CN114181655A - Environment-friendly MS glue without stannate and preparation method thereof - Google Patents
Environment-friendly MS glue without stannate and preparation method thereof Download PDFInfo
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- CN114181655A CN114181655A CN202111458081.6A CN202111458081A CN114181655A CN 114181655 A CN114181655 A CN 114181655A CN 202111458081 A CN202111458081 A CN 202111458081A CN 114181655 A CN114181655 A CN 114181655A
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- 239000003292 glue Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229940071182 stannate Drugs 0.000 title abstract description 12
- 125000005402 stannate group Chemical group 0.000 title abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000004014 plasticizer Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 54
- -1 aminoethyl aminopropyl Chemical group 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 14
- 239000013522 chelant Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920006335 epoxy glue Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910001134 stannide Inorganic materials 0.000 claims 7
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 8
- 238000009924 canning Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000009461 vacuum packaging Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007969 cellular immunity Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 210000004324 lymphatic system Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000004526 silane-modified polyether Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 210000001541 thymus gland Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and discloses an environment-friendly MS adhesive without stannate, which comprises the following raw materials in parts by weight: 50-100 parts of alkoxy end-capped polyether resin, 50-100 parts of environment-friendly plasticizer, 40-80 parts of filler, 4-10 parts of tackifier, 4-10 parts of water removing agent, 4-20 parts of coupling agent and 2-10 parts of catalyst. According to the environment-friendly MS glue without tin compounds, a catalyst of titanate and amine is used, the MS glue does not contain tin compounds, and the used plasticizer is also a non-o-benzene environment-friendly plasticizer, so that the current environment-friendly requirement is met; meanwhile, the MS glue prepared by the invention also has excellent bonding performance, the shear strength reaches more than 4MPa, the tensile strength reaches more than 6MPa, the curing performance is excellent, and the surface drying time is less than 10 min.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an environment-friendly MS adhesive without stannate and a preparation method thereof.
Background
The sealant prepared by taking MS Polymer as a base material is called MS glue for short. The MS glue is similar to a combination of silicone glue and PU glue, and has excellent elastic elongation of the silicone glue and good strength of the PU glue.
The existing MS glue needs to be solidified by adding a large amount of organic tin catalysts due to lower reaction activity of silane modified polyether polymers, and the organic tin catalysts are harmful to organisms, and the main damage is as follows: the central nervous system can cause leukoedema, suppression of thymus and lymphatic system, cellular immunity disturbance, and hormone secretion inhibition to cause diabetes and hyperlipidemia; toxicity to humans: local irritation to skin, respiratory tract, cornea, etc. Therefore, the existing MS glue has great harm to the environment and human health and does not meet the requirement of environmental protection.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the environment-friendly MS glue without stannate and the preparation method thereof, which have the advantage of meeting the environment-friendly requirement and solve the problem that a substance capable of replacing an organotin catalyst must be found as soon as possible to promote the curing of the silane modified sealant.
(II) technical scheme
In order to achieve the purpose of meeting the requirement of environmental protection, the invention provides the following technical scheme: an environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 50-100 parts of alkoxy end-capped polyether resin, 50-100 parts of environment-friendly plasticizer, 40-80 parts of filler, 4-10 parts of tackifier, 4-10 parts of water removing agent, 4-20 parts of coupling agent and 2-10 parts of catalyst.
Preferably, the alkoxy-terminated polyether resin is a trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 1000-100000 mPa.s.
Preferably, the environmentally friendly plasticizer includes one or more of non-ortho-benzene citric acid esters, polyester plasticizers, epoxy gum methyl esters, tricresyl phosphate, and dioctyl sebacate.
Preferably, the filler comprises one or more of fumed silica, polyamide wax, silica micropowder, colloidal calcium carbonate, ground calcium carbonate and quartz powder.
Preferably, the tackifier is aminoethyl aminopropyl cage-type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage-type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
Preferably, the water removing agent comprises one or more of vinyltrimethoxysilane and vinyltriethoxysilane.
Preferably, the coupling agent comprises one or more of methyltrimethoxysilane, aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Preferably, the catalyst comprises one or more of tetra-n-propyl titanate, isopropyl titanate, titanate chelate, primary amine organic oligomer and organic zirconium chelate.
A preparation method of an environment-friendly MS glue without tin compounds comprises the following steps:
s1: adding the alkoxy-terminated polyether resin, the environment-friendly plasticizer, the tackifier and the filler into a stirring kettle, stirring and heating to 120 ℃ for 100-;
s2: cooling the materials to below 50 ℃, introducing nitrogen, then adding the water removing agent, the coupling agent and the catalyst, and continuing stirring for 1 h;
s3: after stirring, discharging, canning, and vacuum packaging and storing.
Preferably, in the step S1, when the moisture content is greater than 800ppm, the stirring is continued until the moisture content of the raw material is detected, and the moisture content of the raw material is less than 800 ppm.
(III) advantageous effects
Compared with the prior art, the invention provides the environment-friendly MS glue without stannate and the preparation method thereof, and the MS glue has the following beneficial effects:
1. according to the environment-friendly MS glue without tin compounds, a catalyst of titanate and amine is used, the MS glue does not contain tin compounds, and the used plasticizer is also a non-o-benzene environment-friendly plasticizer, so that the current environment-friendly requirement is met; meanwhile, the MS glue prepared by the invention also has excellent bonding performance, the shear strength reaches more than 4MPa, the tensile strength reaches more than 6MPa, the curing performance is excellent, and the surface drying time is less than 10 min.
2. According to the preparation method of the environment-friendly MS glue without tin compounds, the alkoxy-terminated polyether resin, the environment-friendly plasticizer, the tackifier and the filler are fully mixed in a vacuum stirring mode, the moisture of the raw materials is ensured to reach the required standard in a raw material moisture detection mode, and the bonding and curing performance of the prepared MS glue is improved.
Drawings
FIG. 1 is a schematic diagram of the synthesis steps of aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 50 parts of alkoxy-terminated polyether resin, 50 parts of environment-friendly plasticizer, 40 parts of filler, 4 parts of tackifier, 4 parts of water removing agent, 4 parts of coupling agent and 2 parts of catalyst.
The alkoxy-terminated polyether resin is trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 1000 mPa.s.
The environmentally friendly plasticizer includes a non-ortho-benzene citric acid ester, a polyester plasticizer, and dioctyl sebacate.
The filler includes fumed silica, polyamide wax, ground calcium carbonate, and quartz powder.
The tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
The water removing agent comprises vinyltrimethoxysilane and vinyltriethoxysilane.
The coupling agent comprises methyltrimethoxysilane, aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
The catalyst comprises tetra-n-propyl titanate, isopropyl titanate and titanate chelate.
Example 2
An environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 65 parts of alkoxy-terminated polyether resin, 72 parts of environment-friendly plasticizer, 53 parts of filler, 6 parts of tackifier, 7 parts of water removing agent, 8 parts of coupling agent and 6 parts of catalyst.
The alkoxy-terminated polyether resin is trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 15000 mPa.s.
The environment-friendly plasticizer comprises epoxy glue methyl ester, tricresyl phosphate and dioctyl sebacate.
The filler comprises one or more of colloid calcium carbonate, heavy calcium carbonate and quartz powder.
The tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
The water scavenger comprises vinyl trimethoxy silane.
The coupling agent comprises aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
The catalyst comprises tetra-n-propyl titanate, isopropyl titanate, primary amine organic oligomer and organic zirconium chelate.
Example 3
An environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 70 parts of alkoxy-terminated polyether resin, 66 parts of environment-friendly plasticizer, 72 parts of filler, 10 parts of tackifier, 8 parts of water removing agent, 12 parts of coupling agent and 5 parts of catalyst.
Preferably, the alkoxy-terminated polyether resin is a trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 30000 mPa.s.
The environment-friendly plasticizer comprises non-o-benzene citrate, epoxy glue methyl ester and tricresyl phosphate.
The filler comprises fumed silica, silica micropowder, colloidal calcium carbonate and ground calcium carbonate.
The tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
The water scavenger comprises vinyl triethoxysilane.
The coupling agent comprises methyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane.
The catalyst comprises tetra-n-propyl titanate, titanate chelate and organic zirconium chelate.
Example 4
An environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 100 parts of alkoxy-terminated polyether resin, 88 parts of environment-friendly plasticizer, 65 parts of filler, 7 parts of tackifier, 6 parts of water removing agent, 13 parts of coupling agent and 7 parts of catalyst.
The alkoxy-terminated polyether resin is trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 50000 mPa.s.
The environment-friendly plasticizer comprises non-o-benzene citrate and dioctyl sebacate.
The filler comprises silicon micropowder, colloidal calcium carbonate and ground calcium carbonate.
The tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
The water removing agent comprises vinyltrimethoxysilane and vinyltriethoxysilane.
The coupling agent comprises methyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
The catalyst comprises tetra-n-propyl titanate, titanate chelate and primary amine organic oligomer.
Example 5
An environment-friendly MS glue without stannate comprises the following raw materials in parts by weight: 100 parts of alkoxy-terminated polyether resin, 100 parts of environment-friendly plasticizer, 80 parts of filler, 10 parts of tackifier, 10 parts of water removing agent, 20 parts of coupling agent and 10 parts of catalyst.
The alkoxy-terminated polyether resin is trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 100000 mPa.s.
The environment-friendly plasticizer comprises non-o-benzene citric acid ester, polyester plasticizer, epoxy glue methyl ester, tricresyl phosphate and dioctyl sebacate.
The filler comprises fumed silica, polyamide wax, silica micropowder, colloidal calcium carbonate and quartz powder.
The tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
The water removing agent comprises vinyltrimethoxysilane and vinyltriethoxysilane.
The coupling agent comprises methyltrimethoxysilane, aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
The catalyst comprises tetra-n-propyl titanate, titanate chelate, primary amine organic oligomer and organic zirconium chelate.
Examples of the experiments
(1) Tensile Strength the tensile strength was evaluated in accordance with GB/T528-2009 "determination of tensile stress strain Properties of vulcanizates or thermoplastics".
(2) Shear strength
The shear strength was evaluated according to GBT 7124-.
Example 6, the preparation method of the environment-friendly MS glue without tin compound comprises the following steps:
s1: adding alkoxy-terminated polyether resin, an environment-friendly plasticizer, a tackifier and a filler into a stirring kettle, stirring and heating to 100 ℃, then vacuumizing and stirring for 2 hours, detecting the moisture of the raw materials after stirring, and carrying out the next step if the moisture content is less than 800 ppm;
s2: cooling the materials to below 50 ℃, filling nitrogen, adding a water removing agent, a coupling agent and a catalyst, and continuously stirring for 1 h;
s3: after stirring, discharging, canning, and vacuum packaging and storing.
And in the step S1, when the moisture content is more than 800ppm, continuing stirring until the moisture of the raw materials is detected and is less than 800 ppm.
Through a vacuum stirring mode, the alkoxy-terminated polyether resin, the environment-friendly plasticizer, the tackifier and the filler are fully mixed, raw material moisture is ensured to reach the required standard through a mode of detecting raw material moisture, and the bonding and curing performance of the prepared MS adhesive is improved.
Experimental control:
experimental and comparative groups were prepared and aminoethylaminopropyl polyhedral oligomeric silsesquioxanes were synthesized in the same manner as in example 5;
preparation of experimental groups:
1. the following materials were charged into a closed evacuable heated vessel: adding 80 parts of alkoxy end-capped polyether resin, 30 parts of citric acid ester, 4 parts of aminoethyl aminopropyl cage-type silsesquioxane and 50 parts of colloidal calcium carbonate into a stirring kettle, stirring and heating to 100 ℃, then vacuumizing and stirring for 2 hours, detecting the moisture of the raw materials after stirring is finished, continuously vacuumizing, heating, stirring and dewatering until the moisture content is less than 800ppm, and entering the next step;
2. after the materials are cooled to below 50 ℃, introducing nitrogen, adding 4 parts of vinyltrimethoxysilane, 12 parts of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 8 parts of titanate chelate, and continuously stirring for 1h in the nitrogen atmosphere;
3. after stirring, discharging, canning, and vacuum packaging and storing.
Preparation of control group:
1. the following materials were charged into a closed evacuable heated vessel: adding 80 parts of alkoxy end-capped polyether resin, 30 parts of citric acid ester, 0 part of aminoethyl aminopropyl cage-type silsesquioxane and 50 parts of colloidal calcium carbonate into a stirring kettle, stirring and heating to 100 ℃, then vacuumizing and stirring for 2 hours, detecting the moisture of the raw materials after stirring is finished, continuously vacuumizing, heating, stirring and dewatering until the moisture content is less than 800ppm, and entering the next step;
2. after the materials are cooled to below 50 ℃, introducing nitrogen, adding 4 parts of vinyltrimethoxysilane, 12 parts of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 8 parts of titanate chelate, and continuously stirring for 1h in the nitrogen atmosphere;
after stirring, discharging, canning, and vacuum packaging and storing.
The experimental and control groups were compared: the formula of the experimental group is added with the aminoethyl aminopropyl cage-type silsesquioxane, the control group is not added with the aminoethyl aminopropyl cage-type silsesquioxane, compared with the control group, the experimental group has better bonding strength and faster reaction speed, the shear strength of the product prepared by the experimental group is more than 4MPa, the surface drying time is 5min, the shear strength of the product prepared by the control group is only 2MPa, and the surface drying time is more than 10 min.
According to the tin compound-free environment-friendly MS adhesive and the preparation method thereof, a titanate catalyst and an amine catalyst are used, tin compounds are not contained, and the used plasticizer is also a non-o-benzene environment-friendly plasticizer, so that the current environment-friendly requirement is met; meanwhile, the MS glue prepared by the invention also has excellent bonding performance, the shear strength reaches more than 4MPa, the tensile strength is more than 6MPa, the curing performance is excellent, and the surface drying time is less than 10 min; through a vacuum stirring mode, the alkoxy-terminated polyether resin, the environment-friendly plasticizer, the tackifier and the filler are fully mixed, raw material moisture is ensured to reach the required standard through a mode of detecting raw material moisture, and the bonding and curing performance of the prepared MS adhesive is improved.
It is to be noted that the term "comprises," "comprising," or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The environment-friendly MS glue without tin compounds is characterized by comprising the following raw materials in parts by weight: 50-100 parts of alkoxy end-capped polyether resin, 50-100 parts of environment-friendly plasticizer, 40-80 parts of filler, 4-10 parts of tackifier, 4-10 parts of water removing agent, 4-20 parts of coupling agent and 2-10 parts of catalyst.
2. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the alkoxy-terminated polyether resin is trimethoxy-terminated polyether resin, and the viscosity of the alkoxy-terminated polyether resin is 1000-100000 mPa.s.
3. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the environment-friendly plasticizer comprises one or more of non-o-benzene citrate, polyester plasticizer, epoxy glue methyl ester, tricresyl phosphate and dioctyl sebacate.
4. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the filler comprises one or more of fumed silica, polyamide wax, silica micropowder, colloidal calcium carbonate, ground calcium carbonate and quartz powder.
5. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the tackifier is aminoethyl aminopropyl cage type silsesquioxane, and the synthesis steps of the aminoethyl aminopropyl cage type silsesquioxane are as follows:
a1: 20g of deionized water, 0.42g of tetrabutylammonium hydroxide serving as a catalyst and 62g of isopropanol serving as a reaction raw material are sequentially added into a 500ml round-bottom flask;
a2: after fully and uniformly stirring, regulating the reaction temperature to 40 ℃, and then dropwise adding 80.50g of aminoethyl aminopropyl trimethoxy silane into a reaction bottle through a constant-pressure funnel;
a3: after the dropwise addition, continuously stirring and reacting for 5 hours, then raising the temperature to 80 ℃, and continuously stirring and reacting for 20 hours;
a4: the mixture in the reaction flask was filtered to give a white powdery solid, which was dried under vacuum for 24 hours to give the aminoethylaminopropyl polyhedral oligomeric silsesquioxane.
6. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the water removing agent comprises one or more of vinyltrimethoxysilane and vinyltriethoxysilane.
7. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the coupling agent comprises one or more of methyltrimethoxysilane, aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
8. The environment-friendly MS glue without stannides according to claim 1, wherein the MS glue comprises: the catalyst comprises one or more of tetra-n-propyl titanate, isopropyl titanate, titanate chelate, primary amine organic oligomer and organic zirconium chelate.
9. The preparation method of the environment-friendly MS glue without tin compounds based on the claims 1-8 is characterized by comprising the following steps:
s1: adding the alkoxy-terminated polyether resin, the environment-friendly plasticizer, the tackifier and the filler into a stirring kettle, stirring and heating to 120 ℃ for 100-;
s2: cooling the materials to below 50 ℃, introducing nitrogen, then adding the water removing agent, the coupling agent and the catalyst, and continuing stirring for 1 h.
10. The method as claimed in claim 9, wherein in step S1, when the moisture content is greater than 800ppm, the stirring is continued until the moisture content of the raw material is detected, and the moisture content of the raw material is less than 800 ppm.
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