CN105602509B - Anti-aging automotive interior adhesive of environment-friendly type and preparation method thereof - Google Patents
Anti-aging automotive interior adhesive of environment-friendly type and preparation method thereof Download PDFInfo
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- CN105602509B CN105602509B CN201610035923.XA CN201610035923A CN105602509B CN 105602509 B CN105602509 B CN 105602509B CN 201610035923 A CN201610035923 A CN 201610035923A CN 105602509 B CN105602509 B CN 105602509B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of anti-aging automotive interior adhesives of environment-friendly type, prepare raw material and include：SBS, hydroxy-end capped super branched polyurethane, HO SBS, White Mineral Oil, dimethyl sulfoxide (DMSO), antioxidant and silane-modified super-branched polyimide；Wherein, the silane-modified super-branched polyimide is prepared by the raw material for including epoxy silane coupling agent and amino-terminated hyperbranched polyimides.The invention also discloses the methods for preparing the anti-aging automotive interior adhesive of the environment-friendly type.
Description
Technical field
The invention belongs to bond to use glue field, more particularly it relates to a kind of anti-aging automotive interior adhesive of environment-friendly type
And preparation method thereof.
Background technology
With the development of automobile industry, automotive trim is more and more luxurious, therefore the dosage of automotive upholstery adhesive glue
It is increasing.At present in automotive trim adhesive therefor, due to the use of the organic solvent of non-environmental protection, a large amount of first are usually contained
The harmful substances such as aldehyde, benzene, dimethylbenzene cause health huge threat.In addition, automotive interior adhesive of the prior art is also
There are initial bonding strength is weak and the shortcomings that anti-aging property is poor, it would be highly desirable to solve.
Hence it is highly desirable to by the improvement of formula and production technology, high cohesive force, the highly resistance of a kind of environment-friendly type are prepared
Aged automobile interior trim glue.
Invention content
To solve the above-mentioned problems, one aspect of the present invention provides a kind of anti-aging automotive interior adhesive of environment-friendly type, system
Standby raw material includes：
The SBS of 100 parts by weight；
The hydroxy-end capped super branched polyurethane of 150~200 parts by weight；
The HO-SBS of 10~40 parts by weight；
The White Mineral Oil of 50~100 parts by weight；
The dimethyl sulfoxide (DMSO) of 20~50 parts by weight；
The antioxidant of 0.5~2 parts by weight；With
The silane-modified super-branched polyimide of 5~20 parts by weight；
Wherein, the silane-modified super-branched polyimide is by including epoxy silane coupling agent and amino-terminated hyperbranched
The raw material of polyimides is prepared.
In one embodiment, the hydroxy-end capped super branched polyurethane is by including diisocyanate and trihydroxylic alcohol
Raw material is prepared.
In one embodiment, the diisocyanate is selected from isophorone diisocyanate, 4 ' 4- diphenyl methanes
Diisocyanate, hexamethylene diisocyanate and 2, any one or more in 4 toluene di-isocyanate(TDI)s；Described three
Any one or more of first alcohol in glycerine, trimethylolpropane and polyether-tribasic alcohol.
In one embodiment, in the HO-SBS, the grafting rate of hydroxyl is 25-40%.
In one embodiment, the antioxidant is BHT or DLTP.
In one embodiment, the super-branched polyimide is by triamine and dianhydride in molar ratio 1：（1~1.3）It prepares
It obtains.
In one embodiment, the triamine is selected from 2,4,6- triamido pyridines and three（4- aminophenyls）In amine
Any one or two kinds.
In one embodiment, the dianhydride is selected from pyromellitic dianhydride, 3,4,9,10- tetracarboxylic anhydrides, 4,4'-
(hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, 3,3', 4,4'- benzophenone
Any one or more in tetracarboxylic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride.
Another aspect of the present invention provides a kind of method for preparing the anti-aging automotive interior adhesive of environment-friendly type, including following step
Suddenly：
1）First White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are put into stainless steel cauldron, are warming up to 120 ~ 130 DEG C
Afterwards, SBS, HO-SBS are added in, and by temperature of reaction kettle control within 140 DEG C；
2）Hydroxy-end capped super branched polyurethane and silane-modified hyperbranched polyamides are put into after SBS and HO-SBS all dissolving
Imines stirs the control of stainless steel cauldron temperature 30 ~ 60 minutes within 155 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
It is preferably carried out in mode in one kind, wherein the step 2）In temperature be 140 DEG C.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise.
" optional " or " optionally " refer to that the item described thereafter or event may or may not occur, and this is retouched
State the situation that the situation occurred including event and event do not occur.
Approximate term in specification and claims is used for modifying quantity, represents specific the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, it is approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
It combines and/or exchanges, these ranges include all subranges contained therebetween if not stated otherwise.
One aspect of the present invention provides a kind of offer a kind of a kind of anti-aging automotive interior adhesive of environment-friendly type of offer, prepares
Raw material includes：
The SBS of 100 parts by weight；
The hydroxy-end capped super branched polyurethane of 150~200 parts by weight；
The HO-SBS of 10~40 parts by weight；
The White Mineral Oil of 50~100 parts by weight；
The dimethyl sulfoxide (DMSO) of 20~50 parts by weight；
The antioxidant of 0.5~2 parts by weight；With
The silane-modified super-branched polyimide of 5~20 parts by weight；
Wherein, the silane-modified super-branched polyimide is by including epoxy silane coupling agent and amino-terminated hyperbranched
The raw material of polyimides is prepared；
Preferably, raw material is prepared to include：
The SBS of 100 parts by weight；
The hydroxy-end capped super branched polyurethane of 180 parts by weight；
The HO-SBS of 30 parts by weight；
The White Mineral Oil of 80 parts by weight；
The dimethyl sulfoxide (DMSO) of 30 parts by weight；
The antioxidant of 1 parts by weight；With
The silane-modified super-branched polyimide of 10 parts by weight；
Wherein, the silane-modified super-branched polyimide is by including epoxy silane coupling agent and amino-terminated hyperbranched
The raw material of polyimides is prepared.
Term " SBS " of the present invention refers to styrene-butadiene-styrene three block thermoplastic elastomer (TPE).It is described
There are two features in structure by SBS：First, strand is less than soft elastomeric polybutadiene PB sections and glass of room temperature by glass transition temperature
Glass temperature is mutually embedding higher than PS sections of the stiff plastic polystyrene of room temperature to be formed；Second, both blocks are that mechanics is incompatible, with
Microscopic dimensions are separated to form " island " structure of two-phase laminated flow, and when polystyrene content is relatively low, PS is divided into isolated
Region is around the PB continuous phases of rubber.Due to the presence of plastics phase so that the movement of rubber molecule segment is by certain limit
System makes thermoplastic elastomer have the performance of vulcanization rubber, with vulcanization rubber the difference is that the crosslinking of plastics phase is reversible object
Reason crosslinking, when it is dissolved in organic solvent or heating melting, plastics are mutually dissolved or melting, lose crosslinked action；And molten
Agent volatilization or melt cool down, and mutually meeting precipitation and separation comes out, and restore original physical crosslinking state plastics again.For the application
SBS be not particularly limited, can be it is commercially available or synthesis.The structure of SBS and the content of molecular weight and styrene have closely
Contact, as a kind of preferred embodiment of the present invention, in SBS, the content of styrene is 40wt%.
Term " hydroxy-end capped super branched polyurethane " of the present invention is by including the raw material of diisocyanate and trihydroxylic alcohol
It is prepared.
It is prepared for the super branched polyurethane of the application by using A2+B3 methods, and obtain the polymerization of hydroxy-end capped sealing end
Object, specific method are：
1) diisocyanate and trihydroxylic alcohol are dissolved separately in polar solvent, respectively obtain diisocyanate solution and three
First alcoholic solution, it is 5~30% to control its mass concentration；
Wherein, the diisocyanate is isophorone diisocyanate, 4 ' 4- methyl diphenylene diisocyanates, six Asias
Any one or more in methyl diisocyanate or 2,4- toluene di-isocyanate(TDI), it is preferable that the diisocyanate is
2,4- toluene di-isocyanate(TDI)s；
The trihydroxylic alcohol is glycerine, trimethylolpropane or polyether-tribasic alcohol, it is preferable that the trihydroxylic alcohol is poly-
Ether trihydroxylic alcohol；
2) under 30~100 DEG C, protective atmosphere, diisocyanate solution is added in ternary alcoholic solution by side stirring, wherein
The molar ratio of the isocyanate group of diisocyanate and the hydroxyl of trihydroxylic alcohol is 8：9~1：3；After the completion of diisocyanate adds in, instead
Architecture heat preservation is answered to react 10~30h；Then protective agent is added in into reaction system, the reaction was continued at 30~100 DEG C 5~10h；
3) after after reaction, being evaporated under reduced pressure out solvent, obtained material is dissolved through tetrahydrofuran, in methyl alcohol sedimentation and
After filtering, by it in 50~140 DEG C of vacuum drying 10~for 24 hours, the super branched polyurethane containing hydroxyl purified；
Preferably, the molar ratio of the hydroxyl of the isocyanate group and trihydroxylic alcohol of the diisocyanate is 1：2.
In one embodiment, the solvent that the diisocyanate solution, ternary alcoholic solution use is dimethyl Asia
Sulfone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N, one in N- dimethyl pyrrolidones, tetrahydrofuran or toluene
Kind or several mixing.
In one embodiment, the protective agent is phenol, caprolactam, ethylene glycol ethyl ether or methyl ethyl ketoxime；It protects
The addition for protecting agent is the 1~60% of diisocyanate molal quantity.
Hydroxy-end capped super branched polyurethane can increase substantially the initial bonding strength of colloid, so as to provide the beneficial skill of the present invention
Art effect.
Term " HO-SBS " of the present invention refers to be prepared by SBS, hydrogen peroxide, anhydrous formic acid.The system of the HO-SBS
Preparation Method is：It is furnished in the 250ml four-hole bottles of condenser pipe, mechanical agitation, thermometer one, the SBS of 5g is put into 50ml chlorine
In imitative, and then 50ml anhydrous formic acids and 5ml hydrogen peroxide are slowly added drop-wise in reaction bulb respectively.It is stirred at 50 DEG C~80 DEG C
Reaction one day is mixed, after reaction, reaction solution is poured into methanol solution and is precipitated, is filtered, methanol repeatedly washs, and gained is cotton-shaped
Object at 40 DEG C in vacuum drying dry 8h to get；Respectively, the grafting of hydroxyl is obtained at 50 DEG C, 70 DEG C and 80 DEG C
Rate is respectively 25%, 33% and 40%.
As a kind of preferred embodiment of the present invention, in the HO-SBS, the grafting rate of hydroxyl is 25-40%.
As a kind of preferred embodiment of the present invention, in the HO-SBS, the grafting rate of hydroxyl is 33%.
It is not particularly limited for the White Mineral Oil of the application, can be commercially available commercially produced product.
Term " antioxidant " of the present invention refers to that the oxidation of high polymer causes macromolecular chain to be broken, be crosslinked, make performance
It degenerates, the compound of oxidation process can be prevented or inhibited.Antioxidant is divided into free radical terminator and hydrogen peroxide decomposition agent two
Class.The free radical terminator mainly generates inactive free radical by chain tra nsfer or forms stable product, makes chain termination.Position
Hinder phenol, aromatic amine and certain cyclic hydrocarbon are good free radical stabilizers, phenolic compound generally uses at a lower temperature, compared with
Antioxidant is poor under high-temperature, aminated compounds such as aromatic amine.The effect of hydrogen peroxide decomposition agent is that hydroperoxides are decomposed
For non-free radical product.In order to realize beneficial effects of the present invention, as a kind of preferred embodiment of the present invention, the antioxygen
Agent is BHT or DLTP.
Term " silane-modified super-branched polyimide " of the present invention is sealed by including epoxy silane coupling agent and amino
The raw material of end super-branched polyimide is prepared.
In one embodiment, the preparation method of the silane-modified super-branched polyimide includes：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, sequentially add the triamine of 1mmol, the dianhydride of 1~1.3 mmol, 2 mmol benzoic acid,
The organic good solvent of 0.5~3 mL isoquinolin and 10~500 mL.Logical nitrogen protection, after 0.1~1 0h, it is warming up to 100~
160 oC reacts 1~4 h, then heats to 180 oC~220 oC reacts 2~20 h.After reaction, it is down to room temperature and incites somebody to action anti-
Solution is answered to pour into methanol, a large amount of solids are precipitated.After the solid is washed repeatedly with methanol, filter and by the solid being collected into
In vacuum drying oven, 30~80oC dries 2~10 h and obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts of polyimides, epoxy type silane coupling agent are added in the three-necked flask being completely dried
1~30 part of KH-560 and appropriate good solvent after stirring 5~50min under inert gas shielding, are heated to 60~100 DEG C instead
After answering 0.1~10h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after mistake
After filter, 1 h~for 24 hours to get silane-modified super-branched polyimide is dried at 20 DEG C~80 DEG C in vacuum drying oven；
Preferably, the super-branched polyimide is by triamine and dianhydride in molar ratio 1：1.1 it is prepared.
In one embodiment, the triamine is selected from 2,4,6- triamido pyridines and three（4- aminophenyls）In amine
Any one or two kinds；Preferably, the triamine is 2,4,6- triamido pyridines.
In one embodiment, the dianhydride is selected from pyromellitic dianhydride, 3,4,9,10- tetracarboxylic anhydrides, 4,4'-
(hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, 3,3', 4,4'- benzophenone
Any one or more in tetracarboxylic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride；Preferably, the dianhydride is selected from 4,4'- (six
Fluorine isopropyl alkene) any one or two kinds in two anhydride phthalic acids and bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides；
It is highly preferred that the dianhydride is 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids.
Silane-modified super-branched polyimide can effectively improve the cohesive force and ageing resistance of interior trim glue, therefore carry
The advantageous effects of the present invention are supplied.
Another aspect of the present invention provides a kind of method for preparing the anti-aging automotive interior adhesive of environment-friendly type, including following step
Suddenly：
1）First White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are put into stainless steel cauldron, are warming up to 120 ~ 130 DEG C
Afterwards, SBS, HO-SBS are added in, and by temperature of reaction kettle control within 140 DEG C；
2）Hydroxy-end capped super branched polyurethane and silane-modified hyperbranched polyamides are put into after SBS and HO-SBS all dissolving
Imines stirs the control of stainless steel cauldron temperature 30 ~ 60 minutes within 155 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
It is preferably carried out in mode in one kind, wherein the step 2）In temperature be 140 DEG C.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
If it is raw materials used to be all commercially available in addition, without other explanations, and number used in following material would be weight
Part.
Raw material：
A1：SBS（The content of styrene is 40wt%）
B1：HO-SBS（The grafting rate of hydroxyl is 25%）
B2：HO-SBS（The grafting rate of hydroxyl is 40%）
B3：HO-SBS（The grafting rate of hydroxyl is 33%）
C1：Super branched polyurethane, preparation method are：
0.04 mole of isophorone diisocyanate is dissolved in the toluene of 20mL, obtains diisocyanate solution, so
0.03 mole of glycerine is dissolved in 20mL dimethyl sulphoxide solutions afterwards, obtains ternary alcoholic solution, it is then that the trihydroxylic alcohol is molten
Liquid is added in the three-necked flask with magnetic agitation and reflux, under 40 DEG C, nitrogen protection, under stirring thereto
It is slowly added to the toluene solution of the isophorone diisocyanate；
After dripping, then system the reaction was continued at 40 DEG C 10h adds in 0.002 mole of phenol into reaction medium,
Heating, reacts 5h at 100 DEG C；
After reaction, it is evaporated under reduced pressure out solvent.Products therefrom methanol-tetrahydrofuran（Volume ratio（1/10））Dissolving,
Sedimentation 3 times, filtering, 60 DEG C of vacuum drying for 24 hours, obtain super branched polyurethane.
C2：Super branched polyurethane, preparation method are：
0.01 mole of 4 ' 4- methyl diphenylene diisocyanates are dissolved in the toluene of 20mL, it is molten to obtain diisocyanate
Then 0.02 mole of trimethylol propane is dissolved in 20mL dimethyl sulphoxide solutions by liquid, obtain ternary alcoholic solution, then by institute
It states ternary alcoholic solution to be added in the three-necked flask with magnetic agitation and reflux, under 40 DEG C, nitrogen protection, make in stirring
It is slowly added to the toluene solution of 4 ' the 4- methyl diphenylene diisocyanates thereto under；
After dripping, then system the reaction was continued at 40 DEG C 10h is added in into reaction medium in oneself of 0.002 mole
Amide, heating, reacts 5h at 100 DEG C；
After reaction, it is evaporated under reduced pressure out solvent.Products therefrom methanol-tetrahydrofuran（Volume ratio（1/10））Dissolving,
Sedimentation 3 times, filtering, 60 DEG C of vacuum drying for 24 hours, obtain super branched polyurethane.
C3：Super branched polyurethane, preparation method are：
0.03 mole of 2,4- toluene di-isocyanate(TDI)s are dissolved in the toluene of 20mL, obtain diisocyanate solution, so
0.04 mole of polyether-tribasic alcohol is dissolved in 20mL dimethyl sulphoxide solutions afterwards, obtains ternary alcoholic solution, then by the ternary
Alcoholic solution is added in the three-necked flask with magnetic agitation and reflux, 40 DEG C, nitrogen protection under, under stirring to
Wherein it is slowly added to the toluene solution of 4 ' the 4- methyl diphenylene diisocyanates；
After dripping, then system the reaction was continued at 40 DEG C 10h is added in into reaction medium in oneself of 0.002 mole
Amide, heating, reacts 5h at 100 DEG C；
After reaction, it is evaporated under reduced pressure out solvent.Products therefrom methanol-tetrahydrofuran（Volume ratio（1/10））Dissolving,
Sedimentation 3 times, filtering, 60 DEG C of vacuum drying for 24 hours, obtain super branched polyurethane.
D1：White Mineral Oil
E1：Dimethyl sulfoxide (DMSO)
F1：BHT
F2：DLTP
G1：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, the three of 1mmol is sequentially added（4- aminophenyls）The pyromellitic dianhydride of amine, 1 mmol
, 2 mmol benzoic acid, 2mL isoquinolin and 200mL dimethyl sulfoxide (DMSO).Logical nitrogen is protected, and after 5 h, is warming up to 140 oC is anti-
4 h are answered, then heat to 180 oC reacts 20 h.After reaction, it is down to room temperature and pours into reaction solution in methanol, be precipitated
A large amount of solids.After the solid is washed repeatedly with methanol, filter and by the solid being collected into vacuum drying oven, 50oC is dried
10 h obtain amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
G2：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, the three of 1mmol is sequentially added（4- aminophenyls）The Pyromellitic Acid of amine, 1.1 mmol
Acid anhydride, 2 mmol benzoic acid, 2mL isoquinolin and 200mL dimethyl sulfoxide (DMSO).Logical nitrogen is protected, and after 5 h, is warming up to 140 oC
4 h are reacted, then heat to 180 oC reacts 20 h.After reaction, it is down to room temperature and pours into reaction solution in methanol, analyse
Go out a large amount of solids.After the solid is washed repeatedly with methanol, filter and by the solid being collected into vacuum drying oven, 50oC is done
Dry 10 h obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
G3：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, the three of 1mmol is sequentially added（4- aminophenyls）The Pyromellitic Acid of amine, 1.3 mmol
Acid anhydride, 2 mmol benzoic acid, 2mL isoquinolin and 200mL dimethyl sulfoxide (DMSO).Logical nitrogen is protected, and after 5 h, is warming up to 140 oC
4 h are reacted, then heat to 180 oC reacts 20 h.After reaction, it is down to room temperature and pours into reaction solution in methanol, analyse
Go out a large amount of solids.After the solid is washed repeatedly with methanol, filter and by the solid being collected into vacuum drying oven, 50oC is done
Dry 10 h obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
G4：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, 2,4, the 6- triamido pyridines of 1mmol are sequentially added, the dianhydride of 1.1 mmol is equal benzene
Tetracarboxylic acid anhydride, 2 mmol benzoic acid, 2mL isoquinolin and 200mL dimethyl sulfoxide (DMSO).Logical nitrogen is protected, and after 5 h, is warming up to
140 oC reacts 4 h, then heats to 180 oC reacts 20 h.After reaction, it is down to room temperature and reaction solution is poured into methanol
In, a large amount of solids are precipitated.After the solid is washed repeatedly with methanol, filter and by the solid being collected into vacuum drying oven, 50oC dries 10 h and obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
G5：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, sequentially add 2,4, the 6- triamido pyridines of 1mmol, 1.1 mmol it is bicyclic
[2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, 2 mmol benzoic acid, the dimethyl of 2mL isoquinolin and 200mL are sub-
Sulfone.Logical nitrogen is protected, and after 5 h, is warming up to 140 oC reacts 4 h, then heats to 180 oC reacts 20 h.After reaction, it drops
It is poured into methanol to room temperature and by reaction solution, a large amount of solids is precipitated.After the solid is washed repeatedly with methanol, filter and will receive
The solid collected is in vacuum drying oven, and 50oC dries 10 h and obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
G6：Silane-modified super-branched polyimide, preparation method include：
（1）The preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, 2,4, the 6- triamido pyridines of 1mmol, 4, the 4'- (hexafluoros of 1.1 mmol are sequentially added
Isopropyl alkene) two anhydride phthalic acids, 2 mmol benzoic acid, 2mL isoquinolin and 200mL dimethyl sulfoxide (DMSO).Logical nitrogen protection, 5 h
Afterwards, 140 are warming up to oC reacts 4 h, then heats to 180 oC reacts 20 h.After reaction, it is down to room temperature and will react molten
Liquid is poured into methanol, and a large amount of solids are precipitated.After the solid is washed repeatedly with methanol, filter and by the solid being collected into vacuum
In baking oven, 50oC dries 10 h and obtains amino-terminated hyperbranched polyimides；
（2）The preparation of silane-modified super-branched polyimide
Amino-terminated hyperbranched 10 parts by weight of polyimides are added in the three-necked flask being completely dried, epoxy type silane is even
Join 10 parts by weight of agent KH-560 and dimethyl sulfoxide (DMSO), after stirring 20min under inert gas shielding, be heated to 80 DEG C of reactions 5
After h, room temperature is down to, solution is poured into methanol, there is Precipitation；With methanol repeatedly wash removal solvent after filter after, Yu Zhen
50 times drying are for 24 hours to get silane-modified super-branched polyimide in empty baking oven.
Embodiment 11）The F1 of the D1 of 50 parts by weight, the E1 of 20 parts by weight and 0.5 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 10 parts by weight B1, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C1 of 150 parts by weight and the G1 of 5 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 21）The F1 of the D1 of 100 parts by weight, the E1 of 50 parts by weight and 2 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 10 parts by weight B1, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C1 of 200 parts by weight and the G1 of 20 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 3
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B1, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C1 of 180 parts by weight and the G1 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 4
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B2, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C2 of 180 parts by weight and the G1 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 5
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B2, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G1 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 6
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G1 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 7
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G2 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 8
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G3 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 9
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G4 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 10
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G5 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 11
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G6 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Embodiment 12
1）The F2 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight and the G6 of 15 parts by weight are put into after SBS and HO-SBS all dissolving,
The control of stainless steel cauldron temperature is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Comparative example 1
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in 100 parts by weight A1, and by temperature of reaction kettle control 140 DEG C with
It is interior；
2）The C3 of 180 parts by weight is put into after SBS and HO-SBS all dissolving, by stainless steel cauldron
Temperature control is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Comparative example 2
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）After SBS and HO-SBS all dissolving, by the control of stainless steel cauldron temperature in 140 DEG C of stirrings
30 minutes；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Comparative example 3
1）The F1 of the D1 of 80 parts by weight, the E1 of 35 parts by weight and 1 parts by weight are first put into stainless steel
In reaction kettle, after being warming up to 120 DEG C, add in the A1 of 100 parts by weight, 25 parts by weight B3, and by temperature of reaction kettle
Control is within 140 DEG C；
2）The C3 of 180 parts by weight is put into after SBS and HO-SBS all dissolving, by stainless steel cauldron
Temperature control is stirred 30 minutes at 140 DEG C；
3）- 0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
Test result
The automotive interior adhesive obtained to above-described embodiment 1~12 and comparative example 1~3 is tested, and test method is as follows：
Tensile property：Tensile strength and elongation at break are measured according to JIS K6251.
Ageing resistance is tested：It is handled 400 hours in 80 DEG C of water, then measures its adhesive tensile resistance strength retention.
Adhesion strength：It is measured according to ASTM 882-99.
Peel strength：It is measured according to GB/T 7122-1996.
Above-mentioned test result is shown in Table 1
Table 1
Data above can be seen that with not using hydroxy-end capped super branched polyurethane, HO-SBS and silane-modified over-expense
The product for changing polyimides is compared, and automotive interior adhesive prepared by the present invention has better resistance to ag(e)ing and adhesive property, because
This provides the advantageous effects of the present invention.
Aforementioned example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim
The range as wide as possible that requirement is contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is that appended claim is not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will not formed due to the inaccuracy that language is expressed and not
The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended
Claim covers.
Claims (9)
1. a kind of anti-aging automotive interior adhesive of environment-friendly type, prepares raw material and includes：
The SBS of 100 parts by weight；
The hydroxy-end capped super branched polyurethane of 150~200 parts by weight；
The HO-SBS of 10~40 parts by weight；
The White Mineral Oil of 50~100 parts by weight；
The dimethyl sulfoxide (DMSO) of 20~50 parts by weight；
The antioxidant of 0.5~2 parts by weight；With
The silane-modified super-branched polyimide of 5~20 parts by weight；
Wherein, the silane-modified super-branched polyimide is by including epoxy silane coupling agent and amino-terminated hyperbranched polyamides
The raw material of imines is prepared；The grafting rate of hydroxyl is 33% in the HO-SBS.
2. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, the hydroxy-end capped super branched polyurethane is by including two
The raw material of isocyanates and trihydroxylic alcohol is prepared.
3. the anti-aging automotive interior adhesive of the environment-friendly type of claim 2, wherein, the diisocyanate is selected from two isocyanide of isophorone
Acid esters, 4 ' 4- methyl diphenylene diisocyanates, hexamethylene diisocyanate and 2, it is arbitrary in 4 toluene di-isocyanate(TDI)s
It is one or more；The trihydroxylic alcohol in glycerine, trimethylolpropane and polyether-tribasic alcohol any one or it is more
Kind.
4. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, the antioxidant is BHT or DLTP.
5. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, the super-branched polyimide is pressed by triamine and dianhydride
Molar ratio 1：(1~1.3) is prepared.
6. the anti-aging automotive interior adhesive of the environment-friendly type of claim 5, wherein, the triamine be selected from 2,4,6- triamido pyridines and
Any one in three (4- aminophenyls) amine or two kinds.
7. the anti-aging automotive interior adhesive of the environment-friendly type of claim 5, wherein, the dianhydride is selected from pyromellitic dianhydride, 3,4,9,
10- tetracarboxylic anhydrides, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acids two
Acid anhydride, 3,3', any one or more in 4,4'- benzophenone tetracarboxylics dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride.
8. the method for the anti-aging automotive interior adhesive of environment-friendly type as described in claim 1~7 any one is prepared, including following step
Suddenly：
1) first White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are put into stainless steel cauldron, after being warming up to 120~130 DEG C, added
Enter SBS, HO-SBS, and by temperature of reaction kettle control within 140 DEG C；
2) hydroxy-end capped super branched polyurethane is put into after SBS and HO-SBS all dissolving and silane-modified hyperbranched polyamides is sub-
Amine stirs the control of stainless steel cauldron temperature 30~60 minutes within 155 DEG C；
3) -0.085Mpa will be evacuated in reaction kettle, is packed after discharging, cooling.
9. the method for the anti-aging automotive interior adhesive of preparation environment-friendly type of claim 8, wherein the temperature in the step 2) is 140
℃。
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| CN110484190B (en) * | 2019-09-05 | 2021-05-18 | 山西省应用化学研究所(有限公司) | Solvent-free single-component moisture-curing polyurethane adhesive for caravan bodies and preparation method thereof |
| CN112646535B (en) * | 2020-12-23 | 2022-07-12 | 广东龙马新材料科技有限公司 | High-strength environment-friendly wood board adhesive and preparation method thereof |
| CN113549254B (en) * | 2021-08-16 | 2022-10-28 | 中国科学技术大学 | Method for preparing modified vulcanized rubber and modified vulcanized rubber |
| CN115558284B (en) * | 2022-11-09 | 2023-07-04 | 南通北风橡塑制品有限公司 | Glass fiber reinforced polyurethane composite board and preparation method thereof |
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| CN101824294A (en) * | 2010-04-30 | 2010-09-08 | 安徽安大华泰新材料有限公司 | Preparation method of tetrabasic copolymerized waterborne polyurethane automotive interior adhesive |
| CN105073849A (en) * | 2012-12-11 | 2015-11-18 | 粘合剂研究股份有限公司 | Reactive film adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824294A (en) * | 2010-04-30 | 2010-09-08 | 安徽安大华泰新材料有限公司 | Preparation method of tetrabasic copolymerized waterborne polyurethane automotive interior adhesive |
| CN105073849A (en) * | 2012-12-11 | 2015-11-18 | 粘合剂研究股份有限公司 | Reactive film adhesive |
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