CN110305314A - A kind of solubility Environment-friendlyadhesive adhesive and its preparation process - Google Patents
A kind of solubility Environment-friendlyadhesive adhesive and its preparation process Download PDFInfo
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- CN110305314A CN110305314A CN201910600665.9A CN201910600665A CN110305314A CN 110305314 A CN110305314 A CN 110305314A CN 201910600665 A CN201910600665 A CN 201910600665A CN 110305314 A CN110305314 A CN 110305314A
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- dihydroxybiphenyl
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 116
- 239000000853 adhesive Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims abstract description 47
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004952 Polyamide Substances 0.000 claims abstract description 21
- 229920002647 polyamide Polymers 0.000 claims abstract description 21
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004327 boric acid Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 10
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 90
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 37
- 238000010792 warming Methods 0.000 claims description 34
- -1 dihydroxybiphenyl amine Chemical class 0.000 claims description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 239000004642 Polyimide Substances 0.000 claims description 21
- 229920001721 polyimide Polymers 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 17
- 229960004756 ethanol Drugs 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000005690 diesters Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- 150000003504 terephthalic acids Chemical class 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- MKYHWXZCJIAMMY-UHFFFAOYSA-N 3-hydroxypyridine-2-carbonyl chloride Chemical compound OC1=CC=CN=C1C(Cl)=O MKYHWXZCJIAMMY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000011026 diafiltration Methods 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 60
- 229910018557 Si O Inorganic materials 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 238000009825 accumulation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 230000005588 protonation Effects 0.000 description 8
- 125000005372 silanol group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- PSAYJRPASWETSH-UHFFFAOYSA-N pyridine-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CC=N1 PSAYJRPASWETSH-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of soluble Environment-friendlyadhesive adhesive, each component materials including following component: 40-45 parts of dihydroxybiphenyl polyamide, 80-90 parts of dimethylformamide, 4-7 parts of basic copper carbonate, 34-38 parts of siliconization pyridone, 30-34 parts of boric acid, 120-130 parts of solvent.Adhesive unevenness prepared by the present invention, which can be realized, is still able to maintain physical aspect under 500 DEG C of high temperature, can be used normally, and can be achieved at the same time and directly dissolve in alcohol solvent, while adhesive property is high, and peel strength reaches 21.6N.cm‑1。
Description
Technical field
The invention belongs to adhesive preparation field, it is related to a kind of soluble Environment-friendlyadhesive adhesive and its preparation process.
Background technique
Polyimides is widely used in every field as heat-resisting material, while polyimides is based on aromatic rings
Chain has high conjugacy, is difficult to dissolve in common polar solvent, machine-shaping property is poor, simultaneously for existing
For polyimides adhesive, due to its heat-resistant quality with higher, can at 350 DEG C normal use, but for more
High-temperature then can not achieve, while solidify after existing adhesive use, then after prolonged use if desired by bonding part
Position separation then needs to carry out by mechanical means, and the adhesive that bond site is pasted after isolation still has residual, is unfavorable for
The utilization again of object.
Summary of the invention
The purpose of the present invention is to provide a kind of soluble Environment-friendlyadhesive adhesive and its preparation process, the adhesive by
Benzidine is used in the polyimides main chain of preparation, benzidine connects phenyl ring by amide, is connected so that forming two on main chain
The phenyl ring that is connected with by amide of phenyl ring, three phenyl ring form alternately repeated structure, so that entire main chain is formed and turned round
Bent non-public planar structure, by passing through non-public affairs between monomer inside dihydroxybiphenyl amine and tetracarboxylic acid acid diester diacid chloride monomer
The form of plane exists, so that the polymer molecule segment formed is distorted, destroys the conjugation of polymer molecular chain
System, the tightness degree for effectively reducing molecule segment accumulation improve the molten of polymer to reduce intermolecular force
Performance is solved, while introducing pyridine ring on adhesive main chain, the protonation of the polarity nitrogen-atoms on pyridine ring can be improved poly-
Dissolubility of the object in polar solvent is closed, while containing siloxanes key on pyridine ring, wherein the bond energy of Si-O key is high, the rotation of key
Freedom is larger, improves the polarizability of entire polymer, the dissolubility of adhesive is further improved, according to similar compatibility
Principle can dissolve in ethanol so that the adhesive is highly soluble in polar molecule, can be realized the bonding part to object
Position is directly separated by impregnating dissolution adhesive, and the adhesive dissolved can be reduced costs with recycling and reusing, is solved
Existing adhesive solvability of having determined is poor, solidifies after use, then after prolonged use if desired separates bond site then
It needs to carry out by mechanical means, and the adhesive that bond site is pasted after isolation still has residual, is unfavorable for object again
The problem of secondary utilization.
The peel strength of adhesive prepared by the present invention reaches 21.6N.cm-1, pass through boric acid and phenolic hydroxyl group on polymer
Between effect crosslinking silicone pyridone reduce the accumulation of molecule branch so that polymer is hyperbranched, improve glue
The viscosity and adhesive property of glutinous agent, while pyridine ring introduces on polymer branch, the protonation of the polarity nitrogen-atoms on pyridine ring
Effect can be improved the flexibility of polymer, and then improve the adhesive property of adhesive, while containing siloxanes on pyridine ring
Key, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then can be improved the dissolubility and flexibility of polymer,
The thermal expansion coefficient for reducing polymer simultaneously, improves the adhesive property of adhesive, while the siloxanes key on adhesive main chain exists
Hydrolysis generates silanol group in the water of certain temperature, is connected between adjacent silanol group by hydrogen bond, so that the bonding of adhesive
Performance improves, and solves the problems, such as that existing adhesive for polyurethane adhesive property is low.
The present invention passes through the effect crosslinking silicone pyridone between boric acid and phenolic hydroxyl group on polymer, so that poly-
It is hyperbranched to close object, reduces the accumulation of molecule branch, while pyridine ring introduces on polymer branch, pyridine ring itself has centainly
Heat resistance and chemical stability so that the thermal stability of polymer improves, while containing siloxanes key on pyridine ring,
Wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then reduces the thermal expansion coefficient of polymer, improves its thermostabilization
Property, adhesive modified is still able to maintain physical aspect at 500 DEG C, can be used normally, can be used under high temperature being glued
It closes, solves for existing polyimides adhesive, it, can be normal at 350 DEG C due to its heat-resistant quality with higher
The problem of using, but then can not achieve for higher temperature.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of solubility Environment-friendlyadhesive adhesive, each component materials including following component:
40-45 parts of dihydroxybiphenyl polyamide, 80-90 parts of dimethylformamide, 4-7 parts of basic copper carbonate, siliconization
34-38 parts of pyridone, 30-34 parts of boric acid, 120-130 parts of solvent；
The specific preparation process of dihydroxybiphenyl polyamide is as follows:
Step 1: pyromellitic acid anhydride being dissolved in acetone, is warming up to after 70 DEG C and dehydrated alcohol is added thereto and to first
Benzene sulfonic acid, constant temperature back flow reaction 4-5h, obtained product is rotated, and then passes through deionized water and saturated sodium-chloride respectively
Solution is cleaned, and is placed into 50 DEG C of baking oven and is dried, and esterification terephthalic acids is obtained, due in pyromellitic acid anhydride
Two anhydride groups ring-opening reaction occurs with ethyl alcohol under the catalytic action of p-methyl benzenesulfonic acid, generate benzoic ether and benzoic acid
Base；Dehydrated alcohol 0.48-0.52g is added in every gram of pyromellitic acid anhydride, p-methyl benzenesulfonic acid 0.1g is added；
Step 2: the esterification terephthalic acids and acetone that prepare in step 1 being added in flask, are warming up to 80 DEG C of reflux, simultaneously
Thionyl chloride is added into flask, back flow reaction 5h is evaporated crystallization to obtained reaction mixture, and obtained crystal is led to
Dehydrated alcohol washing is crossed, is then dried in 50 DEG C of baking oven, obtains tetracarboxylic acid acid diester diacid chloride, reaction structure formula is as schemed
Shown in 1, due to containing benzoic acid functional group in esterification terephthalic acids, chloro is carried out under the action of thionyl chloride, generates acyl
Chlorine；Thionyl chloride 1.1-1.2g is added in every gram of esterification terephthalic acids；
Step 3: the tetracarboxylic acid acid diester diacid chloride prepared in step 2 is added in reaction vessel, while water being added thereto,
It is warming up to 70 DEG C after stirring and dissolving, dihydroxybiphenyl amine is then added thereto, constant temperature back flow reaction 3h is cooled to mistake after room temperature
Filter washing is dry, obtains dihydroxybiphenyl polyamide, and reaction structure formula is as shown in Fig. 2, two in tetracarboxylic acid acid diester diacid chloride
Amino substitution reaction occurs for the amino in acid chloride groups and dihydroxybiphenyl amine, generates amide groups, tetracarboxylic acid acid diester diacid chloride and
Dihydroxybiphenyl amine is crosslinked by amide substitution reaction, is formed polymer, is contained phenolic hydroxyl group on main polymer chain, not only mention
The high solubility property of polymer, while phenolic hydroxyl group provides reaction site, and polymer is crosslinked by boric acid,
Boron content in adhesive is improved, and improves the super collateralization of adhesive, and then mentions the adhesive adhesive property generated
Height, thermal stability enhancing；Simultaneously because containing benzidine in dihydroxybiphenyl amine, benzidine connects phenyl ring by amide, so that
The phenyl ring that two connected phenyl ring are connected with by amide is formed on main chain, three phenyl ring form alternately repeated structure, in turn
So that entire main chain forms the non-public planar structure of distortion, inside dihydroxybiphenyl amine and tetracarboxylic acid acid diester diacid chloride monomer
Exist by way of non-fair face between monomer, so that the polymer molecule segment formed is distorted, destroys
The conjugated system of polymer molecular chain effectively reduces the tightness degree of molecule segment accumulation, to reduce intermolecular interaction
Power improves the solubility property of polymer；Dihydroxybiphenyl amine 0.65-0.71g is added in every gram of tetracarboxylic acid acid diester diacid chloride；
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
Dihydroxybiphenyl polyamide is added in reaction kettle the first step, while dimethylformamide and alkali being added thereto
Formula copper carbonate, is warming up to 100 DEG C and is stirred to react 3h, is then warming up to 120 DEG C of reaction 2h again, and side border ring condenses in reaction process
Collect the ethyl alcohol after decomposing so that in dihydroxybiphenyl polyamide in ester group and amine reaction process ester group towards the direction of decomposition into
Row, and then reaction efficiency is improved, while the fixed addition of basic copper carbonate can be improved point of ester group in dihydroxybiphenyl polyamide
Efficiency is solved, so that the carboxylic acid after decomposing directly is reacted with amino, improves amidation process process, it is cooling after fully reacting
It to room temperature, is then filtered, is dried with acetone washing, obtain dihydroxybiphenyl polyimides, reaction structure formula such as Fig. 3 institute
Show；
3- hydroxyl -2- pyridine carboxylic acid adding into acetone is warming up to 80 DEG C of reflux, two is then added thereto by second step
Chlorine sulfoxide, constant temperature back flow reaction 5h obtain 3- hydroxyl -2- pyridinecarboxylic chloride then by revolving；Every gram of 3- hydroxyl -2- pyridine
Thionyl chloride 1.18-1.21g is added in formic acid；
3- hydroxyl -2- the pyridinecarboxylic chloride prepared in second step is added in reaction vessel third step, while adding thereto
Enter acetone, 80 DEG C of reflux are warming up to after stirring and dissolving, is then added amino silane thereto, constant temperature back flow reaction 6-10h, then
It is cooled to after room temperature dry with sodium sulphate after being washed with sodium bicarbonate solution, then carried out column, and obtained pure siliconization
Pyridone, reaction structure formula are as shown in Figure 4；Amino silane 1.43-1.49g is added in every gram of 3- hydroxyl -2- pyridinecarboxylic chloride；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while being added thereto by the 4th step
Then the siliconization pyridone prepared in third step is added thereto, is stirred 3- in 70 DEG C of stirring and dissolvings for solvent
Boric acid is added dropwise after 5min into reaction kettle, is vigorously stirred when being added dropwise, isothermal reaction 1h, then heats to after being added dropwise completely
90 DEG C of reaction 3h, are cooled to room temperature after fully reacting, will carry out filtration washing drying after the discharge of the material in reaction kettle, obtaining can
Dissolubility adhesive, reaction structure formula as shown in figure 5, pass through the effect crosslinking silicone between boric acid and phenolic hydroxyl group on polymer
Changing pyridone reduces the accumulation of molecule branch so that polymer is hyperbranched, improves the viscosity and caking property of adhesive
Can, while pyridine ring introduces on polymer branch, pyridine ring itself has certain heat resistance and chemical stability, so that
The thermal stability of polymer improves, while the protonation of the polarity nitrogen-atoms on pyridine ring can be improved polymer in polarity
Dissolubility in solvent, and can be improved the flexibility of polymer, and then improve the adhesive property of adhesive, while in pyridine
Contain siloxanes key on ring, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then can be improved the molten of polymer
Solution property and flexibility, while the thermal expansion coefficient of polymer is reduced, improve the adhesive property of adhesive；Wherein solvent be acetone,
One of carbon tetrachloride, dehydrated alcohol；
Specific use process is as follows for the adhesive: adhesive is added what water and dehydrated alcohol were mixed with the ratio of 1:10
In solvent, solvent is heated to 40 DEG C, then stirs 30-40min, sticky colloid is obtained, that is, can be used directly；Due to gluing
Containing siloxanes key in agent, hydrolysis generates silanol group in the water of certain temperature, it is connected between adjacent silanol group by hydrogen bond, into
And the adhesive property of adhesive is improved；Since the entire main chain of adhesive forms the non-public planar structure of distortion, and then make it
Solubility property improves, while pyridine ring is introduced on adhesive main chain, and the protonation of the polarity nitrogen-atoms on pyridine ring can
Dissolubility of the polymer in polar solvent is improved, while containing siloxanes key on pyridine ring, wherein the bond energy of Si-O key is high, key
Rotation freedom it is larger, improve the polarizability of entire polymer, the dissolubility of adhesive further improved, according to phase
Like compatibility principle, so that the adhesive is highly soluble in polar molecule；
The recycling dissolution process process of adhesive is as follows: after the object surface bonded by adhesive is washed with water completely
Drying, impregnates 6-10h for the object after drying in dehydrated alcohol, then takes out object, and bonded part separates in object, gluing
Agent is dissolved in dehydrated alcohol, and object can continue to use, while the dehydrated alcohol for dissolving adhesive is evaporated crystallization, is returned
Dehydrated alcohol dissolution is received, obtained crystal is solid adhesive, is continued to use, and can not only realize the recycling benefit of adhesive
With, while can be realized the cleaning of object surface bonding place, object is continued to use, and can be direct by ethyl alcohol
It is recycled, ethyl alcohol is nontoxic, is conducive to the protection of environment.
Beneficial effects of the present invention:
For adhesive prepared by the present invention by using benzidine in the polyimides main chain of preparation, benzidine passes through amide
Phenyl ring is connected, so that forming the phenyl ring that two connected phenyl ring are connected with by amide on main chain, three phenyl ring form alternately weight
Multiple structure passes through dihydroxybiphenyl amine and tetracarboxylic acid acid diester so that entire main chain forms the non-public planar structure of distortion
Exist by way of non-fair face between monomer inside diacid chloride monomer, so that the polymer molecule segment hair formed
Raw distortion, destroys the conjugated system of polymer molecular chain, the tightness degree of molecule segment accumulation is effectively reduced, to drop
Active force between low molecule improves the solubility property of polymer, while pyridine ring, the pole on pyridine ring are introduced on adhesive main chain
The protonation of property nitrogen-atoms can be improved dissolubility of the polymer in polar solvent, while contain siloxanes on pyridine ring
Key, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, improves the polarizability of entire polymer, further mentions
The high dissolubility of adhesive, according to similar compatibility principle, so that the adhesive is highly soluble in polar molecule, in ethanol
It can dissolve, can be realized and directly pass through immersion dissolution adhesive to the bond site of object and separate, and dissolve viscous
Mixture can be reduced costs with recycling and reusing, and it is poor to solve existing adhesive solvability, be solidified after use, then in length
If desired bond site separation is then needed to carry out by mechanical means after time use, and bond site is pasted after isolation
Adhesive the problem of still having residual, being unfavorable for the utilization again of object.
The peel strength of adhesive prepared by the present invention reaches 21.6N.cm-1, pass through boric acid and phenolic hydroxyl group on polymer
Between effect crosslinking silicone pyridone reduce the accumulation of molecule branch so that polymer is hyperbranched, improve glue
The viscosity and adhesive property of glutinous agent, while pyridine ring introduces on polymer branch, the protonation of the polarity nitrogen-atoms on pyridine ring
Effect can be improved the flexibility of polymer, and then improve the adhesive property of adhesive, while containing siloxanes on pyridine ring
Key, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then can be improved the dissolubility and flexibility of polymer,
The thermal expansion coefficient for reducing polymer simultaneously, improves the adhesive property of adhesive, while the siloxanes key on adhesive main chain exists
Hydrolysis generates silanol group in the water of certain temperature, is connected between adjacent silanol group by hydrogen bond, so that the bonding of adhesive
Performance improves, and solves the problems, such as that existing adhesive for polyurethane adhesive property is low.
The present invention passes through the effect crosslinking silicone pyridone between boric acid and phenolic hydroxyl group on polymer, so that poly-
It is hyperbranched to close object, reduces the accumulation of molecule branch, while pyridine ring introduces on polymer branch, pyridine ring itself has centainly
Heat resistance and chemical stability so that the thermal stability of polymer improves, while containing siloxanes key on pyridine ring,
Wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then reduces the thermal expansion coefficient of polymer, improves its thermostabilization
Property, adhesive modified is still able to maintain physical aspect at 500 DEG C, can be used normally, can be used under high temperature being glued
It closes, solves for existing polyimides adhesive, it, can be normal at 350 DEG C due to its heat-resistant quality with higher
The problem of using, but then can not achieve for higher temperature.
Adhesive unevenness prepared by the present invention, which can be realized, is still able to maintain physical aspect under 500 DEG C of high temperature, can be normal
It uses, and can be achieved at the same time and directly dissolved in alcohol solvent, while adhesive property is high, peel strength reaches
21.6N.cm-1。
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is tetracarboxylic acid acid diester diacid chloride reaction structure formula of the present invention；
Fig. 2 is dihydroxybiphenyl polyamide reaction structural formula of the present invention；
Fig. 3 is dihydroxybiphenyl polyimides reaction structure formula of the present invention；
Fig. 4 is siliconization pyridone reaction structure formula of the present invention；
Fig. 5 is soluble adhesive reaction structure formula.
Specific embodiment
Fig. 1-5 is please referred to be described in detail in conjunction with following examples；
Embodiment 1:
The specific preparation process of dihydroxybiphenyl polyamide is as follows:
Step 1: 1kg pyromellitic acid anhydride being dissolved in acetone, is warming up to after 70 DEG C that 0.48kg is added thereto is anhydrous
Ethyl alcohol and 0.1kg p-methyl benzenesulfonic acid, constant temperature back flow reaction 4-5h, obtained product is rotated, then respectively by go from
Sub- water and saturated sodium chloride solution are cleaned, and are placed into 50 DEG C of baking oven and are dried, and esterification terephthalic acids is obtained, due to
With ethyl alcohol ring-opening reaction occurs for two anhydride groups in pyromellitic acid anhydride under the catalytic action of p-methyl benzenesulfonic acid, generates
Benzoic ether and benzoxy；
Step 2: the esterification terephthalic acids and acetone that prepare in 1kg step 1 are added in flask, 80 DEG C of reflux are warming up to,
1.1kg thionyl chloride is added into flask simultaneously, back flow reaction 5h is evaporated crystallization to obtained reaction mixture, and incites somebody to action
The crystal arrived is washed by dehydrated alcohol, is then dried in 50 DEG C of baking oven, obtains tetracarboxylic acid acid diester diacid chloride, due to
It is esterified in terephthalic acids and contains benzoic acid functional group, chloro is carried out under the action of thionyl chloride, generate acyl chlorides；
Step 3: the tetracarboxylic acid acid diester diacid chloride prepared in 1kg step 2 being added in reaction vessel, while being added thereto
Water is warming up to 70 DEG C after stirring and dissolving, and 0.71kg dihydroxybiphenyl amine, constant temperature back flow reaction 3h, cooling are then added thereto
Filtration washing is dry after to room temperature, obtains dihydroxybiphenyl polyamide.
Embodiment 2:
The specific preparation process of dihydroxybiphenyl polyamide is as follows:
Step 1: 1kg pyromellitic acid anhydride being dissolved in acetone, is warming up to after 70 DEG C that 0.52kg is added thereto is anhydrous
Ethyl alcohol and 0.1kg p-methyl benzenesulfonic acid, constant temperature back flow reaction 4-5h, obtained product is rotated, then respectively by go from
Sub- water and saturated sodium chloride solution are cleaned, and are placed into 50 DEG C of baking oven and are dried, and esterification terephthalic acids is obtained；
Step 2: the esterification terephthalic acids and acetone that prepare in 1kg step 1 are added in flask, 80 DEG C of reflux are warming up to,
1.2kg thionyl chloride is added into flask simultaneously, back flow reaction 5h is evaporated crystallization to obtained reaction mixture, and incites somebody to action
The crystal arrived is washed by dehydrated alcohol, is then dried in 50 DEG C of baking oven, obtains tetracarboxylic acid acid diester diacid chloride, due to
It is esterified in terephthalic acids and contains benzoic acid functional group, chloro is carried out under the action of thionyl chloride, generate acyl chlorides；
Step 3: the tetracarboxylic acid acid diester diacid chloride prepared in 1kg step 2 being added in reaction vessel, while being added thereto
Water is warming up to 70 DEG C after stirring and dissolving, and 0.71kg dihydroxybiphenyl amine, constant temperature back flow reaction 3h, cooling are then added thereto
Filtration washing is dry after to room temperature, obtains dihydroxybiphenyl polyamide.
Embodiment 3:
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
The first step, dihydroxybiphenyl polyamide prepared by 4kg embodiment 1 is added in reaction kettle, while being added thereto
8kg dimethylformamide and 0.4kg basic copper carbonate, are warming up to 100 DEG C and are stirred to react 3h, are then warming up to 120 DEG C of reactions again
2h, the ethyl alcohol after decomposing is collected in border ring condensation in side in reaction process, is cooled to room temperature after fully reacting, is then filtered,
It is dried with acetone washing, obtains dihydroxybiphenyl polyimides；
5kg3- hydroxyl -2- pyridine carboxylic acid adding into acetone is warming up to 80 DEG C of reflux, is then added thereto by second step
5.9kg thionyl chloride, constant temperature back flow reaction 5h obtain 3- hydroxyl -2- pyridinecarboxylic chloride then by revolving；Every gram of 3- hydroxyl-
Thionyl chloride 1.18-1.21g is added in 2- pyridine carboxylic acid；
Third step, by the 5kg3- hydroxyl -2- pyridinecarboxylic chloride prepared in second step be added reaction vessel in, while to its
Middle addition acetone is warming up to 80 DEG C of reflux after stirring and dissolving, and 7.15kg amino silane, constant temperature back flow reaction are then added thereto
6-10h, is then cooled to after room temperature dry with sodium sulphate after being washed with sodium bicarbonate solution, then carried out column, and obtained pure
Siliconization pyridone；Amino silane 1.43-1.49g is added in every gram of 3- hydroxyl -2- pyridinecarboxylic chloride；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while being added thereto by the 4th step
Then the siliconization prepared in 3.4kg third step is added in 70 DEG C of stirring and dissolvings in 12kgN, dinethylformamide thereto
Pyridone is stirred after 3-5min and 3kg boric acid is added dropwise into reaction kettle, is vigorously stirred when being added dropwise, and is added dropwise complete
Isothermal reaction 1h afterwards then heats to 90 DEG C of reaction 3h, is cooled to room temperature after fully reacting, after the material discharge in reaction kettle
It is filtered washing drying, obtains soluble adhesive.
Embodiment 4:
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
The first step, dihydroxybiphenyl polyamide prepared by 4.5kg embodiment 2 are added in reaction kettle, while adding thereto
Enter 9kg dimethylformamide and 0.7kg basic copper carbonate, be warming up to 100 DEG C and be stirred to react 3h, is then warming up to 120 DEG C again instead
2h is answered, the ethyl alcohol after decomposing is collected in border ring condensation in side in reaction process, is cooled to room temperature after fully reacting, was then carried out
Filter, is dried with acetone washing, obtains dihydroxybiphenyl polyimides；
5kg3- hydroxyl -2- pyridine carboxylic acid adding into acetone is warming up to 80 DEG C of reflux, is then added thereto by second step
6.05kg thionyl chloride, constant temperature back flow reaction 5h obtain 3- hydroxyl -2- pyridinecarboxylic chloride then by revolving；
Third step, by the 5kg3- hydroxyl -2- pyridinecarboxylic chloride prepared in second step be added reaction vessel in, while to its
Middle addition acetone is warming up to 80 DEG C of reflux after stirring and dissolving, and 7.45kg amino silane, constant temperature back flow reaction are then added thereto
6-10h, is then cooled to after room temperature dry with sodium sulphate after being washed with sodium bicarbonate solution, then carried out column, and obtained pure
Siliconization pyridone；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while being added thereto by the 4th step
Then the siliconization prepared in 3.8kg third step is added in 70 DEG C of stirring and dissolvings in 13kgN, dinethylformamide thereto
Pyridone is stirred after 3-5min and 3.4kg boric acid is added dropwise into reaction kettle, is vigorously stirred, drips when being added dropwise
Isothermal reaction 1h, then heats to 90 DEG C of reaction 3h, is cooled to room temperature after fully reacting after complete, and the material in reaction kettle is discharged
It is dry that filtration washing is carried out afterwards, obtains soluble adhesive.
Embodiment 5:
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
The first step, dihydroxybiphenyl polyamide prepared by 4kg embodiment 1 is added in reaction kettle, while being added thereto
8kg dimethylformamide and 0.4kg basic copper carbonate, are warming up to 100 DEG C and are stirred to react 3h, are then warming up to 120 DEG C of reactions again
2h, the ethyl alcohol after decomposing is collected in border ring condensation in side in reaction process, is cooled to room temperature after fully reacting, is then filtered,
It is dried with acetone washing, obtains dihydroxybiphenyl polyimides；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while being added thereto by second step
Then 3.4kg amino silane is added thereto, is stirred 3- in 50 DEG C of stirring and dissolvings for 12kgN, dinethylformamide
3kg toluene di-isocyanate(TDI) is added dropwise after 5min into reaction kettle, is vigorously stirred when being added dropwise, isothermal reaction after being added dropwise completely
3h is cooled to room temperature after fully reacting, and by carrying out after the material discharge in reaction kettle, filtration washing is dry, obtains soluble gluing
Agent.
Embodiment 6:
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
The first step, dihydroxybiphenyl polyamide prepared by 4kg embodiment 1 is added in reaction kettle, while being added thereto
8kg dimethylformamide and 0.4kg basic copper carbonate, are warming up to 100 DEG C and are stirred to react 3h, are then warming up to 120 DEG C of reactions again
2h, the ethyl alcohol after decomposing is collected in border ring condensation in side in reaction process, is cooled to room temperature after fully reacting, is then filtered,
It is dried with acetone washing, obtains dihydroxybiphenyl polyimides；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while being added thereto by second step
Then 3.4kg3- hydroxyl -2- pyridine carboxylic acid, stirring is added in 70 DEG C of stirring and dissolvings in 12kgN, dinethylformamide thereto
3kg boric acid is added dropwise into reaction kettle after mixing 3-5min, is vigorously stirred when being added dropwise, isothermal reaction 1h after being added dropwise completely,
90 DEG C of reaction 3h are then heated to, are cooled to room temperature after fully reacting, filtration washing will be carried out after the material discharge in reaction kettle
It is dry, obtain soluble adhesive.
Embodiment 7:
A kind of preparation process of solubility Environment-friendlyadhesive adhesive, specific preparation process are as follows:
The first step, dihydroxybiphenyl polyamide prepared by 4kg embodiment 1 is added in reaction kettle, while being added thereto
8kg dimethylformamide and 0.4kg basic copper carbonate, are warming up to 100 DEG C and are stirred to react 3h, are then warming up to 120 DEG C of reactions again
2h, the ethyl alcohol after decomposing is collected in border ring condensation in side in reaction process, is cooled to room temperature after fully reacting, is then filtered,
It is dried with acetone washing, obtains dihydroxybiphenyl polyimides adhesive.
Embodiment 8:
Adhesive prepared by embodiment 3-7 is added in the solvent that water and dehydrated alcohol are mixed with the ratio of 1:10, will be molten
Agent is heated to 40 DEG C, then stirs 30-40min, obtains colloid, and obtained colloid is then coated with one layer of shape on surface plate surface
Identical fritter is put into anhydrous by the fritter of the glue film clip same volume size of preparation respectively at glue film in homogeneous thickness
Impregnated in ethyl alcohol 6h, 10h, 16h, for 24 hours, 48h, remaining solid in dehydrated alcohol is then taken out, after being wiped with blotting paper point
Quality before also known as picking and placing is M0, remaining solid masses is m after dissolution1, wherein dissolution rateMeasurement
The results are shown in Table 1；
Dissolution rate (%) of 1 glue film of table after impregnating different time in dehydrated alcohol
| Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| 6h | 100 | 100 | 75.3 | 84.5 | 46.7 |
| 10h | 100 | 100 | 82.1 | 89.7 | 52.3 |
| 16h | 100 | 100 | 86.2 | 93.4 | 58.9 |
| 24h | 100 | 100 | 88.4 | 98.6 | 67.2 |
| 48h | 100 | 100 | 88.6 | 99.8 | 68.8 |
As shown in Table 1, it since the entire main chain of adhesive forms the non-public planar structure of distortion, and then makes it dissolve performance and mentions
Height, while pyridine ring is introduced on adhesive main chain, the protonation of the polarity nitrogen-atoms on pyridine ring can be improved polymer
Dissolubility in polar solvent, while containing siloxanes key on pyridine ring, wherein the bond energy of Si-O key is high, and the rotation of key is free
Property it is larger, improve the polarizability of entire polymer, further improve the dissolubility of adhesive, according to similar compatibility original
Reason, so that the adhesive is highly soluble in polar molecule, so that 6h can be completely molten in ethanol for the adhesive of preparation
Solution；When simultaneously on main polymer chain without introducing pyridine ring and no introducing siloxy group, solution rate is reduced, while
It can not be completely dissolved when impregnating for a long time.
Embodiment 9:
By the glue film in the embodiment 3-7 prepared in embodiment 8 350 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C yes
State, the results are shown in Table 2:
Table 2: the thermal weight loss rate of adhesive different time
As shown in Table 2, made on polymer by the effect crosslinking silicone pyridone between boric acid and phenolic hydroxyl group
It is hyperbranched to obtain polymer, reduces the accumulation of molecule branch, while pyridine ring introduces on polymer branch, pyridine ring itself has
Certain heat resistance and chemical stability so that the thermal stability of polymer improves, while containing silicon oxygen on pyridine ring
Alkane key, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then reduces the thermal expansion coefficient of polymer, improves it
Thermal stability, adhesive modified are still able to maintain physical aspect at 500 DEG C, can be used normally, can be used under high temperature
It is bonded.
Embodiment 10
Adhesive property measurement is carried out to the adhesive of embodiment 3-7 preparation, specific measurement result is as shown in table 3；
Table 3: to the measurement result of the adhesive peel strength of embodiment 3-7 preparation
| Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Peel strength (N.cm-1) | 21.5 | 21.6 | 18.3 | 17.9 | 12.16 |
As shown in Table 3, the peel strength of the adhesive reaches 21.6N.cm-1, pass through boric acid and phenolic hydroxyl group on polymer
Between effect crosslinking silicone pyridone reduce the accumulation of molecule branch so that polymer is hyperbranched, improve glue
The viscosity and adhesive property of glutinous agent, while pyridine ring introduces on polymer branch, the protonation of the polarity nitrogen-atoms on pyridine ring
Effect can be improved the flexibility of polymer, and then improve the adhesive property of adhesive, while containing siloxanes on pyridine ring
Key, wherein the bond energy of Si-O key is high, and the rotation freedom of key is larger, and then can be improved the dissolubility and flexibility of polymer,
The thermal expansion coefficient for reducing polymer simultaneously, improves the adhesive property of adhesive, while the siloxanes key on adhesive main chain exists
Hydrolysis generates silanol group in the water of certain temperature, is connected between adjacent silanol group by hydrogen bond, so that the bonding of adhesive
Performance improves.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (7)
1. a kind of solubility Environment-friendlyadhesive adhesive, which is characterized in that each component materials including following component:
40-45 parts of dihydroxybiphenyl polyamide, 80-90 parts of dimethylformamide, 4-7 parts of basic copper carbonate, siliconization hydroxyl
34-38 parts of pyridine, 30-34 parts of boric acid, 120-130 parts of solvent；
The specific preparation process of dihydroxybiphenyl polyamide is as follows:
Step 1: pyromellitic acid anhydride being dissolved in acetone, is warming up to after 70 DEG C and dehydrated alcohol is added thereto and to toluene sulphur
Acid, constant temperature back flow reaction 4-5h, obtained product is rotated, and then passes through deionized water and saturated sodium chloride solution respectively
It is cleaned, places into 50 DEG C of baking oven and dried, obtain esterification terephthalic acids；
Step 2: the esterification terephthalic acids and acetone that prepare in step 1 being added in flask, are warming up to 80 DEG C of reflux, while to burning
Thionyl chloride is added in bottle, back flow reaction 5h is evaporated crystallization to obtained reaction mixture, and obtained crystal is passed through nothing
Water-ethanol washing, is then dried in 50 DEG C of baking oven, obtains tetracarboxylic acid acid diester diacid chloride；
Step 3: the tetracarboxylic acid acid diester diacid chloride prepared in step 2 being added in reaction vessel, while water being added thereto, is stirred
It is warming up to 70 DEG C after dissolution, dihydroxybiphenyl amine is then added thereto, constant temperature back flow reaction 3h crosses diafiltration after being cooled to room temperature
Drying is washed, dihydroxybiphenyl polyamide is obtained.
2. a kind of soluble Environment-friendlyadhesive adhesive according to claim 1, which is characterized in that every gram of pyromellitic acid anhydride
P-methyl benzenesulfonic acid 0.1g is added in middle addition dehydrated alcohol 0.48-0.52g.
3. a kind of soluble Environment-friendlyadhesive adhesive according to claim 1, which is characterized in that in every gram of esterification terephthalic acids
Thionyl chloride 1.1-1.2g is added.
4. a kind of soluble Environment-friendlyadhesive adhesive according to claim 1, which is characterized in that every gram of two acyl of tetracarboxylic acid acid diester
Dihydroxybiphenyl amine 0.65-0.71g is added in chlorine.
5. a kind of soluble Environment-friendlyadhesive adhesive according to claim 1, which is characterized in that siliconization pyridone
Specific preparation process is as follows: 1. by 3- hydroxyl -2- pyridine carboxylic acid adding into acetone, being warming up to 80 DEG C of reflux, then adds thereto
Enter thionyl chloride, constant temperature back flow reaction 5h obtains 3- hydroxyl -2- pyridinecarboxylic chloride then by revolving；
2. the 3- hydroxyl -2- pyridinecarboxylic chloride of preparation is added in reaction vessel, while acetone being added thereto, after stirring and dissolving
80 DEG C of reflux are warming up to, amino silane is then added thereto, constant temperature back flow reaction 6-10h uses carbon after being then cooled to room temperature
It is dry with sodium sulphate after sour hydrogen sodium solution washing, column was then carried out, pure siliconization pyridone is obtained.
6. a kind of preparation process of solubility Environment-friendlyadhesive adhesive, which is characterized in that specific preparation process is as follows:
Dihydroxybiphenyl polyamide is added in reaction kettle the first step, while dimethylformamide and alkali formula carbon being added thereto
Sour copper, is warming up to 100 DEG C and is stirred to react 3h, is then warming up to 120 DEG C of reaction 2h again, and border ring condensation in side is collected in reaction process
Ethyl alcohol after decomposition is cooled to room temperature after fully reacting, is then filtered, dried with acetone washing, obtains dihydroxybiphenyl
Polyimides；
The dihydroxybiphenyl polyimides prepared in the first step is added in reaction kettle, while solvent being added thereto by second step,
In 70 DEG C of stirring and dissolvings, siliconization pyridone is then added thereto, is stirred after 3-5min into reaction kettle dropwise
Boric acid is added, is vigorously stirred when being added dropwise, isothermal reaction 1h, then heats to 90 DEG C of reaction 3h, fully reacting after being added dropwise completely
After be cooled to room temperature, by carrying out after the material discharge in reaction kettle, filtration washing is dry, obtains soluble adhesive.
7. a kind of preparation process of soluble Environment-friendlyadhesive adhesive according to claim 6, which is characterized in that the adhesive
Specific use process is as follows: adhesive being added in the solvent that water and dehydrated alcohol are mixed with 1:10 ratio, solvent is heated
To 40 DEG C, 30-40min is then stirred, obtains sticky colloid.
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| WO2021261424A1 (en) * | 2020-06-26 | 2021-12-30 | 群栄化学工業株式会社 | Resin, method for producing same, thermosetting resin composition, and cured product |
| JP7527860B2 (en) | 2020-06-26 | 2024-08-05 | 群栄化学工業株式会社 | Resin, its manufacturing method, thermosetting resin composition and cured product |
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Application publication date: 20191008 |