CN118325031A - Amino compound modified polyurethane elastomer and preparation method thereof - Google Patents
Amino compound modified polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN118325031A CN118325031A CN202410590629.XA CN202410590629A CN118325031A CN 118325031 A CN118325031 A CN 118325031A CN 202410590629 A CN202410590629 A CN 202410590629A CN 118325031 A CN118325031 A CN 118325031A
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- diisocyanate
- chain extender
- polyurethane elastomer
- amino compound
- modified polyurethane
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- -1 Amino compound Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920003225 polyurethane elastomer Polymers 0.000 title claims description 41
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- 239000004970 Chain extender Substances 0.000 claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 19
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 12
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 241001112258 Moca Species 0.000 description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004427 diamine group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 125000003827 glycol 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
- 208000014674 injury Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to an amino compound modified polyurethane and a preparation method thereof, belonging to the technical field of impact-resistant protective materials. The method comprises the following steps: s1, uniformly mixing the polyol after vacuum dehydration with diisocyanate, adding a catalyst under stirring, and reacting to obtain a prepolymer I; s2, dissolving a chain extender in an organic solvent to obtain a chain extender mixture II; s3, adding the chain extender mixture II into the prepolymer I, and removing the organic solvent after the reaction to obtain the polyurethane impact resistant material containing the amino bond. The amino compound in the amino compound modified polyurethane is used as a chain extender to form a ureido with stronger polarity, and stronger bifurcate hydrogen bonds are formed between hard segments, so that the interaction between the hard segments is increased, the microphase separation degree is improved, and the mechanical property of the polyurethane is improved.
Description
Technical Field
The invention relates to an amino compound modified polyurethane elastomer and a preparation method thereof, belonging to the technical field of impact-resistant protective materials.
Background
Impact is a very common phenomenon, as small as hammer nails in life, as large as collisions between automobiles, ships and aircraft, which are classified as impact phenomena. Polyurethane elastomer (PU) needs to possess characteristics such as softness, light and comfortable when as individual impact protection material, can absorb and disperse impact energy when receiving external force impact to avoid and alleviate the injury to the human body, play key role in protecting the threat aspects such as blunt ware, sharp nail, sword and stab as personal protective equipment in daily life even for military use, our building structure also often face the condition of suffering the impact simultaneously, and most common for example high-rise building is suffered the striking of wind-induced aircraft, and the aircraft is suffered the striking of bird and hail and all can put forward serious challenge to the ability of current engineering structure bearing impact load. Impact loads are characterized by their instantaneous impact, i.e. the forces vary widely in a very short period of time, and the resulting losses are unpredictable and pose a serious threat to personal and social security.
At present, the protection structure is mostly made of metal materials, and in order to reduce destructive damage of impact load to the structures, the traditional protection and impact-resistant measures usually consider to reinforce building components by adopting steel plates, aluminum plates and the like; however, when the steel plates are used for engineering and practical reinforcement of the structural member, the weight of the building structural member is obviously increased due to the addition of the steel plates, and the reinforcement cost and the reinforcement process are high.
However, the quality of the existing polyurethane protective articles is general, the user experience of users is affected, even the safety problem of users cannot be protected, and when the polyurethane is applied to the transportation industry, the building industry or sports equipment, the improvement of the impact resistance of the polyurethane is very important. For example, in the production of sports goods such as various exercise equipment, sports facilities, and protective equipment, it is necessary to produce materials having more excellent properties such as elasticity, toughness, impact resistance, etc. to secure the quality of exercise, performance of competition, and life safety. Or if the polyurethane material is used as a sole, the polyurethane material has certain elasticity, but has limited capability of absorbing impact force, and is easy to impact ankle and knee in the process of sports.
However, the current impact-resistant polyurethane elastomer materials use glycol chain extenders with different chain lengths to modify the structure and morphology. However, when it is subjected to external forces, stress concentration and cracking may occur, and various signs indicate that the impact resistance is still to be improved.
Disclosure of Invention
The technical solution of the invention is as follows: the polyurethane elastomer modified by the amino compounds overcomes the defects of strength and shock resistance of polyurethane materials, the double-fork hydrogen bonds formed between hard segments of the polyurethane elastomer are stronger, acting force between the hard segments is also enhanced, micro-phase separation is promoted, mechanical properties are enhanced, and shock resistance is also more excellent.
The technical scheme of the invention is as follows:
an amino compound modified polyurethane elastomer, the structural formula of which is as follows:
the molecular weight of the modified polyurethane elastomer is 2000-3000.
A preparation method of an amino compound modified polyurethane elastomer comprises the following steps:
s1, uniformly mixing the polyol after vacuum dehydration with diisocyanate, adding a catalyst under the condition of stirring (the stirring speed is 200r/min and the nitrogen environment is protected), reacting to obtain a prepolymer I, and cooling to room temperature;
The vacuum dehydration of the polyol is as follows: vacuum dehydrating the polyol at 105-120 deg.c, cooling to 80-85 deg.c and mixing with diisocyanate;
s2, dissolving a chain extender in an organic solvent to obtain a chain extender mixture II;
s3, adding the chain extender mixture II into the prepolymer I, reacting (the reaction time is more than 30min, stirring is carried out during the reaction, the stirring speed is 200r/min, the nitrogen environment is protected), and removing the organic solvent to obtain the polyurethane impact resistant material containing the amino bond.
The method for removing the organic solvent comprises the following steps: pouring the mixture after the reaction into a polytetrafluoroethylene mold, placing the mold into a vacuum oven, and curing the mold for more than 24 hours at 70-90 ℃ after the mold is vacuumized for 5-10min at room temperature to obtain a polyurethane elastomer;
Preferably, in step S1, the polyhydric alcohol is selected from at least one of polytetrahydrofuran ether glycol (PTMEG), polytetramethylene glycol (PTMG), polypropylene glycol (PPG) and polyethylene glycol (PEG);
The number average molecular weight of the polyatomic alcohol is 1760-2080;
Preferably, in step S1, the diisocyanate is selected from at least one of 4,4' -diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI), 1,5' -Naphthalene Diisocyanate (NDI);
Preferably, in step S1, the molar ratio of the polyol to the diisocyanate is 1:2;
The catalyst is dibutyl tin dilaurate, and the dosage is 0.01-0.1% of the total mass of the polyol and the diisocyanate; the reaction temperature is 80-85 ℃; the reaction time was about 3 hours.
Preferably, in step S2, the chain extender is at least one of isophorone diamine (IPDA), p-phenylenediamine (english name p-PHENYLENEDIAMINE), 1, 6-hexamethylenediamine (english name 1, 6-Diaminohexane), and 4,4' -methylenebis (2-chloroaniline) (MOCA);
the organic solvent is at least one of N, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide;
Preferably, in step S2, the mass ratio of the chain extender to the organic solvent is 1: 40-65, the chain extender and the organic solvent are dissolved by ultrasonic waves at proper time so as to be uniformly mixed.
Preferably, in step S3, the molar ratio of chain extender mixture II to diisocyanate is 1:2; the reaction temperature is room temperature;
preferably, in step S3, the chain extender mixture II is synthesized with the prepolymer I by the steps of: firstly, the chain extender mixture II is added into a constant pressure dropping funnel, and is slowly and gradually added into the prepolymer I dropwise under the protection of nitrogen, and then the reaction is carried out for more than 30 minutes. After the reaction, the reaction solution is washed, filtered and dried in a vacuum oven to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides an amino compound modified polyurethane elastomer, which is novel high-performance impact-resistant polyurethane, and adopts diamine chain extender as chain extender, so that generated urea groups have stronger polarity, stronger bifurcate hydrogen bonds are formed between hard segments, acting force between the hard segments is enhanced, microphase separation is improved, and mechanical properties are enhanced. The polyurethane impact resistant material containing amino bonds with high hydrogen bond density can be formed by adopting the diamine chain extender with short branched chain and symmetry, which is beneficial to microphase separation, and has wider elastic platform area and higher mechanical strength. And various properties of the polymer are improved, the preparation process is simple, the operation is easy, and the method is suitable for commercial production.
The invention provides an amino compound modified polyurethane elastomer, wherein the reaction temperature of the prepolymer synthesis in the preparation of the polyurethane elastomer is 80-85 ℃ which is an important condition that the prepolymer can be successfully carried out.
The invention provides an amino compound modified polyurethane elastomer, wherein in the preparation of the polyurethane elastomer, the isocyanate content of a prepolymer needs to be controlled, and the excessive isocyanate content can cause the difficulty in molding a polyurethane structure and can not obtain the polyurethane elastomer; too many hydroxyl groups in the main raw materials can cause the mechanical property of polyurethane to be reduced.
The invention provides an amino compound modified polyurethane elastomer, which can change the response characteristic of a structure under impact loading, enhance the protective performance of the polyurethane elastomer and enable the polyurethane elastomer to have excellent impact resistance.
The invention provides an amino compound modified polyurethane elastomer, and an impact protection polyurethane material prepared by using a diamine chain extender is different from the traditional polyurethane material and has excellent impact resistance.
The invention provides an amino compound modified polyurethane elastomer which can be compounded with other organic and inorganic materials, so that a compound system presents relevant responsiveness in the protection process and has wide application prospect.
The invention relates to an amino compound modified polyurethane and a preparation method thereof, belonging to the technical field of impact-resistant protective materials. The method comprises the following steps: s1, uniformly mixing the polyol after vacuum dehydration with diisocyanate, adding a catalyst under stirring, and reacting to obtain a prepolymer I; s2, dissolving a chain extender in an organic solvent to obtain a chain extender mixture II; s3, adding the chain extender mixture II into the prepolymer I, and removing the organic solvent after the reaction to obtain the polyurethane impact resistant material containing the amino bond. The amino compound in the amino compound modified polyurethane is used as a chain extender to form a ureido with stronger polarity, and stronger bifurcate hydrogen bonds are formed between hard segments, so that the interaction between the hard segments is increased, the microphase separation degree is improved, and the mechanical property of the polyurethane is improved. The invention provides a preparation method of an amino compound modified polyurethane elastomer, which achieves the final aim by a solvent method.
Drawings
FIG. 1 is an infrared spectrum of an amino bond-containing polyurethane impact material prepared using different chain extenders (e.g., IPDA, p-phenylenediamine, moCA, 1, 6-hexamethylenediamine) in a polyurethane blank;
FIG. 2 is a graph showing the results of mechanical property testing of polyurethane impact resistant materials containing amine bonds prepared with different chain extenders (e.g., IPDA, p-phenylenediamine, moCA, 1, 6-hexamethylenediamine);
Table 1 shows the mechanical property test data of polyurethane impact resistant materials containing amino bonds prepared by using different chain extenders (such as IPDA, p-phenylenediamine, moCA, 1, 6-hexamethylenediamine);
Table 2 shows Hopkinson bar data for polyurethane impact materials containing amine linkages prepared using different chain extenders (e.g., IPDA, p-phenylenediamine, moCA, 1, 6-hexamethylenediamine).
Detailed Description
The following description is of the preferred embodiments of the invention and is not intended to limit the scope of the invention, but is intended to cover any modifications, equivalents, and improvements within the spirit and principles of the invention.
Example 1
In this example, the molecular weight of polytetrahydrofuran ether glycol is 2000, isophorone diisocyanate is used as diisocyanate, IPDA is used as chain extender, and the molecular weight is 170.3.
500G of polytetrahydrofuran ether glycol is added into a reaction kettle, the temperature is raised to 120 ℃ after the tightness is checked, the raw materials are stirred at the speed of 200r/min, and the reaction is carried out for 4 hours until the dehydrated P2000 is obtained.
20G of polytetrahydrofuran ether glycol, 4.44g of isophorone diisocyanate and one drop of dibutyltin dilaurate are added into a 100mL three-neck flask, the temperature is raised to 85 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after 3h of reaction.
Dissolving the prepolymer obtained by the reaction in the step (2) in N, N-dimethylformamide, and fully dissolving the prepolymer in the room temperature environment.
Taking 1.70g of IPDA and N, N-dimethylformamide, fully mixing, then adding the mixture drop by drop into the container in the step (2), and reacting for 30min at room temperature after the mixture is fully added; pouring the polyurethane into a polytetrafluoroethylene container, and then placing the container into a baking oven at 70 ℃ for curing for 12 hours to obtain the polyurethane impact-resistant material containing amino bonds.
The structural formula of the chain extender IPDA is as follows:
Example 2
In this example, the molecular weight of polytetrahydrofuran ether glycol is 2000, the diisocyanate is isophorone diisocyanate, the chain extender is p-phenylenediamine, and the molecular weight is 108.1.
500G of polytetrahydrofuran ether glycol is added into a reaction kettle, the temperature is raised to 120 ℃ after the tightness is checked, the raw materials are stirred at the speed of 200r/min, and the reaction is carried out for 4 hours until the dehydrated P2000 is obtained.
20G of polytetrahydrofuran ether glycol, 4.44g of isophorone diisocyanate and one drop of dibutyltin dilaurate are added into a 100mL three-neck flask, the temperature is raised to 85 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after 3h of reaction.
Dissolving the prepolymer obtained by the reaction in the step (2) in N, N-dimethylformamide, and fully dissolving the prepolymer in the room temperature environment.
Taking 1.08g of p-phenylenediamine and N, N-dimethylformamide, fully mixing, then adding the mixture drop by drop into the container in the step (2), and reacting for 30min at room temperature after all the mixture is added; pouring the polyurethane into a polytetrafluoroethylene container, and then placing the container into a baking oven at 70 ℃ for curing for 12 hours to obtain the polyurethane impact-resistant material containing amino bonds.
The structural formula of the chain extender p-phenylenediamine is as follows:
Example 3
In the embodiment, the molecular weight of polytetrahydrofuran ether glycol is 2000, isophorone diisocyanate is selected as diisocyanate, the chain extender is 1, 6-hexamethylenediamine, and the molecular weight is 116.2.
500G of polytetrahydrofuran ether glycol is added into a reaction kettle, the temperature is raised to 120 ℃ after the tightness is checked, the raw materials are stirred at the speed of 200r/min, and the reaction is carried out for 4 hours until the dehydrated P2000 is obtained.
20G of polytetrahydrofuran ether glycol, 4.44g of isophorone diisocyanate and one drop of dibutyltin dilaurate are added into a 100mL three-neck flask, the temperature is raised to 85 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after 3h of reaction.
Dissolving the prepolymer obtained by the reaction in the step (2) in N, N-dimethylformamide, and fully dissolving the prepolymer in the room temperature environment.
1.16G of 1, 6-hexamethylenediamine is taken and melted in a baking oven, then is fully mixed with N, N-dimethylformamide, and is added into the container in the step (2) drop by drop, and after all the materials are added, the materials react for 30min at room temperature; pouring the polyurethane into a polytetrafluoroethylene container, and then placing the container into a baking oven at 70 ℃ for curing for 12 hours to obtain the polyurethane impact-resistant material containing amino bonds.
The chain extender 1, 6-hexamethylenediamine has the following structural formula:
Example 4
In this example, the molecular weight of polytetrahydrofuran ether glycol is 2000, isophorone diisocyanate is used as diisocyanate, the chain extender is 4,4' -methylenebis (2-chloroaniline) (MOCA), and the molecular weight is 267.2.
500G of polytetrahydrofuran ether glycol is added into a reaction kettle, the temperature is raised to 120 ℃ after the tightness is checked, the raw materials are stirred at the speed of 200r/min, and the reaction is carried out for 4 hours until the dehydrated P2000 is obtained.
20G of polytetrahydrofuran ether glycol, 4.44g of isophorone diisocyanate and one drop of dibutyltin dilaurate are added into a 100mL three-neck flask, the temperature is raised to 85 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after 3h of reaction.
Dissolving the prepolymer obtained by the reaction in the step (2) in N, N-dimethylformamide, and fully dissolving the prepolymer in the room temperature environment.
Taking 2.67g of 4,4' -methylenebis (2-chloroaniline) and N, N-dimethylformamide, adding the mixture into the container in the step (2) drop by drop, and reacting the mixture at room temperature for 30min after the mixture is fully added; pouring the polyurethane into a polytetrafluoroethylene container, and then placing the container into a baking oven at 70 ℃ for curing for 12 hours to obtain the polyurethane impact-resistant material containing amino bonds.
The chain extender 4,4' -methylenebis (2-chloroaniline) has the following structural formula:
Comparative example 1
The comparative example is the preparation of polyurethane matrix
500G of polytetrahydrofuran ether glycol is added into a reaction kettle, the temperature is raised to 120 ℃ after the tightness is checked, the raw materials are stirred at the speed of 200r/min, and the reaction is carried out for 4 hours until dehydrated polytetrahydrofuran ether glycol is obtained.
275G of polytetrahydrofuran ether glycol dehydrated in the step (1) and 225g of 4,4' -diphenylmethane diisocyanate are added into a reaction kettle, the temperature is raised to 80 ℃, the raw materials are stirred at the speed of 200r/min to be uniformly mixed, and the polyurethane prepolymer is obtained after the reaction for 4 hours.
36G of polytetrahydrofuran ether glycol, 10g of polyether 330N polyol, 3.75g of 1, 4-butanediol and 1g of defoamer in the step (1) are sequentially added into a container, 44g of the prepolymer in the step (2) is added, the solution is stirred for 20s at a stirring rate of 2000r/min, then the solution is pumped for 4min in a vacuum oven, and the solution is poured into a polytetrafluoroethylene container and then is put into an oven at 70 ℃ for curing for more than 2h, so as to obtain the polyurethane elastomer.
The infrared spectroscopic test was conducted on the end products prepared in examples 1 to 4 and comparative example 1, and the results are shown in fig. 1, and the infrared spectroscopic results of the end products obtained in examples 1 to 4 are substantially similar to those of comparative example 1, except that the absorption peak occurring in the vicinity of 1700cm -1 indicates the presence of the urethane carbonyl group stretching vibration, and the presence of the urea bond is more reactive than the c=o stretching vibration of comparative example 1.
The tensile test was performed on the final products prepared in examples 1 to 4 and comparative example 1, under the condition that a 500N mechanical sensor was used, the size of the test sample was selected to be a small test sample of 2mm×35mm, and the tensile rate was 50mm/min, as shown in fig. 2, it can be obtained that the mechanical properties of the polyurethane sample after the modification with the amine-based compound are shown in table 1, the tensile strength after the treatment with IPDA is 32MPa, the tensile strength after the treatment with p-phenylenediamine is 24MPa, the tensile strength after the treatment with 1, 6-hexamethylenediamine is 14MPa, and 255%, 167% and 55.5% of the tensile strength (9 MPa) of the polyurethane elastomer are improved, and the elongation at break after the treatment with 4,4' -methylenebis (2-chloroaniline) in example 4 is 2300% of the polyurethane elastomer is improved by 170% of the tensile strength (850%) compared with the polyurethane elastomer in comparative example 1, which indicates that the amine-based compound modified polyurethane can be used as a polyurethane elastomer modifier, and the polyurethane elastomer has greatly improved mechanical properties and elongation at break.
The Hopkinson bar test is performed on the end products prepared in examples 1 to 4 and comparative example 1, and the size of the test sample is 13mm in diameter, so that the mechanical properties of the polyurethane sample after being modified by the amino substances are shown in table 2, the compressive stress after being treated by IPDA is 30MPa, the compressive stress after being treated by p-phenylenediamine is 25.8MPa, the compressive stress after being treated by 1, 6-hexamethylenediamine is 27.9MPa, and the compressive stress after being treated by 4,4' -methylenebis (2-chloroaniline) is 22.2MPa, and compared with the compressive stress (12 MPa) of the polyurethane elastomer in comparative example 1, the improvement of 150%, 115%, 132.5% and 85% is achieved, so that the amino compound modified polyurethane can be used as a polyurethane elastomer modifier to greatly improve the impact resistance of polyurethane.
TABLE 1 mechanical Property test data
Table 2 impact resistance test data
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. An amino compound modified polyurethane elastomer is characterized in that the modified polyurethane elastomer has the structural formula:
The molecular weight of the modified polyurethane elastomer is 1000-3000.
2. The preparation method of the amino compound modified polyurethane elastomer is characterized by comprising the following steps of:
S1, uniformly mixing the polyol after vacuum dehydration with diisocyanate, adding a catalyst under stirring, reacting to obtain a prepolymer I, and cooling to room temperature;
s2, dissolving a chain extender in an organic solvent to obtain a chain extender mixture II;
s3, adding the chain extender mixture II into the prepolymer I, and removing the organic solvent after the reaction to obtain the polyurethane impact resistant material containing the amino bond.
3. The method for preparing the amino compound modified polyurethane elastomer according to claim 2, which is characterized in that:
In the step S1, the stirring speed is 200r/min, and the nitrogen environment is protected; ;
the vacuum dehydration of the polyol is as follows: vacuum dehydrating the polyol at 105-120deg.C, and cooling to 80-85deg.C;
the polyatomic alcohol is at least one selected from polytetrahydrofuran ether glycol, polytetramethylene glycol, polypropylene glycol and polyethylene glycol;
The number average molecular weight of the polyatomic alcohol is 1760-2080;
The diisocyanate is at least one selected from 4,4' -diphenylmethane diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and 1,5' -naphthalene diisocyanate;
The molar ratio of the polyatomic alcohol to the diisocyanate is 1:2;
The catalyst is dibutyl tin dilaurate, and the dosage is 0.01% -0.1% of the total mass of the polyol and the diisocyanate; the reaction temperature is 80-85 ℃; the reaction time is 2.5-3.5h.
4. The method for preparing the amino compound modified polyurethane elastomer according to claim 2, which is characterized in that:
in the step S2, the chain extender is at least one of isophorone diamine, p-phenylenediamine, 1, 6-hexamethylenediamine and 4,4' -methylenebis;
the organic solvent is at least one of N, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide;
the mass ratio of the chain extender to the organic solvent is 1:40-65;
the chain extender and the organic solvent are dissolved by ultrasonic waves so as to be uniformly mixed.
5. The method for preparing the amino compound modified polyurethane elastomer according to claim 2, which is characterized in that:
In the step S3, the molar ratio of the chain extender mixture II to the diisocyanate is 1:2; the reaction temperature is room temperature; the reaction time is 30min-2h; stirring is carried out during mixing, the stirring speed is 200r/min, and the nitrogen environment is protected.
6. The method for preparing the amino compound modified polyurethane elastomer according to claim 2, which is characterized in that:
The method for removing the organic solvent comprises the following steps: pouring the mixture after the reaction into a polytetrafluoroethylene mold, placing the mold into a vacuum oven, and curing the mold for more than 24 hours at 70-90 ℃ after the mold is vacuumized for 5-10min at room temperature to obtain the polyurethane elastomer.
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