CN117645854A - Multi-component polyacrylate adhesive and production method thereof - Google Patents
Multi-component polyacrylate adhesive and production method thereof Download PDFInfo
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- CN117645854A CN117645854A CN202410126828.5A CN202410126828A CN117645854A CN 117645854 A CN117645854 A CN 117645854A CN 202410126828 A CN202410126828 A CN 202410126828A CN 117645854 A CN117645854 A CN 117645854A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 76
- 239000000853 adhesive Substances 0.000 title claims abstract description 73
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 238000004132 cross linking Methods 0.000 claims abstract description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 49
- 230000002209 hydrophobic effect Effects 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- KNDQHSIWLOJIGP-RNGGSSJXSA-N (3ar,4r,7s,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound C1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 KNDQHSIWLOJIGP-RNGGSSJXSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- CVAGYCLEIYGJQT-UHFFFAOYSA-N dichloro(dioctyl)silane Chemical group CCCCCCCC[Si](Cl)(Cl)CCCCCCCC CVAGYCLEIYGJQT-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 abstract description 2
- 125000005462 imide group Chemical group 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012774 insulation material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical group [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- -1 norbornene imide Chemical class 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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Abstract
The invention relates to the technical field of adhesives and discloses a multi-component polyacrylate adhesive and a production method thereof. The crosslinking monomer contains a rigid norbornene ring and an imide ring, and the cohesive force of the crosslinked polyacrylate adhesive is larger, so that the crosslinked polyacrylate adhesive has stronger bonding performance, and on the other hand, the high crosslinking degree can prevent the movement of a molecular chain, so that the high temperature resistance of the polyacrylate adhesive can be enhanced from different angles.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a multi-component polyacrylate adhesive and a production method thereof.
Background
With the development of technology and the increasing attention of people to environmental protection, building heat insulation materials become an integral part of modern buildings. The materials not only provide heat preservation and insulation functions for the building, but also have the advantages of energy conservation, environmental protection, safety and the like, and are an important way for realizing green building. At present, heat insulation materials such as rubber and plastic foam are required to be adhered to the outer sides of air pipes, building walls or pipelines by using back glue, so that heat insulation effect is achieved. Because the acrylic adhesive has the advantages of strong binding power, good insulativity, high curing speed, chemical corrosion resistance and the like, the acrylic adhesive is commonly used as a back adhesive of a heat insulation material. However, the polyacrylic acid adhesive has poor high temperature resistance and poor water resistance, so that the polyacrylic acid adhesive is very easy to warp and even degum in a damp and hot environment, and further the heat insulation material falls off, and the heat insulation effect cannot be ensured, so that the development of the polyacrylic acid adhesive with the environment resistance is of great significance.
The invention patent CN202010847235.X discloses a high temperature resistant acrylate pressure sensitive adhesive and a preparation method thereof, wherein the high temperature resistant performance of the acrylate pressure sensitive adhesive can be effectively improved by using 1-adamantane methacrylate and soft and hard monomers of acrylic acid and the like to match, and the stability of an adamantane rigid structure is utilized, so that the high temperature resistant performance of the polyacrylate adhesive can be enhanced by introducing the rigid structure into the polyacrylate adhesive, but the scheme does not consider the problem of poor waterproof performance of the polyacrylate adhesive, and certain defects still exist when the polyacrylate adhesive is used as a back adhesive of a heat insulation material.
Based on the above, the multi-component polyacrylate adhesive provided by the invention has good high temperature resistance and water resistance, can be directly used as a back adhesive of a heat insulation material, and can effectively avoid the falling phenomenon of the heat insulation material in a damp and hot environment.
Disclosure of Invention
The invention aims to provide a multi-component polyacrylate adhesive and a production method thereof, which solve the problems of poor high temperature resistance and poor water resistance of the polyacrylate adhesive.
The aim of the invention can be achieved by the following technical scheme:
a method for producing a multi-component polyacrylate adhesive comprising the steps of:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, raising the temperature to 75-80 ℃ under the condition of continuous stirring, adding one third of an initiator into the polymerization kettle, stirring for 30-60min, and marking the obtained prepolymer as a prepolymer;
second step, crosslinking
Adding a crosslinking monomer into a polymerization kettle, adding the rest initiator into the kettle again after adding, further raising the temperature to 80-85 ℃, carrying out heat preservation treatment for 8-12h under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive;
the hydrophobic monomer is a block polymer containing a fluorine-containing hydrophobic chain segment and a siloxane hydrophobic chain segment in the structure;
the crosslinking monomer is a norbornene-terminated silicone oil derivative.
Further preferably, the polyacrylate adhesive is produced by using the following components in parts by weight: 50-60 parts of butyl acrylate, 60-70 parts of isooctyl acrylate, 3-6 parts of acrylic acid, 0.2-0.6 part of hydroxyethyl acrylate, 1-3 parts of hydrophobic monomer, 300-400 parts of ethyl acetate, 0.3-0.6 part of initiator and 1-2 parts of crosslinking monomer.
Further preferably, the hydrophobic monomer is prepared by the following method:
taking a polymerization kettle, introducing nitrogen into the kettle to discharge oxygen, sequentially adding hexafluorobisphenol A and tetrahydrofuran into the kettle, starting stirring, after a uniform solution is formed, starting heating, maintaining the temperature at 50-60 ℃, adding dichlorosilane derivatives with the same mass into the kettle in three times under the stirring condition, keeping stirring for 4-6h after each time of 20-30min, adding hydroxyethyl acrylate into the kettle to end cap, stirring for 30-60min, using triethylamine to adjust the pH value to 6.5-7, and discharging to obtain the hydrophobic monomer.
Specifically, the hexafluorobisphenol A structure contains a fluorine-containing hydrophobic chain segment and two equivalents of hydroxyl active substituent groups, can be substituted with silicon-chlorine substituent groups in the dichlorosilane derivative, and can be subjected to continuous and stable substitution reaction by adding reactants in batches to form a block polymer containing the fluorine-containing hydrophobic chain segment and the siloxane hydrophobic chain segment in the structure, and the block polymer is blocked by using hydroxyethyl acrylate to prepare the hydrophobic monomer.
Further preferably, the dichlorosilane derivative is di-n-octyldichlorosilane or dichlorodimethylsilane.
Further preferably, the molar ratio of hexafluorobisphenol a to dichlorosilane derivative is 1:1.
Further preferably, the initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile, or azobiscyano valeric acid.
Further preferably, the crosslinking monomer is prepared by the following method:
stirring and mixing amino-terminated silicone oil and toluene uniformly, adding cis-5-norbornene-exo-2, 3-dicarboxylic anhydride after the amino-terminated silicone oil and toluene are completely dissolved, stirring at 70-80 ℃ for 40-60min, reducing the temperature to 30-40 ℃, continuously adding a catalyst under the stirring condition, after the amino-terminated silicone oil and toluene are completely added, preserving heat and stirring for 12-18h, decompressing and evaporating to remove the solvent, cooling and discharging to obtain the crosslinking monomer.
Specifically, under the high temperature condition, the terminal amino group of the terminal amino silicone oil can be condensed with the anhydride group of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to form an acidamide silicone oil derivative, and under the action of a catalyst, the amic acid is further dehydrated for ring closure to form a norbornene imide terminated silicone oil derivative, namely a crosslinking monomer.
Further preferably, the amino-terminated silicone oil has a weight average molecular weight of 1000.
Further preferably, the catalyst is a compound of sodium acetate, acetic anhydride and triethylamine, and the mass ratio is 0.1-0.2:0.3-0.4:1.
A multi-component polyacrylate adhesive is prepared by the production method.
The invention has the beneficial effects that:
1) The hydrophobic monomer structure prepared by the invention contains both the fluorine-containing hydrophobic chain segment and the siloxane hydrophobic chain segment, so that the surface energy is lower, the polyacrylate adhesive can be free to the surface layer in the curing process, and a super-hydrophobic layer can be formed on the surface to isolate water vapor, so that the water is difficult to permeate into the polyacrylate adhesive, and a good waterproof effect is achieved. In addition, after the rigid benzene ring and siloxane in the hydrophobic monomer are introduced into the side chain of the polyacrylate, the high temperature resistance of the polyacrylate adhesive can be enhanced to a certain extent.
2) The cross-linking monomer prepared by the invention contains a rigid norbornene ring and an imide ring, after cross-linking, the rigid heterocycle can be introduced into a polyacrylate main chain, so that the stability of a polyacrylate molecular chain is improved, the high-temperature resistance of the polyacrylate adhesive is enhanced, and meanwhile, the silicone oil in the cross-linking monomer contains a large number of silicon-oxygen bonds with high bond energy and can be broken only by absorbing more heat, so that the high-temperature resistance of the polyacrylate adhesive can be further enhanced. In addition, the molecular chains of the crosslinked polyacrylate adhesive are in an crosslinked structure, and the crosslinking density is high, so that the crosslinked polyacrylate adhesive has higher cohesive force and higher adhesive property, and the movement of the molecular chains can be blocked due to high crosslinking degree, so that the prepared polyacrylate adhesive has excellent high-temperature resistance from different angles.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FT-IR diagram of a hydrophobic monomer according to example 1 of the invention;
FIG. 2 is an FT-IR chart of a crosslinking monomer of example 2 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of hydrophobic monomers
Taking a polymerization kettle, introducing nitrogen into the kettle to discharge oxygen, sequentially adding 1.2g of hexafluorobisphenol A and tetrahydrofuran into the kettle, starting stirring, after a uniform solution is formed, starting heating, maintaining the temperature at 55 ℃, adding 0.46g of dichlorodimethylsilane with the same mass into the kettle in three times under the stirring condition, keeping the interval of 20min each time, continuing stirring for 6h after the addition is finished, adding hydroxyethyl acrylate into the kettle to end-cap, stirring for 40min, using triethylamine to adjust the pH value to 7, and discharging to obtain the hydrophobic monomer.
The hydrophobic monomer is subjected to infrared spectrum analysis by using a Nicolet 6700 type Fourier transform infrared spectrometer (FT-IR), and the spectrum range is 4000-500 cm -1 The analysis results are shown in FIG. 1, in which 3096cm -1 、3084cm -1 And 3062cm -1 The absorption peak at the position is attributed to C-H stretching vibration peak on benzene ring, 3031cm -1 The absorption peak at the position is attributed to C-H stretching vibration peak of carbon-carbon double bond in the hydroxyl ethyl acrylate of the end capping agent, which is 1719cm -1 The absorption peak at the position is attributed to a C=O stretching vibration peak in hydroxyethyl acrylate, 1368cm -1 The absorption peak at the position is attributed to C-F characteristic absorption peak, 1072cm -1 The absorption peak at this point is assigned to the Si-O characteristic absorption peak.
Example 2
Preparation of crosslinking monomers
Stirring and mixing 1.5g of amino-terminated silicone oil with weight average molecular weight of 1000 with toluene uniformly, adding 0.5g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride after the amino-terminated silicone oil is completely dissolved, stirring at 75 ℃ for 60min, reducing the temperature to 30 ℃, continuously adding 0.03g of sodium acetate and 0.07g of acetic anhydride under the stirring condition, dropwise adding 0.2g of triethylamine, keeping the temperature and stirring for 16h after the amino-terminated silicone oil is completely added, removing the solvent by reduced pressure evaporation, cooling and discharging to obtain the crosslinking monomer.
FIG. 2 is a chart of IR analysis test of crosslinking monomer, available for analysis, 3012cm -1 The absorption peak at the position is characterized by the characteristic absorption peak of C-H of a carbon-carbon double bond in norbornene, which is 1698cm -1 The absorption peak at which is assigned to the c=o characteristic absorption peak in the imide structure, 1310cm -1 The absorption peak at the position is characterized by C-N characteristic absorption peak of 1095cm -1 The absorption peak at this point is assigned to the Si-O characteristic absorption peak.
Example 3
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 50 parts of butyl acrylate, 60 parts of isooctyl acrylate, 3 parts of acrylic acid, 0.2 part of hydroxyethyl acrylate, 1 part of the hydrophobic monomer prepared in the embodiment 1 of the invention, 300 parts of ethyl acetate, 0.3 part of azodiisobutyronitrile and 1 part of the crosslinking monomer prepared in the embodiment 2 of the invention;
the polyacrylate adhesive is prepared by the following method:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, raising the temperature to 75 ℃ under the condition of continuous stirring, adding one third of azodiisobutyronitrile into the polymerization kettle, stirring for 30min, and marking the obtained product as a prepolymer;
second step, crosslinking
Adding the crosslinking monomer into a polymerization kettle, adding the rest initiator into the kettle again after adding, further raising the temperature to 80 ℃, carrying out heat preservation treatment for 8 hours under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive.
Example 4
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 55 parts of butyl acrylate, 65 parts of isooctyl acrylate, 5 parts of acrylic acid, 0.3 part of hydroxyethyl acrylate, 2.5 parts of the hydrophobic monomer prepared in the embodiment 1 of the invention, 360 parts of ethyl acetate, 0.4 part of azodiisobutyronitrile and 1.5 parts of the crosslinking monomer prepared in the embodiment 2 of the invention;
the polyacrylate adhesive is prepared by the following method:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, raising the temperature to 80 ℃ under the condition of continuous stirring, adding one third of azodiisobutyronitrile into the polymerization kettle, stirring for 40min, and marking the obtained product as a prepolymer;
second step, crosslinking
Adding the crosslinking monomer into a polymerization kettle, adding the residual azodiisobutyronitrile into the kettle again after adding, further raising the temperature to 85 ℃, carrying out heat preservation treatment for 9 hours under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive.
Example 5
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 60 parts of butyl acrylate, 70 parts of isooctyl acrylate, 6 parts of acrylic acid, 0.6 part of hydroxyethyl acrylate, 3 parts of the hydrophobic monomer prepared in the embodiment 1 of the invention, 400 parts of ethyl acetate, 0.6 part of azo-bis-isoheptanenitrile and 2 parts of the crosslinking monomer prepared in the embodiment 2 of the invention;
the polyacrylate adhesive is prepared by the following method:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, filling nitrogen as a protective gas, increasing the temperature to 80 ℃ under the condition of continuous stirring, adding one third of azodiisoheptonitrile into the polymerization kettle, stirring for 60min, and marking the obtained product as a prepolymer;
second step, crosslinking
Adding the crosslinking monomer into a polymerization kettle, adding the residual azodiisoheptonitrile into the kettle again after adding, further raising the temperature to 85 ℃, carrying out heat preservation treatment for 12 hours under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive.
Comparative example 1
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 55 parts of butyl acrylate, 65 parts of isooctyl acrylate, 5 parts of acrylic acid, 0.3 part of hydroxyethyl acrylate, 360 parts of ethyl acetate, 0.4 part of azodiisobutyronitrile and 1.5 parts of the crosslinking monomer prepared in the embodiment 2 of the invention;
the polyacrylate adhesive is prepared by the following method:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate and ethyl acetate into a polymerization kettle, filling nitrogen as a protective gas, increasing the temperature to 80 ℃ under the condition of continuous stirring, adding one third of azodiisobutyronitrile into the polymerization kettle, stirring for 40min, and marking the obtained product as a prepolymer;
second step, crosslinking
Adding the crosslinking monomer into a polymerization kettle, adding the residual azodiisobutyronitrile into the kettle again after adding, further raising the temperature to 85 ℃, carrying out heat preservation treatment for 9 hours under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive.
Comparative example 2
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 55 parts of butyl acrylate, 65 parts of isooctyl acrylate, 5 parts of acrylic acid, 0.3 part of hydroxyethyl acrylate, 2.5 parts of hydrophobic monomer prepared in the embodiment 1 of the invention, 360 parts of ethyl acetate, 0.4 part of azodiisobutyronitrile and 1.5 parts of N, N' -methylenebisacrylamide;
the polyacrylate adhesive is prepared by the following method:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, raising the temperature to 80 ℃ under the condition of continuous stirring, adding one third of azodiisobutyronitrile into the polymerization kettle, stirring for 40min, and marking the obtained product as a prepolymer;
second step, crosslinking
Adding N, N' -methylene bisacrylamide into a polymerization kettle, adding the rest azodiisobutyronitrile into the kettle again after adding, further raising the temperature to 85 ℃, carrying out heat preservation treatment for 9h under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive.
Comparative example 3
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 55 parts of butyl acrylate, 65 parts of isooctyl acrylate, 5 parts of acrylic acid, 0.3 part of hydroxyethyl acrylate, 2.5 parts of hydrophobic monomer prepared in the embodiment 1 of the invention, 360 parts of ethyl acetate and 0.4 part of azodiisobutyronitrile;
the polyacrylate adhesive is prepared by the following method:
sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, increasing the temperature to 80 ℃ under the condition of continuous stirring, adding azobisisobutyronitrile into the polymerization kettle, and stirring for 8 hours to obtain the polyacrylate adhesive.
Comparative example 4
A multi-component polyacrylate adhesive comprises the following raw materials in parts by weight: 55 parts of butyl acrylate, 65 parts of isooctyl acrylate, 5 parts of acrylic acid, 0.3 part of hydroxyethyl acrylate, 360 parts of ethyl acetate and 0.4 part of azodiisobutyronitrile;
the polyacrylate adhesive is prepared by the following method:
sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate and ethyl acetate into a polymerization kettle, filling nitrogen as a protective gas, increasing the temperature to 80 ℃ under the condition of continuous stirring, adding azodiisobutyronitrile into the polymerization kettle, and stirring for 8 hours to obtain the polyacrylate adhesive.
Performance detection
The polyacrylate adhesives prepared in examples 3 to 5 and comparative examples 1 to 4 were uniformly coated on the corona surface of a PET film having a thickness of 25. Mu.m, and the coating amount was controlled to be 30g/m 3 Initial tackiness test is carried out according to national standard GB/T4852-2002; 180-degree peel strength test is carried out according to national standard GB/T2792-2014; according to national standard GB/T4851-2014, testing the adhesion duration of the adhesive at the temperature of 85 ℃; water contact angle test was performed using a PZ-200SD contact angle tester;
the test results are shown in the following table:
analysis of the test results shows that the polyacrylate adhesive prepared by adding the hydrophobic monomer and the crosslinking monomer has strong bonding performance and good high temperature resistance and water resistance compared with the polyacrylate adhesive prepared by not adding the hydrophobic monomer and the crosslinking monomer.
The polyacrylate adhesive prepared in comparative example 1 does not use a hydrophobic monomer as a raw material, and it is obvious that the high temperature resistance and the water resistance are reduced to different degrees, because the molecular side chain of the polyacrylate adhesive prepared without adding the hydrophobic monomer does not contain a rigid benzene ring and siloxane.
Comparative example 2 used conventional N, N' -methylenebisacrylamide as a crosslinking agent, although good adhesive properties were maintained, high temperature resistance was significantly reduced.
Comparative example 3 does not use a crosslinking agent, resulting in a significant reduction in the adhesive properties of the prepared polyacrylate adhesive, and a further reduction in the high temperature resistance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. A method for producing a multi-component polyacrylate adhesive comprising the steps of:
first step, prepolymerization
Sequentially adding butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl acrylate, a hydrophobic monomer and ethyl acetate into a polymerization kettle, charging nitrogen as a protective gas, raising the temperature to 75-80 ℃ under the condition of continuous stirring, adding one third of an initiator into the polymerization kettle, stirring for 30-60min, and marking the obtained prepolymer as a prepolymer;
second step, crosslinking
Adding a crosslinking monomer into a polymerization kettle, adding the rest initiator into the kettle again after adding, further raising the temperature to 80-85 ℃, carrying out heat preservation treatment for 8-12h under the stirring condition, and then cooling and discharging to obtain the polyacrylate adhesive;
the hydrophobic monomer is a block polymer containing a fluorine-containing hydrophobic chain segment and a siloxane hydrophobic chain segment in the structure;
the crosslinking monomer is a norbornene-terminated silicone oil derivative;
the crosslinking monomer is prepared by the following method:
stirring and mixing amino-terminated silicone oil and toluene uniformly, adding cis-5-norbornene-exo-2, 3-dicarboxylic anhydride after the amino-terminated silicone oil and toluene are completely dissolved, stirring at 70-80 ℃ for 40-60min, reducing the temperature to 30-40 ℃, continuously adding a catalyst under the stirring condition, after the amino-terminated silicone oil and toluene are completely added, preserving heat and stirring for 12-18h, decompressing and evaporating to remove the solvent, cooling and discharging to obtain the crosslinking monomer.
2. The method for producing a multi-component polyacrylate adhesive according to claim 1, wherein the polyacrylate adhesive is produced by using the following components in parts by weight: 50-60 parts of butyl acrylate, 60-70 parts of isooctyl acrylate, 3-6 parts of acrylic acid, 0.2-0.6 part of hydroxyethyl acrylate, 1-3 parts of hydrophobic monomer, 300-400 parts of ethyl acetate, 0.3-0.6 part of initiator and 1-2 parts of crosslinking monomer.
3. A method of producing a multi-component polyacrylate adhesive according to any one of claims 1-2, wherein the hydrophobic monomer is prepared by:
taking a polymerization kettle, introducing nitrogen into the kettle to discharge oxygen, sequentially adding hexafluorobisphenol A and tetrahydrofuran into the kettle, starting stirring, after a uniform solution is formed, starting heating, maintaining the temperature at 50-60 ℃, adding dichlorosilane derivatives with the same mass into the kettle in three times under the stirring condition, keeping stirring for 4-6h after each time of 20-30min, adding hydroxyethyl acrylate into the kettle to end cap, stirring for 30-60min, using triethylamine to adjust the pH value to 6.5-7, and discharging to obtain the hydrophobic monomer.
4. A method of producing a multi-component polyacrylate adhesive according to claim 3, wherein the dichlorosilane derivative is di-n-octyldichlorosilane or dichlorodimethylsilane.
5. A method of producing a multi-component polyacrylate adhesive according to claim 3, wherein the molar ratio of hexafluorobisphenol a to dichlorosilane derivative is 1:1.
6. The method of producing a multi-component polyacrylate adhesive according to any one of claims 1 to 2, wherein the initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile, or azobiscyano valeric acid.
7. The method for producing a multicomponent polyacrylate adhesive according to claim 1, wherein the amino terminated silicone oil has a weight average molecular weight of 1000.
8. The method for producing a multi-component polyacrylate adhesive according to claim 1, wherein the catalyst is a composite of sodium acetate, acetic anhydride and triethylamine in a mass ratio of 0.1-0.2:0.3-0.4:1.
9. A multi-component polyacrylate adhesive produced by the production process of claim 1.
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