CN105602509A - Environment-friendly anti-aging automobile inner decorating glue and preparation method thereof - Google Patents
Environment-friendly anti-aging automobile inner decorating glue and preparation method thereof Download PDFInfo
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- CN105602509A CN105602509A CN201610035923.XA CN201610035923A CN105602509A CN 105602509 A CN105602509 A CN 105602509A CN 201610035923 A CN201610035923 A CN 201610035923A CN 105602509 A CN105602509 A CN 105602509A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses environment-friendly anti-aging automobile inner decorating glue. The glue is prepared from SBS, hydroxy-terminated hyperbranched polyurethane, HO-SBS, white mineral oil, dimethyl sulfoxide, antioxidant and silane modified hyperbranched polyimide, wherein the silane modified hyperbranched polyimide is prepared from raw materials including epoxy silane coupling agent and amino-terminated hyperbranched polyimide. The invention further discloses a preparation method of the environment-friendly anti-aging automobile inner decorating glue.
Description
Technical field
The invention belongs to bonding and use glue field, more specifically, the present invention relates to anti-aging automotive interior adhesive of a kind of environment-friendly type and preparation method thereof.
Background technology
Along with the development of automobile industry, automotive trim is more and more luxurious, and therefore the consumption of automotive upholstery adhesive glue is also increasing. In automotive trim adhesive therefor, owing to using the organic solvent of non-environmental protection, conventionally contain the harmful substances such as a large amount of formaldehyde, benzene, dimethylbenzene at present, health is caused to huge threat. In addition, also there is the weak and poor shortcoming of ageing resistace of initial bonding strength in automotive interior adhesive of the prior art, urgently to be resolved hurrily.
Therefore, be starved of by the improvement of formula and production technology, prepare a kind of high cohesive force, high resistance aged automobile interior trim glue of environment-friendly type.
Summary of the invention
In order to address the above problem, one aspect of the present invention provides a kind of environment-friendly type anti-aging automotive interior adhesive, and its raw materials comprises:
The SBS of 100 weight portions;
The hydroxy-end capped super branched polyurethane of 150～200 weight portions;
The HO-SBS of 10～40 weight portions;
The White Mineral Oil of 50～100 weight portions;
The dimethyl sulfoxide (DMSO) of 20～50 weight portions;
The antioxidant of 0.5～2 weight portion; With
The silane-modified super-branched polyimide of 5～20 weight portions;
Wherein, described silane-modified super-branched polyimide is prepared by the raw material that comprises epoxy silane coupling agent and amino-terminated hyperbranched polyimides.
In one embodiment, described hydroxy-end capped super branched polyurethane is prepared by the raw material that comprises vulcabond and trihydroxylic alcohol.
In one embodiment, described vulcabond be selected from IPDI, 4 ' 4-methyl diphenylene diisocyanate, hexamethylene diisocyanate and 2,4 toluene di-isocyanate(TDI)s any one or multiple; Described trihydroxylic alcohol be selected from glycerine, trimethylolpropane and polyether-tribasic alcohol any one or multiple.
In one embodiment, in described HO-SBS, the percent grafting of hydroxyl is 25-40%.
In one embodiment, described antioxidant is BHT or DLTP.
In one embodiment, described super-branched polyimide is by triamine and dianhydride 1:(1～1.3 in molar ratio) prepare.
In one embodiment, described triamine is selected from any one or two kinds in 2,4,6-triamido pyridine and three (4-aminophenyl) amine.
In one embodiment, described dianhydride is selected from pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic acid acid anhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, dicyclo [2.2.2] are pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, Isosorbide-5-Nitrae, any one in 5,8-naphthalenetetracarbacidic acidic dianhydride or multiple.
Another aspect of the present invention provides a kind of method of preparing the anti-aging automotive interior adhesive of environment-friendly type, comprises the following steps:
1) first White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are dropped in stainless steel cauldron, be warming up to after 120 ~ 130 DEG C, add SBS, HO-SBS, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into hydroxy-end capped super branched polyurethane and silane-modified super-branched polyimide until SBS and HO-SBS, stainless steel cauldron temperature is controlled to 155 DEG C with interior stirring 30 ~ 60 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
In one preferably in embodiment, wherein said step 2) in temperature be 140 DEG C.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description in detail.
Detailed description of the invention
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprising can more easily understand present disclosure. In following description and claims, can mention a large amount of terms, these terms are defined as following implication.
Singulative comprises plural number discussion object, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that item or the event described thereafter can occur or not occur, and this description comprises the situation of event generation and the situation that event does not occur.
Approximate term in description and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises approach to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function. Accordingly, modify a numerical value with " approximately ", " approximately " etc., mean and the invention is not restricted to this accurate numerical value. In some example, approximate term may be corresponding to the precision of the instrument of measurement numerical value. In present specification and claims, circumscription can combine and/or exchange, if do not illustrate in addition that these scopes comprise contained all subranges therebetween.
One aspect of the present invention provides one to provide one to provide a kind of environment-friendly type anti-aging automotive interior adhesive, and its raw materials comprises:
The SBS of 100 weight portions;
The hydroxy-end capped super branched polyurethane of 150～200 weight portions;
The HO-SBS of 10～40 weight portions;
The White Mineral Oil of 50～100 weight portions;
The dimethyl sulfoxide (DMSO) of 20～50 weight portions;
The antioxidant of 0.5～2 weight portion; With
The silane-modified super-branched polyimide of 5～20 weight portions;
Wherein, described silane-modified super-branched polyimide is prepared by the raw material that comprises epoxy silane coupling agent and amino-terminated hyperbranched polyimides;
Preferably, its raw materials comprises:
The SBS of 100 weight portions;
The hydroxy-end capped super branched polyurethane of 180 weight portions;
The HO-SBS of 30 weight portions;
The White Mineral Oil of 80 weight portions;
The dimethyl sulfoxide (DMSO) of 30 weight portions;
The antioxidant of 1 weight portion; With
The silane-modified super-branched polyimide of 10 weight portions;
Wherein, described silane-modified super-branched polyimide is prepared by the raw material that comprises epoxy silane coupling agent and amino-terminated hyperbranched polyimides.
Term of the present invention " SBS " refers to polystyrene-butadiene-styrene three inlay section thermal plastic elastic bodies. Described SBS structurally has two features: one, and strand is formed higher than the hard plastic polystyrene PS section phase embedding of room temperature lower than soft elasticity polybutadiene PB section and the vitrification point of room temperature by vitrification point; Its two, these two kinds of blocks are that mechanics is inconsistent, with microscopic dimensions be separated form two " island " structures that are separated, in the time that polystyrene content is lower, PS is divided into isolated region, is around the PB continuous phase of rubber. Due to the existence of plastics phase, the motion of rubber molecule segment is subject to certain restrictions, make thermoplastic elastomer there is the performance of vulcanized rubber, with vulcanized rubber difference be, the crosslinked of plastics phase is reversible physical crosslinking, in the time that it is dissolved in organic solvent or heating and melting, plastics are dissolved or melting mutually, lose crosslinked action; And good in solvent evaporates or melt cooling, plastics mutually again can precipitation and separation out, and recover original physical crosslinking state. Be not particularly limited for the application's SBS, can be commercially available or synthesize. The structure of SBS and molecular weight and cinnamic content are closely connected, and as a kind of optimal way of the present invention, in SBS, cinnamic content is 40wt%.
Term of the present invention " hydroxy-end capped super branched polyurethane " is prepared by the raw material that comprises vulcabond and trihydroxylic alcohol.
Super branched polyurethane for the application is standby by employing A2+B3 legal system, and obtains the polymer of hydroxy-end capped end-blocking, and concrete grammar is:
1) vulcabond and trihydroxylic alcohol are dissolved in respectively in polar solvent, obtain respectively vulcabond solution and trihydroxylic alcohol solution, controlling its mass concentration is 5～30%;
Wherein, described vulcabond be in IPDI, 4 ' 4-methyl diphenylene diisocyanate, hexamethylene diisocyanate or 2,4-toluene di-isocyanate(TDI) any one or multiple, preferably, described vulcabond is 2,4-toluene di-isocyanate(TDI);
Described trihydroxylic alcohol is glycerine, trimethylolpropane or polyether-tribasic alcohol, and preferably, described trihydroxylic alcohol is polyether-tribasic alcohol;
2) under 30～100 DEG C, protective atmosphere, stir on limit, and vulcabond solution is added in trihydroxylic alcohol solution, and wherein the mol ratio of the isocyanate group of vulcabond and the hydroxyl of trihydroxylic alcohol is 8:9～1:3; After vulcabond has added, reaction system insulation reaction 10～30h; Then in reaction system, add protective agent, at 30～100 DEG C, continue reaction 5～10h;
3) after reaction finishes, decompression distillation goes out after solvent, gained material is dissolved through oxolane, in methyl alcohol sedimentation and filter after, the vacuum drying 10～24h by it at 50～140 DEG C, obtains the super branched polyurethane that contains hydroxyl of purifying;
Preferably, the mol ratio of the isocyanate group of described vulcabond and the hydroxyl of trihydroxylic alcohol is 1:2.
In one embodiment, described vulcabond solution, the solvent that trihydroxylic alcohol solution adopts are dimethyl sulfoxide (DMSO), N, N-dimethylacetylamide, DMF, N, the mixing of one or more in N-dimethyl pyrrolidone, oxolane or toluene.
In one embodiment, described protective agent is phenol, caprolactam, ethylene glycol ethyl ether or methyl ethyl ketoxime; Protectant addition is 1～60% of vulcabond molal quantity.
Hydroxy-end capped super branched polyurethane can increase substantially the initial bonding strength of colloid, thereby useful technique effect of the present invention is provided.
Term of the present invention " HO-SBS " refers to by SBS, hydrogen peroxide, anhydrous formic acid to be prepared. The preparation method of described HO-SBS is: be furnished with in the 250ml four-hole bottle of condenser pipe, mechanical agitation, thermometer one, the SBS of 5g is put in 50ml chloroform, and then 50ml anhydrous formic acid and 5ml hydrogen peroxide are added drop-wise in reaction bulb respectively slowly. Stirring reaction one day at 50 DEG C～80 DEG C, after reaction finishes, pours reactant liquor in methanol solution into and precipitates, and filters, and methyl alcohol repeatedly washs, and gained floccule is dried at 40 DEG C in vacuum drying to 8h, to obtain final product; Respectively, the percent grafting that obtains hydroxyl at 50 DEG C, 70 DEG C and 80 DEG C is respectively 25%, 33% and 40%.
As a kind of preferred embodiment of the present invention, in described HO-SBS, the percent grafting of hydroxyl is 25-40%.
As a kind of preferred embodiment of the present invention, in described HO-SBS, the percent grafting of hydroxyl is 33%.
White Mineral Oil for the application is not particularly limited, and can be commercially available commercially produced product.
Term of the present invention " antioxidant " refers to that the oxidation of high polymer causes macromolecular chain to rupture, be cross-linked, make performance depreciation, can prevent or suppress the compound of oxidizing process. Antioxidant is divided into free radical terminator and hydrogen peroxide decomposition agent two classes. Described free radical terminator is mainly shifted and is generated inactive free radical or form stable product by chain, makes chain termination. Sterically hindered phenol, aromatic amine and some cyclic hydrocarbon are good free radical stabilizers, and phenolic compound generally uses at a lower temperature, and under higher temperature, antioxidant is poor, and aminated compounds is as aromatic amine. The effect of hydrogen peroxide decomposition agent is that hydroperoxides are decomposed into non-free radical product. In order to realize beneficial effect of the present invention, as a kind of preferred embodiment of the present invention, described antioxidant is BHT or DLTP.
Term of the present invention " silane-modified super-branched polyimide " is prepared by the raw material that comprises epoxy silane coupling agent and amino-terminated hyperbranched polyimides.
In one embodiment, the preparation method of described silane-modified super-branched polyimide comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively the organic good solvent of dianhydride, 2mmol benzoic acid, 0.5～3mL isoquinolin and the 10～500mL of triamine, the 1～1.3mmol of 1mmol. Logical nitrogen protection, after 0.1～10h, is warming up to 100～160oC reacts 1～4h, is then warming up to 180oC～220oC reacts 2～20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 30～80oC is dry, and 2～10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add 10 parts of amino-terminated hyperbranched polyimides, epoxy type silane coupler KH-5601～30 part and appropriate good solvent, under inert gas shielding, stir after 5～50min, be heated to after 60～100 DEG C of reaction 0.1～10h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, at 20 DEG C～80 DEG C, dry 1h～24h, obtain silane-modified super-branched polyimide;
Preferably, described super-branched polyimide by triamine and dianhydride in molar ratio 1:1.1 prepare.
In one embodiment, described triamine is selected from any one or two kinds in 2,4,6-triamido pyridine and three (4-aminophenyl) amine; Preferably, described triamine is 2,4,6-triamido pyridine.
In one embodiment, described dianhydride is selected from pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic acid acid anhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, dicyclo [2.2.2] are pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, Isosorbide-5-Nitrae, any one in 5,8-naphthalenetetracarbacidic acidic dianhydride or multiple; Preferably, described dianhydride be selected from 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids and dicyclo [2.2.2] pungent-7-alkene-2, any one in 3,5,6-tetracarboxylic dianhydride or two kinds; More preferably, described dianhydride is 4,4'-(hexafluoro isopropyl alkene), two anhydride phthalic acids.
Silane-modified super-branched polyimide can improve cohesive force and the ageing resistance of interior trim glue effectively, and therefore useful technique effect of the present invention is provided.
Another aspect of the present invention provides a kind of method of preparing the anti-aging automotive interior adhesive of environment-friendly type, comprises the following steps:
1) first White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are dropped in stainless steel cauldron, be warming up to after 120 ~ 130 DEG C, add SBS, HO-SBS, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into hydroxy-end capped super branched polyurethane and silane-modified super-branched polyimide until SBS and HO-SBS, stainless steel cauldron temperature is controlled to 155 DEG C with interior stirring 30 ~ 60 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
In one preferably in embodiment, wherein said step 2) in temperature be 140 DEG C.
Below by embodiment, the present invention is specifically described. Be necessary to be pointed out that at this; following examples are only for the invention will be further described; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if there is no other explanation, raw materials used is all commercially available, and following material umber used is weight portion.
Raw material:
The cinnamic content of A1:SBS(is 40wt%)
The percent grafting of B1:HO-SBS(hydroxyl is 25%)
The percent grafting of B2:HO-SBS(hydroxyl is 40%)
The percent grafting of B3:HO-SBS(hydroxyl is 33%)
C1: super branched polyurethane, its preparation method is:
The IPDI of 0.04 mole is dissolved in to the toluene of 20mL, obtain vulcabond solution, then 0.03 mole of glycerine is dissolved in to 20mL dimethyl sulphoxide solution, obtain trihydroxylic alcohol solution, then described trihydroxylic alcohol solution is joined in the there-necked flask with magnetic agitation and reflux, under 40 DEG C, nitrogen protection, under stirring action, slowly add wherein the toluene solution of described IPDI;
After dripping, system continues reaction 10h at 40 DEG C, and then to the phenol that adds 0.002 mole in reaction medium, heating is reacted 5h at 100 DEG C;
After reaction finishes, decompression distillation goes out solvent. Methyl alcohol-oxolane for products therefrom (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, and 60 DEG C of vacuum drying 24h, obtain super branched polyurethane.
C2: super branched polyurethane, its preparation method is:
4 ' the 4-methyl diphenylene diisocyanate of 0.01 mole is dissolved in to the toluene of 20mL, obtain vulcabond solution, then 0.02 mole of trimethylol propane is dissolved in to 20mL dimethyl sulphoxide solution, obtain trihydroxylic alcohol solution, then described trihydroxylic alcohol solution is joined in the there-necked flask with magnetic agitation and reflux, under 40 DEG C, nitrogen protection, under stirring action, slowly add wherein the toluene solution of 4 ' described 4-methyl diphenylene diisocyanate;
After dripping, system continues reaction 10h at 40 DEG C, and then to the caprolactam that adds 0.002 mole in reaction medium, heating is reacted 5h at 100 DEG C;
After reaction finishes, decompression distillation goes out solvent. Methyl alcohol-oxolane for products therefrom (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, and 60 DEG C of vacuum drying 24h, obtain super branched polyurethane.
C3: super branched polyurethane, its preparation method is:
By 0.03 mole 2,4-toluene di-isocyanate(TDI) is dissolved in the toluene of 20mL, obtain vulcabond solution, then 0.04 mole of polyether-tribasic alcohol is dissolved in to 20mL dimethyl sulphoxide solution, obtain trihydroxylic alcohol solution, then described trihydroxylic alcohol solution is joined in the there-necked flask with magnetic agitation and reflux, under 40 DEG C, nitrogen protection, under stirring action, slowly add wherein the toluene solution of 4 ' described 4-methyl diphenylene diisocyanate;
After dripping, system continues reaction 10h at 40 DEG C, and then to the caprolactam that adds 0.002 mole in reaction medium, heating is reacted 5h at 100 DEG C;
After reaction finishes, decompression distillation goes out solvent. Methyl alcohol-oxolane for products therefrom (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, and 60 DEG C of vacuum drying 24h, obtain super branched polyurethane.
D1: White Mineral Oil
E1: dimethyl sulfoxide (DMSO)
F1：BHT
F2：DLTP
G1: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively the dimethyl sulfoxide (DMSO) of pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and the 200mL of three (4-aminophenyl) amine, the 1mmol of 1mmol. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
G2: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively the dimethyl sulfoxide (DMSO) of pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and the 200mL of three (4-aminophenyl) amine, the 1.1mmol of 1mmol. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
G3: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively the dimethyl sulfoxide (DMSO) of pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and the 200mL of three (4-aminophenyl) amine, the 1.3mmol of 1mmol. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
G4: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively 2,4 of 1mmol, the dianhydride of 6-triamido pyridine, 1.1mmol is the dimethyl sulfoxide (DMSO) of pyromellitic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and 200mL. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
G5: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively 2,4 of 1mmol, the dicyclo [2.2.2] of 6-triamido pyridine, 1.1mmol is pungent-7-alkene-2, the dimethyl sulfoxide (DMSO) of 3,5,6-tetracarboxylic dianhydride, 2mmol benzoic acid, 2mL isoquinolin and 200mL. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
G6: silane-modified super-branched polyimide, its preparation method comprises:
(1) preparation of amino-terminated hyperbranched polyimides
In dry three-necked bottle, add successively 2,4 of 1mmol, 4 of 6-triamido pyridine, 1.1mmol, the dimethyl sulfoxide (DMSO) of 4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 2mmol benzoic acid, 2mL isoquinolin and 200mL. Logical nitrogen protection, after 5h, is warming up to 140oC reacts 4h, is then warming up to 180oC reacts 20h. After reaction finishes, be down to room temperature and reaction solution is poured in methyl alcohol, separating out a large amount of solids. By this solid with after methyl alcohol cyclic washing, suction filtration and by the solid of collecting in vacuum drying oven, 50oC is dry, and 10h obtains amino-terminated hyperbranched polyimides;
(2) preparation of silane-modified super-branched polyimide
In the there-necked flask of bone dry, add amino-terminated hyperbranched polyimides 10 weight portions, epoxy type silane coupler KH-56010 weight portion and dimethyl sulfoxide (DMSO), under inert gas shielding, stir after 20min, be heated to after 80 DEG C of reaction 5h, be down to room temperature, solution is poured in methyl alcohol, had Precipitation; After filtering after methyl alcohol cyclic washing removal solvent, in vacuum drying oven, dry 24h 50 times, obtain silane-modified super-branched polyimide.
Embodiment 11) first the F1 of the E1 of the D1 of 50 weight portions, 20 weight portions and 0.5 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B1 of 10 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C1 of 150 weight portions and the G1 of 5 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 21) first the F1 of the E1 of the D1 of 100 weight portions, 50 weight portions and 2 weight portions is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B1 of 10 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C1 of 200 weight portions and the G1 of 20 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 3
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B1 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C1 of 180 weight portions and the G1 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 4
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B2 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C2 of 180 weight portions and the G1 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 5
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B2 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G1 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 6
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G1 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 7
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G2 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 8
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G3 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 9
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G4 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 10
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G5 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 11
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G6 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Embodiment 12
1) first the F2 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into the C3 of 180 weight portions and the G6 of 15 weight portions until SBS and HO-SBS,
Stainless steel cauldron temperature is controlled to 140 DEG C to be stirred 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Comparative example 1
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) after all dissolving, SBS and HO-SBS drop into the C3 of 180 weight portions, by stainless steel cauldron
Temperature is controlled at 140 DEG C and stirs 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Comparative example 2
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) after SBS and the whole dissolvings of HO-SBS, stainless steel cauldron temperature is controlled to 140 DEG C of stirrings
30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Comparative example 3
1) first the F1 of the E1 of the D1 of 80 weight portions, 35 weight portions and 1 weight portion is dropped into stainless steel
In reactor, be warming up to after 120 DEG C, add the A1 of 100 weight portions, the B3 of 25 weight portions, and temperature of reaction kettle is controlled in 140 DEG C;
2) after all dissolving, SBS and HO-SBS drop into the C3 of 180 weight portions, by stainless steel cauldron
Temperature is controlled at 140 DEG C and stirs 30 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
Test result
The automotive interior adhesive that above-described embodiment 1～12 and comparative example 1～3 are obtained is tested, and method of testing is as follows:
Tensile property: hot strength and elongation at break are measured according to JISK6251.
Ageing resistance test: process in the water of 80 DEG C 400 hours, then measure its adhesive tensile resistance strength retention.
Adhesion strength: measure according to ASTM882-99.
Peel strength: measure according to GB/T7122-1996.
Above-mentioned test result is in table 1
Table 1
Above data can be found out, compared with not using the product of hydroxy-end capped super branched polyurethane, HO-SBS and silane-modified super-branched polyimide, automotive interior adhesive prepared by the present invention has better resistance to ag(e)ing and adhesive property, and therefore useful technique effect of the present invention is provided.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure. Appended claim is intended to the wide as far as possible scope that requirement it is contemplated that, and the embodiment presenting is herein only according to the explanation of the embodiment of the selection of the combination of all possible embodiment. Therefore, applicant's purpose is the selectional restriction that appended claim is not illustrated the example of feature of the present invention. And progress in science and technology will form because the inaccurate former of language performance thereby the possible equivalent of not considered at present or son are replaced, and these variations also should be interpreted as being covered by appended claim possible in the situation that.
Claims (10)
1. the anti-aging automotive interior adhesive of environment-friendly type, its raw materials comprises:
The SBS of 100 weight portions;
The hydroxy-end capped super branched polyurethane of 150～200 weight portions;
The HO-SBS of 10～40 weight portions;
The White Mineral Oil of 50～100 weight portions;
The dimethyl sulfoxide (DMSO) of 20～50 weight portions;
The antioxidant of 0.5～2 weight portion; With
The silane-modified super-branched polyimide of 5～20 weight portions;
Wherein, described silane-modified super-branched polyimide is prepared by the raw material that comprises epoxy silane coupling agent and amino-terminated hyperbranched polyimides.
2. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, described hydroxy-end capped super branched polyurethane is prepared by the raw material that comprises vulcabond and trihydroxylic alcohol.
3. the anti-aging automotive interior adhesive of the environment-friendly type of claim 2, wherein, described vulcabond be selected from IPDI, 4 ' 4-methyl diphenylene diisocyanate, hexamethylene diisocyanate and 2,4 toluene di-isocyanate(TDI)s any one or multiple; Described trihydroxylic alcohol be selected from glycerine, trimethylolpropane and polyether-tribasic alcohol any one or multiple.
4. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, in described HO-SBS, hydroxyl
Percent grafting is 25-40%.
5. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, described antioxidant is BHT or DLTP.
6. the anti-aging automotive interior adhesive of the environment-friendly type of claim 1, wherein, described super-branched polyimide is by triamine and dianhydride 1:(1～1.3 in molar ratio) prepare.
7. the anti-aging automotive interior adhesive of the environment-friendly type of claim 6, wherein, described triamine is selected from any one or two kinds in 2,4,6-triamido pyridine and three (4-aminophenyl) amine.
8. the anti-aging automotive interior adhesive of the environment-friendly type of claim 6, wherein, described dianhydride is selected from pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic acid acid anhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, dicyclo [2.2.2] are pungent-7-alkene-2, and 3,5,6-tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 1, any one in 4,5,8-naphthalenetetracarbacidic acidic dianhydride or multiple.
9. the method for preparing the anti-aging automotive interior adhesive of environment-friendly type, comprises the following steps:
1) first White Mineral Oil, dimethyl sulfoxide (DMSO) and antioxidant are dropped in stainless steel cauldron, be warming up to after 120 ~ 130 DEG C, add SBS, HO-SBS, and temperature of reaction kettle is controlled in 140 DEG C;
2) all after dissolving, drop into hydroxy-end capped super branched polyurethane and silane-modified super-branched polyimide until SBS and HO-SBS, stainless steel cauldron temperature is controlled to 155 DEG C with interior stirring 30 ~ 60 minutes;
3) by reaction kettle for vacuumizing to-0.085Mpa, discharging, cooling rear packaging.
10. the method for preparing the anti-aging automotive interior adhesive of environment-friendly type of claim 9, wherein said step 2) in temperature be 140 DEG C.
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| CN110078888A (en) * | 2019-04-04 | 2019-08-02 | 华南理工大学 | With the porous organic polymer and the preparation method and application thereof of thiocarbamide structure connection |
| CN110484190A (en) * | 2019-09-05 | 2019-11-22 | 山西省应用化学研究所(有限公司) | Caravan vehicle body solvent-free single-component moisture cure urethanes adhesive and preparation method thereof |
| CN112646535A (en) * | 2020-12-23 | 2021-04-13 | 广东龙马新材料科技有限公司 | High-strength environment-friendly wood board adhesive and preparation method thereof |
| CN113549254A (en) * | 2021-08-16 | 2021-10-26 | 中国科学技术大学 | Method for preparing modified vulcanized rubber and modified vulcanized rubber |
| CN115558284A (en) * | 2022-11-09 | 2023-01-03 | 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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| CN110078888A (en) * | 2019-04-04 | 2019-08-02 | 华南理工大学 | With the porous organic polymer and the preparation method and application thereof of thiocarbamide structure connection |
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| CN110484190A (en) * | 2019-09-05 | 2019-11-22 | 山西省应用化学研究所(有限公司) | Caravan vehicle body solvent-free single-component moisture cure urethanes adhesive and preparation method thereof |
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| CN112646535A (en) * | 2020-12-23 | 2021-04-13 | 广东龙马新材料科技有限公司 | High-strength environment-friendly wood board adhesive 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 |
| CN113549254A (en) * | 2021-08-16 | 2021-10-26 | 中国科学技术大学 | Method for preparing modified vulcanized rubber and modified vulcanized rubber |
| 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 |
| CN115558284A (en) * | 2022-11-09 | 2023-01-03 | 南通北风橡塑制品有限公司 | Glass fiber reinforced polyurethane composite board and preparation method thereof |
| 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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