CN117487123A - High-toughness high-strength polyurethane rock climbing fulcrum material and preparation method thereof - Google Patents
High-toughness high-strength polyurethane rock climbing fulcrum material and preparation method thereof Download PDFInfo
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- CN117487123A CN117487123A CN202311846508.9A CN202311846508A CN117487123A CN 117487123 A CN117487123 A CN 117487123A CN 202311846508 A CN202311846508 A CN 202311846508A CN 117487123 A CN117487123 A CN 117487123A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 31
- 230000009194 climbing Effects 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 239000011435 rock Substances 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 title claims abstract description 25
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 amine ether polyol Chemical class 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000002250 absorbent Substances 0.000 claims abstract description 7
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 150000003384 small molecules Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 150000001718 carbodiimides Chemical group 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 3
- 230000000655 anti-hydrolysis Effects 0.000 claims description 3
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000011496 polyurethane foam Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
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- 238000005299 abrasion Methods 0.000 description 11
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 7
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- 230000008859 change Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000258957 Asteroidea Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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Classifications
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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
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane materials, and particularly relates to a high-toughness high-strength polyurethane rock climbing fulcrum material and a preparation method thereof. The composite material comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 27-43 parts of polyether polyol, 7-12 parts of small molecule chain extender, 43-64 parts of amine ether polyol, 0.8-1.3 parts of water absorbent, 0.2-0.5 part of hydrolysis inhibitor, 0.2-0.5 part of coupling agent and 0.1-0.5 part of catalyst; the component B comprises the following raw materials in parts by mass: 0-6 parts of polyester polyol, 16-32 parts of ether ester polyol and 62-84 parts of isocyanate. The invention has high toughness, high strength, high wear resistance and excellent ageing resistance. The invention also provides a preparation method of the alloy, which is formed by casting at normal temperature and has simple operation process.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to a high-toughness high-strength polyurethane rock climbing fulcrum material and a preparation method thereof.
Background
Along with the continuous improvement of social life quality, rock climbing exercise becomes interesting exercise favored by indoor and outdoor exercise lovers, and the quality problem of rock climbing support points is related to the safety and durability of the exercise. At present, most of common rock climbing fulcra in the market are polymer materials such as epoxy resin, phenolic resin and the like, but the volatility of smell, ageing resistance of the materials and high rigidity often influence the use effect and the service life of the materials, and meanwhile, resource waste can be generated in the preparation and forming process, so that the rock climbing fulcra does not accord with the environmental protection and energy saving trend of the current state.
Rock climbing exercises can be divided into indoor rock climbing and outdoor rock climbing, and when the rock climbing support point is used for outdoor exercises, higher performance requirements are required. The outdoor winter-summer-hot air temperature difference, extreme weather such as rain and snow and the like, and loss and aging after natural insolation, and the influence factors can change the performance of the rock climbing support point.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-toughness high-strength polyurethane rock climbing fulcrum material which has high toughness, high strength, high wear resistance and excellent ageing resistance. The invention also provides a preparation method of the alloy, which is formed by casting at normal temperature and has simple operation process.
The high-toughness high-strength polyurethane rock climbing fulcrum material comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass:
27-43 parts of polyether polyol,
7-12 parts of small molecule chain extender,
43-64 parts of amine ether polyol,
0.8 to 1.3 parts of water absorbent,
0.2 to 0.5 part of hydrolysis resistance agent,
0.2-0.5 part of coupling agent,
0.1-0.5 part of a catalyst;
the component B comprises the following raw materials in parts by mass:
0-6 parts of polyester polyol,
16-32 parts of ether ester polyol,
62-84 parts of isocyanate.
Preferably, the mass ratio of the component A to the component B is 100 (90-110).
Preferably, the polyether polyol is inovaol F330N, a number average molecular weight 5000, a functionality of 3, manufactured by new materials limited, northwest, shandong.
Preferably, the small molecule chain extender is 3, 3-dichloro-4, 4-diaminodiphenylmethane (MOCA); the water absorbent is XS-3A; the hydrolysis resisting agent is carbodiimide; the coupling agent is gamma-glycidol ether oxypropyl trimethoxy silane (KH-560); the catalyst is one or two of bismuth neodecanoate and oleic acid.
Preferably, the amine ether polyol is prepared by the following steps: preparing raw materials of diethyl toluenediamine and propylene oxide according to a mass ratio of 100:75, adding all the diethyl toluenediamine into a reaction vessel after the reaction vessel is dried and free of impurities, starting stirring and heating to 90 ℃, adding 15% -20% of the total amount of the propylene oxide into the reaction vessel, starting the reaction, stopping heating when the pressure of the reaction vessel is reduced from 0.3-0.4 MPa to 0.15MPa, adding the rest propylene oxide, controlling the temperature to be not more than 110 ℃, and reacting at 95-105 ℃ for 24-30 hours to obtain the catalyst. Further preferred, the amine ether polyol is E405, molecular weight 500, functionality 4, manufactured by Shandong monoway polyurethane Co., ltd.
Preferably, the polyester polyol is PE-2316, a number average molecular weight 1600, a functionality of 2.05, manufactured by Shandong mononwei polyurethane Co., ltd.
Preferably, the ether ester polyol is prepared by: adding adipic acid, terephthalic acid, PTMG650, 1, 6-hexanediol and triisopropanolamine into a reaction vessel according to the mass ratio of 70:30:107:77.5:8.3, starting stirring, starting water discharge when the temperature is raised to 135-140 ℃, controlling the condensation reflux temperature to 100-105 ℃, then slowly raising the temperature to 220-240 ℃ and controlling the temperature raising time to be within 10-15 h, vacuumizing after terephthalic acid is completely opened in the reaction system, keeping the vacuum degree at-0.09 to-0.1 MPa, sampling and testing the hydroxyl value and the acid value of the reaction system, and performing index qualification discharging when the hydroxyl value reaches 72+/-2 mgKOH/g and the acid value is smaller than 1.0 mgKOH/g. Further preferred, the ether ester polyol is PE-3416 produced by Shandong monoway polyurethane Co., ltd, having a molecular weight of 1600 and a functionality of 2.05.
Preferably, the isocyanate is one or more of diphenylmethane diisocyanate, carbodiimide-uretonimine modified MDI, polymethylene polyphenyl isocyanate (PM 200), toluene diisocyanate (TDI-80).
The preparation method of the high-toughness high-strength polyurethane rock climbing fulcrum material comprises the following steps:
(1) And (3) preparation of the component A: mixing polyether polyol, a small molecular chain extender, amine ether polyol, a water absorbent, an anti-hydrolysis agent, a coupling agent and a catalyst, using a high-speed dispersing machine for 1000-1500 r/min, fully and uniformly stirring, vacuumizing, removing bubbles and packaging to obtain a component A;
(2) And (3) preparation of a component B: reacting polyester polyol, ether ester polyol and isocyanate with the moisture content controlled below 0.05 percent for 2-3 hours at the temperature of 75-85 ℃ to obtain a prepolymer with the isocyanate content of 18.5-24.5 percent, vacuumizing, removing bubbles and packaging to obtain a component B;
(3) Mixing the component A and the component B at room temperature, uniformly stirring by using a high-speed stirrer at 500-1500 r/min, vacuumizing to remove bubbles, pouring into a mold, curing at room temperature for 3-7 days or completely hardening, and then placing into a baking oven at 80-100 ℃ for curing for 8-12 hours to obtain the modified polyurethane foam.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the amine ether polyol prepared by the reaction of the diethyl toluenediamine and the epoxypropane is used as the raw material of the component A, so that the high toughness and high strength of the polyurethane rock climbing pivot are ensured, the high temperature resistance and ageing resistance of the material are improved, the use temperature range of the polyurethane rock climbing material is increased, and the service life of the polyurethane rock climbing material is prolonged;
2. according to the invention, adipic acid and terephthalic acid are used as dicarboxylic acid of polyether ester, PTMG650, triisopropanolamine and 1, 6-hexanediol are used as raw materials of component B, so that the product has the characteristics of high hardness and high temperature resistance, and has higher toughness and wear resistance;
3. the amine ether polyol and the ether ester polyol are synthesized by introducing different raw materials, so that the advantages of polyether polyol and polyester polyol are combined, the ageing resistance and the high temperature resistance of the system are improved, the high toughness and the high hardness are realized, and the application range and the application scene of the polyurethane rock climbing fulcrum material are greatly expanded; the shape and the color of the finished product can be changed according to different requirements, the toughness is high, the wear resistance is good, the high-temperature can still keep higher hardness, and the properties of the outdoor natural environment are not obviously different after being placed for three months;
4. the invention has simple manufacturing process and low energy consumption, can be quickly solidified and molded without the need of a preliminary preheating molding stage, and is easy for large-scale industrial production.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples.
All materials used in the examples, except as specified, were either commercially available or prepared by existing methods. The raw materials in the examples all had moisture contents of 0.05% or less.
Some of the raw material parameters of examples 1 to 4 and comparative examples 1 to 4 are as follows:
inonol F330N: polyether polyol, number average molecular weight 5000, functionality 3, new material limited of norwegian in shandong;
MOCA: small molecule chain extender, 3-dichloro-4, 4-diaminodiphenylmethane, a company of special fine chemical industry, hunan, suzhou, city;
e405: amine ether polyol, number average molecular weight 500, functionality 4, shandong monoowei polyurethane stock, inc;
diethyl toluene diamine: amine ether polyol raw material, shandong Starfish chemical Co., ltd.
Propylene oxide: amine ether polyol raw material, shandong Kaolin chemical Co., ltd.
XS-3A: water-absorbing agent, large Lian Haixin chemical company, inc;
carbodiimide: hydrolysis inhibitor, sangtong New Material technology Co., ltd;
KH560: silane coupling agent, gamma-glycidol ether oxypropyl trimethoxysilane, isman technology Co;
CU-A: oleic acid catalyst, shandong Naen Biotechnology Co., ltd;
CB-18: bismuth neodecanoate, available from taixing city Cheng Ling, inc;
MDI-50: diphenylmethane diisocyanate, tabacco to Van Chemie group Co., ltd;
PM200: polymethylene polyphenyl isocyanate, tabacco to the chemical group of Vanilla Co., ltd;
CD-C: carbodiimide-uretonimine modified MDI, kechua polymer (chinese) limited;
TDI-80: toluene diisocyanate, a product of the company Van Chemie, inc.;
PE-2316: polyester polyol having a number average molecular weight of 1600 and a functionality of 2.05, available from shandong monoowei polyurethane stock, inc;
PE-3416: the ether ester polyol has a number average molecular weight of 1600 and a functionality of 2.05, available from Shandong mononoc polyurethane Co., ltd.
Adipic acid: organic dibasic acid, shandong Hua Lu constant rise chemical Co., ltd.
Terephthalic acid: dicarboxylic acids, constant force petrochemical Co., ltd.
PTMG650: polyether polyol, number average molecular weight 650, functionality 2, china petrochemical group Co.
Triisopropanolamine: alcoholic amine polyol, red Baoli group Co., ltd.
1, 6-hexanediol: small molecule alcohols, yuanli chemical group Co., ltd.
Example 1
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 34 parts of INOVOL F330N, 10 parts of MOCA, 54 parts of E405, 1.0 part of XS-3A, 0.5 part of carbodiimide, 0.3 part of KH560, 0.16 part of CU-A and 0.04 part of CB-18, using a high-speed disperser 1300r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 25 parts of PE-3416 and 75 parts of CD-C (compact disc-C) in parts by weight, slowly heating to 78 ℃, reacting for 2.5 hours to obtain a prepolymer with 20.7% of isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:110, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 7 days, and curing in a 100 ℃ oven for 10 hours to obtain the composite material.
Example 2
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 27 parts of INOVOL F330N, 7 parts of MOCA, 64 parts of E405, 0.8 part of XS-3A, 0.2 part of an anti-hydrolysis agent, 0.5 part of KH560, 0.45 part of CU-A and 0.05 part of CB-18, using a high-speed dispersing machine 1000r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 16 parts of PE-3416, 67.2 parts of CD-C and 16.8 parts of MDI-50 in parts by weight, slowly heating to 75 ℃, reacting for 2 hours to obtain a prepolymer with 24.5% isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:100, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, completely hardening, and then placing into a 100 ℃ oven for curing for 12 hours to obtain the composite material.
Example 3
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 43 parts of INOVOL F330N, 12 parts of MOCA, 43 parts of E405, 0.9 part of XS-3A, 0.3 part of carbodiimide, 0.4 part of KH560, 0.37 part of CU-A and 0.03 part of CB-18, using a high-speed disperser 1500r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 16 parts of PE-3416, 6 parts of PE-2316, 63 parts of CD-C and 15 parts of PM-200, slowly heating to 75 ℃, reacting for 3 hours to obtain a prepolymer with the isocyanate content of 21.9%, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:90, stirring uniformly at room temperature by using a 1500r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 5 days, and curing in a 90 ℃ oven for 8 hours to obtain the composite material.
Example 4
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: 100 parts by mass of component A, namely mixing 40 parts of INOVOL F330N, 8 parts of MOCA, 50 parts of E405, 1.3 parts of XS-3A, 0.4 part of carbodiimide, 0.2 part of KH560, 0.08 part of CU-A and 0.02 part of CB-18, using a high-speed dispersing machine 1200r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 32 parts of PE-3416, 6 parts of PE-2316, 40.3 parts of CD-C, 12.4 parts of MDI-50 and 9.3 parts of TDI-80, slowly heating to 80 ℃ for 3 hours, reacting to obtain a prepolymer with 18.5% of isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:110, stirring uniformly at room temperature by using a 500r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 3 days, and curing in an oven at 80 ℃ for 8 hours to obtain the composite material.
Comparative example 1
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 34 parts of INOVOL F330N, 10 parts of MOCA, 54 parts of E405, 1.0 part of XS-3A, 0.5 part of carbodiimide, 0.3 part of KH560, 0.16 part of CU-A and 0.04 part of CB-18, using a high-speed disperser 1300r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 25 parts of PE2316 and 75 parts of CD-C (compact disc-C) in parts by weight, slowly heating to 78 ℃, reacting for 2.5 hours to obtain a prepolymer with 20.7% of isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:110, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 7 days or curing at the temperature of 100 ℃ for 10 hours, and finally obtaining the modified epoxy resin.
Comparative example 2
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 34 parts of INOVOL F330N, 10 parts of MOCA, 54 parts of C305 (New materials Co., ltd., yinuo-Norway, shandong), 1.0 part of XS-3A, 0.5 part of carbodiimide, 0.3 part of KH560, 0.16 part of CU-A and 0.04 part of CB-18, and then fully stirring uniformly by using a high-speed disperser 1300r/min, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 25 parts of PE-3416 and 75 parts of CD-C (compact disc-C) in parts by weight, slowly heating to 78 ℃, reacting for 2.5 hours to obtain a prepolymer with 20.7% of isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:110, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 7 days or curing at the temperature of 100 ℃ for 10 hours, and finally obtaining the modified epoxy resin.
Comparative example 3
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 34 parts of INOVOL F330N, 10 parts of MOCA, 54 parts of E405, 1.0 part of XS-3A, 0.5 part of carbodiimide, 0.3 part of KH560, 0.16 part of CU-A and 0.04 part of CB-18, using a high-speed disperser 1300r/min to fully and uniformly stir, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: based on 100 parts by mass, mixing 7 parts of C210, 18 parts of C220 (Nanowei New material Co., ltd.) and 75 parts of CD-C, slowly heating to 78 ℃, reacting for 2.5 hours to obtain a prepolymer with 20.7% isocyanate, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:110, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 7 days or curing at the temperature of 100 ℃ for 10 hours, and finally obtaining the modified epoxy resin.
Comparative example 4
The preparation method comprises the following steps:
(1) And (3) preparation of the component A: the component A is prepared by mixing, by mass, 100 parts of component A, 34 parts of INOVOL F330N, 10 parts of MOCA, 54 parts of C305 (New materials Co., ltd., yinuo-Norway, shandong), 1.0 part of XS-3A, 0.5 part of carbodiimide, 0.3 part of KH560, 0.16 part of CU-A and 0.04 part of CB-18, and then fully stirring uniformly by using a high-speed disperser 1300r/min, vacuumizing and defoaming, and packaging to obtain the component A;
(2) And (3) preparation of a component B: the preparation method comprises the steps of (1) mixing 14 parts of PE-2316, 51.6 parts of CD-C and 34.4 parts of MDI-50 by weight, slowly heating to 75 ℃, reacting for 2 hours to obtain a prepolymer with isocyanate content of 26.0%, vacuumizing, defoaming and packaging to obtain the component B;
(3) Mixing the component A and the component B according to the mass ratio of 100:90, stirring uniformly at room temperature by using a 1000r/min high-speed stirrer, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 7 days or curing at the temperature of 100 ℃ for 10 hours, and finally obtaining the modified epoxy resin.
Performance testing
The performance test was conducted on examples 1 to 4 and comparative examples 1 to 4 according to the following criteria, and the results are shown in Table 1 below.
Hardness: GB/T531-1999; tensile strength and elongation at break: GB/T528-2009; abrasion resistance: ISO4649:2017 (E).
Table 1 performance test tables for examples 1 to 4 and comparative examples 1 to 4
As can be seen from comparison of examples 1-4 and comparative examples 1-4, after the ether ester polyol and the amine ether polyol are introduced into the polyurethane material, the novel product has high general hardness, excellent wear resistance, high-temperature hardness, obvious improvement of the wear resistance, and obvious improvement of the retention rate of mechanical properties after three months of natural exposure.
Compared with comparative example 1, example 1 has high-temperature hardness, excellent wear resistance, and obviously improved tensile strength and elongation at break before and after natural exposure, mainly because of the introduction of the ether ester polyol into the material B in example 1, compared with the traditional polyester polyol, the polyester polyol has good high-temperature resistance, wear resistance, and higher toughness and aging resistance.
Compared with comparative example 2, example 1 has high hardness at 80 ℃, excellent performance before and after natural exposure, and lower abrasion, mainly because of the amine ether polyol introduced into the material A in example 1, and has good high temperature resistance, higher toughness and aging resistance and excellent abrasion resistance compared with the traditional polyether polyol.
Compared with comparative example 3, example 1 has high normal temperature hardness and high temperature hardness, excellent tensile strength and elongation at break before and after natural exposure, and obviously lower abrasion, mainly because of the introduction of the ether ester polyol into the material B in example 1, and has excellent abrasion resistance, better toughness, high temperature resistance and aging resistance compared with the traditional polyether polyol.
Compared with the examples 1-4, the comparative example 4 has obviously lower high-temperature hardness, tensile strength and elongation at break before and after natural exposure and also has obviously improved abrasion, mainly because: the comparative example 4 has neither an amine-ether polyol raw material nor an ether-ester polyol raw material, resulting in poor high temperature resistance and aging resistance, and lower strength, toughness and abrasion resistance as compared with examples 1 to 4.
Comparative example 4 has low high-temperature hardness, high rate of change of properties before and after natural exposure, and poor abrasion resistance as compared with comparative examples 1 and 3, mainly because the conventional polyether raw material cannot satisfy its excellent high-temperature resistance, aging resistance, and abrasion resistance without the amine ether polyol raw material in comparative example 4.
Comparative example 4 showed a tendency of slightly higher high temperature hardness, lower abrasion, and increased change rate before and after natural exposure compared with comparative example 2 because the conventional polyester raw material was used without the ether ester polyol raw material in comparative example 4, and thus the aging resistance was significantly lowered although the abrasion resistance and high temperature resistance were slightly improved.
In conclusion, the invention can simultaneously meet the product characteristics of high toughness, high strength, high wear resistance and excellent ageing resistance of the polyurethane rock climbing pivot.
Claims (8)
1. The high-toughness high-strength polyurethane rock climbing fulcrum material is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by mass:
27-43 parts of polyether polyol,
7-12 parts of small molecule chain extender,
43-64 parts of amine ether polyol,
0.8 to 1.3 parts of water absorbent,
0.2 to 0.5 part of hydrolysis resistance agent,
0.2-0.5 part of coupling agent,
0.1-0.5 part of a catalyst;
the component B comprises the following raw materials in parts by mass:
0-6 parts of polyester polyol,
16-32 parts of ether ester polyol,
62-84 parts of isocyanate;
the mass ratio of the component A to the component B is 100 (90-110).
2. The high toughness high strength polyurethane rock climbing fulcrum material of claim 1, wherein the polyether polyol is inonol F330N.
3. The high-toughness high-strength polyurethane rock climbing fulcrum material of claim 1, wherein the small molecule chain extender is 3, 3-dichloro-4, 4-diaminodiphenylmethane; the water absorbent is XS-3A; the hydrolysis resisting agent is carbodiimide; the coupling agent is gamma-glycidol ether oxypropyl trimethoxy silane; the catalyst is one or two of bismuth neodecanoate and oleic acid.
4. The high-toughness high-strength polyurethane rock climbing fulcrum material of claim 1, wherein the preparation method of the amine ether polyol comprises the following steps: preparing raw materials of diethyl toluenediamine and propylene oxide according to a mass ratio of 100:75, adding all the diethyl toluenediamine into a reaction vessel after the reaction vessel is dried and free of impurities, starting stirring and heating to 90 ℃, adding 15% -20% of the total amount of the propylene oxide into the reaction vessel, starting the reaction, stopping heating when the pressure of the reaction vessel is reduced from 0.3-0.4 MPa to 0.15MPa, adding the rest propylene oxide, controlling the temperature to be not more than 110 ℃, and reacting at 95-105 ℃ for 24-30 hours to obtain the catalyst.
5. The high-toughness high-strength polyurethane rock climbing fulcrum material of claim 1, wherein the polyester polyol is PE-2316.
6. The high-toughness high-strength polyurethane rock climbing fulcrum material of claim 1, wherein the preparation method of the ether ester polyol comprises the following steps: adding adipic acid, terephthalic acid, PTMG650, 1, 6-hexanediol and triisopropanolamine into a reaction vessel according to the mass ratio of 70:30:107:77.5:8.3, starting stirring, starting water discharge when the temperature is raised to 135-140 ℃, controlling the condensation reflux temperature to 100-105 ℃, then raising the temperature to 220-240 ℃ and controlling the temperature raising time to be within 10-15 h, vacuumizing after the terephthalic acid is completely opened, keeping the vacuum degree at-0.09 to-0.1 MPa, and discharging when the hydroxyl value reaches 72+/-2 mgKOH/g and the acid value is smaller than 1.0 mgKOH/g.
7. The high-toughness high-strength polyurethane climbing fulcrum material according to claim 1, wherein the isocyanate is one or more of diphenylmethane diisocyanate, carbodiimide-uretonimine modified MDI, polymethylene polyphenyl isocyanate, toluene diisocyanate.
8. A method for preparing the high-toughness high-strength polyurethane rock climbing fulcrum material according to any one of claims 1-7, which is characterized by comprising the following steps:
(1) And (3) preparation of the component A: mixing polyether polyol, a small molecular chain extender, amine ether polyol, a water absorbent, an anti-hydrolysis agent, a coupling agent and a catalyst, and vacuumizing and defoaming to obtain a component A;
(2) And (3) preparation of a component B: reacting polyester polyol, ether ester polyol and isocyanate with the moisture content controlled below 0.05 percent for 2-3 hours at the temperature of 75-85 ℃ to obtain a prepolymer with the isocyanate content of 18.5-24.5 percent, and vacuumizing and defoaming to obtain a component B;
(3) Mixing the component A and the component B at room temperature, uniformly stirring by using a high-speed stirrer at 500-1500 r/min, vacuumizing, defoaming, pouring into a mold, curing at room temperature for 3-7 days or completely hardening, and then placing into a baking oven at 80-100 ℃ for curing for 8-12 hours to obtain the modified polyurethane foam.
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