CN108690547B - Polyurethane adhesive for rubber shoes and preparation method and application thereof - Google Patents
Polyurethane adhesive for rubber shoes and preparation method and application thereof Download PDFInfo
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- CN108690547B CN108690547B CN201810683504.6A CN201810683504A CN108690547B CN 108690547 B CN108690547 B CN 108690547B CN 201810683504 A CN201810683504 A CN 201810683504A CN 108690547 B CN108690547 B CN 108690547B
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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
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a polyurethane adhesive for rubber shoes, which comprises 50-80 parts by weight of sulfur-containing polyurethane resin, 1-20 parts by weight of toughening agent, 2-20 parts by weight of needle-shaped filler, 0.05-5 parts by weight of coupling agent and 20-60 parts by weight of solvent, wherein the sulfur-containing polyurethane resin is obtained by mixing polythiol with 4 or more functional groups or a mixture of the polythiol and dihydric alcohol with at least one isocyanate selected from polyisocyanate compounds, polyisothiocyanate compounds and polyisothiocyanate compounds containing isocyanate groups, and finally good bonding force and stability in the bonding of rubber soles and polyurethane materials are realized.
Description
Technical Field
The invention relates to the field of polyurethane adhesives, in particular to the field of polyurethane adhesives for rubber soles, and also relates to a preparation method and application of the polyurethane adhesives for the rubber soles.
Background
The shoe making industry is a basic industry of China and is a closely related industry, and the development prospect of the industry is good due to huge market demand. With the discovery of the industry, the types of shoes are more and more, the functional subdivision is more and more detailed, and the demand is larger and larger.
Rubber shoes are important in the shoemaking industry, natural rubber is soft and suitable for indoor home use, but has poor wear resistance, the wear resistance of artificially synthesized rubber is greatly improved, and the application range is wider and wider. The PU (polyurethane) is a leather substance which develops rapidly in years and is widely used in the field of shoe making, but because the basic performance difference between polyurethane and rubber is large, the bonding effect of the conventional adhesive is poor, and how to obtain the adhesive which can bond the rubber sole and the PU material firmly is urgent need, the inventor carries out systematic research aiming at the problem and obtains the technical content of the invention.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems mentioned in the background technology, through systematic research, structural design is carried out through adhesive matrix resin and fillers, sulfur-containing polyurethane and needle-shaped fillers are selected, wherein sulfur element can realize vulcanization with rubber, and the adhesive force is comprehensively improved through penetrability of the needle-shaped fillers.
The invention also provides a preparation method and application of the polyurethane adhesive for rubber shoes.
Summary of The Invention
The core of the invention is to provide a polyurethane adhesive for rubber shoes, which comprises 50-80 parts by weight of sulfur-containing polyurethane resin, 1-20 parts by weight of toughening agent, 2-20 parts by weight of needle-shaped filler, 0.05-5 parts by weight of coupling agent and 20-60 parts by weight of solvent.
As a preferable technical scheme, the sulfur element in the sulfur-containing polyurethane resin is partially introduced into the structure by polythiol or sulfur-containing isocyanate.
As a preferable embodiment, the sulfur-containing polyurethane resin is obtained from a polythiol having 4 or more functional groups or a mixture with a diol and at least one isocyanate selected from the group consisting of a polyisocyanate compound, a polyisothiocyanate compound and an isocyanate group-containing polyisothiocyanate compound.
As a preferable embodiment, the molar ratio of the functional groups (NCO + NCS)/(OH + SH) is 1: 2-3.
As a preferred technical scheme, the toughening agent is hydroxyl-terminated nitrile rubber or carboxyl-terminated nitrile rubber.
As a preferable technical scheme, the sulfur-containing polyurethane resin is used in combination with high and low molecular weights, the high molecular weight is 3-10 ten thousand weight average molecular weight, and the low molecular weight is 5000-10000 weight average molecular weight.
Preferably, the needle-shaped filler is silicon carbide whiskers or needle-shaped wollastonite, and is preferably pretreated by stearic acid.
As a preferred technical scheme, the coupling agent can be KH550 or KH 560.
The invention also provides a preparation method of the polyurethane adhesive for the rubber shoes, which is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding the needle-shaped filler into an alcohol/water solvent of a coupling agent, stirring for 1-12 hours, and drying for later use;
(2) and (2) adding the sulfur-containing polyurethane resin, the toughening agent and the dried product obtained in the step (1) into the solvent, and uniformly stirring.
The invention further provides an application of the polyurethane adhesive for rubber shoes in the adhesion of rubber soles and polyurethane materials.
As a preferred technical scheme, the rubber is natural rubber or artificial synthetic rubber.
As a preferred technical scheme, the synthetic rubber is preferably wear-resistant rubber, environment-friendly rubber, air rubber, viscous rubber, hard rubber or carbon-added rubber.
Detailed Description
The following detailed description of the embodiments of the invention is provided to enable the skilled person and the public to understand the principles and mechanisms of the embodiments of the invention in more detail.
In order to solve the problems in the background art, the invention provides a polyurethane adhesive for rubber shoes, which comprises 50-80 parts by weight of sulfur-containing polyurethane resin, 1-20 parts by weight of a toughening agent, 2-20 parts by weight of a needle-shaped filler, 0.05-5 parts by weight of a coupling agent and 20-60 parts by weight of a solvent.
The invention adopts the mercapto group-containing polyurethane resin, wherein the polyurethane matrix has good compatibility with PU and strong bonding stability, and meanwhile, in order to improve the bonding to rubber, mercapto groups are introduced into the polyurethane structure, wherein a plurality of mercapto groups can crosslink unsaturated structures in rubber (natural rubber or artificial synthetic rubber), thereby realizing chemical crosslinking, realizing stable linkage of the two and improving the bonding performance between rubber materials and Polyurethane (PU) materials.
The introduction of sulfydryl can reduce the flexibility of the adhesive, and the flexibility can be improved by adding a supplementary toughening agent or a plasticizer; compared with the traditional ball filler or quasi-ball filler, the needle filler adopts the needle fibers to increase the adhesive force of the adhesive, the protruding part can penetrate into the rubber or PU material to improve the adhesive force of the adhesive, and in order to improve the dispersibility and the compatibility with the matrix of the filler, the needle filler can be modified by adopting a coupling agent in advance. The selection of the three points realizes high bonding strength, bonding stability and flexibility of the adhesive.
(Sulfur-containing polyurethane resin)
The reason why the sulfur-containing polyurethane resin is used in the present invention has been described in the above section. This section focuses on the structural design of the sulfur-containing polyurethane resin below and the reasons for selecting the above structure.
In the preparation of the sulfur-containing polyurethane resin, sulfur is introduced by raw materials for polyurethane preparation, and mainly the polythiol and the sulfur-containing isocyanate are partially introduced into the structure; however, in the preparation, the hardness of the adhesive obtained by only reacting the polythiol with the sulfur-containing isocyanate is very high (refer to CN1215737A), and the adhesive is not suitable for being used as an adhesive. In order to solve the above problems, the present invention employs a mixed active hydrogen component of a polyol thiol and a diol, which can improve the flexibility of the adhesive and reduce the crystallinity and crosslinking degree thereof, and it is preferable that the sulfur-containing polyurethane resin is obtained from a polythiol having 4 or more functional groups or a mixture with a diol and at least one isocyanate selected from the group consisting of polyisocyanate compounds, polyisothiocyanate compounds and polyisothiocyanate compounds containing isocyanate groups.
In the choice of polythiol, the invention selects the polythiol using at least 4 functional groups, which has a larger content of residual or reserved thiol groups at the side position after the isocyanate reaction, and has a significant enhancement on adhesion, and the polythiol using at least 4 functional groups can refer to the preparation method in CN1215737A, and the specific structure includes but is not limited to the following substances:
the structures specifically disclosed in the patent publication CN1215737A are all introduced into the present invention, and are not listed here, and the thiols with the above structures are all suitable for the present invention.
The polyol may be used in any kind commonly used in the art without specific limitation. The types commonly used in the prior art may be: ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and the like.
The polyisocyanate compound can be selected from aliphatic polyisocyanate and aromatic polyisocyanate, preferably aliphatic polyisocyanate, and optionally ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, butylene diisocyanate, etc.;
the polyisothiocyanate compound may be 1, 2-diisothiocyanatoethane, 1, 3-diisothiocyanatopropane, 1, 4-diisothiocyanatobutane, 1, 6-diisothiocyanatohexane, cyclohexane diisothiocyanate.
As the polyisothiocyanate compound containing an isocyanate group, 1-isothiocyanato-3-isocyanatopropane, 1-isothiocyanato-5-isocyanatopentane, 1-isothiocyanato-6-isocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isothiocyanato-4-isocyanatocyclohexane and the like can be used.
When the production parameters are selected, the molar ratio of the functional group ratio (NCO + NCS)/(OH + SH) is 1:2-3, it is more preferable that the number of moles of OH is larger than that of SH, and it is further preferable that the number of moles of OH is 2 times or more the number of moles of SH; the molar number of NCS is 40% or less of the total molar amount of NCO + NCS, and NCS may not be contained.
Meanwhile, in order to balance the flexibility and the adhesive force of the adhesive, the sulfur-containing polyurethane resin is used in a high-low molecular weight matching mode, the proportion of sulfur element (sulfydryl) in high molecular weight is low, but the flexibility is good, the proportion of sulfur element (sulfydryl) in low molecular weight is high, good adhesion can be achieved, and the matching effect of the sulfur-containing polyurethane resin and the low molecular weight is excellent.
The sulfur-containing polyurethane resin has a high molecular weight of 3-10 ten thousand and a low molecular weight of 5000-10000, and the weight of the high molecular weight sulfur-containing polyurethane resin is preferably more than twice that of the low molecular weight structure.
(needle-like Filler)
The needle-shaped filler is selected to improve the adhesive force, and the needle-shaped filler is preferably treated by a coupling agent to improve the dispersibility and the compatibility. The needle-shaped filler is silicon carbide whisker and needle-shaped wollastonite, preferably is pretreated by stearic acid, and the coupling agent can be KH550 or KH 560.
The needle-shaped filler pre-treated by stearic acid is further preferably adopted because stearic acid and a coupling agent have synergistic effect in simultaneous treatment, so that the dispersion effect is improved compared with that of the needle-shaped filler used by the method, and the technical effect of improving the adhesive force is improved.
(other Components)
A plurality of auxiliary components can be added, and common plasticizers, toughening agents, antioxidants, ultraviolet absorbers, dispersing agents, compatilizers, solvents, reinforcing fillers, brightening fillers and bulking fillers are suitable for the system, and can be added on the premise of not reducing basic performance according to actual conditions.
As a preferable type of the auxiliary agent, the toughening agent is hydroxyl-terminated nitrile rubber or carboxyl-terminated nitrile rubber, the solvent can be toluene, xylene and the like, and the antioxidant can be 168, 1010, 1098 and the like.
(applications)
The product structure and composition of the invention are developed for specific application, and are suitable for bonding of polyurethane materials and rubber materials, and particularly relate to bonding of rubber materials containing unsaturated bonds. Specifically, the polyurethane adhesive for rubber shoes is used for bonding a rubber sole and a polyurethane material, wherein the rubber is natural rubber or synthetic rubber, and the synthetic rubber is preferably wear-resistant rubber, environment-friendly rubber, air rubber, viscous rubber, hard rubber or carbon-added rubber.
Advantageous technical effects
According to the invention, through the structural design and composition selection of the product, the sulfur-containing polyurethane rubber is adopted as a matrix, and through the selection of an active hydrogen component and an isocyanate component, the matrix resin capable of balancing flexibility and adhesive force is obtained; and proper needle-shaped filler is adopted to improve the adhesive force. Comprehensively realizes good bonding force and stability in the bonding of the rubber sole and the polyurethane material, is superior to common adhesives, and belongs to a special adhesive.
Detailed Description
In order to make the technical solutions of the present invention more intuitive and understandable for the skilled person, several exemplary embodiments are selected below for describing, which do not limit the scope of the present invention, and any embodiments that do not depart from the basic concept of the present invention are within the scope of the present invention.
[ PREPARATION EXAMPLES section ]
Preparation A1
1mol of
Uniformly mixing with 3mol of 1, 3-propylene glycol, drying in vacuum, further uniformly mixing with 2mol of dried hexamethylene diisocyanate, adding a small amount of acetone for assisting dissolution, and reacting at 80 ℃ for about 3 hours in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A1 with the weight average molecular weight of about 6 ten thousand.
Preparation B1
1mol of
Uniformly mixing with 3mol of 1, 3-propylene glycol, drying in vacuum, further uniformly mixing with 2mol of dried hexamethylene diisocyanate, adding a small amount of acetone for assisting dissolution, and reacting at 80 ℃ for about 30min in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin B1 with the weight average molecular weight of about 8000.
Preparation A2
1mol of
Uniformly mixing with 3mol of 1, 3-propylene glycol, drying in vacuum, further uniformly mixing with 1.5mol of dried hexamethylene diisocyanate and 0.5mol of 1, 6-diisothiocyanatohexane, adding a small amount of acetone for assisting dissolution, and reacting at 80 ℃ for about 3 hours in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A2 with the weight average molecular weight of about 6.5 ten thousand.
Preparation B2
1mol of
Mixing with 3mol of 1, 3-propanediol, vacuum drying, further mixing with 1.5mol of dried hexamethylene diisocyanate and 0.5mol of 1, 6-diisothiocyanatohexane, adding a small amount of acetone to assist dissolution, adding 0.1g of dilaurateThe reaction was carried out at 80 ℃ for about 30min in the presence of butyltin, whereby a sulfur-containing urethane resin B2 having a weight-average molecular weight of about 8000 was obtained.
Preparation A3
2mol of 1, 4-butanedithiol and 3mol of 1, 3-propanediol are uniformly mixed, dried in vacuum, further uniformly mixed with 2mol of dried hexamethylene diisocyanate, added with a small amount of acetone for assisting dissolution, and reacted at 80 ℃ for about 3 hours in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A3 with the weight-average molecular weight of about 6 ten thousand.
Preparation B3
2mol of 1, 4-butanedithiol and 3mol of 1, 3-propanediol are uniformly mixed, vacuum drying is carried out, further 2mol of dried hexamethylene diisocyanate are uniformly mixed, a small amount of acetone is added for assisting dissolution, and the mixture is reacted for about 30min at 80 ℃ in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A3 with the weight average molecular weight of 7000.
Preparation A4
1mol of
Uniformly mixing with 3mol of 1, 3-propylene glycol, drying in vacuum, further uniformly mixing with 0.5mol of dried hexamethylene diisocyanate and 1.5mol of 1, 6-diisothiocyanatohexane, adding a small amount of acetone for assisting dissolution, and reacting at 80 ℃ for about 3 hours in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A4 with the weight average molecular weight of about 6.5 ten thousand.
Preparation B4
1mol of
Uniformly mixing with 3mol of 1, 3-propylene glycol, drying in vacuum, further uniformly mixing with 0.5mol of dried hexamethylene diisocyanate and 1.5mol of 1, 6-diisothiocyanato hexane, adding a small amount of acetone for assisting dissolution, and reacting at 80 ℃ for about 3 inches in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin B4 with the weight average molecular weight of about 8000.
Preparation A5
4mol of 1, 3-propanediol is uniformly mixed, vacuum drying is carried out, and further, 0.5mol of dried hexamethylene diisocyanate and 1.5mol of 1, 6-diisothiocyanato hexane are uniformly mixed, a small amount of acetone is added for assisting dissolution, and the mixture is reacted for about 3 hours at 80 ℃ in the presence of 0.1g of dibutyltin dilaurate to obtain the sulfur-containing polyurethane resin A5 with the weight-average molecular weight of about 6.5 ten thousand.
Preparation B5
4mol of 1, 3-propylene glycol is uniformly mixed, vacuum drying is carried out, and further, 0.5mol of dried hexamethylene diisocyanate and 1.5mol of 1, 6-diisothiocyanato hexane are uniformly mixed, a small amount of acetone is added for assisting dissolution, and the mixture is reacted for about 30min at 80 ℃ in the presence of 0.1g of dibutyltin dilaurate to obtain sulfur-containing polyurethane resin B5 with the weight average molecular weight of about 6500.
Preparation C1
100 parts by weight of silicon carbide whiskers and 0.5 part by weight of KH560 were stirred in an alcohol-water solution for about 3 hours, and dried for use, and labeled C1.
Preparation C2
100 parts by weight of silicon carbide whiskers and 0.5 part by weight of stearic acid were mixed uniformly, and further stirred with 0.5 part by weight of KH560 in an alcohol-water solution for about 3 hours, and dried for use, which was designated as C2.
Preparation C3
100 parts by weight of silicon carbide whiskers and 1 part by weight of KH560 were stirred in an aqueous alcohol solution for about 3 hours, and dried for use, and labeled C3.
Preparation C4
100 parts by weight of potassium hexatitanate fine powder and 1 part by weight of KH560 were stirred in an alcohol aqueous solution for about 3 hours, and dried for use, and labeled C4.
[ EXAMPLES section ]
The following examples and comparative examples were prepared in essentially the same manner by the general method of preparation: (1) adding the needle-shaped filler into an alcohol/water solvent of a coupling agent, stirring for 1-12 hours, and drying for later use (namely part C of preparation example); (2) and (2) adding the sulfur-containing polyurethane resin, the toughening agent and the dried product obtained in the step (1) into a solvent, uniformly stirring, and adding other auxiliaries.
The selection and the amount of each component are as follows:
[ test methods ]
1. Peel strength
Peel strength was performed using the standard of GB19340-2014, which cites GB/T532-2008, with the two adherends tested being 0.5mm natural rubber film and 0.5mm PU leather, respectively.
2. Thermal aging resistance
The heat aging resistance was measured by the same method as the above test, and the peel strength was measured.
3. Elongation at break
The test of the elongation at break is carried out with reference to GB/T30776-2014.
[ test results ]
From the above results, it can be found that the sulfur-containing urethane rubber, the active hydrogen component and the isocyanate realize the matrix resin with balanced flexibility and adhesion through the structural design and composition selection of the product; meanwhile, the proper needle-shaped filler improves the adhesive force, and the selection of the plurality of structures and components realizes good adhesive force and stability in the adhesion of the rubber sole and the polyurethane material, and is superior to similar products in the market.
Claims (6)
1. A polyurethane adhesive for rubber shoes, which is characterized in that: comprises 50-80 parts of sulfur-containing polyurethane resin, 1-20 parts of toughening agent, 2-20 parts of needle-shaped filler, 0.05-5 parts of coupling agent and 20-60 parts of solvent;
the sulfur-containing polyurethane resin is obtained from a polythiol having 4 or more functional groups or a mixture with a diol and at least one isocyanate selected from a polyisocyanate compound, a polyisothiocyanate compound and an isocyanate group-containing polyisothiocyanate compound;
the sulfur-containing polyurethane resin is used in combination with high and low molecular weights, the high molecular weight is 3-10 ten thousand of weight average molecular weight, and the low molecular weight is 5000-10000 of weight average molecular weight;
the needle-shaped filler is silicon carbide whisker which is pretreated by stearic acid.
2. The polyurethane adhesive for rubber shoes according to claim 1, characterized in that: the molar ratio of the functional groups (NCO + NCS)/(OH + SH) is 1: 2-3.
3. The polyurethane adhesive for rubber shoes according to claim 1, characterized in that: the toughening agent is hydroxyl-terminated nitrile rubber or carboxyl-terminated nitrile rubber.
4. The polyurethane adhesive for rubber shoes according to claim 1, characterized in that: the coupling agent is KH550 or KH 560.
5. The method for preparing the polyurethane adhesive for rubber shoes according to any one of claims 1 to 4, characterized in that: the preparation method comprises the following steps:
(1) adding the needle-shaped filler into an alcohol/water solvent of a coupling agent, stirring for 1-12 hours, and drying for later use;
(2) and (2) adding the sulfur-containing polyurethane resin, the toughening agent and the dried product obtained in the step (1) into the solvent, and uniformly stirring.
6. Use of the polyurethane adhesive for rubber shoes according to any one of claims 1 to 4 for bonding a rubber sole to a polyurethane material, wherein the rubber is natural rubber or synthetic rubber.
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| CN201810683504.6A CN108690547B (en) | 2018-06-28 | 2018-06-28 | Polyurethane adhesive for rubber shoes and preparation method and application thereof |
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| CN111621185A (en) * | 2020-07-24 | 2020-09-04 | 榕珍新材料科技发展(上海)有限公司 | Sprayable solvent-free two-component polyurethane putty and preparation method and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20180103713A1 (en) * | 2016-10-19 | 2018-04-19 | Su Hwan Lim | Running shoe capable of representing various designs |
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| CN105199652B (en) * | 2015-10-28 | 2017-10-24 | 中国工程物理研究院化工材料研究所 | Low melting viscosity thermoplastic polyurethane hot melt adhesive and preparation method thereof |
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| US20180103713A1 (en) * | 2016-10-19 | 2018-04-19 | Su Hwan Lim | Running shoe capable of representing various designs |
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