CN107987779A - A kind of reaction type polyurethane hot-melt adhesive and its preparation method and application - Google Patents
A kind of reaction type polyurethane hot-melt adhesive and its preparation method and application Download PDFInfo
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- CN107987779A CN107987779A CN201711291104.2A CN201711291104A CN107987779A CN 107987779 A CN107987779 A CN 107987779A CN 201711291104 A CN201711291104 A CN 201711291104A CN 107987779 A CN107987779 A CN 107987779A
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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
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of reaction type polyurethane hot-melt adhesive and its preparation method and application, the reaction type polyurethane hot-melt adhesive is prepared by the raw material including following components：The parts by weight of 100 parts by weight of polyester polyol~120；The parts by weight of 1 parts by weight of polyether polyol~150；The parts by weight of 50 parts by weight of isocyanates~100；The parts by weight of 50 parts by weight of modifying agent~350；The parts by weight of 1 parts by weight of chain extender~5；The parts by weight of 1 parts by weight of antioxidant~5；The parts by weight of 0.01 parts by weight of catalyst~0.1；The mass content of the polyether polyol ethylene oxide is 40%~50%, and hydroxyl value is 21KOH/mg~112KOH/mg；The modifying agent is (1~6) by mass ratio：1 tackifying resin and filler composition.The present invention is by adding the polyether polyol with extra fine quality content epoxy ethane, and under the modifying agent collective effect of certain content component, hot melt adhesive is improved in uncured preceding water permeability, obtained product has good high temperature without trickling performance, faster deep cure and excellent thixotropy, can be used as hot melt adhesive for car light application.
Description
Technical field
The present invention relates to polyurethane sealant technical field, is to be related to a kind of reaction type polyurethane hot melt more specifically
Glue and its preparation method and application.
Background technology
Reaction type polyurethane hot-melt adhesive (abbreviation PUR)：It is pre- containing end NCO polyurethane in moisture-curable polyurethane hot melt adhesive component
Aggressiveness, produces under the condition of high temperature, moisture or active hydrogen thing in active functional group and air or on adherend after heating
Qualitative response and form part cross-linked structure, make the performance such as adhesive strength, chemicals-resistant, heat-resisting, hydrolysis better than general heat
Melten gel.Reaction type polyurethane hot-melt adhesive is widely used in the industries such as carpenter, weaving, automobile, electronics, household electrical appliances.Reaction type polyurethane heat
The synthesis of melten gel is one and chemically reacts the process being combined with physical mixed.Reaction type polyurethane hot-melt adhesive in the prior art
The chemical reaction of synthesis generally refers to the reaction of isocyanates and multicomponent alcoholics compound, and wherein isocyanates uses hexichol
Dicyclohexylmethane diisocyanate (abbreviation MDI), and multicomponent alcoholics compound be number average molecular 1000~5000 polyester and
Polyethers.
At present, performance report of many car lights in reaction type polyurethane hot-melt adhesive patent on reaction type polyurethane hot-melt adhesive
Road, which is concentrated mainly on, improves heat resistance and adhesive property aspect, high temperature trickling property and follow-up deep cure on concrete application
Report it is less.Chinese patent such as Publication No. CN103740316A discloses a kind of car light moisture-curable polyurethane hot melt adhesive
And preparation method thereof, to basic performances such as the adhesive properties, melt viscosity, open hour of car light reaction type polyurethane hot-melt adhesive
Detailed elaboration has been carried out, but since the frock in car light preparation process can there are many high-low-positions, the poly- ammonia of popular response type
Ester hot melt adhesive when in use, often because trickling causes cloth glue uneven, causes technique unstable；Knot in conventional formulation at the same time
Crystalline substance polyester polyol amount is larger, and the performed polymer to be formed is reacted with isocyanates since its crosslink density is larger, and water penetration is poor,
Along with car light can only top it is permeable, therefore deep cure is slower, often all cannot within one month in China's winter some car lights
The problem of being fully cured, trickling occurred to glue heating again, so that the appearance for the problems such as causing car light leak, hazing.
Therefore, also there are high temperature trickling property is poor, deep cure is relatively slow and does not have for reaction type polyurethane of the prior art
Standby thixotropic technical problem, it is difficult to realize as hot melt adhesive for car light and further apply.
The content of the invention
In view of this, it is an object of the invention to provide a kind of reaction type polyurethane hot-melt adhesive and preparation method thereof and should
There is good high temperature without trickling performance, faster deep cure and excellent with, reaction type polyurethane hot-melt adhesive provided by the invention
Different thixotropy, can be used as hot melt adhesive for car light application.
The present invention provides a kind of reaction type polyurethane hot-melt adhesive, is prepared by the raw material including following components：
The parts by weight of 100 parts by weight of polyester polyol~120；
The parts by weight of 1 parts by weight of polyether polyol~150；
The parts by weight of 50 parts by weight of isocyanates~100；
The parts by weight of 50 parts by weight of modifying agent~350；
The parts by weight of 1 parts by weight of chain extender~5；
The parts by weight of 1 parts by weight of antioxidant~5；
The parts by weight of 0.01 parts by weight of catalyst~0.1；
The mass content of the polyether polyol ethylene oxide be 40%~50%, hydroxyl value for 21KOH/mg~
112KOH/mg；
The modifying agent is (1~6) by mass ratio：1 tackifying resin and filler composition.
Preferably, the polyester polyol is selected from succinic acid-butanediol ester glycol, tetramethylene adipate glycol, ethanedioic acid
One or more in glycol ester glycol and adipic acid hexylene glycol esterdiol.
Preferably, the tackifying resin is selected from acrylic resin, hydroxyl terminated polyurethane, Petropols, polyolefins and increases
One or more in viscosity resin and terpene resin.
Preferably, one or more of the filler in carbon black, hydrophobicity gas-phase silica and powdered whiting.
Preferably, the chain extender is selected from the one or more in 1,4-butanediol, ethylene glycol and 1,6- hexylene glycol.
Preferably, the catalyst is selected from dibutyl tin laurate, organo-bismuth, triethylenediamine and dimorpholine base two
One or more in ethylether.
Present invention also offers a kind of preparation method of the reaction type polyurethane hot-melt adhesive described in above-mentioned technical proposal, including
Following steps：
It is dehydrated after polyester polyol, polyether polyol, antioxidant and tackifying resin are mixed, adds isocyanates and expansion
Chain agent is reacted, and is eventually adding filler and catalyst carries out vacuum defoamation, reaction type polyurethane hot melt is obtained after being uniformly dispersed
Glue.
Preferably, the temperature of the dehydration be 105 DEG C~130 DEG C, vacuum≤- 0.095MPa, the time for 1.5h~
2.5h。
Preferably, it is described to add the process that isocyanates and chain extender are reacted and be specially：
At 75 DEG C~85 DEG C, first add isocyanates and be warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, add expansion
Chain agent the reaction was continued 0.5h~1h, to the reaction was complete.
Present invention also offers the reaction type polyurethane hot-melt adhesive or above-mentioned technical proposal described in a kind of above-mentioned technical proposal
Application of the reaction type polyurethane hot-melt adhesive that the preparation method is prepared in hot melt adhesive for car light.
The present invention provides a kind of reaction type polyurethane hot-melt adhesive and its preparation method and application, the reaction type polyurethane
Hot melt adhesive is prepared by the raw material including following components：The parts by weight of 100 parts by weight of polyester polyol~120；Polyether polyol 1
The parts by weight of parts by weight~150；The parts by weight of 50 parts by weight of isocyanates~100；The parts by weight of 50 parts by weight of modifying agent~350；Chain extension
The parts by weight of 1 parts by weight of agent~5；The parts by weight of 1 parts by weight of antioxidant~5；The parts by weight of 0.01 parts by weight of catalyst~0.1；It is described poly-
The mass content of ethoxylated polyhydric alcohol ethylene oxide is 40%~50%, and hydroxyl value is 21KOH/mg~112KOH/mg；The modifying agent
It is (1~6) by mass ratio：1 tackifying resin and filler composition.Compared with prior art, the present invention has specific by addition
The polyether polyol of the ethylene oxide of mass content, and under the collective effect of the modifying agent in certain content component, improve hot melt
For glue in uncured preceding water permeability, obtained reaction type polyurethane hot-melt adhesive has good high temperature without trickling performance, comparatively fast
Deep cure and excellent thixotropy, hot melt adhesive for car light application can be used as.It is test result indicates that provided by the invention anti-
Answer type polyurethane hot melt adhesive that there is suitable open hour and preferable thixotropy in applied at elevated temperature；As hot melt adhesive for car light
Even it will not still trickle when car light high-low-position reaches 90 ° of drops, cloth glue is uniform, and deep cure is very fast.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's all other embodiments obtained without making creative work, belong to this hair
The scope of bright protection.
The present invention provides a kind of reaction type polyurethane hot-melt adhesive, is prepared by the raw material including following components：
The parts by weight of 100 parts by weight of polyester polyol~120；
The parts by weight of 1 parts by weight of polyether polyol~150；
The parts by weight of 50 parts by weight of isocyanates~100；
The parts by weight of 50 parts by weight of modifying agent~350；
The parts by weight of 1 parts by weight of chain extender~5；
The parts by weight of 1 parts by weight of antioxidant~5；
The parts by weight of 0.01 parts by weight of catalyst~0.1；
The mass content of the polyether polyol ethylene oxide be 40%~50%, hydroxyl value for 21KOH/mg~
112KOH/mg；
The modifying agent is (1~6) by mass ratio：1 tackifying resin and filler composition.
In the present invention, the polyester polyol is preferably crystalline polyester polyols；The crystalline polyester polyols
The effect for improving initial bonding force is primarily served, while helps to shorten the open hour of hot melt adhesive.In the present invention, the polyester
The hydroxyl value of polyalcohol is preferably 21KOH/mg~56KOH/mg, and water content is preferably smaller than equal to 0.1%.In the present invention, it is described
Polyester polyol be preferably selected from succinic acid-butanediol ester glycol, tetramethylene adipate glycol, ethanedioic acid glycol ester glycol and
One or more in adipic acid hexylene glycol esterdiol, more preferably adipic acid hexylene glycol esterdiol or succinic acid-butanediol ester two
Alcohol.The present invention is not particularly limited the source of the polyester polyol, using above-mentioned fourth two well known to those skilled in the art
Sour butyl glycol ester diol, tetramethylene adipate glycol, the city of ethanedioic acid glycol ester glycol and adipic acid hexylene glycol esterdiol
Sell commodity.In the present invention, the reaction type polyurethane hot-melt adhesive include the parts by weight of 100 parts by weight~120 polyester it is more
First alcohol.
In the present invention, the mass content of the polyether polyol ethylene oxide (EO) is 40%~50%, and hydroxyl value is
21KOH/mg~112KOH/mg, is preferably 56KOH/mg, and water content is preferably smaller than equal to 0.1%.In the present invention, it is described poly-
Ethoxylated polyhydric alcohol is preferably selected from polyoxypropyleneglycol, polypropylene oxide triol and one kind or more in polytetrahydrofuran ether glycol
Kind；The present invention is not particularly limited the species of the polyether polyol and source, using the polyethers for meeting above-mentioned parameter requirement
The commercial goods of polyalcohol.In the present invention, the reaction type polyurethane hot-melt adhesive includes the parts by weight of 1 parts by weight~150
Polyether polyol, be preferably the parts by weight of 100 parts by weight~150.
In the present invention, the isocyanates is preferably selected from toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate
(IPDI), two isocyanide of methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI) and hexa-methylene
One or more in acid esters (HDI), more preferably methyl diphenylene diisocyanate (MDI).The present invention is to the isocyanic acid
The source of ester is not particularly limited, using above-mentioned toluene di-isocyanate(TDI) (TDI) well known to those skilled in the art, isophorone
Diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI) and six are sub-
The commercial goods of methyl diisocyanate (HDI).In the present invention, the reaction type polyurethane hot-melt adhesive includes 50 weight
Part~100 parts by weight isocyanates, be preferably the parts by weight of 60 parts by weight~75.
In the present invention, the modifying agent is (1~6) by mass ratio：1 tackifying resin and filler composition.In the present invention
In, the tackifying resin be preferably selected from acrylic resin, hydroxyl terminated polyurethane, Petropols, polyolefins tackifying resin and
One or more in terpene resin, more preferably acrylic resin or hydroxyl terminated polyurethane.The present invention sets the thickening
The source of fat is not particularly limited, using aforesaid propylene acid resin well known to those skilled in the art, hydroxyl terminated polyurethane, stone
The commercial goods of oleoresin, polyolefins tackifying resin and terpene resin.
In the present invention, the filler is preferably selected from one kind in carbon black, hydrophobicity gas-phase silica and powdered whiting
Or it is a variety of, it is more preferably carbon black or hydrophobicity gas-phase silica.The present invention is not particularly limited the source of the filler, uses
The commercial goods of above-mentioned carbon black well known to those skilled in the art, hydrophobicity gas-phase silica and powdered whiting.
The present invention is primarily served using the modifying agent of certain content component to be improved melt viscosity, reduces mobility and raising
Resistance to elevated temperatures, and certain thixotropy is kept, so that the thixotropic effects under reaching a high temperature.In the present invention, the response type
Polyurethane hot melt includes the modifying agent of the parts by weight of 50 parts by weight~350, is preferably the parts by weight of 125 parts by weight~175.
In the present invention, the chain extender be preferably selected from 1,4-butanediol, ethylene glycol and one kind in 1,6- hexylene glycol or
It is a variety of, it is more preferably 1,4-butanediol or ethylene glycol.The present invention is not particularly limited the source of the chain extender, using ability
It is above-mentioned from the commercial goods of 1,4-butanediol, ethylene glycol and 1,6- hexylene glycol known to field technique personnel.In the present invention,
The reaction type polyurethane hot-melt adhesive includes the chain extender of the parts by weight of 1 parts by weight~5, is preferably the parts by weight of 1 parts by weight~2.
In the present invention, the antioxidant is preferably selected from 2,6-di-tert-butyl p-methylphenol, four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester, the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three
One or more in (2.4- di-tert-butyl-phenyls) phosphite ester and double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, more
Preferably 2,6- di-tert-butyl methyl phenols.The present invention is not particularly limited the source of the antioxidant, using this area
Above-mentioned 2,6- di-tert-butyl methyl phenols, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] known to technical staff
Pentaerythritol ester, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three (2.4- di-tert-butyl-phenyls) are sub-
The commercial goods of phosphate and double (3,5- di-tert-butyl-hydroxy phenyls) thioethers.In the present invention, the response type gathers
Urethane hot melt adhesive includes the antioxidant of the parts by weight of 1 parts by weight~5, is preferably 1 parts by weight.
In the present invention, the catalyst is preferably selected from dibutyl tin laurate, organo-bismuth, triethylenediamine and two
One or more in morpholinyl Anaesthetie Ether (DMDEE), more preferably dibutyl tin laurate, organo-bismuth and dimorpholine base
One or both of Anaesthetie Ether (DMDEE).The present invention is not particularly limited the source of the catalyst, using this area
Above-mentioned dibutyl tin laurate, organo-bismuth, triethylenediamine and dimorpholine base Anaesthetie Ether known to technical staff
(DMDEE) commercial goods.In the present invention, the reaction type polyurethane hot-melt adhesive includes the weight of 0.01 parts by weight~0.1
The antioxidant of part is measured, is preferably the parts by weight of 0.05 parts by weight~0.1.
The present invention has the polyether polyol of the ethylene oxide of extra fine quality content by addition, and in certain content component
Modifying agent collective effect under, improve hot melt adhesive uncured preceding water permeability, accelerate finished product deep cure, obtain
Reaction type polyurethane hot-melt adhesive has good high temperature without trickling performance, faster deep cure and excellent thixotropy, can
As hot melt adhesive for car light application.
Present invention also offers a kind of preparation method of the reaction type polyurethane hot-melt adhesive described in above-mentioned technical proposal, including
Following steps：
It is dehydrated after polyester polyol, polyether polyol, antioxidant and tackifying resin are mixed, adds isocyanates and expansion
Chain agent is reacted, and is eventually adding filler and catalyst carries out vacuum defoamation, reaction type polyurethane hot melt is obtained after being uniformly dispersed
Glue.
The present invention first mixes polyester polyol, polyether polyol, antioxidant and tackifying resin；The process of the mixing
It is preferred that it is specially：
Polyester polyol, polyether polyol and antioxidant are mixed, 75 DEG C~85 DEG C is warming up to, adds tackifying resin,
Complete mixed process.
In the present invention, the temperature of the dehydration is preferably 105 DEG C~130 DEG C, more preferably 115 DEG C~120 DEG C；It is described
The vacuum of dehydration preferably≤- 0.095MPa；The time of the dehydration is preferably 1.5h~2.5h, more preferably 2h.
After completing the dehydration, the present invention adds isocyanates in the reaction system and chain extender is reacted；Institute
Stating the process that addition isocyanates and chain extender are reacted preferably is specially：
At 75 DEG C~85 DEG C, first add isocyanates and be warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, add expansion
Chain agent the reaction was continued 0.5h~1h, to the reaction was complete.
After completing the reaction process, the present invention adds filler in the reaction system and catalyst carries out vacuum defoamation, point
Reaction type polyurethane hot-melt adhesive is obtained after dissipating uniformly.In the present invention, the time of the vacuum defoamation is preferably 0.5h~1h.
Present invention also offers the reaction type polyurethane hot-melt adhesive or above-mentioned technical proposal described in a kind of above-mentioned technical proposal
Application of the reaction type polyurethane hot-melt adhesive that the preparation method is prepared in hot melt adhesive for car light.It is provided by the invention
Reaction type polyurethane hot-melt adhesive is in addition to common hot melt adhesive for car light characteristic, when having suitable open in applied at elevated temperature
Between and preferable thixotropy；As hot melt adhesive for car light, hot melt adhesive is heated to the temperature in use of practical application, with PUR glue rifles
Uniformly to beat in the light trough of certain slope, or even will not still trickle when car light high-low-position reaches 90 ° of drops, cloth glue is uniform, and
Deep cure is very fast, is adapted to be applied in car light assembling field.
The present invention provides a kind of reaction type polyurethane hot-melt adhesive and its preparation method and application, the reaction type polyurethane
Hot melt adhesive is prepared by the raw material including following components：The parts by weight of 100 parts by weight of polyester polyol~120；Polyether polyol 1
The parts by weight of parts by weight~150；The parts by weight of 50 parts by weight of isocyanates~100；The parts by weight of 50 parts by weight of modifying agent~350；Chain extension
The parts by weight of 1 parts by weight of agent~5；The parts by weight of 1 parts by weight of antioxidant~5；The parts by weight of 0.01 parts by weight of catalyst~0.1；It is described poly-
The mass content of ethoxylated polyhydric alcohol ethylene oxide is 40%~50%, and hydroxyl value is 21KOH/mg~112KOH/mg；The modifying agent
It is (1~6) by mass ratio：1 tackifying resin and filler composition.Compared with prior art, the present invention has specific by addition
The polyether polyol of the ethylene oxide of mass content, and under the collective effect of the modifying agent in certain content component, improve hot melt
For glue in uncured preceding water permeability, obtained reaction type polyurethane hot-melt adhesive has good high temperature without trickling performance, comparatively fast
Deep cure and excellent thixotropy, hot melt adhesive for car light application can be used as.It is test result indicates that provided by the invention anti-
Answer type polyurethane hot melt adhesive that there is suitable open hour and preferable thixotropy in applied at elevated temperature；As hot melt adhesive for car light
Even it will not still trickle when car light high-low-position reaches 90 ° of drops, cloth glue is uniform, and deep cure is very fast.
In order to further illustrate the present invention, it is described in detail below by following embodiments.Following embodiments of the present invention
Raw material used is commercial goods.
Embodiment 1
The raw materials used formula ratio ginseng of embodiment 1 is shown in Table 1.
The raw materials used formula ratio of 1 embodiment 1 of table
| Raw material | Parts by weight |
| Adipic acid hexylene glycol esterdiol (hydroxyl value 31KOH/mg) | 100 |
| Polyether polyol (EO contents 40%, hydroxyl value 56KOH/mg) | 150 |
| MDI | 75 |
| Acrylic resin 2740 | 100 |
| 1,4- butanediols | 1 |
| Antioxidant 2,6- di-tert-butyl methyl phenols | 1 |
| Carbon black | 75 |
| Catalyst DMDEE | 0.1 |
Adipic acid hexylene glycol esterdiol, polyether polyol and antioxidant are added in reaction kettle by formula ratio, are warming up to
80 DEG C, the acrylic resin 2740 of formula ratio is added, is warming up to 115 DEG C~120 DEG C, in vacuum≤- 0.095MPa conditions
Lower dehydration 2h, to water content≤500ppm, is then cooled to 80 DEG C, adds the MDI of formula ratio, is warming up to 95 DEG C of reaction 1h, then
1,4-butanediol the reaction was continued 1h is added, to the reaction was complete, the carbon black and catalyst DMDEE, vacuum for being eventually adding formula ratio take off
Steep 0.5h~1h, to be dispersed with stirring uniformly after can plastic emitting it is filling, obtain reaction type polyurethane hot-melt adhesive.
Embodiment 2
The raw materials used formula ratio ginseng of embodiment 2 is shown in Table 2.
The raw materials used formula ratio of 2 embodiment 2 of table
Adipic acid hexylene glycol esterdiol, polyether polyol and antioxidant are added in reaction kettle by formula ratio, are warming up to
80 DEG C, the TPU of formula ratio is added, 115 DEG C~120 DEG C is warming up to, 2h is dehydrated under the conditions of vacuum≤- 0.095MPa, extremely
Water content≤500ppm, is then cooled to 80 DEG C, adds the MDI of formula ratio, is warming up to 95 DEG C of reaction 1h, adds Isosorbide-5-Nitrae-fourth two
Alcohol the reaction was continued 1h, to the reaction was complete, is eventually adding the white carbon R974 and catalyst DMDEE of formula ratio, vacuum defoamation 0.5h
~1h, to be dispersed with stirring uniformly after can plastic emitting it is filling, obtain reaction type polyurethane hot-melt adhesive.
Embodiment 3
The raw materials used formula ratio ginseng of embodiment 3 is shown in Table 3.
The raw materials used formula ratio of 3 embodiment 3 of table
| Raw material | Parts by weight |
| Succinic acid-butanediol ester glycol (hydroxyl value 31KOH/mg) | 120 |
| Polyether polyol (EO contents 50%, hydroxyl value 56KOH/mg) | 100 |
| MDI | 65 |
| Acrylic resin 1630 | 110 |
| Ethylene glycol | 2 |
| Antioxidant 2,6- di-tert-butyl methyl phenols | 1 |
| Carbon black | 50 |
| Catalyst dibutyltin dilaurylate and organo-bismuth (1:1) | 0.1 |
Succinic acid-butanediol ester glycol, polyether polyol and antioxidant are added in reaction kettle by formula ratio, are warming up to
80 DEG C, the acrylic resin 1630 of formula ratio is added, is warming up to 115 DEG C~120 DEG C, in vacuum≤- 0.095MPa conditions
Lower dehydration 2h, to water content≤500ppm, is then cooled to 80 DEG C, adds the MDI of formula ratio, is warming up to 95 DEG C of reaction 1h, then
Ethylene glycol the reaction was continued 1h is added, to the reaction was complete, is eventually adding the carbon black and catalyst dibutyltin dilaurylate of formula ratio
And organo-bismuth (1:1), vacuum defoamation 0.5h~1h, to be dispersed with stirring uniformly after can plastic emitting it is filling, obtain reaction type polyurethane
Hot melt adhesive.
Comparative example
The raw materials used formula ratio ginseng of comparative example is shown in Table 4.
The raw materials used formula ratio of 4 comparative example of table
| Raw material | Parts by weight |
| Adipic acid hexylene glycol esterdiol (hydroxyl value 31KOH/mg) | 150 |
| Polyether polyol PPG2000 (hydroxyl value 56KOH/mg) | 105 |
| MDI | 90 |
| Acrylic resin 2740 | 150 |
| 1,4- butanediols | 2 |
| Antioxidant 2,6- di-tert-butyl methyl phenols | 1 |
| Catalyst dibutyltin dilaurylate and organo-bismuth (1:1) | 0.1 |
Adipic acid hexylene glycol esterdiol, polyether polyol PPG2000 and antioxidant are added in reaction kettle by formula ratio,
Be warming up to 80 DEG C, add the acrylic resin 2740 of formula ratio, be warming up to 115 DEG C~120 DEG C, vacuum≤-
2h is dehydrated under the conditions of 0.095MPa, to water content≤500ppm, 80 DEG C is then cooled to, adds the MDI of formula ratio, be warming up to 95
DEG C reaction 1h, adds 1,4-butanediol the reaction was continued 1h, to the reaction was complete, be eventually adding the catalyst dibutyltin cinnamic acid of formula ratio
Dibutyl tin and organo-bismuth (1:1), vacuum defoamation 0.5h~1h, to be dispersed with stirring uniformly after can plastic emitting it is filling, reacted
Type polyurethane hot melt adhesive.
The properties of the reaction type polyurethane hot-melt adhesive provided the embodiment of the present invention 1~3 and comparative example are detected,
Wherein, deep cure is tested：Under 23 ± 2 DEG C, 50 ± 5% humidity, hot melt adhesive is beaten on curing depth plate, 24 it is small when after use
Vernier caliper tests curing depth；Trickling property：Hot melt adhesive is heated to the temperature in use of practical application, is uniformly beaten with PUR glue rifles
In the light trough of certain slope, whether observation glue can trickle displacement.As a result ginseng is shown in Table 5.
The properties data for the reaction type polyurethane hot-melt adhesive that 5 embodiment of the present invention 1~3 of table and comparative example provide
As shown in Table 5, the reaction type polyurethane hot-melt adhesive that the embodiment of the present invention 1~3 provides not only has good high temperature
Without trickling performance, and there is faster deep cure and excellent adhesive property, can as the thixotroping of car light high temperature without
Trickle reaction type polyurethane hot-melt adhesive.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or use the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Most wide scope.
Claims (10)
1. a kind of reaction type polyurethane hot-melt adhesive, is prepared by the raw material including following components：
The parts by weight of 100 parts by weight of polyester polyol~120；
The parts by weight of 1 parts by weight of polyether polyol~150；
The parts by weight of 50 parts by weight of isocyanates~100；
The parts by weight of 50 parts by weight of modifying agent~350；
The parts by weight of 1 parts by weight of chain extender~5；
The parts by weight of 1 parts by weight of antioxidant~5；
The parts by weight of 0.01 parts by weight of catalyst~0.1；
The mass content of the polyether polyol ethylene oxide is 40%~50%, and hydroxyl value is 21KOH/mg~112KOH/mg；
The modifying agent is (1~6) by mass ratio：1 tackifying resin and filler composition.
2. reaction type polyurethane hot-melt adhesive according to claim 1, it is characterised in that the polyester polyol is selected from fourth two
In sour butyl glycol ester diol, tetramethylene adipate glycol, ethanedioic acid glycol ester glycol and adipic acid hexylene glycol esterdiol
It is one or more.
3. reaction type polyurethane hot-melt adhesive according to claim 1, it is characterised in that the tackifying resin is selected from acrylic acid
One or more in resin, hydroxyl terminated polyurethane, Petropols, polyolefins tackifying resin and terpene resin.
4. reaction type polyurethane hot-melt adhesive according to claim 1, it is characterised in that the filler is selected from carbon black, hydrophobic
One or more in property gas-phase silica and powdered whiting.
5. reaction type polyurethane hot-melt adhesive according to claim 1, it is characterised in that the chain extender is selected from Isosorbide-5-Nitrae-fourth two
One or more in alcohol, ethylene glycol and 1,6- hexylene glycol.
6. reaction type polyurethane hot-melt adhesive according to claim 1, it is characterised in that the catalyst is selected from tin dilaurate
One or more in dibutyl tin, organo-bismuth, triethylenediamine and dimorpholine base Anaesthetie Ether.
7. a kind of preparation method of claim 1~6 any one of them reaction type polyurethane hot-melt adhesive, comprises the following steps：
It is dehydrated after polyester polyol, polyether polyol, antioxidant and tackifying resin are mixed, adds isocyanates and chain extender
Reacted, be eventually adding filler and catalyst carries out vacuum defoamation, reaction type polyurethane hot-melt adhesive is obtained after being uniformly dispersed.
8. preparation method according to claim 7, it is characterised in that the temperature of the dehydration is 105 DEG C~130 DEG C, very
Reciprocal of duty cycle≤- 0.095MPa, time are 1.5h~2.5h.
9. preparation method according to claim 7, it is characterised in that the addition isocyanates and chain extender are reacted
Process be specially：
At 75 DEG C~85 DEG C, first add isocyanates and be warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, add chain extender
The reaction was continued 0.5h~1h, to the reaction was complete.
10. described in a kind of claim 1~6 any one of them reaction type polyurethane hot-melt adhesive or any one of claim 7~9
Application of the reaction type polyurethane hot-melt adhesive that is prepared of preparation method in hot melt adhesive for car light.
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| CN109957372A (en) * | 2019-04-01 | 2019-07-02 | 江南大学 | A kind of environment-friendly type polyester hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN110330626A (en) * | 2019-05-30 | 2019-10-15 | 上海唯万密封科技有限公司 | Sealing fire-resistant high-resiliency polyurethane and its processing technology |
| CN110819292A (en) * | 2019-11-25 | 2020-02-21 | 杭州之江新材料有限公司 | Polyurethane hot melt adhesive for vehicle lamp |
| CN110894414A (en) * | 2019-11-10 | 2020-03-20 | 苏州欧纳克纳米科技有限公司 | High-water-resistance polyurethane adhesive |
| CN110894415A (en) * | 2019-11-10 | 2020-03-20 | 苏州欧纳克纳米科技有限公司 | Polyurethane adhesive |
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| CN111205804A (en) * | 2020-03-12 | 2020-05-29 | 烟台德邦科技有限公司 | Moisture-curing polyurethane hot melt adhesive and preparation method thereof |
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| CN113462339A (en) * | 2020-03-30 | 2021-10-01 | 南通天洋新材料有限公司 | Preparation method of sebum and sweat resistant moisture-curing polyurethane hot melt adhesive |
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