CN109401719B - Dual-curing polyurethane hot melt adhesive as well as preparation method and application method thereof - Google Patents
Dual-curing polyurethane hot melt adhesive as well as preparation method and application method thereof Download PDFInfo
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- CN109401719B CN109401719B CN201811124667.7A CN201811124667A CN109401719B CN 109401719 B CN109401719 B CN 109401719B CN 201811124667 A CN201811124667 A CN 201811124667A CN 109401719 B CN109401719 B CN 109401719B
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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
-
- 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
- C08G18/42—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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
Abstract
The invention discloses a dual-curing polyurethane hot melt adhesive and a preparation method and a use method thereof, wherein the raw material components of the polyurethane hot melt adhesive comprise a main material and an auxiliary material; the main material comprises the following raw material components: polyester polyol, polyether polyol, a chemical modifier, isocyanate and a chain extender; the auxiliary materials comprise the following raw material components: physical modifier, catalyst, silane coupling agent, photoinitiator, antioxidant and white carbon black. According to the technical scheme, the UV light/moisture dual-curing polyurethane hot melt adhesive has the advantages of the moisture-curing polyurethane hot melt adhesive and the UV curing hot melt adhesive, and the defects of the moisture-curing polyurethane hot melt adhesive and the UV curing hot melt adhesive are improved; the UV light/wet dual-curing polyurethane hot melt adhesive is synthesized by adopting a chemical modifier and blended with an acrylate diluent, so that the compatibility among all components is improved, and a polyurethane hot melt adhesive product which is high in initial bonding strength, good in toughness, strong in weather resistance and convenient to construct is obtained.
Description
Technical Field
The invention relates to a polyurethane hot melt adhesive, in particular to a dual-curing polyurethane hot melt adhesive and a preparation method and a use method thereof.
Background
The hot melt adhesive is solid at room temperature, is melted into viscous liquid when heated to a certain temperature, becomes solid after being cooled to the room temperature, and has strong bonding effect.
UV light curing refers to a process in which a photoinitiator is rapidly decomposed into free radicals under the irradiation of ultraviolet light with proper wavelength and intensity to initiate unsaturated organic matter to form macromolecules through crosslinking. The UV curing speed is high, energy and time are saved, pollution is less, the product performance is excellent, but the UV curing agent can only be applied to transparent materials, the development and application time is short, and the technology is immature. The moisture curing refers to a process that-NCO is used as a terminal group of hot melt adhesive, after the hot melt adhesive is coated on the surface of a substrate in a melting way, the-NCO reacts with trace moisture or other compounds containing active hydrogen or moisture in the air on the surface of the substrate to form a cross-linked network and enhance the adhesive force. The moisture curing is simple to operate, the final bonding strength is high, the green and environment-friendly effects are achieved, the production process is mature, the curing time is long, and the initial adhesion is low.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a dual-curing polyurethane hot melt adhesive, a preparation method and a use method thereof, which are used for solving the problems in the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a dual-curing polyurethane hot melt adhesive, which comprises the following raw material components of a main material and an auxiliary material;
the main material comprises the following raw material components: polyester polyols, polyether polyols, chemical modifiers, isocyanates and
a chain extender;
the auxiliary materials comprise the following raw material components: physical modifier, catalyst, silane coupling agent, photoinitiator, antioxidant and white carbon black.
Preferably, the molar ratio of the polycarbonate polyol, the polyether polyol, the isocyanate, the chemical modifier and the chain extender in the main material is 1: (0.1-0.5): (1-10): (0.1-1): (0.1 to 1).
More preferably, the molar ratio of the polycarbonate polyol, the polyether polyol, the isocyanate, the chemical modifier and the chain extender in the main material is: 1: (0.1-0.5): (2-6): (0.2-0.8): (0.2-0.8).
Preferably, the amount of the physical modifier is 15-40 parts by weight based on 100 parts of the main material. More preferably, the physical modifier is used in an amount of 20 to 35 parts by weight.
Preferably, the silane coupling agent is used in an amount of not more than 5 parts by weight based on 100 parts of the main material. More preferably, the silane coupling agent is used in an amount of not more than 3 parts by weight.
Preferably, the photoinitiator is used in an amount of not more than 5 parts by weight based on 100 parts of the main material. More preferably, the photoinitiator is used in an amount of not more than 3 parts by weight.
Preferably, the antioxidant is used in an amount of not more than 5 parts by weight based on 100 parts of the main material. More preferably, the antioxidant is used in an amount of not more than 3 parts by weight.
Preferably, the white carbon black is used in an amount of not more than 5 parts by weight based on 100 parts of the main material. More preferably, the white carbon black is used in an amount of not more than 3 parts by weight. Preferably, the catalyst is added in catalytic amounts. Preferably, the number average molecular weight of the polyester polyol is 2000-5000. More preferably, the polyester polyol is a mixture of molecular weights 2000 and 3000, and the molar ratio of the two is n2000:n3000＝1:(0.1～0.3)。
More preferably, the polyester polyol is a 1, 6-hexanediol adipate diol.
Preferably, the polyether polyol is polytetrahydrofuran diol.
Preferably, the number average molecular weight of the polyether polyol is 1500-3500.
Preferably, the isocyanate is one or two of 4, 4' -diphenylmethane diisocyanate and isophorone diisocyanate. When the isocyanate is a mixture of the two, the molar ratio of 4, 4' diphenylmethane diisocyanate to isophorone diisocyanate is 1: (0.1-0.5).
Preferably, the chemical modifier is 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate.
Preferably, the chain extender is 1, 4-butanediol.
Preferably, the physical modifier is a mixture of tackifying resin and diluent monomer. More preferably, the mass ratio of the diluent monomer to the tackifying resin is 1: (0.6-2.0).
Preferably, the diluent monomer is one or two of tetrahydrofuran acrylate (abbreviated as THFA) and ethoxyethoxyethyl acrylate (abbreviated as EOEOEA). More preferably, the diluent monomer is a mixture of both. More preferably, the mass ratio of the tetrahydrofuran acrylate to the ethoxyethoxyethyl acrylate is 1: (0.6-2.0).
Preferably, the tackifying resin is an acrylic resin. More preferably, the acrylic resin has a number average molecular weight of 2000 to 4000.
Preferably, the catalyst is an organotin catalyst. More preferably, the catalyst is dibutyltin dilaurate.
Preferably, the silane coupling agent is selected from one or more of gamma-methacryloxypropyltrimethoxysilane (KH-550), gamma-glycidoxypropyltrimethoxysilane (KH-560) and gamma-methacryloxypropyltrimethoxysilane (KH-570).
Preferably, the photoinitiator is one or more of benzoin ethyl ether (BEE for short), diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (TPO for short) and 1-hydroxycyclohexyl phenyl ketone (HCPK for short). More preferably, when there are more than one, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide is used in an amount of not more than 80% of benzoin ethyl ether; or 1-hydroxycyclohexyl phenyl ketone is used in an amount of not more than 80% of benzoin ethyl ether.
Preferably, the antioxidant is one or two of antioxidant 1010 and antioxidant 1076.
Preferably, the white carbon black is fumed silica.
Preferably, the water content of the feed components described herein is less than 1 g/kg. The raw material components can be purchased already reaching the water content requirement, or subjected to dehydration treatment by means of heating, vacuum heating and the like.
The invention also discloses a preparation method of the dual-curing polyurethane hot melt adhesive, which comprises the following steps:
1) mixing polyester polyol, polyether polyol, a physical modifier and an antioxidant;
2) adding isocyanate and a catalyst for reaction;
3) adding a chemical modifier, a chain extender and a silane coupling agent for reaction;
4) adding white carbon black, adding a photoinitiator under the condition of avoiding ultraviolet irradiation, reacting, discharging and packaging.
Preferably, the method further comprises the step of heating and curing the product obtained after encapsulation. More preferably, the addition is made at the time of curing
The heating temperature is 70-100 ℃. More preferably, the aging time is not less than 3 hours.
Preferably, the raw material components are subjected to a thermal dehydration treatment in step 1).
Preferably, in steps 2), 3) or/and 4), the addition is carried out under an inert gas atmosphere. To avoid introducing water
Or water vapor.
Preferably, in the step 2), 3) or/and 4), the reaction temperature is 20-100 ℃.
Preferably, in step 2), 3) or/and 4), the reaction is carried out under vacuum.
Preferably, the packaging container or package in step 4) is selected from a uv-opaque material. Such as aluminum foil bags and the like.
Preferably, in step 4), the discharge is carried out under the protection of inert gas.
Preferably, in the step 4), the temperature of the system is 70-100 ℃ during discharging.
The invention also discloses a using method of the dual-curing polyurethane hot melt adhesive, which comprises the steps of heating to be completely melted, gluing, irradiating under ultraviolet light, and standing and solidifying until the final adhesive strength is reached. Preferably, the heating temperature is 80-130 ℃.
According to the technical scheme, the UV light/moisture dual-curing polyurethane hot melt adhesive has the advantages of the moisture-curing polyurethane hot melt adhesive and the UV curing hot melt adhesive, and the defects of the moisture-curing polyurethane hot melt adhesive and the UV curing hot melt adhesive are improved; 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate is used as a chemical modifier to synthesize the UV light/wet dual-curing polyurethane hot melt adhesive, and an acrylate diluent is used for blending, so that the compatibility among the components is improved, and the polyurethane hot melt adhesive product which has high initial bonding strength, good toughness, strong weather resistance and convenient construction is obtained.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. 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 addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Example 1
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 13.50g of polyhexamethylene adipate glycol with the molecular weight of 3000, 18.00g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10101.70 g of antioxidant, 17.00g of acrylic resin, 13.80g of tetrahydrofuran acrylate and 8.29g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 37.80g of 4, 4' -diphenylmethane diisocyanate (MDI), 3.73g of isophorone diisocyanate (IPDI) and 1.70g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 5.50g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 1.42g of chain extender 1, 4-butanediol, KH-5601.50 g of silane coupling agent and KH-5701.05 g of the chain extender, closing the nitrogen, and reacting for 60min under the conditions that the temperature is 85-95 ℃ and the absolute pressure is less than 100 Pa;
(4) and introducing nitrogen to remove vacuum, adding 1.70g of fumed silica and 3.91g of benzoin ethyl ether, then closing the nitrogen, continuously stirring for 30min at 85-95 ℃ under the absolute pressure of less than 100Pa, quickly discharging under the protection of the nitrogen, and packaging in an aluminum foil bag.
(5) After packaging, the product is cured for 6 hours in an oven at the temperature of 80-85 ℃, and the obtained product is marked as A.
Example 2
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 20.25g of polyhexamethylene adipate glycol with the molecular weight of 3000, 9.00g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10101.72 g of antioxidant, 25.72g of acrylic resin, 10.97g of tetrahydrofuran acrylate and 16.45g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 33.36g of 4, 4' -diphenylmethane diisocyanate (MDI), 9.88g of isophorone diisocyanate (IPDI) and 1.72g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 7.71g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 1.22g of chain extender 1, 4-butanediol, KH-5600.92 g of silane coupling agent and KH-5700.80 g of the chain extender, closing the nitrogen, and reacting for 60min under the conditions that the temperature is 85-95 ℃ and the absolute pressure is less than 100 Pa;
(4) introducing nitrogen to relieve vacuum, adding 1.72g of fumed silica, 3.20g of benzoin ethyl ether and 1.95g of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, then closing the nitrogen, continuously stirring for 30min at 85-95 ℃ under the absolute pressure of less than 100Pa, quickly discharging under the protection of nitrogen, and packaging in an aluminum foil bag;
(5) curing for 8h in an oven at 80-85 ℃ after packaging, and marking the obtained product as B.
Example 3
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 27.0g of polyhexamethylene adipate glycol with the molecular weight of 3000, 27.0g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10102.00 g of antioxidant, 24.0g of acrylic resin, 20.00g of tetrahydrofuran acrylate and 19.99g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 41.34g of 4, 4' -diphenylmethane diisocyanate (MDI), 9.18g of isophorone diisocyanate (IPDI) and 2.00g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 4.41g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 1.01g of chain extender 1, 4-butanediol, KH-5600.60 g of silane coupling agent and KH-5700.40 g of chain extender, closing the nitrogen, and reacting for 60min under the conditions that the temperature is 85-95 ℃ and the absolute pressure is less than 100 Pa;
(4) and introducing nitrogen to relieve vacuum, adding 2.00g of fumed silica, 2.50g of benzoin ethyl ether and 1.10g of 1-hydroxycyclohexyl phenyl ketone, then closing the nitrogen, continuously stirring for 30min at 85-95 ℃ under the absolute pressure of less than 100Pa, quickly discharging under the protection of the nitrogen, and packaging in an aluminum foil bag.
(5) Curing for 8h in an oven at 80-85 ℃ after packaging, and marking the obtained product as C.
Example 4
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 33.75g of polyhexamethylene adipate glycol with the molecular weight of 3000, 22.5g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10102.04 g of antioxidant, 28.46g of acrylic resin, 12.29g of tetrahydrofuran acrylate and 8.03g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 40.85g of 4, 4' -diphenylmethane diisocyanate (MDI), 6.43g of isophorone diisocyanate (IPDI) and 2.04g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 8.82g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 0.81g of 1, 4-butanediol serving as a chain extender, KH-5600.52 g of a silane coupling agent and KH-5700.50 g of the silane coupling agent, then closing the nitrogen and reacting for 60min under the conditions of 85-95 ℃ and absolute pressure of less than 100 Pa;
(4) and introducing nitrogen to relieve vacuum, adding 2.04g of fumed silica, 2.5g of benzoin ethyl ether and 0.75g of 1-hydroxycyclohexyl phenyl ketone, then closing the nitrogen, continuously stirring for 30min at 85-95 ℃ under the absolute pressure of less than 100Pa, quickly discharging under the protection of the nitrogen, and packaging in an aluminum foil bag.
(5) After packaging, the product is cured in an oven at 85 ℃ for 7h, and the obtained product is marked as D.
Example 5
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 40.5g of polyhexamethylene adipate glycol with the molecular weight of 3000, 13.5g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10102.07 g of antioxidant, 26.84g of acrylic resin, 16.89g of tetrahydrofuran acrylate and 20.27g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 39.26g of 4, 4' -diphenylmethane diisocyanate (MDI), 14.94g of isophorone diisocyanate (IPDI) and 2.07g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 6.60g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate, 1.63g of chain extender 1, 4-butanediol, KH-5601.2 g of silane coupling agent and KH-5700.86 g of silane coupling agent, then closing the nitrogen and reacting for 60min under the conditions of 85-95 ℃ and absolute pressure less than 100 Pa;
(4) and introducing nitrogen to relieve vacuum, adding 2.07g of fumed silica, 2.3g of benzoin ethyl ether and 1.83g of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, then closing the nitrogen, continuously stirring for 30min at 85-95 ℃ under the absolute pressure of less than 100Pa, quickly discharging under the protection of nitrogen, and packaging in an aluminum foil bag.
(5) After packaging, the product is cured in an oven at 85 ℃ for 7h, and the obtained product is marked as E.
Comparative example 1
(1) 90.00g of polyhexamethylene adipate glycol with the molecular weight of 2000, 27.0g of polyhexamethylene adipate glycol with the molecular weight of 3000, 9.0g of polytetrahydrofuran ether glycol with the molecular weight of 2000, 10101.72 g of antioxidant, 25.50g of acrylic resin, 14.51g of tetrahydrofuran acrylate and 11.0g of ethoxyethyl acrylate are weighed and added into a four-neck flask with the volume of 1.0L, stirred and heated to 110-120 ℃, and vacuum dehydration is carried out for 120min under the absolute pressure of 80 Pa.
(2) Cooling to 80 ℃, introducing nitrogen to relieve vacuum, adding 30.88g of 4, 4' -diphenylmethane diisocyanate (MDI), 11.49g of isophorone diisocyanate (IPDI) and 1.7g of dibutyltin dilaurate serving as a catalyst, closing the nitrogen, and reacting for 60min at the temperature of 85-95 ℃ and the absolute pressure of less than 100 Pa;
(3) introducing nitrogen to relieve vacuum, adding 1.63g of chain extender 1, 4-butanediol, KH-5601.0 g of silane coupling agent and KH-5700.70 g, then closing the nitrogen and reacting for 60min under the conditions that the temperature is 85-95 ℃ and the absolute pressure is less than 100 Pa;
(4) and introducing nitrogen to remove vacuum, adding 1.7g of fumed silica, then closing the nitrogen, continuously stirring for 30min at the temperature of 85-95 ℃ and under the absolute pressure of less than 100Pa, quickly discharging under the protection of the nitrogen, and packaging in an aluminum foil bag.
(5) After packaging, the product was cured in an oven at 85 ℃ for 7h, and the obtained product was marked F.
Example 6
In this example, the molar ratio of polycarbonate polyol, polyether polyol, isocyanate, chemical modifier and chain extender in the main material is 1: 0.2: 2: 0.2: 0.5.
in the auxiliary materials of this example, the physical modifier is 20 parts by weight based on 100 parts of the main material; 5 parts by weight of a silane coupling agent; 3 parts of photoinitiator; 3 parts of antioxidant; 3 parts of white carbon black; the amount of the catalyst is the amount of the catalyst.
The steps and parameters of the preparation method of the hot melt adhesive in this example are the same as those in example 1.
Example 7
In this example, the molar ratio of polycarbonate polyol, polyether polyol, isocyanate, chemical modifier and chain extender in the main material is 1: 0.5: 6: 0.5: 0.2.
in the auxiliary materials of this example, the physical modifier is 35 parts by weight based on 100 parts of the main material; 3 parts by weight of a silane coupling agent; 2 parts of photoinitiator; 2 parts of antioxidant; 4 parts of white carbon black; the amount of the catalyst is the amount of the catalyst.
The steps and parameters of the preparation method of hot melt adhesive in this example are the same as those of example 1
Example 8
In this example, the molar ratio of polycarbonate polyol, polyether polyol, isocyanate, chemical modifier and chain extender in the main material is 1: 0.4: 6: 0.3: 0.8.
in the auxiliary materials of this example, the physical modifier is 25 parts by weight based on 100 parts of the main material; 2 parts by weight of a silane coupling agent; 3 parts of photoinitiator; 4 parts of antioxidant; 3 parts of white carbon black; the amount of the catalyst is the amount of the catalyst.
The steps and parameters of the preparation method of the hot melt adhesive in this example are the same as those in example 1.
Example 9
In this example, the molar ratio of polycarbonate polyol, polyether polyol, isocyanate, chemical modifier and chain extender in the main material is 1: 0.5: 2: 0.8: 0.6.
in the auxiliary materials of this example, the physical modifier is 30 parts by weight based on 100 parts of the main material; 4 parts by weight of a silane coupling agent; 2 parts of photoinitiator; 2 parts of antioxidant; 3 parts of white carbon black; the amount of the catalyst is the amount of the catalyst.
The steps and parameters of the preparation method of the hot melt adhesive in this example are the same as those in example 1.
Sample testing
(1) Melt viscosity:
the measurement is carried out at 120 ℃ and the sealed polyurethane hot melt adhesive is placed in a syringe heater of HL-YR123 at 110 ℃ for 30min according to the standard HG/T3660-1999. At the moment, the hot melt adhesive is already molten fluid, the molten fluid is quickly poured into a sleeve in a DV-II + pro Viscometer, 10.0 +/-0.2 g of the hot melt adhesive is weighed, the temperature is set at 120 ℃ and is kept for 20 minutes, and the internal temperature of the hot melt adhesive is uniform and defoamed. The constant temperature melt viscosity of the hot melt adhesive was measured at a temperature of 120 ℃.
(2) Bonding strength:
2 strips of the hot melt adhesive tape with the width of 1mm, the length of more than 25mm and the thickness of 0.3mm are uniformly coated on a glass plate with the specification of 25mm width, 100mm length and 5mm thickness at the positions 6mm away from two edges along the length direction of the glass plate. The thickness of the adhesive tape was controlled by using a 0.15mm diameter steel wire, two glass plates were immediately bonded together by a second glass plate of the same specification in a direction perpendicular to the first glass plate, and the bonded joint was pressed with 1.5 kg force for 15 seconds, irradiated with a 1000W high pressure mercury lamp for 10 seconds, and then placed in a constant temperature and humidity chamber to test the bonding strength after 15min and 72h, respectively, as the initial bonding strength and the final bonding strength of the sample.
(3) Tensile strength and elongation at break:
the gum sample was prepared in accordance with ASTM D638, and was formed into a sheet-like shape having a width of 6mm and a thickness of 0.5mm, and a dumbbell-like shape. The sample is placed in a constant temperature and humidity box (humidity is 60 percent and temperature is 25 ℃) for 72 hours, and then the tensile strength and the elongation at break of the rubber sample are tested according to the method of ASTM D638 standard, the tensile speed is 100mm/min, and the test temperature is 25 ℃. The resulting tensile strength and elongation at break are respectively recorded as TS0And EL0。
(4) And (3) weather resistance test: the gum sample was prepared in accordance with ASTM D638, and was formed into a sheet-like shape having a width of 6mm and a thickness of 0.5mm, and a dumbbell-like shape. Placing a sample in a constant temperature and humidity box (with the humidity of 60 percent and the temperature of 25 ℃) for 72 hours, then placing the sample in a high-low temperature damp-heat aging box for weather resistance test for 240 hours, wherein the test process is automatically carried out by the aging box, and the specific steps comprise firstly testing for 10 hours under the conditions of the temperature of 80 ℃ and the humidity of 80 percent, then testing for 10 hours under the conditions of-40 ℃ and the humidity of 80 percent, and then alternately carrying out the test until the total test time is 240 hours. After the test is finished, the tensile strength and the elongation at break are tested, the tensile speed is 100mm/min, and the test temperature is 25 ℃. The resulting tensile strength and elongation at break are respectively recorded as TS1And EL1. The weatherability of each sample is characterized by its tensile strength change (α) and elongation at break change (β) as calculated by the following formula:
table 1 performance test values for the examples and comparative examples
As can be seen from the data in Table 1, the initial adhesive strength and the final adhesive strength of the products in examples 1 to 5 and 6 to 9 of the invention are respectively 424 to 581 percent higher and 8.6 to 36.7 percent higher than those of the comparative product F, which indicates that the initial adhesive strength can be obviously improved in the photocuring process, and the addition of the chemical modifier has a certain positive effect on the improvement of the final adhesive strength. On the other hand, the tensile strength and the elongation at break of the products in the embodiments 1 to 5 and the embodiments 6 to 9 of the invention are respectively higher than those of the comparative product (F) by more than 4.7 percent and 21.5 percent, and particularly, the change rates of the tensile strength and the elongation at break of the products A to E after high and low temperature damp heat aging tests are also much smaller than those of the product F, which shows that the toughness and the weather resistance of the product can be improved by adding the chemical modifier.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A dual-curing polyurethane hot melt adhesive is characterized in that the raw material components of the polyurethane hot melt adhesive comprise main materials and auxiliary materials;
the main material comprises the following raw material components: polyester polyol, polyether polyol, a chemical modifier, isocyanate and a chain extender;
the auxiliary materials comprise the following raw material components: physical modifier, catalyst, silane coupling agent, photoinitiator, antioxidant and white carbon black; the polyester polyol is poly adipic acid-1, 6-hexanediol glycol;
the polyether polyol is polytetrahydrofuran diol;
the isocyanate is one or two of 4, 4' -diphenylmethane diisocyanate and isophorone diisocyanate;
the chemical modifier is 2- (4-benzoyl-3-hydroxyphenoxy) ethyl methacrylate;
the chain extender is 1, 4-butanediol;
the physical modifier is a mixture of tackifying resin and diluent monomer;
the mass ratio of the diluent monomer to the tackifying resin is 1: (0.6-2.0);
the diluent monomer is one or two of tetrahydrofuran acrylate and ethoxy ethyl acrylate;
the tackifying resin is acrylic resin;
the silane coupling agent is selected from one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane;
the photoinitiator is one or more of benzoin ethyl ether, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide and 1-hydroxycyclohexyl phenyl ketone;
the molar ratio of polycarbonate polyol, polyether polyol, isocyanate, chemical modifier and chain extender in the main material is 1: (0.1-0.5): (1-10): (0.1-1): (0.1 to 1);
based on 100 parts of main material, the use amount of the physical modifier is 15-40 parts by weight, the use amount of the silane coupling agent is not more than 5 parts by weight, the use amount of the photoinitiator is not more than 5 parts by weight, the use amount of the antioxidant is not more than 5 parts by weight, and the use amount of the white carbon black is not more than 5 parts by weight.
2. The dual cure polyurethane hot melt adhesive of claim 1, comprising one or more of the following features:
the number average molecular weight of the polyester polyol is 2000-5000;
the number average molecular weight of the polyether polyol is 1500-3500.
3. The dual cure polyurethane hot melt adhesive of claim 1, comprising one or more of the following features:
the catalyst is an organic tin catalyst;
the antioxidant is one or two of antioxidant 1010 and antioxidant 1076;
the white carbon black is fumed silica;
the water content of the raw material components is less than 1 g/kg.
4. A method for preparing the dual-curing polyurethane hot melt adhesive as claimed in any one of claims 1 to 3, comprising the following steps:
1) mixing polyester polyol, polyether polyol, a physical modifier and an antioxidant;
2) adding isocyanate and a catalyst for reaction;
3) adding a chemical modifier, a chain extender and a silane coupling agent for reaction;
4) adding white carbon black, adding a photoinitiator under the condition of avoiding ultraviolet irradiation, reacting, discharging and packaging.
5. The method for preparing dual cure polyurethane hot melt adhesive according to claim 4, characterized in that, the method further comprises the step of heating and curing the product obtained after encapsulation.
6. The method for preparing a dual cure polyurethane hot melt adhesive according to claim 5, characterized by comprising one or more of the following features:
the heating temperature is 70-100 ℃ during curing;
the curing time is not less than 3 h.
7. The method for preparing a dual cure polyurethane hot melt adhesive according to claim 4, characterized by comprising one or more of the following features:
in the step 2), 3) or/and 4), the charging is carried out under the inert gas protection atmosphere;
in the step 2), 3) or/and 4), the reaction temperature is 20-100 ℃;
in steps 2), 3) or/and 4), the reaction is carried out under vacuum.
8. The method for preparing a dual cure polyurethane hot melt adhesive according to claim 4, characterized by comprising one or more of the following features:
in the step 4), the packaging container or package selects materials which can not be penetrated by ultraviolet rays;
in the step 4), discharging is carried out under the protection of inert gas;
in the step 4), the system temperature is 70-100 ℃ during discharging.
9. The use method of the dual-curing polyurethane hot melt adhesive as claimed in any one of claims 1 to 3, wherein the dual-curing polyurethane hot melt adhesive is heated to be completely melted, then is applied with glue and irradiated under ultraviolet light, and is placed and cured until the final adhesive strength is achieved.
10. The use method of the dual-curing polyurethane hot melt adhesive as claimed in claim 9, wherein the heating temperature is 80-130 ℃.
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| CN110229644B (en) * | 2019-06-05 | 2021-09-03 | 格丽泰新材料科技（苏州）有限公司 | Reactive polyurethane hot melt adhesive and preparation method and application thereof |
| JP2022541473A (en) * | 2019-07-17 | 2022-09-26 | アルケマ フランス | (Meth)acrylate-functionalized oligomers and methods of preparing and using such oligomers |
| CN110452655A (en) * | 2019-07-31 | 2019-11-15 | 东莞市澳中电子材料有限公司 | A kind of light/wet double solidification polyurethane hot melts and preparation method thereof |
| CN111154067A (en) * | 2020-01-21 | 2020-05-15 | 江苏景宏新材料科技有限公司 | Low-viscosity high-peel-strength UV (ultraviolet) curing composite adhesive and preparation method thereof |
| WO2021212358A1 (en) * | 2020-04-22 | 2021-10-28 | 北京理工大学 | Hot-melt reaction type polyurethane material, preparation method therefor and use thereof |
| WO2023196484A1 (en) * | 2022-04-07 | 2023-10-12 | Basf Se | Dual curable pressure sensitive adhesive |
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