CN112175571B - Polyurethane spray adhesive and preparation method thereof - Google Patents
Polyurethane spray adhesive and preparation method thereof Download PDFInfo
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- CN112175571B CN112175571B CN202011062705.8A CN202011062705A CN112175571B CN 112175571 B CN112175571 B CN 112175571B CN 202011062705 A CN202011062705 A CN 202011062705A CN 112175571 B CN112175571 B CN 112175571B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
- C09J11/06—Non-macromolecular additives organic
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention belongs to the field of polyurethaneThe technical field of ester, in particular to polyurethane spray glue and a preparation method thereof. The polyurethane spray glue comprises a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: (15-25); the main agent at least comprises 35-55 parts of polyol, 30-50 parts of inorganic filler, 4-6 parts of viscosity reducer, 4-6 parts of adhesion promoter, 0.5-1.5 parts of foam stabilizer and 0.5-1.5 parts of cross-linking agent in parts by weight. The polyurethane spray adhesive provided by the invention has the dosage of 350-2The operation time is long, the complete curing time is less than 2 days, and the construction is convenient; meanwhile, the alloy can maintain excellent tensile shear strength and plane tensile strength at the temperature of between 40 ℃ below zero and 70 ℃, and is particularly suitable for aluminized zinc plates or other metal plates.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to polyurethane spray glue and a preparation method thereof.
Background
At present, polyurethane produced at home and abroad is prepared by two main materials of polyester polyol and isocyanate, and has the following defects: firstly, the price of the two raw materials is high, so that the cost of the product manufactured by the two raw materials is high, and the product is not easy to popularize and apply; secondly, the product made of the two raw materials has high density and heavy weight, so that the application of the product is limited; thirdly, the hardness of the product is low, so that some products with high required hardness cannot be applied; fourthly, in the production of polyurethane, the operation time is too short to bring inconvenience to the construction, and the hardness of the cured adhesive film is not suitable for an aluminum plate, an aluminum-zinc plated plate or other metal plates, which is a great technical problem in the current production.
The existing two-component polyurethane spray adhesive also has the defects of large using amount, narrow application range, poor curing effect, weak caking property and the like, and limits the application of the two-component polyurethane spray adhesive on aluminum-plated zinc plates or other metal plates.
Disclosure of Invention
In order to solve the technical problem, a first aspect of the present invention provides a polyurethane spray adhesive, which includes a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: (15-25); the main agent at least comprises 35-55 parts of polyol, 30-50 parts of inorganic filler, 4-6 parts of viscosity reducer, 4-6 parts of adhesion promoter, 0.5-1.5 parts of foam stabilizer and 0.5-1.5 parts of cross-linking agent in parts by weight.
As a preferred technical solution, the polyol includes polyether polyol, vegetable oil polyol, polycaprolactone polyol; the mass ratio of the polyether polyol to the vegetable oil polyol to the polycaprolactone polyol is (10-20): (15-25): 10.
as a preferable technical proposal, the polyether polyol comprises polyether polyol with a hydroxyl value of 100-200mgKOH/g and polyether polyol with a hydroxyl value of 10-60 mgKOH/g; the mass ratio of the polyether polyol with the hydroxyl value of 100-200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is (2.5-3.5): 1.
as a preferred technical scheme, the inorganic filler is selected from one or more of attapulgite, titanium dioxide and calcium carbonate.
As a preferable technical scheme, the viscosity reducer is selected from one or more of an organic alkane ketone, an organic silicon oligomer, an organic phthalate, and an organic glycol ether.
As a preferable technical scheme, the adhesion promoter is selected from one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and benzyl methoxy dimethylsilane.
As a preferred technical scheme, the cross-linking agent is selected from one or more of dicumyl peroxide, di- (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 2, 4-diamino-3, 5-dimethylsulfochlorobenzene.
As a preferable technical scheme, the main agent also comprises 0.5-1.5 parts of wetting agent, 0.5-1.5 parts of dispersing agent and 0.5-1.5 parts of chain extender by weight.
As a preferable technical scheme, the chain extender is a compound containing 2-4 amino groups.
The second aspect of the invention provides a preparation method of the polyurethane spray adhesive, which comprises the following steps:
(1) preparation of the main agent: putting polyalcohol and viscosity reducer into a reaction kettle, stirring uniformly, adding inorganic filler, adhesion promoter, cross-linking agent and foam stabilizer, heating to 90-100 deg.C, vacuum dehydrating until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 50-70 deg.C, stirring uniformly, and barreling to obtain main agent;
(2) and (3) uniformly mixing the main agent and the curing agent, and curing to obtain the polyurethane spray adhesive.
Has the advantages that: the polyurethane spray adhesive provided by the invention has the dosage of 350-2The operation time is long, the complete curing time is less than 2 days, and the construction is convenient; meanwhile, the alloy can maintain excellent tensile shear strength and plane tensile strength at the temperature of between 40 ℃ below zero and 70 ℃, and is particularly suitable for aluminized zinc plates or other metal plates.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problem, a first aspect of the present invention provides a polyurethane spray adhesive, which includes a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: (15-25); the main agent at least comprises 35-55 parts of polyol, 30-50 parts of inorganic filler, 4-6 parts of viscosity reducer, 4-6 parts of adhesion promoter, 0.5-1.5 parts of foam stabilizer and 0.5-1.5 parts of cross-linking agent in parts by weight.
In one embodiment, the mass ratio of the main agent to the curing agent is 100: 20.
main agent
In one embodiment, the main agent at least comprises polyol 45, inorganic filler 40, viscosity reducer 5 parts, adhesion promoter 1 part, foam stabilizer 1 part and cross-linking agent 1 part by weight.
Polyhydric alcohols
In one embodiment, the polyol comprises one or more of a polyether polyol, a vegetable oil polyol, a polycaprolactone polyol; preferably, the polyol comprises polyether polyol, vegetable oil polyol and polycaprolactone polyol.
In a preferred embodiment, the mass ratio of the polyether polyol, the vegetable oil polyol and the polycaprolactone polyol is (10-20): (15-25): 10; more preferably, the mass ratio of the polyether polyol, the vegetable oil polyol and the polycaprolactone polyol is 15: 20: 10.
(polyether polyol)
In one embodiment, the polyether polyol is selected from one or more of HSH-204, HSH-206, HSH-210, HSH-215, HSH-220, HSH-230, HSH-240, HSH-260, HSH-280, HSH-303, HSH-305, HSH-310, HSH-330N, HSH-360, HSH-390, HSH-403A, HSH-6020.
In a preferred embodiment, the polyether polyols include polyether polyols having a hydroxyl value of 100-200mgKOH/g and polyether polyols having a hydroxyl value of 10-60 mgKOH/g.
In the present invention, the hydroxyl value is the number of milligrams of potassium hydroxide (KOH) corresponding to the hydroxyl group in 1g of the sample, and is expressed as mgKOH/g.
In a preferred embodiment, the mass ratio of the polyether polyol having a hydroxyl value of 100-200mgKOH/g to the polyether polyol having a hydroxyl value of 10-60mgKOH/g is (2.5-3.5): 1; more preferably, the mass ratio of the polyether polyol with the hydroxyl value of 100-200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is 3: 1.
the density of the carbamate generated by the reaction of the polyether polyol with the hydroxyl value of 100-200mgKOH/g and the curing agent is higher; the co-reaction curing effect of polyether polyols with hydroxyl values of 10-60mgKOH/g is enhanced, which shows that in the reaction process, the density of the urethane groups serving as hard segments is more dispersed through the cooperation of the polyether polyols with different hydroxyl values, so that the intermolecular force can be kept balanced, the better curing time can be adjusted, and the cured adhesive film has proper hardness and is not prone to wrinkle or fracture.
In a preferred embodiment, the polyether polyol having a hydroxyl value of 100-200mgKOH/g is selected from one or more of HSH-206, HSH-210, HSH-310; more preferably, the polyether polyol having a hydroxyl value of 100-.
In a preferred embodiment, the polyether polyol having a hydroxyl value of from 10 to 60mgKOH/g is selected from one or more of HSH-230, HSH-240, HSH-260, HSH-280, HSH-330N, HSH-360, HSH-390; more preferably, the polyether polyol having a hydroxyl value of 10 to 60mgKOH/g is HSH-330N, available from Nantong Jiuzzize chemical Co.
When the hydroxyl value of the polyether polyol is more than 300mgKOH/g, the product generated after curing contains more polar groups, so that the intermolecular force is large and is difficult to diffuse, thereby prolonging the construction time; on the other hand, when the hydroxyl value is less than 10mgKOH/g, the cured product has few polar groups, and the adhesion with the base material is obviously reduced; in addition, it is found that the reactivity and the curing phenomenon are different for different polyether polyols, and it is preferable that the polyether polyols include polyether polyols having a hydroxyl value of 100-200mgKOH/g and polyether polyols having a hydroxyl value of 10-60mgKOH/g, wherein the mass ratio of the two is preferably 3: 1.
(vegetable oil polyol)
In the invention, the plant polyol is a raw material which can replace petroleum polyether polyol to produce polyurethane. The raw materials of miscellaneous tree, moso bamboo powder, moso bamboo fiber and vegetable oil, such as soybean oil, castor oil and the like, are put into a reaction kettle to carry out a series of reactions, thereby generating the plant polyol.
In one embodiment, the vegetable oil polyol has a functionality of 3.
In one embodiment, the vegetable oil polyol is a castor oil polyol.
In a preferred embodiment, the castor oil polyol is selected from the group consisting of URIC F-15, URIC F-25, URIC F-40, URIC F-60, URIC F-135.
In a preferred embodiment, the castor oil polyol has an acid number of from 0.6 to 0.8 mgKOH/g; more preferably, the castor oil polyol has an acid value of 0.8 mgKOH/g.
In the present invention, the acid value represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substance, unit: (KOH)/(mg/g).
In the preferred embodiment of the present invention, the plant polyol is URIC F-135, which is commercially available from Beijing Sengtai and science and technology Limited.
(polycaprolactone polyol)
In the invention, the polycaprolactone polyol is prepared by ring-opening polymerization of epsilon-caprolactone under the condition that a metal organic compound (such as tetraphenyltin) is used as a catalyst and dihydroxy or trihydroxy is used as an initiator, belongs to a polymerization type polyester, and has different molecular weight and disproportionation degree according to the type and the using amount of a starting material.
In one embodiment, the polycaprolactone polyol is a hydroxyl terminated linear polyester diol.
In a preferred embodiment, the number average molecular weight of the polycaprolactone polyol is 1000-3000; preferably, the number average molecular weight of the polycaprolactone polyol is 2000.
In a preferred embodiment, the polycaprolactone polyol is CAPA 2200, available from Kagao shogao New Material science, Inc.
The polycaprolactone polyol is preferably a hydroxyl terminated linear polyester diol; particularly preferred is a polycaprolactone polyol having a number average molecular weight of 2000, such as CAPA 2200, which is a standard grade linear polyester diol made from caprolactone monomers and terminated primarily by hydroxyl groups.
In a preferred embodiment, the mass ratio of the polyether polyol to the polycaprolactone polyol is (10-20): 10; preferably, the mass ratio of the polyether polyol to the polycaprolactone polyol is 15: 10.
because the contents of the polyether polyol with the hydroxyl value of 100-200mgKOH/g and the polyether polyol with the hydroxyl value of 10-60mgKOH/g are increased, hard segment groups are increased, intermolecular force is increased, and the hardness is higher; the addition of the polycaprolactone polyol can reduce the separation degree of the soft and hard mixed micro-phase, particularly the hydroxyl-terminated linear polyester diol with the number average molecular weight of 1000-3000 is longer, the molecular structure arrangement can be more dense, the elastic crosslinking points are relatively dispersed, and the adhesive property of the adhesive is enhanced, so that the mass ratio of the polyether polyol to the polycaprolactone polyol is (10-20): 10 is preferred.
Inorganic filler
In one embodiment, the inorganic filler is selected from one or more of attapulgite, titanium dioxide, calcium carbonate; preferably, the inorganic filler is attapulgite.
In one embodiment, the attapulgite has a mesh size of 200-400 meshes; preferably, the mesh number of the attapulgite is 300-350 meshes; more preferably, the attapulgite has a mesh size of 325 mesh and is purchased from a manufacturer of mineral products entitled to Lingshou county.
The inorganic filler is attapulgite, is a water-containing magnesium-rich aluminosilicate clay mineral with a chain lamellar structure, forms a channel parallel to a chain between tetrahedral strips, can adsorb gas in a curing reaction and reduce foaming, and the hydroxyl on the surface of the inorganic filler reacts with a curing agent to introduce metal ions into a hard section, and is also easily chelated by active amino after the reaction, so that the curing effect is improved.
Viscosity reducer
In one embodiment, the viscosity reducer is selected from one or more of an alkanone organic matter, an organic silicon oligomer, a phthalate organic matter and a glycol ether organic matter; preferably, the viscosity reducer is a glycol ether organic matter.
In a preferred embodiment, the glycol ether organic is triethylene glycol monoether and/or triethylene glycol diether; more preferably, the viscosity reducer is a mixture of triethylene glycol monoether and triethylene glycol diether.
In a preferred embodiment, the mass ratio of triethylene glycol monoether to triethylene glycol diether is 1: (0.8-1.2); more preferably, the mass ratio of the triethylene glycol monoether to the triethylene glycol diether is 1: 1.
usually, the viscosity reducer is usually phthalate, although the viscosity reducer can promote the curing reaction progress and improve the curing time, the viscosity reducer can still damage the crystallinity of polyurethane molecules in an adhesive film, and is toxic, by adopting a mixture of triethylene glycol monoethers and triethylene glycol diethers, the triethylene glycol monoethers have proper alcohol ether chain segments and high regularity, and simultaneously can increase the content of polyurethane hard segments by cooperating with a chain extender, the intermolecular force is improved, the ether bond contained in the triethylene glycol monoethers can block water, and the viscosity of the triethylene glycol diethers can be effectively reduced by similar compatibility, so that the comprehensive performance of the polyurethane is more excellent in the presence of the special viscosity reducer.
In a preferred embodiment, the triethylene glycol monoether is triethylene glycol monobutyl ether, formula C10H22O4CAS registry number 143-22-6.
In a preferred embodiment, the triethylene glycol diether is triethylene glycol dimethyl ether and-Or triethylene glycol diglycidyl ether; more preferably, the triethylene glycol diether is triethylene glycol dimethyl ether with the molecular formula C8H18O4CAS registry number 112-49-2.
Adhesion promoter
In one embodiment, the adhesion promoter is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzylmethoxydimethylsilane; preferably, the adhesion promoter is benzyl methoxy dimethylsilane.
In the invention, the molecular formula of the benzyl methoxyl dimethylsilane is C6H5CH2SI(OCH3)(CH3)2CAS registry number 36094-19-6, purchased from Hippon high chemistry, Inc.
The adhesion promoter is preferably a phenoxy dimethyl silane compound which can form large pi conjugation with a benzene ring in a polyurethane structure, so that the adhesion promoter can be used for cooperatively fixing an elastic chain segment of polyurethane, improving the adhesion and forming a cross-linked network structure with the surface of an inorganic substrate, and is particularly suitable for aluminum plates, aluminum-plated zinc plates or other metal plates.
Foam homogenizing agent
In one embodiment, the foam stabilizer is selected from one or more of DC-193, DC-3042 and DC-3043; preferably, the foam stabilizer is DC-193, available from Dow Corning.
Crosslinking agent
In one embodiment, the crosslinking agent is selected from one or more of dicumyl peroxide, di- (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane, 2, 4-diamino-3, 5-dimethylsulfochlorobenzene; preferably, the cross-linking agent is 2, 4-diamino-3, 5-dimethylsulfochlorobenzene.
In the invention, the molecular formula of the 2, 4-diamino-3, 5-dimethylthio chlorobenzene is C8H11N2S2Cl, structural formula
The main agent also comprises 0.5 to 1.5 parts by weight of wetting agent, 0.5 to 1.5 parts by weight of dispersant and 0.5 to 1.5 parts by weight of chain extender.
The main agent also comprises 1 part of wetting agent, 1 part of dispersing agent and 1 part of chain extender in parts by weight.
Wetting agent
In one embodiment, the wetting agent is selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, isopropylidene glycol, isobutylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1,2, 6-hexanetriol, 1, 8-octanediol, 1, 2-octanediol, BYK-330; preferably, the wetting agent is BYK-330, purchased from Bick chemical, Germany.
BYK-330 dramatically reduces the surface tension of the coating system, and in particular improves substrate wetting and prevents cratering. At the same time, the smoothness and gloss of the surface are improved.
Dispersing agent
In one embodiment, the dispersant is selected from one or more of alkyl ammonium salts of polycarboxylic acids, salts of unsaturated polyamine amides with carboxyl group-containing polyesters, spreading oils, sodium polyacrylates, sodium pyrophosphates; preferably, the dispersant is an alkyl ammonium salt of a polycarboxylic acid and/or a salt of an unsaturated polyamine amide with a carboxyl group-containing polyester.
In the present invention, the alkyl ammonium salt of polycarboxylic acid includes, but is not limited to, BYK-W961.
In the present invention, the salt of the unsaturated polyamine amide with the carboxyl group-containing polyester includes, but is not limited to, BYK-W968.
In a more preferred embodiment, the dispersant is BYK-W968, purchased from Bick chemical, Germany.
Chain extender
In one embodiment, the chain extender is a compound containing 2 to 4 amino groups.
In one embodiment, the chain extender is selected from one or more of diethylenetriamine, ethylenediamine, diethylenediamine, triethylenetetramine; preferably, the chain extender is diethylenetriamine.
In the invention, the molecular formula of the diethylenetriamine is C4H13N3It is yellow, hygroscopic, transparent, viscous liquid with irritant ammonia smell, flammable and strong alkaline. Is soluble in water, acetone, benzene, ethanol, methanol, etc., is insoluble in n-heptane, and is corrosive to copper and its alloy. Melting point-35 deg.C, boiling point 207 deg.C, relative density 0.9586(20, 20 deg.C), and refractive index 1.4810. Flash point 94 ℃. The product has reactivity of secondary amine, is easy to react with various compounds, and the derivatives thereof have wide application. It is easy to absorb moisture and carbon dioxide in the air.
The chain extender is diethylenetriamine containing 3 active amino groups, the inorganic filler can be fixed after curing, the reduction of the cohesiveness of the polyurethane caused by the excessive content of the inorganic filler is avoided, but the reaction activity of the chain extender and the curing agent is higher, the operation time is too short to bring inconvenience to the construction, and in order to improve the operation time, the curing agent is preferably a polyisocyanate curing agent with the isocyanate content of less than 15 wt%.
Curing agent
In one embodiment, the curing agent is an isocyanate-based curing agent.
In a preferred embodiment, the curing agent is a polyisocyanate curing agent having an isocyanate content of less than 15% by weight.
In a more preferred embodiment, the curative is the German Bayer BAYER curative L75(C), available from Bayer corporation.
The second aspect of the present invention provides a preparation method of the above polyurethane adhesive, comprising the following steps:
(1) preparation of the main agent: putting polyalcohol and viscosity reducer into a reaction kettle, stirring uniformly, adding inorganic filler, adhesion promoter, cross-linking agent and foam stabilizer, heating to 90-100 deg.C, vacuum dehydrating until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 50-70 deg.C, stirring uniformly, and barreling to obtain main agent;
(2) and (3) uniformly mixing the main agent and the curing agent, and curing to obtain the polyurethane spray adhesive.
In one embodiment, the preparation method of the polyurethane glue comprises the following steps:
(1) preparation of the main agent: putting polyalcohol and viscosity reducer into a reaction kettle, stirring uniformly, adding inorganic filler, chain extender, adhesion promoter, cross-linking agent, foam stabilizer, wetting agent and dispersant, heating to 90-100 ℃, vacuum dehydrating until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 50-70 ℃, stirring uniformly, and barreling to obtain a main agent;
(2) and (3) uniformly mixing the main agent and the curing agent, and curing to obtain the polyurethane spray adhesive.
In a preferred embodiment, the preparation method of the polyurethane glue comprises the following steps:
(1) preparation of the main agent: putting polyol and a viscosity reducer into a reaction kettle, stirring uniformly, adding an inorganic filler, a chain extender, an adhesion promoter, a cross-linking agent, a foam stabilizer, a wetting agent and a dispersing agent, heating to 95 ℃, dehydrating in vacuum until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 60 ℃, stirring uniformly, and barreling to obtain a main agent;
(2) and (3) uniformly mixing the main agent and the curing agent, and curing to obtain the polyurethane spray adhesive.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a polyurethane spray including a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: 15; the main agent comprises 35 parts of polyol, 30 parts of inorganic filler, 4 parts of viscosity reducer, 4 parts of adhesion promoter, 0.5 part of foam stabilizer, 0.5 part of cross-linking agent, 0.5 part of wetting agent, 0.5 part of dispersing agent and 0.5 part of chain extender in parts by weight;
the polyol comprises polyether polyol, vegetable oil polyol and polycaprolactone polyol; the mass ratio of the polyether polyol to the vegetable oil polyol to the polycaprolactone polyol is 10: 15: 10;
the polyether polyol comprises polyether polyol with a hydroxyl value of 100-200mgKOH/g and polyether polyol with a hydroxyl value of 10-60 mgKOH/g; the mass ratio of the polyether polyol with the hydroxyl value of 100-200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is 3: 1; the polyether polyol with the hydroxyl value of 100-200mgKOH/g is HSH-310 which is purchased from Nantong Jiuzzize chemical Co., Ltd; the polyether polyol with the hydroxyl value of 10-60mgKOH/g is HSH-330N, and is purchased from Nantong Jiuzzize chemical Co., Ltd;
the plant polyol is URIC F-135, purchased from Beijing Senchangtai and science and technology Limited liability company;
the polycaprolactone polyol is CAPA 2200, which is purchased from Guangzhou Hao Yi New Material science and technology GmbH;
the inorganic filler is attapulgite; the mesh number of the attapulgite is 325 meshes, and the attapulgite is purchased from a Lingshou county entitled mineral product processing factory;
the viscosity reducer is a mixture of triethylene glycol monoether and triethylene glycol diether; the mass ratio of the triethylene glycol monoether to the triethylene glycol diether is 1: 1; the triethylene glycol monoether is triethylene glycol monobutyl ether; the triethylene glycol diether is triethylene glycol dimethyl ether;
the adhesion promoter is benzyl methoxy dimethylsilane;
the foam stabilizer is DC-193 and is purchased from Dow Corning company;
the cross-linking agent is 2, 4-diamino-3, 5-dimethylsulfochlorobenzene;
the wetting agent was BYK-330, purchased from Bick chemical, Germany;
the dispersant was BYK-W968, purchased from Bike chemical, Germany;
the chain extender is diethylene triamine;
the curative was a German Bayer BAYER curative L75(C), purchased from Bayer corporation.
The preparation method of the polyurethane adhesive comprises the following steps:
(1) preparation of the main agent: putting polyol and a viscosity reducer into a reaction kettle, stirring uniformly, adding an inorganic filler, a chain extender, an adhesion promoter, a cross-linking agent, a foam stabilizer, a wetting agent and a dispersing agent, heating to 95 ℃, dehydrating in vacuum until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 60 ℃, stirring uniformly, and barreling to obtain a main agent;
(2) and (3) uniformly mixing the main agent and the curing agent, and curing to obtain the polyurethane spray adhesive.
Example 2
Embodiment 2 provides a polyurethane spray including a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: 25; the main agent comprises 55 parts of polyol, 50 parts of inorganic filler, 6 parts of viscosity reducer, 6 parts of adhesion promoter, 1.5 parts of foam stabilizer, 1.5 parts of cross-linking agent, 1.5 parts of wetting agent, 1.5 parts of dispersing agent and 1.5 parts of chain extender in parts by weight;
the polyol is the same as in example 1, except that the mass ratio of the polyether polyol, the vegetable oil polyol and the polycaprolactone polyol is 20: 25: 10;
the inorganic filler is the same as in example 1;
the viscosity reducer is the same as that in example 1;
the adhesion promoter is benzyl methoxy dimethylsilane;
the foam stabilizer is DC-193 and is purchased from Dow Corning company;
the cross-linking agent is 2, 4-diamino-3, 5-dimethylsulfochlorobenzene;
the wetting agent was BYK-330, purchased from Bick chemical, Germany;
the dispersant was BYK-W968, purchased from Bike chemical, Germany;
the chain extender is diethylene triamine;
the curative was a German Bayer BAYER curative L75(C), purchased from Bayer corporation.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Example 3
Embodiment 3 provides a polyurethane spray including a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: 20; the main agent comprises, by weight, 45 parts of polyol, 40 parts of inorganic filler, 5 parts of viscosity reducer, 1 part of adhesion promoter, 1 part of foam stabilizer, 1 part of cross-linking agent, 1 part of wetting agent, 1 part of dispersing agent and 1 part of chain extender;
the polyol is the same as in example 1, except that the mass ratio of the polyether polyol, the vegetable oil polyol and the polycaprolactone polyol is 15: 20: 10;
the inorganic filler is the same as in example 1;
the viscosity reducer is the same as that in example 1;
the adhesion promoter is benzyl methoxy dimethylsilane;
the foam stabilizer is DC-193 and is purchased from Dow Corning company;
the cross-linking agent is 2, 4-diamino-3, 5-dimethylsulfochlorobenzene;
the wetting agent was BYK-330, purchased from Bick chemical, Germany;
the dispersant was BYK-W968, purchased from Bike chemical, Germany;
the chain extender is diethylene triamine;
the curative was a German Bayer BAYER curative L75(C), purchased from Bayer corporation.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Example 4
Example 4 provides a polyurethane spray and a preparation method thereof, which are the same as example 3, except that the mass ratio of the polyether polyol with the hydroxyl value of 100 and 200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is 2.5: 1.
example 5
Example 5 provides a polyurethane spray and a preparation method thereof, which are the same as example 3, except that the mass ratio of the polyether polyol with the hydroxyl value of 100 and 200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is 3.5: 1.
example 6
Example 6 provides a polyurethane spray and a preparation method thereof, which are the same as example 3, except that the mass ratio of the polyether polyol with the hydroxyl value of 100-: 3.
example 7
Example 7 provides a polyurethane spray and a preparation method thereof, which are the same as example 3, except that the HSH-310 is replaced by HSH-6020, the hydroxyl value of the HSH-6020 is 390-430mgKOH/g, and the polyurethane spray is purchased from Nantong Jiuzze chemical Co.
Example 8
Example 8 provides a polyurethane spray and method of making the same as example 3, except that CAPA 2200 was replaced with BASF Capromer PD1-10 PCL, available from Pasteur.
Example 9
Example 9 provides a polyurethane spray and a method of making the same as example 3, except that there is no polyether polyol having a hydroxyl number of 10 to 60 mgKOH/g.
Example 10
Example 10 provides a polyurethane spray and a method for preparing the same, which are the same as example 3 except that no polyether polyol having a hydroxyl value of 100 and 200mgKOH/g is used.
Example 11
Embodiment 11 provides a polyurethane spray and a preparation method thereof, which are different from those in embodiment 3 only in that the mass ratio of the polyether polyol, the vegetable oil polyol and the polycaprolactone polyol is 30: 20: 5.
example 12
Example 12 provides a polyurethane spray and a method for preparing the same as example 3, except that attapulgite is replaced with activated clay, which was purchased from Shandong Xinwangda Biotech Co., Ltd.
Example 13
Example 13 provides a polyurethane spray and a method for making the same, as example 3, except that the viscosity reducing agent is dibutyl phthalate.
Example 14
Example 14 provides a polyurethane spray and method of making the same as example 3 except that triglyme is not present.
Example 15
Example 15 provides a polyurethane spray and a method of making the same as example 3, except that diethylenetriamine is replaced with ethylenediamine.
Example 16
Example 16 provides a polyurethane spray and a method of making the same as example 3, except that phenylmethylmethoxydimethylsilane is replaced with 3-aminopropyltriethoxysilane.
Example 17
Example 17 provides a polyurethane spray and a method for preparing the same as example 3, except that the german BAYER curing agent L75(C) was replaced with wanhua PM200 MDI, purchased from guangzhou xing cheng mercy and trade limited company.
Performance testing
1. Operable time: the polyurethane adhesive of the just prepared examples 1 to 17 is kept at 25 ℃ (note: when the influence of the test temperature on the operable time of the polyurethane adhesive is kept, the polyurethane adhesive is kept at the corresponding temperature condition), the time t0 for uniformly blending is recorded, the viscosity of the polyurethane adhesive is measured once every 0.5h by using an NDJ-1 rotational viscometer, the time t1 when the viscosity of the polyurethane adhesive exceeds 300mPa.s is recorded, the time t1-t0 is the operable time of the polyurethane adhesive, wherein the operable time is more than 35min and is recorded as A, the operable time is 25-35min and is recorded as B, the operable time is less than 25min and is recorded as C, and the test results are shown in Table 1.
2. Initial bond formation time: the polyurethane adhesive of examples 1-17 which was just prepared was kept at 25 ℃ (note: when the influence of the test temperature on the initial adhesion force formation time of the polyurethane adhesive was kept at the corresponding temperature condition), the time t0 for uniformly blending was recorded, the viscosity of the polyurethane adhesive was measured every 1h with an NDJ-1 rotational viscometer, the time t1 when the viscosity of the polyurethane adhesive exceeded 60000mpa.s was recorded, and t1-t0 was the initial adhesion force formation time of the polyurethane adhesive, wherein the initial adhesion force formation time was greater than 7h and recorded as a, the initial adhesion force formation time was 6-7h and not equal to 6h and recorded as B, the initial adhesion force formation time was 4-6h and recorded as C, the initial adhesion force formation time was less than 4h and recorded as D, and the test results are shown in table 1.
3. Tensile shear strength: the tensile shear strength of the polyurethane adhesive described in examples 1-17 was tested by referring to GB/T7124-2008 method, wherein A represents a tensile shear strength of more than 7MPa, B represents a tensile shear strength of 6-7MPa, C represents a tensile shear strength of 3-6MPa and not equal to 6MPa, D represents a tensile shear strength of less than 3MPa, and the test results are shown in Table 1.
4. Plane tensile strength: the plane tensile strength of the polyurethane adhesives described in examples 1 to 17 was measured by reference to the method of GB/T528, wherein a value of A is given for a plane tensile strength of more than 0.2MPa, a value of B is given for a plane tensile strength of 0.1 to 0.2MPa, and a value of C is given for a plane tensile strength of less than 0.1MPa, and the results are shown in Table 1.
TABLE 1
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (5)
1. The polyurethane spray adhesive is characterized by comprising a main agent and a curing agent; the mass ratio of the main agent to the curing agent is 100: (15-25); the main agent comprises 35-55 parts of polyhydric alcohol, 30-50 parts of inorganic filler, 4-6 parts of viscosity reducer, 4-6 parts of adhesion promoter, 0.5-1.5 parts of foam stabilizer and 0.5-1.5 parts of cross-linking agent in parts by weight;
the viscosity reducer is a mixture of triethylene glycol monoether and triethylene glycol diether; the mass ratio of the triethylene glycol monoether to the triethylene glycol diether is 1: (0.8-1.2);
the polyol comprises polyether polyol, vegetable oil polyol and polycaprolactone polyol; the mass ratio of the polyether polyol to the vegetable oil polyol to the polycaprolactone polyol is (10-20): (15-25): 10; the plant polyol is URIC F-135; the polycaprolactone polyol is CAPA 2200;
the polyether polyol comprises polyether polyol with a hydroxyl value of 100-200mgKOH/g and polyether polyol with a hydroxyl value of 10-60 mgKOH/g; the mass ratio of the polyether polyol with the hydroxyl value of 100-200mgKOH/g to the polyether polyol with the hydroxyl value of 10-60mgKOH/g is (2.5-3.5): 1; the polyether polyol with the hydroxyl value of 100-200mgKOH/g is HSH-310; the polyether polyol with the hydroxyl value of 10-60mgKOH/g is HSH-330N;
the curing agent is a curing agent L75 (C); the adhesion promoter is benzyl methoxy dimethylsilane.
2. The polyurethane spray according to claim 1, wherein the inorganic filler is selected from one or more of attapulgite, titanium dioxide and calcium carbonate.
3. The polyurethane spray adhesive of claim 1, wherein the main agent further comprises 0.5-1.5 parts by weight of a wetting agent, 0.5-1.5 parts by weight of a dispersant, and 0.5-1.5 parts by weight of a chain extender.
4. The polyurethane spray according to claim 3, wherein the chain extender is a compound containing 2 to 4 amino groups.
5. A method for preparing the polyurethane spray according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparation of the main agent: putting polyalcohol and viscosity reducer into a reaction kettle, stirring uniformly, adding inorganic filler, adhesion promoter, cross-linking agent and foam stabilizer, heating to 90-100 deg.C, vacuum dehydrating until the mass fraction of water in the material is less than or equal to 0.1%, cooling to 50-70 deg.C, stirring uniformly, and barreling to obtain main agent;
(2) and uniformly mixing the main agent and the curing agent to obtain the polyurethane spray adhesive.
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