe making is characterized by comprising the following steps:
step one, preparing a polyurethane prepolymer: reacting the mixed polyol with diiso-nitrile acid ester to obtain a first intermediate, and then reacting the first intermediate, inorganic nano-powder and a chain extender to obtain a polyurethane prepolymer;
step two, preparing a modified polyurethane prepolymer: reacting the polyurethane prepolymer in the step one with epoxy resin to obtain a second intermediate, and then reacting the second intermediate with a cross-linking agent to obtain a modified polyurethane prepolymer;
and step three, sequentially adding inorganic micron powder and an organic solvent into the modified polyurethane prepolymer in the step two, and uniformly stirring to obtain the glue.
6. The method for preparing the glue for shoemaking according to claim 5, wherein, in the step one, an additional step one is further included before the mixed polyol and the diisocyanate react, and the additional step one is specifically: vacuum drying the mixed polyol until the water content of the mixed polyol is 0.01-0.1%.
7. The preparation method of the glue for shoemaking according to claim 5, characterized in that, in the first step, the reaction temperature of the mixed polyol and the diisocyanate is 60-85 ℃, and the reaction time is 1-2 h; the reaction temperature of the first intermediate, the inorganic nano powder and the chain extender is 60-85 ℃, and the reaction time is 0.5-1 h.
8. The preparation method of the glue for making shoes according to claim 5, wherein in the second step, the reaction temperature of the polyurethane prepolymer and the epoxy resin is 60-90 ℃, and the reaction time is 2-4 h.
9. The preparation method of the glue for shoemaking according to claim 5, characterized in that, after the third step, a fourth step is further included, wherein the fourth step specifically comprises: and distilling the glue, stopping distilling when the content of the organic solvent is lower than 0.05%, and adding deionized water until the solid content in the glue is 50-60%.
10. The method for preparing glue for shoes as claimed in claim 9, wherein the temperature of distillation in step four is controlled to 50-70 ℃.
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| CN1796481A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院化学研究所 | Adhesive composition of polyurethane in use for shoes and prepartion method |
| CN102887988A (en) * | 2012-10-24 | 2013-01-23 | 阿特斯(中国)投资有限公司 | Photovoltaic backplane adhesive and preparation method thereof |
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| CN1796481A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院化学研究所 | Adhesive composition of polyurethane in use for shoes and prepartion method |
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| CN103409100A (en) * | 2013-08-16 | 2013-11-27 | 长春市三化实业有限责任公司 | Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof |
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