CN117264173A - High-strength and high-toughness thermoplastic elastomer with double hard phases and preparation method thereof - Google Patents
High-strength and high-toughness thermoplastic elastomer with double hard phases and preparation method thereof Download PDFInfo
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- CN117264173A CN117264173A CN202311110046.4A CN202311110046A CN117264173A CN 117264173 A CN117264173 A CN 117264173A CN 202311110046 A CN202311110046 A CN 202311110046A CN 117264173 A CN117264173 A CN 117264173A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000376 reactant Substances 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000007142 ring opening reaction Methods 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- 230000009977 dual effect Effects 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- -1 diamine organic compound Chemical class 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-strength and high-toughness thermoplastic elastomer with double hard phases and a preparation method thereof. Meanwhile, the high toughness of the thermoplastic elastomer is endowed by utilizing the difference of the strength of the acting forces between two different hard phases, and the problem of insufficient strength and toughness of the existing thermoplastic elastomer is solved.
Description
Technical Field
The invention belongs to the technical field of elastomer preparation, and in particular relates to a double hard phase high-strength high-toughness thermoplastic elastomer.
Background
Thermoplastic elastomers, which are a polymer material composed of alternating hard and soft segments, are widely used in daily life, and are known for their excellent deformability and toughness. The strength mainly derives from a hard phase formed by stacking and arranging hard segment molecular chains, so that the higher the rigidity of a hard segment structure is, the stronger the intermolecular acting force is, the higher the content of hard segment components is, the higher the strength and modulus of the obtained thermoplastic elastomer are, but the toughness is reduced. In addition, the existence of the soft segment can reduce the strength of the thermoplastic elastomer to a certain extent, and can increase the viscosity of the polymer, so that the thermoplastic elastomer can not effectively recover the deformation in a short time like a chemically crosslinked elastomer when the thermoplastic elastomer is greatly deformed, and the instant rebound resilience is poor. Therefore, in order to balance various indexes of mechanical properties, the ratio of the hard segment to the soft segment is usually kept in a proper range, and a thermoplastic elastomer with excellent rebound performance and high strength in CN115010896B and a preparation method thereof are disclosed, wherein the preparation steps comprise the steps of firstly placing at least two soft segment monomers in a solvent, adding the hard segment monomers for reaction to obtain an initial reactant, and then reacting a chain extender with the initial reactant to obtain the thermoplastic elastomer. Wherein the soft segment monomer is selected from two or more of glycol oligomers and/or diamine oligomers which are not compatible in thermodynamics, the glycol oligomers are selected from one or more of polycaprolactone diol, polytetrahydrofuran diol, double-end hydroxyl polyethylene glycol, double-end hydroxyl polypropylene glycol and double-end hydroxyl polydimethylsiloxane, the diamine oligomers are selected from one or more of polyetheramine and double-end amino polydimethylsiloxane, and the hard segment units are diisocyanate. The high strength and the high modulus of the thermoplastic elastomer are endowed by multiple hydrogen bonds in isocyanate hard segment monomers, and the excellent toughness and the high rebound property of the thermoplastic elastomer are endowed by the characteristic of thermodynamic incompatibility between at least two soft segment monomers of diol oligomers and diamine oligomers, so that the tensile strength of the prepared high rebound and high strength thermoplastic elastomer can reach 80MPa, and the elongation at break is close to 1000%. Although the strength and resilience of the thermoplastic elastomer are improved to a certain extent, the thermoplastic elastomer is limited to the patent mainly comprising different soft segments, but the soft segment monomers and the hard segment monomers are simultaneously added for reaction, so that the soft segment monomers are enriched to form a soft segment phase and the hard segment monomers are weakly regulated to form a hard segment phase, and the improvement of the strength and the toughness is limited to a certain extent.
Disclosure of Invention
The invention provides a high-strength and high-toughness thermoplastic elastomer with double hard phases and a preparation method thereof, which aims to solve the problems that the enrichment of hard phase and soft phase of a thermoplastic elastomer prepared by two soft phase monomers and one hard phase monomer is weak and the improvement of the strength and toughness is limited.
The invention is realized by the following technical scheme:
a preparation method of a double hard phase high-strength and high-toughness thermoplastic elastomer comprises the following steps:
s1, dissolving a hard segment unit I in a solvent, and then adding a ring-opening monomer and a catalyst, wherein the hard segment unit I and the ring-opening monomer are polymerized to obtain an initial reactant;
s2, mixing the initial reactant in the S1 with diisocyanate in a solvent, and adding a catalyst to react to obtain a secondary reactant;
s3, adding the hard segment unit II into a secondary reactant, and enabling the hard segment unit II to react with the secondary reactant to obtain a double-hard-phase thermoplastic elastomer;
the hard segment unit I is a glycol organic matter, and the expression of the glycol organic matter is as follows:
wherein R1 represents an organic unit containing an aromatic hydrocarbon structure or a cyclic structure;
the ring-opening monomer is caprolactone;
the hard segment unit II is a diamine organic compound and comprises one or more of 1, 2-ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, oxalyl dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and adipoyl diamine.
Further, the number of rings of the R1 aromatic hydrocarbon structure or the cyclic structure in the glycol organic matter is more than or equal to 1. Preferably, the glycol organics include one or more of hydrobenzine, isopear mountain alcohol.
Further, the solvent in S1 and S2 includes one or more of N, N '-dimethylformamide, N' -dimethylacetamide, methylene chloride, chloroform, and tetrahydrofuran.
Further, the molar ratio of the hard segment unit I to the ring-opening monomer in the S1 is 2-50:1.
Further, the catalyst in S1 is stannous octoate, and the addition amount of the stannous octoate is 0.1-1% of the total mass of the hard segment unit I and the ring-opening monomer; the catalyst in S2 is dibutyl tin dilaurate, and the addition amount of the dibutyl tin dilaurate is 0.1-1% of the total mass of the initial reactant and the diisocyanate.
Further, the polymerization reaction temperature in S1 is 100-150 ℃ and the reaction time is 60-1200 min.
Further, the ratio of the initial reactant to the diisocyanate in S2 is 1-8:2-10.
Further, the diisocyanate includes one or more of isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate.
Further, the reaction temperature in S2 is 40-100 ℃ and the reaction time is 10-120 min.
Further, the molar ratio of the hard segment unit II to the secondary reactant in the S3 is 1-10: :1 to 10. Preferably, the molar ratio of hard segment unit two to secondary reactant is 1:1 to 2.
Further, the reaction temperature in S3 is 40-100 ℃ and the reaction time is 60-1200 min.
Compared with the prior art, the beneficial effects are that:
the invention adopts two different hard segment monomers of diol organic matters and diamine organic compounds with aromatic hydrocarbon structures or cyclic structures, firstly, the hard segment units I of the diol organic matters react with soft segments, and then are compounded with the hard segment units II of the diamine organic compounds. Meanwhile, the high toughness of the thermoplastic elastomer is provided by utilizing the difference of the strength of the acting force between two different hard phases. Experiments show that the high-strength and high-toughness thermoplastic elastomer prepared by the method has the tensile strength of 50MPa at most and the elongation at break of 2000 percent.
Drawings
FIG. 1 is a uniaxial tensile stress-strain test chart of thermoplastic elastomers prepared in examples and comparative examples.
Detailed Description
The present invention is further illustrated and described below with reference to examples, which are not intended to be limiting in any way. Unless otherwise indicated, the methods and apparatus used in the examples were conventional in the art and the starting materials used were all conventional commercially available.
Example 1
The embodiment provides a high-strength and high-toughness thermoplastic elastomer with double hard phases, which comprises the following preparation steps:
s1, taking hydrobenzidine as a hard segment unit I, dissolving the hydrobenzidine into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the molar ratio of the hydrobenzidine to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzidine and the caprolactone to obtain an initial reactant. Wherein, the molecular structural formula of the hydrobenzidine is expressed as follows:
s2, dissolving an initial reactant and isophorone diisocyanate in an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to isophorone diisocyanate is 1:2, adding a catalyst dibutyltin dilaurate, the addition amount of which is 1wt% of the raw materials of the reactant, and reacting for 120min at 60 ℃ to obtain a secondary reactant.
S3, adding oxalyl dihydrazide as a hard segment unit II into a secondary reactant, wherein the molar ratio of the oxalyl dihydrazide to the secondary reactant is 1:1, reacting for 600min at 60 ℃ under the protection of inert gas to obtain the thermoplastic elastomer.
Example 2
The embodiment provides a high-strength and high-toughness thermoplastic elastomer with double hard phases, which comprises the following preparation steps:
s1, taking hydrobenzidine as a hard segment unit I, dissolving the hydrobenzidine into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the molar ratio of the hydrobenzidine to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzidine and the caprolactone to obtain an initial reactant.
S2, dissolving an initial reactant and hexamethylene diisocyanate in an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to the hexamethylene diisocyanate is 1:2, adding a catalyst dibutyltin dilaurate, wherein the addition amount is 1wt% of the reactant raw material, and reacting for 120min at 60 ℃ to obtain a secondary reactant.
S3, adding oxalyl dihydrazide as a hard segment unit II into a secondary reactant, wherein the molar ratio of the oxalyl dihydrazide to the secondary reactant is 1:1, reacting for 600min at 60 ℃ under the protection of inert gas to obtain the thermoplastic elastomer.
Example 3
The embodiment provides a high-strength and high-toughness thermoplastic elastomer with double hard phases, which comprises the following preparation steps:
s1, taking isopear mountain alcohol as a hard segment unit I, dissolving the isopear mountain alcohol into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the mol ratio of the isopear mountain alcohol to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzine and the caprolactone to obtain an initial reactant. Wherein, the molecular structural formula of the isopear mountain alcohol is expressed as follows:
s2, dissolving an initial reactant and isophorone diisocyanate in an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to isophorone diisocyanate is 1:2, adding a catalyst dibutyltin dilaurate, the addition amount of which is 1wt% of the raw materials of the reactant, and reacting for 120min at 60 ℃ to obtain a secondary reactant.
S3, adding oxalyl dihydrazide as a hard segment unit II into a secondary reactant, wherein the molar ratio of the oxalyl dihydrazide to the secondary reactant is 1:1, reacting for 600min at 60 ℃ under the protection of inert gas to obtain the thermoplastic elastomer.
Example 4
The embodiment provides a high-strength and high-toughness thermoplastic elastomer with double hard phases, which comprises the following preparation steps:
s1, taking isopear mountain alcohol as a hard segment unit I, dissolving the isopear mountain alcohol into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the mol ratio of the isopear mountain alcohol to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzine and the caprolactone to obtain an initial reactant.
S2, dissolving an initial reactant and hexamethylene diisocyanate in an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to the hexamethylene diisocyanate is 1:2, adding a catalyst dibutyltin dilaurate, wherein the addition amount is 1wt% of the reactant raw material, and reacting for 120min at 60 ℃ to obtain a secondary reactant.
S3, adding oxalyl dihydrazide as a hard segment unit II into a secondary reactant, wherein the molar ratio of the oxalyl dihydrazide to the secondary reactant is 1:1, reacting for 600min at 60 ℃ under the protection of inert gas to obtain the thermoplastic elastomer.
Comparative example 1
The embodiment provides a single hard phase high strength, high toughness thermoplastic elastomer, the preparation steps include:
s1, taking hydrobenzidine as a hard segment unit, dissolving the hydrobenzidine into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the molar ratio of the hydrobenzidine to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzidine and the caprolactone to obtain an initial reactant.
S2, dissolving an initial reactant and hexamethylene diisocyanate into an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to the hexamethylene diisocyanate is 1:2, adding a catalyst dibutyl tin dilaurate, wherein the addition amount is 1wt% of the reactant raw material, and reacting for 120min at 60 ℃ to obtain the thermoplastic elastomer.
Comparative example 2
The embodiment provides a single hard phase high strength, high toughness thermoplastic elastomer, the preparation steps include:
s1, taking isopear mountain alcohol as a hard segment unit, dissolving the isopear mountain alcohol into N, N' -dimethylformamide solution, adding caprolactone and catalyst stannous octoate, wherein the molar ratio of the hydrobenzine to the caprolactone is 10:1, heating the catalyst to 100 ℃ by 1 weight percent of the reactant raw material, reacting for 12 hours under the action of the catalyst, and carrying out ring-opening polymerization reaction on the hydrobenzine and the caprolactone to obtain an initial reactant.
S2, dissolving an initial reactant and hexamethylene diisocyanate into an N, N' -dimethylformamide solution, wherein the molar ratio of the initial reactant to the hexamethylene diisocyanate is 1:2, adding a catalyst dibutyl tin dilaurate, wherein the addition amount is 1wt% of the reactant raw material, and reacting for 120min at 60 ℃ to obtain the thermoplastic elastomer.
The thermoplastic elastomers prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests such as tensile strength, elongation at break and toughness, and the performance test results are shown in Table 1 below:
TABLE 1
| Sample of | Intensity (MPa) | Elongation at break (%) | Toughness (MJ/m) 3 ) |
| Example 1 | 47.8±5.2 | 1746±187 | 500±24 |
| Example 2 | 42.3±3.1 | 1543±181 | 375±31 |
| Example 3 | 29.4±3.2 | 1896±201 | 373±42 |
| Example 4 | 27.3±2.9 | 2241±250 | 384±38 |
| Comparative example 1 | 21.6±1.8 | 596±56 | 110±19 |
| Comparative example 2 | 14.3±1.7 | 503±78 | 60±13 |
Compared with the thermoplastic elastomer synthesized by adopting a single hard phase and a single soft phase in the comparative example, the thermoplastic elastomer synthesized by adopting the double hard phases has obvious improvement in strength and toughness. As shown in the above table, the strength of the single hard phase thermoplastic elastomer prepared from the hydrobenzidine, caprolactone and hexamethylene diisocyanate prepared in comparative example 1 was about 21.6MPa, and the strength of the single hard phase thermoplastic elastomer prepared from the isoglucitol, caprolactone and hexamethylene diisocyanate prepared in comparative example 1 was only about 14.3MPa. The strength of the thermoplastic elastomer prepared by adopting the hydrobenzil cigarette and the oxalyl dihydrazide or the isopear mountain alcohol and the oxalyl dihydrazide as the double hard phases is about 42.3MPa and 27.3MPa respectively, and the strength is improved by about 100 percent. Meanwhile, in terms of toughness performance, the toughness of the single hard phase thermoplastic elastomers prepared in comparative example 1 and comparative example 2 is about 110MJ/m3 and 60MJ/m3, and the toughness of the dual hard phase thermoplastic elastomer prepared in the invention reaches 375MJ/m 3 And 384MJ/m 3 The performance of the material is directly improved by 3 times or even 6 times. The tensile strength of the thermoplastic elastomer with double hard phases prepared by the invention can reach more than 50MPa, the elongation at break is close to 2000 percent, and the toughness can reach 500MJ/m at maximum 3 The effect is obviously improved.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. A preparation method of a double hard phase high-strength and high-toughness thermoplastic elastomer is characterized by comprising the following preparation steps:
s1, dissolving a hard segment unit I in a solvent, and then adding a ring-opening monomer and a catalyst, wherein the hard segment unit I and the ring-opening monomer are polymerized to obtain an initial reactant;
s2, mixing the initial reactant in the S1 with diisocyanate in a solvent, and adding a catalyst to react to obtain a secondary reactant;
s3, adding the hard segment unit II into a secondary reactant, and enabling the hard segment unit II to react with the secondary reactant to obtain a double-hard-phase thermoplastic elastomer;
the hard segment unit I is a glycol organic matter, and the expression of the glycol organic matter is as follows:
wherein R1 represents an organic unit containing an aromatic hydrocarbon structure or a cyclic structure;
the ring-opening monomer is caprolactone;
the hard segment unit II is a diamine organic compound and comprises one or more of 1, 2-ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, oxalyl dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and adipoyl diamine.
2. The method for preparing a dual hard phase high strength, high toughness thermoplastic elastomer according to claim 1, wherein the glycol organic matter comprises one or more of hydrobenzine and isopear mountain alcohol.
3. The process for preparing a dual hard phase, high strength, high toughness thermoplastic elastomer according to claim 1, wherein the molar ratio of hard segment unit one to ring-opening monomer in S1 is from 2 to 50:1.
4. The method for preparing the double hard phase high strength and high toughness thermoplastic elastomer according to claim 1, wherein the catalyst in S1 is stannous octoate, and the addition amount of the stannous octoate is 0.1-1% of the total mass of the hard segment unit I and the ring-opening monomer; the catalyst in S2 is dibutyl tin dilaurate, and the addition amount of the dibutyl tin dilaurate is 0.1-1% of the total mass of the initial reactant and the diisocyanate.
5. The process for producing a dual hard phase high strength, high toughness thermoplastic elastomer according to claim 1, wherein the polymerization temperature in S1 is 100 to 150℃and the reaction time is 60 to 1200 minutes.
6. The process for preparing a dual hard phase, high strength, high toughness thermoplastic elastomer according to claim 1, wherein the ratio of the starting reactant to diisocyanate in S2 is 1-8:2-10.
7. The process for producing a dual hard phase high strength, high toughness thermoplastic elastomer according to claim 1, wherein the reaction temperature in S2 is 40-100℃and the reaction time is 10-120 min.
8. The process for preparing a dual hard phase, high strength, high toughness thermoplastic elastomer according to claim 1, wherein the molar ratio of hard segment unit two to secondary reactant in S3 is 1 to 10:1 to 10.
9. The process for producing a dual hard phase high strength, high toughness thermoplastic elastomer according to claim 1, wherein the reaction temperature in S3 is 40-100℃and the reaction time is 60-1200 min.
10. Thermoplastic elastomer obtainable by the process for the preparation of a dual hard phase, high strength, high toughness thermoplastic elastomer according to any one of claims 1 to 9.
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