CN117924649A - Preparation method of hydrogen bond locking boron-containing supermolecule polyurea elastomer - Google Patents
Preparation method of hydrogen bond locking boron-containing supermolecule polyurea elastomer Download PDFInfo
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- CN117924649A CN117924649A CN202410167314.4A CN202410167314A CN117924649A CN 117924649 A CN117924649 A CN 117924649A CN 202410167314 A CN202410167314 A CN 202410167314A CN 117924649 A CN117924649 A CN 117924649A
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 63
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000000806 elastomer Substances 0.000 title claims abstract description 59
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 36
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 2
- ZPKSAIWDCQVXSQ-UHFFFAOYSA-N (4-aminophenoxy)boronic acid Chemical compound NC1=CC=C(OB(O)O)C=C1 ZPKSAIWDCQVXSQ-UHFFFAOYSA-N 0.000 claims description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229920001169 thermoplastic Polymers 0.000 abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000012958 reprocessing Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000005520 cutting process Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 241000209051 Saccharum Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a preparation method of a hydrogen bond locking boron-containing supermolecular polyurea elastomer, which is characterized in that a controllable molecular sequence of multiple hydrogen bonds and dynamic covalent bond combinations is constructed through chain segment design and synthesis technology, the problems of disordered molecular structure and weakened mechanical property of the traditional crosslinking type polyurea elastomer are solved, and good thermoplastic reprocessing capability is considered. The invention has the advantages of cheap and easily obtained raw materials, simple and efficient preparation process and suitability for mass production.
Description
Technical Field
The invention belongs to the field of thermoplastic (polyurea) elastomers, and particularly relates to a preparation method of a hydrogen bond locking boron-containing supermolecule polyurea elastomer.
Background
Polymeric elastomer materials containing urea (-NHCONH-) segments in the polyurea elastomer backbone were first reported to be successful by Texaco, inc., U.S.A., and were typically prepared by reacting a diisocyanate with a diamine. Compared with the synthesis of the traditional polyurethane material, the reaction does not need severe reaction conditions, can be usually carried out at normal temperature, and does not need to additionally add other catalysts. Compared with other polymers, the polyurea has the characteristics of excellent corrosion resistance, abrasion resistance, water resistance and the like, can be particularly used as a protective coating for concrete buildings and explosion and impact resistance, has higher mechanical strength, good elasticity, chemical stability and thermal stability, and can be used for a long time in a severe environment, so that development and application of the polyurea elastomer are widely focused by domestic and foreign companies and researchers.
The excellent mechanical properties of polyurea elastomers are mainly due to their molecular structure and microphase-separated structure, the hard domains formed by their hard segments often playing the role of reversible physical crosslinking points. The urea bond is rich in N, O, H elements, so that a large number of hydrogen bond interactions can be formed among molecular chains, and the hydrogen bond is widely applied in recent years as an important strategy for overcoming the balance between strength and toughness, thereby improving the mechanical property and the strain rate responsiveness of the elastomer. Meanwhile, the dynamic bond such as boron-oxygen bond is also a key for endowing the elastomer with strain rate sensitivity due to the excellent dynamic exchange characteristic. Therefore, the invention aims to introduce a hydrogen bond and a dynamic cross-linking network without damaging the original characteristics of polyurea, so that the shock resistance is further improved while the mechanical property of a sample is improved, and the anti-impact and anti-explosion application of the polyurea is expanded.
In recent years, research on developing thermoplastic polyurea elastomers having good processability has been actively conducted, for example, patent CN201710188559.5 discloses that thermoplastic polyurea elastomers are prepared by extrusion reaction of aliphatic diamine with dicyanate and polyol, and patent CN202010347326.7 discloses that self-repairing thermoplastic polyurea elastomers are prepared by polymerization of carbon dioxide and diamine, and the thermoplastic polyurea elastomers are all linear molecular chain structures, and have significant differences from chemical crosslinking polyurea elastomers in comprehensive properties. For linear thermoplastic elastomers, the internal part of the linear thermoplastic elastomer is a crosslinked network constructed by physical crosslinking points, and compared with a covalent bond crosslinked network, the linear thermoplastic elastomer is more prone to creep phenomenon, so that the improvement of the creep resistance of the traditional thermoplastic elastomer is important. However, chemically crosslinked thermoset polyurea elastomers suffer from the inability to be repeatedly processed and recycled with difficulty due to stabilization of urea linkages and three-dimensional crosslinked networks. Aiming at the recovery and reprocessing of traditional thermosetting polymers, a plurality of effective strategies are reported by students at home and abroad. Transesterification and reproducible processing are achieved by adding an appropriate amount of catalyst to the thermoset polyurethane [ ZhengN, fangZZ, zouW, etal.Angew.Chem.Int.Ed.,2016,55:11421-11425 ]. Various types of dynamic chemical bonds are introduced into chemical cross-linked networks, including beta transesterification reactions [ damien montanaletal. Science,334,965-968 (2011) ], olefin metathesis reactions, dynamic disulfide bonds, and the like. Under specific working conditions, the damage of the polyurea material or the inside of the coating can shorten the service life, and the dynamic network can endow the material with certain self-repairing capability. Therefore, by constructing a dynamic covalent bond form, the machinability of the material can be maintained, and the comprehensive use performance of the material can be improved.
The traditional polyurea elastomer is prepared and molded by a one-step method, and the problems of undefined molecular structure, irregular formation of intermolecular hydrogen bonds and the like are possibly caused by the excessively rapid reaction, so that the mechanical property of the polyurea elastomer is weakened to a certain extent. Therefore, the invention adopts a prepolymer method to control the structure of the polyurea sequence, adopts solvent dilution to control the reaction process, so that the chain segment sequence is controllable in the sample synthesis stage, and the hydrogen bond stacking is regular, thus forming the supermolecule polyurea elastomer with clear molecular structure and easy regulation.
Disclosure of Invention
The invention aims to develop a hydrogen bond locking boron-containing supermolecular polyurea elastomer, wherein a small molecular borate is used as a chain extender and a cross-linking agent to construct a dynamic cross-linking supermolecular network while dense urea bonds are introduced into a hard segment to realize multiple hydrogen bonds, and the prepared cross-linking polyurea elastomer has the effect of cooperatively improving strength and toughness, and realizes high tensile strength (more than 50 MPa), elongation at break (more than 600 percent), fracture toughness (more than 180MJ/m 3) and excellent thermal repeated processability. Compared with most of polyurea elastomers reported at present, the method can endow the bodily cross-linked polyurea elastomer with recoverability and excellent thermoplastic reprocessing capability by introducing dynamic boron-oxygen bonds, and meanwhile, the preparation process is simple, the reaction condition is mild, the molecular structure design is strong, and batch preparation is easy to realize.
In order to achieve the above purpose, the following technical scheme is adopted:
step (1): after long-chain diamine and short-chain diisocyanate are uniformly diluted by a small amount of solvent, gradually adding diamine monomer diluted liquid into diisocyanate diluted liquid in a dropwise manner to obtain isocyanate-terminated prepolymer A.
Step (2): 100 parts of isocyanate-terminated prepolymer A is weighed, 0-20 parts of trifunctional isocyanate is added, 1-50 parts of isophthalic acid dihydrazide (IPDH) diluent is added, 0.5-30 parts of boron-containing hydroxyl cross-linking agent diluent is added, 0-5 parts of catalyst is added, so that milky suspension is obtained, and the molar ratio of isocyanate to active hydrogen (boron-containing hydroxyl and amino) is ensured to be 1: (0.95-1.05), heating and continuously stirring until the solution is clarified, uniformly pouring the solution into a polytetrafluoroethylene mould, putting the polytetrafluoroethylene mould into a vacuum oven, drying to remove the solvent and solidifying the solvent to obtain the hydrogen bond locking boron-containing supermolecule polyurea elastomer.
Step (3): and (3) taking a proper amount of hydrogen bond to lock the boron-containing supermolecular polyurea elastomer, and adopting a polymer secondary processing mode to obtain a spline for testing.
The long-chain diamine in the step (1) is any one of polyetheramine D400, polyetheramine D1000 and polyetheramine D2000.
The diisocyanate in the step (1) is any one of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI).
The trifunctional isocyanate in the step (2) is any one of hexamethylene diisocyanate trimer (HT-100) and the Saccharum sinensis Roxb (JQ-1).
The boron-containing hydroxyl cross-linking agent in the step (2) is any one or combination of boric acid, phenylboric acid, 1, 4-phenyldiboronic acid, 3-aminophenylboric acid and 4-aminophenylboric acid.
The catalyst in the step (2) is any one of Triethylamine (TEA), dicycloguanidine (TBD) and dibutyl tin dilaurate (DBTDL). The curing temperature in the step (2) is room temperature or 60 ℃, and the curing time is 8-24 hours.
The secondary processing mode of the polymer in the step (3) is any one of compression molding, injection molding and screw extrusion 3D printing molding.
Aiming at the problems of poor creep resistance of the linear polyurea elastomer and poor re-processability of the cross-linked polyurea elastomer, the invention introduces multiple hydrogen bonds through IPDH chain extension and introduces boron-oxygen dynamic bonds to construct the cross-linked polyurea, and develops the hydrogen bond locking boron-containing supermolecule polyurea elastomer.
Compared with the prior art, the invention has the beneficial effects that:
1. the molecular sequence structure is controllable, the preparation process is simple, and the preparation method is suitable for industrial mass production.
2. By introducing the dynamic covalent bond of boron and oxygen, the creep resistance and the metal adhesion performance of the polyurea elastomer are greatly improved, and the polyurea elastomer has excellent repeatable processing performance.
3. By introducing multiple hydrogen bonds, the boron-oxygen dynamic bond is locked, and the strength and toughness of the polyurea elastomer are cooperatively improved.
Drawings
FIG. 1. Molecular structure (a) and infrared spectrum (b) of boron-containing supramolecular polyurea elastomer
FIG. 2 (a) tensile Properties and (b) fatigue resistance Properties of boron-containing supramolecular polyurea elastomer
FIG. 3 thermoplastic processability of boron-containing supramolecular polyurea elastomer
FIG. 4 atomic force microscope image of boron-containing supramolecular polyurea elastomer
FIG. 5 stress relaxation behavior of boron-containing supramolecular polyurea elastomers
Detailed Description
For further explanation of the technical solutions of the present invention, the following description is given in detail with reference to examples, but the scope of the present invention is not limited to these examples, and the modifications and adjustments made by those skilled in the art are all within the scope of the present invention.
Example 1
2.2 Parts of HMDI and 7.6 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.2 part of boric acid is weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is maintained at 60 ℃ for 20 hours, so that a uniform and stable transparent colorless solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain a polyurea elastomer 1; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 2
2.8 Parts of HMDI and 6.9 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.27 part of boric acid is weighed and dissolved in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is carried out for 20 hours at 60 ℃ to obtain a uniform and stable transparent colorless solution. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mixture into a vacuum oven to remove the solvent and solidify the solvent to obtain polyurea elastomer 2; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 3
2.7 Parts of HMDI and 6.6 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.10 part of boric acid and 0.6 part of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is maintained at 60 ℃ for 20 hours, so that a uniform and stable transparent colorless solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the polytetrafluoroethylene mould in a vacuum oven to remove the solvent and solidify the polyurea elastomer 3; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 4
2.6 Parts of HMDI and 6.4 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.1 part of boric acid and 0.9 part of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is maintained at 60 ℃ for 20 hours, so that a uniform and stable transparent colorless solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain a polyurea elastomer 4; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 5
2.6 Parts of HMDI and 6.28 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.02 part of boric acid and 1.1 part of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is maintained at 60 ℃ for 20 hours, so that a uniform and stable transparent colorless solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain a polyurea elastomer 5; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 6
2.6 Parts of HMDI and 6.28 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.02 part of boric acid and 1.1 part of IPDH parts of boric acid are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃ and 0.05ml of DBTDL catalyst is added dropwise, and the mixture is reacted for 20 hours at 60 ℃ to obtain a uniform and stable transparent pale yellow solution. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain a polyurea elastomer 6; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Example 7
2.59 Parts of HMDI and 6.27 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.04 part of 1, 4-phenyldiboronic acid and 1.1 part IPDH parts of the mixture are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the temperature is maintained at 60 ℃ for reacting for 20 hours, so that a uniform and stable transparent colorless solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain a polyurea elastomer 7; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Comparative example 1
2.6 Parts of HMDI and 6.3 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 1.1 parts of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is carried out for 20 hours at 60 ℃ to obtain a uniform and stable transparent colorless solution. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain polyurea elastomer comparative example 1; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Comparative example 2
2.59 Parts of HMDI and 6.28 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 0.03 part of glycerin and 1.1 part of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the temperature of the mixture is maintained at 60 ℃ for 20 hours, so that a uniform and stable transparent solution is obtained. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain polyurea elastomer comparative example 2; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
Comparative example 3
2.1 Parts of IPDI and 6.7 parts of polyether amine D2000 are weighed according to parts by weight, the mixture is reacted for 3 hours at normal temperature and normal pressure under the protection of nitrogen, then 1.2 parts of IPDH are weighed and dispersed in a solvent, the mixture is added into a reaction system at 60 ℃, and the reaction is carried out for 20 hours at 60 ℃ to obtain a uniform and stable transparent colorless solution. Pouring the mixture into a polytetrafluoroethylene mould after uniformly stirring, and placing the mould in a vacuum oven to remove the solvent and solidify the solvent to obtain polyurea elastomer comparative example 3; and (3) performing hot press molding to obtain a film by adopting a flat vulcanizing machine, and cutting the film into standard sample bars for testing.
The foregoing description is only exemplary of the preferred embodiments of the invention and is not intended to limit the invention in any way or in any way whatsoever, but rather, modifications and additions may be made without changing the process of the invention which are also to be considered as being within the scope of the invention. Equivalent changes and modifications made by those skilled in the art using the teachings disclosed above should be considered equivalent embodiments of the present invention, and still fall within the scope of the present invention without departing from the scope thereof.
To examine the mechanical properties of the products obtained in the examples, the products were hot pressed into 1mm thick sheets by a press vulcanizer, and the tensile properties at room temperature were measured by cutting into standard dumbbell bars according to national standards, and the results of each test are shown in Table 1.
Table 1 examples and tensile strength, elongation at break and shore hardness
| Tensile Strength (MPa) | Elongation at break (%) | Fracture toughness (MJ/m 3) | Shore hardness A | |
| Comparative example 1 | 35 | 650 | 116.65 | 95.5 |
| Comparative example 2 | 44 | 686 | 157.40 | 94.5 |
| Comparative example 3 | 23 | 810 | 98.96 | 95 |
| Example 1 | 20 | 1800 | 186.98 | 82 |
| Example 2 | 1.2 | 550 | 5.19 | 90 |
| Example 3 | 20.5 | 585 | 71.08 | 92 |
| Example 4 | 28 | 545 | 90.80 | 94.5 |
| Example 5 | 51 | 670 | 180.35 | 95.5 |
| Example 6 | 45 | 640 | 148.43 | 96 |
| Example 7 | 41 | 650 | 136.10 | 95 |
Claims (9)
1. A preparation method of a hydrogen bond locking boron-containing supermolecular polyurea elastomer is characterized by comprising the following steps:
step (1): after long-chain diamine and short-chain diisocyanate are uniformly diluted by a small amount of solvent, gradually adding diamine monomer diluted liquid into diisocyanate diluted liquid in a dropwise manner to obtain isocyanate-terminated prepolymer A.
Step (2): 100 parts of isocyanate-terminated prepolymer A is weighed, 0-20 parts of trifunctional isocyanate is added, 1-50 parts of isophthalic acid dihydrazide (IPDH) diluent is added, 0.5-30 parts of boron-containing hydroxyl cross-linking agent diluent is added, 0-5 parts of catalyst is added, so that milky suspension is obtained, and the molar ratio of isocyanate to active hydrogen (boron-containing hydroxyl and amino) is ensured to be 1: (0.95-1.05), heating and continuously stirring until the solution is clarified, uniformly pouring the solution into a polytetrafluoroethylene mould, putting the polytetrafluoroethylene mould into a vacuum oven, drying to remove the solvent and solidifying the solvent to obtain the hydrogen bond locking boron-containing supermolecule polyurea elastomer.
Step (3): and (3) taking a proper amount of hydrogen bond to lock the boron-containing supermolecular polyurea elastomer, and adopting a polymer secondary processing mode to obtain a spline for testing.
2. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the long-chain diamine is any one of polyetheramine D400, polyetheramine D1000 and polyetheramine D2000.
3. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the diisocyanate is any one of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI).
4. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the trifunctional isocyanate is any one of hexamethylene diisocyanate trimer (HT-100) and micronaire (JQ-1).
5. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the boron-containing hydroxyl cross-linking agent is any one or a combination of boric acid, phenylboric acid, 1, 4-phenyldiboronic acid, 3-aminophenylboric acid and 4-aminophenylboric acid.
6. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the catalyst is any one of Triethylamine (TEA), dicycloguanidine (TBD) and dibutyl tin dilaurate (DBTDL).
7. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the sequence of the polyurea molecular chains and the crosslinked network structure are controlled in a metering manner by the addition sequence and the addition amount of each additive component.
8. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the curing temperature is room temperature or 60 ℃, and the curing time is 8-24 hours.
9. The method for preparing the hydrogen bond locking boron-containing supermolecular polyurea elastomer according to claim 1, wherein the secondary processing mode of the polymer is any one of compression molding, injection molding and screw extrusion 3D printing.
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