CN107987779B - 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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- CN107987779B CN107987779B CN201711291104.2A CN201711291104A CN107987779B CN 107987779 B CN107987779 B CN 107987779B CN 201711291104 A CN201711291104 A CN 201711291104A CN 107987779 B CN107987779 B CN 107987779B
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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
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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
- C08G18/62—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- 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 by including that the raw material of following components is prepared: 100 parts by weight of polyester polyol~120 parts by weight；1 parts by weight of polyether polyol~150 parts by weight；50 parts by weight of isocyanates~100 parts by weight；50 parts by weight of modifying agent~350 parts by weight；1 parts by weight of chain extender~5 parts by weight；1 parts by weight of antioxidant~5 parts by weight；0.01 parts by weight of catalyst~0.1 parts by weight；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 forms.The present invention has the polyether polyol of extra fine quality content epoxy ethane by addition, 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 fields, are to be related to a kind of reaction type polyurethane hot melt more specifically
Glue and its preparation method and application.
Background technique
Reaction type polyurethane hot-melt adhesive (abbreviation PUR): pre- containing end NCO polyurethane in moisture-curable polyurethane hot melt adhesive ingredient
Aggressiveness generates under the condition of high temperature, moisture or active hydrogen object in active functional group and air or on adherend after heating
Qualitative response and form part cross-linked structure, make the performances 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 combined with physical mixed.Reaction type polyurethane hot-melt adhesive in the prior art
The chemical reaction of synthesis generally refers to reacting for 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.
Currently, performance report of many car lights in reaction type polyurethane hot-melt adhesive patent about reaction type polyurethane hot-melt adhesive
Road, which is concentrated mainly on, improves heat resistance and adhesive property aspect, high temperature trickling property and subsequent deep cure about concrete application
Report it is less.As the Chinese patent of 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 tooling in car light preparation process can have 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 simultaneously
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 in car light can only top it is permeable, therefore deep cure is slower, often all cannot within one month in China's winter certain car lights
The problem of being fully cured, trickling will appear to glue heating again, thus the appearance for the problems such as causing car light leak, hazing.
Therefore, reaction type polyurethane in the prior art there is also high temperature trickling properties poor, deep cure is relatively slow and does not have
Standby thixotropic technical problem, it is difficult to further be applied as hot melt adhesive for car light realization.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of reaction type polyurethane hot-melt adhesive and preparation method thereof and answering
Have 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 adhesives, are prepared by the raw material for including following components:
100 parts by weight of polyester polyol~120 parts by weight；
1 parts by weight of polyether polyol~150 parts by weight；
50 parts by weight of isocyanates~100 parts by weight；
50 parts by weight of modifying agent~350 parts by weight；
1 parts by weight of chain extender~5 parts by weight；
1 parts by weight of antioxidant~5 parts by weight；
0.01 parts by weight of catalyst~0.1 parts by weight；
The mass content of the polyether polyol ethylene oxide be 40%~50%, hydroxyl value be 21KOH/mg~
112KOH/mg；
The modifying agent is (1~6) by mass ratio: 1 tackifying resin and filler forms.
Preferably, the polyester polyol is selected from succinic acid-butanediol ester glycol, tetramethylene adipate glycol, ethanedioic acid
One of pure and mild adipic acid hexylene glycol esterdiol of glycol ester two is a variety of.
Preferably, the tackifying resin is selected from acrylic resin, hydroxyl terminated polyurethane, Petropols, polyolefins and increases
One of viscosity resin and terpene resin are a variety of.
Preferably, the filler is selected from one of carbon black, hydrophobicity gas-phase silica and powdered whiting or a variety of.
Preferably, the chain extender is selected from 1,4-butanediol, ethylene glycol and 1, one of 6- hexylene glycol or a variety of.
Preferably, the catalyst is selected from dibutyl tin dilaurate, organo-bismuth, triethylenediamine and dimorpholine base two
One of ethylether is a variety of.
The present invention also provides a kind of preparation methods of 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 degree≤- 0.095MPa, the time be 1.5h~
2.5h。
Preferably, the process that isocyanates and chain extender is added and is reacted specifically:
At 75 DEG C~85 DEG C, isocyanates is first added and is warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, adds expansion
Chain agent the reaction was continued 0.5h~1h, until fully reacting.
The present invention also provides reaction type polyurethane hot-melt adhesive described in a kind of above-mentioned technical proposal or above-mentioned technical proposals
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 by including that the raw material of following components is prepared: 100 parts by weight of polyester polyol~120 parts by weight；Polyether polyol 1
Parts by weight~150 parts by weight；50 parts by weight of isocyanates~100 parts by weight；50 parts by weight of modifying agent~350 parts by weight；Chain extension
1 parts by weight of agent~5 parts by weight；1 parts by weight of antioxidant~5 parts by weight；0.01 parts by weight of catalyst~0.1 parts by weight；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
Be (1~6) by mass ratio: 1 tackifying resin and filler forms.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.The experimental results showed 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
It 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.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of reaction type polyurethane hot-melt adhesives, are prepared by the raw material for including following components:
100 parts by weight of polyester polyol~120 parts by weight；
1 parts by weight of polyether polyol~150 parts by weight；
50 parts by weight of isocyanates~100 parts by weight；
50 parts by weight of modifying agent~350 parts by weight；
1 parts by weight of chain extender~5 parts by weight；
1 parts by weight of antioxidant~5 parts by weight；
0.01 parts by weight of catalyst~0.1 parts by weight；
The mass content of the polyether polyol ethylene oxide be 40%~50%, hydroxyl value be 21KOH/mg~
112KOH/mg；
The modifying agent is (1~6) by mass ratio: 1 tackifying resin and filler forms.
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 helping 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, described
It is pure and mild that polyester polyol is preferably selected from succinic acid-butanediol ester glycol, tetramethylene adipate glycol, ethanedioic acid glycol ester two
One of adipic acid hexylene glycol esterdiol is a variety of, 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
The city of sour butyl glycol ester diol, tetramethylene adipate glycol, the pure and mild adipic acid hexylene glycol esterdiol of ethanedioic acid glycol ester two
Sell commodity.In the present invention, the reaction type polyurethane hot-melt adhesive includes that 100 parts by weight~120 parts by weight polyester 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, preferably 56KOH/mg, water content are preferably smaller than equal to 0.1%.In the present invention, described poly-
Ethoxylated polyhydric alcohol is preferably selected from one of polyoxypropyleneglycol, the pure and mild polytetrahydrofuran ether glycol of polypropylene oxide three or more
Kind；The present invention is not particularly limited the type 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 1 parts by weight~150 parts by weight
Polyether polyol, preferably 100 parts by weight~150 parts by weight.
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 of acid esters (HDI) is a variety of, 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
The isocyanates of part~100 parts by weight, preferably 60 parts by weight~75 parts by weight.
In the present invention, the modifying agent is (1~6) by mass ratio: 1 tackifying resin and filler forms.In the present invention
In, the tackifying resin be preferably selected from acrylic resin, hydroxyl terminated polyurethane, Petropols, polyolefins tackifying resin and
One of terpene resin is a variety of, more preferably acrylic resin or hydroxyl terminated polyurethane.The present invention sets the thickening
The source of rouge is not particularly limited, using above-mentioned acrylic 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 of carbon black, hydrophobicity gas-phase silica and powdered whiting
Or a variety of, 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
High temperature resistance, and certain thixotropy is kept, thus the thixotropic effects under reaching a high temperature.In the present invention, the response type
Polyurethane hot melt includes 50 parts by weight~350 parts by weight modifying agent, preferably 125 parts by weight~175 parts by weight.
In the present invention, the chain extender is preferably selected from 1,4-butanediol, ethylene glycol and 1, one of 6- hexylene glycol or
It is a variety of, 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 1,4-butanediol, ethylene glycol and 1, the commercial goods of 6- hexylene glycol known to field technique personnel.In the present invention,
The reaction type polyurethane hot-melt adhesive includes 1 parts by weight~5 parts by weight chain extender, preferably 1 parts by weight~2 parts by weight.
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 phenyl) propionic acid] pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three
One of (2.4- di-tert-butyl-phenyl) phosphite ester and bis- (3,5- di-tert-butyl-hydroxy phenyl) thioethers are a variety of, more
Preferably 2,6- di-tert-butyl methyl phenol.The present invention is not particularly limited the source of the antioxidant, using this field
Above-mentioned 2,6- di-tert-butyl methyl phenol known to technical staff, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
Pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three (2.4- di-tert-butyl-phenyls) are sub-
The commercial goods of phosphate and bis- (3,5- di-tert-butyl-hydroxy phenyl) thioethers.In the present invention, the response type is poly-
Urethane hot melt adhesive includes 1 parts by weight~5 parts by weight antioxidant, preferably 1 parts by weight.
In the present invention, the catalyst is preferably selected from dibutyl tin dilaurate, organo-bismuth, triethylenediamine and two
One of morpholinyl Anaesthetie Ether (DMDEE) is a variety of, more preferably dibutyl tin dilaurate, 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 field
Above-mentioned dibutyl tin dilaurate, organo-bismuth known to technical staff, triethylenediamine and dimorpholine base Anaesthetie Ether
(DMDEE) commercial goods.In the present invention, the reaction type polyurethane hot-melt adhesive includes 0.01 parts by weight~0.1 weight
Measure the antioxidant of part, preferably 0.05 parts by weight~0.1 parts by weight.
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.
The present invention also provides a kind of preparation methods of 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 mixed process
It is preferred that specifically:
Polyester polyol, the pure and mild antioxidant of polyether polyols 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 degree of dehydration preferably≤- 0.095MPa；The time of the dehydration is preferably 1.5h~2.5h, more preferably 2h.
After completing the dehydration, isocyanates is added in the present invention in the reaction system and chain extender reacts；Institute
It is preferred to state the process that addition isocyanates and chain extender are reacted specifically:
At 75 DEG C~85 DEG C, isocyanates is first added and is warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, adds expansion
Chain agent the reaction was continued 0.5h~1h, until fully reacting.
After completing the reaction process, filler is added in the present invention 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.
The present invention also provides reaction type polyurethane hot-melt adhesive described in a kind of above-mentioned technical proposal or above-mentioned technical proposals
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 use temperature of practical application, with PUR glue rifle
It uniformly beats 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 suitble to be applied in car light assembly 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 by including that the raw material of following components is prepared: 100 parts by weight of polyester polyol~120 parts by weight；Polyether polyol 1
Parts by weight~150 parts by weight；50 parts by weight of isocyanates~100 parts by weight；50 parts by weight of modifying agent~350 parts by weight；Chain extension
1 parts by weight of agent~5 parts by weight；1 parts by weight of antioxidant~5 parts by weight；0.01 parts by weight of catalyst~0.1 parts by weight；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
Be (1~6) by mass ratio: 1 tackifying resin and filler forms.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.The experimental results showed 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
It 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.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment 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 content 40%, hydroxyl value 56KOH/mg) | 150 |
| MDI | 75 |
| Acrylic resin 2740 | 100 |
| 1,4- butanediol | 1 |
| Antioxidant 2,6- di-tert-butyl methyl phenol | 1 |
| Carbon black | 75 |
| Catalyst DMDEE | 0.1 |
Adipic acid hexylene glycol esterdiol, the pure and mild antioxidant of polyether polyols 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 degree≤- 0.095MPa condition
The MDI of formula ratio is added until water content≤500ppm, is then cooled to 80 DEG C in lower dehydration 2h, is warming up to 95 DEG C of reaction 1h, then
1,4-butanediol the reaction was continued 1h is added, until fully reacting, is eventually adding the carbon black and catalyst DMDEE of formula ratio, vacuum is de-
Steep 0.5h~1h, until 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, the pure and mild antioxidant of polyether polyols 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, is dehydrated 2h under the conditions of vacuum degree≤- 0.095MPa, until
Then water content≤500ppm is cooled to 80 DEG C, the MDI of formula ratio is added, and is warming up to 95 DEG C of reaction 1h, adds Isosorbide-5-Nitrae-fourth two
Alcohol the reaction was continued 1h, until fully reacting, is eventually adding the white carbon black R974 and catalyst DMDEE of formula ratio, vacuum defoamation 0.5h
~1h, until 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 content 50%, hydroxyl value 56KOH/mg) | 100 |
| MDI | 65 |
| Acrylic resin 1630 | 110 |
| Ethylene glycol | 2 |
| Antioxidant 2,6- di-tert-butyl methyl phenol | 1 |
| Carbon black | 50 |
| Catalyst dibutyltin dilaurylate and organo-bismuth (1:1) | 0.1 |
Succinic acid-butanediol ester glycol, the pure and mild antioxidant of polyether polyols 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 degree≤- 0.095MPa condition
The MDI of formula ratio is added until water content≤500ppm, is then cooled to 80 DEG C in lower dehydration 2h, is warming up to 95 DEG C of reaction 1h, then
Ethylene glycol the reaction was continued 1h is added, until fully reacting, is eventually adding the carbon black and catalyst dibutyltin dilaurylate of formula ratio
And organo-bismuth (1:1), vacuum defoamation 0.5h~1h, until 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- butanediol | 2 |
| Antioxidant 2,6- di-tert-butyl methyl phenol | 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 degree≤-
It is dehydrated 2h under the conditions of 0.095MPa, until water content≤500ppm, is then cooled to 80 DEG C, the MDI of formula ratio is added, is warming up to 95
DEG C reaction 1h adds 1,4-butanediol the reaction was continued 1h, until fully reacting, is eventually adding the catalyst dibutyltin cinnamic acid of formula ratio
Dibutyl tin and organo-bismuth (1:1), vacuum defoamation 0.5h~1h, until be dispersed with stirring uniformly after can plastic emitting it is filling, reacted
Type polyurethane hot melt adhesive.
The properties for the reaction type polyurethane hot-melt adhesive that the embodiment of the present invention 1~3 and comparative example provide are detected,
Wherein, deep cure is tested: under 23 ± 2 DEG C, 50 ± 5% humidity, hot melt adhesive being beaten on curing depth plate, is used after 24 hours
Vernier caliper tests curing depth；Trickling property: hot melt adhesive is heated to the use temperature of practical application, is uniformly beaten with PUR glue rifle
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 have 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 above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to 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
Widest scope.
Claims (9)
1. a kind of reaction type polyurethane hot-melt adhesive is prepared by the raw material for including following components:
100 parts by weight of polyester polyol~120 parts by weight；
100 parts by weight of polyether polyol~150 parts by weight；
50 parts by weight of isocyanates~100 parts by weight；
50 parts by weight of modifying agent~350 parts by weight；
1 parts by weight of chain extender~5 parts by weight；
1 parts by weight of antioxidant~5 parts by weight；
0.01 parts by weight of catalyst~0.1 parts by weight；
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 forms；
The tackifying resin is selected from acrylic resin or hydroxyl terminated polyurethane.
2. reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the polyester polyol is selected from fourth two
Sour butyl glycol ester diol, tetramethylene adipate glycol, in the pure and mild adipic acid hexylene glycol esterdiol of ethanedioic acid glycol ester two
It is one or more.
3. reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the filler is selected from carbon black, hydrophobic
Property one of gas-phase silica and powdered whiting or a variety of.
4. reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the chain extender is selected from Isosorbide-5-Nitrae-fourth two
Alcohol, ethylene glycol and 1, one of 6- hexylene glycol or a variety of.
5. reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the catalyst is selected from tin dilaurate
One of dibutyl tin, organo-bismuth, triethylenediamine and dimorpholine base Anaesthetie Ether are a variety of.
6. a kind of preparation method of the described in any item reaction type polyurethane hot-melt adhesives of Claims 1 to 5, comprising the following steps:
It is dehydrated after polyester polyol, polyether polyol, antioxidant and tackifying resin are mixed, adds isocyanates and chain extender
It is reacted, is eventually adding filler and catalyst carries out vacuum defoamation, obtain reaction type polyurethane hot-melt adhesive after being uniformly dispersed.
7. preparation method according to claim 6, which is characterized 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.
8. preparation method according to claim 6, which is characterized in that the addition isocyanates and chain extender are reacted
Process specifically:
At 75 DEG C~85 DEG C, isocyanates is first added and is warming up to 93 DEG C~98 DEG C reaction 0.5h~1.5h, adds chain extender
The reaction was continued 0.5h~1h, until fully reacting.
9. described in a kind of described in any item reaction type polyurethane hot-melt adhesives of Claims 1 to 5 or any one of claim 6~8
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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| CN109957372B (en) * | 2019-04-01 | 2020-07-07 | 江南大学 | Environment-friendly polyester hot-melt 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 |
| CN112300745B (en) * | 2019-08-02 | 2022-07-12 | 万华化学（北京）有限公司 | Moisture-curing reaction type polyurethane hot melt adhesive and preparation method thereof |
| 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 |
| CN110819292B (en) * | 2019-11-25 | 2021-04-02 | 杭州之江新材料有限公司 | Polyurethane hot melt adhesive for vehicle lamp |
| CN110964473A (en) * | 2019-12-13 | 2020-04-07 | 烟台德邦科技有限公司 | Side-coating shading moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| CN111040717A (en) * | 2019-12-25 | 2020-04-21 | 惠州市远安新材料有限公司 | Moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof |
| 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 |
| CN113462339B (en) * | 2020-03-30 | 2023-04-11 | 南通天洋新材料有限公司 | Preparation method of sebum and sweat resistant moisture-curing polyurethane hot melt adhesive |
| CN111690360B (en) * | 2020-06-22 | 2023-03-03 | 万华化学（北京）有限公司 | Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| CN112724905A (en) * | 2020-12-14 | 2021-04-30 | 广东省京极盛新材料科技有限公司 | Reaction type polyurethane hot melt adhesive with ultra-high shear strength at low temperature |
| CN112592687A (en) * | 2020-12-15 | 2021-04-02 | 南通恒华粘合材料科技有限公司 | Reactive polyurethane hot melt adhesive for automobile lamp |
| CN115141592A (en) * | 2021-03-31 | 2022-10-04 | 中科先行(济宁)新材料研究院有限公司 | Antibacterial polypropylene modified polyurethane and preparation method thereof |
| CN113185943B (en) * | 2021-04-15 | 2022-12-20 | 上海抚佳精细化工有限公司 | Polyurethane hot melt adhesive and preparation method and application thereof |
| CN115232591B (en) * | 2022-06-21 | 2023-12-05 | 嘉兴学院 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN115851205A (en) * | 2022-08-02 | 2023-03-28 | 杭州奥方科技有限公司 | Anti-collision and anti-skid heat-activated protective adhesive and preparation method thereof |
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