CN116891562A - Polyurethane formula with excellent comprehensive physical parameters and preparation method thereof - Google Patents
Polyurethane formula with excellent comprehensive physical parameters and preparation method thereof Download PDFInfo
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- CN116891562A CN116891562A CN202311005164.9A CN202311005164A CN116891562A CN 116891562 A CN116891562 A CN 116891562A CN 202311005164 A CN202311005164 A CN 202311005164A CN 116891562 A CN116891562 A CN 116891562A
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- polyol
- naphthalene diisocyanate
- polyurethane
- chain extender
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 239000004814 polyurethane Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 42
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 25
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000012360 testing method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000013461 design Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- 125000004185 ester group Chemical group 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 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 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001610 polycaprolactone Polymers 0.000 description 8
- 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 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 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 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
- C08G18/42—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
- C08G18/28—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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention provides a polyurethane formula with excellent comprehensive physical parameters and a preparation method thereof, wherein the polyurethane formula is mainly prepared from the following raw materials in parts by mass: 20-30 parts of 1, 5-naphthalene diisocyanate, 50-70 parts of polyol and 10-20 parts of chain extender; the chain extender is one or a combination of more of 1, 4-butanediol, 2, 3-butanediol and diethylene glycol. In the invention, the polyurethane material prepared by 1, 5-naphthalene diisocyanate, polyol and chain extender is called YB-B2000, and when the polyol is ether, PTMEG is selected, the prepared polyurethane material is called YB-M-B2000; when PCL is selected as the polyol when it is an ester, the polyurethane material prepared is referred to as YB-Z-B2000. The prepared YB-B2000 has good physical and mechanical properties and can adapt to the actual use requirements of various working conditions.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a polyurethane formula with excellent comprehensive physical parameters and a preparation method thereof.
Background
Polyurethane is called polyurethane, which is a polymer compound formed by reacting isocyanate and polyol, and the structure of the polyurethane contains urea groups and ester groups, and the groups endow polyurethane materials with excellent properties such as wear resistance, oil resistance, corrosion resistance, oxidation resistance, ultraviolet radiation resistance and the like. In industrial production, polyurethane materials can be used to make various seals, rubber products, coatings, adhesives, thermal insulation, foams, and the like. In the construction field, polyurethane materials can be used for manufacturing heat insulation materials, waterproof materials, sound insulation materials and the like. In the transportation field, polyurethane materials may be used to manufacture automotive interiors, automotive seats, tires, aircraft parts, and the like. In daily life, polyurethane materials may be used to make mattresses, sofas, shoes, clothing, gloves, and the like.
In recent years, with the upgrade of market consumption, the market has higher requirements on tear strength, rebound resilience, functionality, heat resistance and the like of polyurethane materials, while the traditional polyurethane materials synthesized by TDI and MDI are insufficient to meet the special demands of part of the market, and in this background, the market demands of NDI-based elastomers are increasing. Along with continuous and intensive research and continuous optimization of the production process, the NDI market scale is expected to be further expanded, and the development potential of the future industry is larger.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a polyurethane material with excellent mechanical properties, wherein the polyurethane material-YB-B2000 prepared by using 1, 5-naphthalene diisocyanate as a hard segment, polyether polyol or polyester polyol as a soft segment and micromolecular polyol as a chain extender has good weather resistance, shock absorption, bearing property, wear resistance, small internal heat generation, tear resistance and the like, has outstanding mechanical properties, is more environment-friendly, and can meet special market demands.
The second purpose of the invention is to provide a preparation method of the polyurethane material formula, which has simple steps, and the prepared polyurethane material has good mechanical properties and can realize industrial production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a polyurethane material with excellent mechanical properties, which is mainly prepared from the following raw materials in parts by weight:
20-30 parts of 1, 5-naphthalene diisocyanate, 50-70 parts of polyol and 10-20 parts of chain extender;
the chain extender is one or a combination of more of 1, 4-butanediol, 2, 3-butanediol and diethylene glycol.
In the present high molecular field, the aromatic diisocyanate with better comprehensive physical and mechanical properties is Toluene Diisocyanate (TDI) < diphenylmethane-diisocyanate (MDI) < terephthalyl diisocyanate (PPDI) < 1, 5-Naphthalene Diisocyanate (NDI), in the invention, the selected 1, 5-naphthalene diisocyanate is NDI, is polyurethane synthesized by diisocyanate components, has higher melting point, high rigidity, regularity and symmetry of molecules, can fundamentally improve the phase separation degree of polyurethane, ensures that the prepared polyurethane material has excellent physical and mechanical properties, and the polyurethane material synthesized by the polyurethane material has excellent dynamic properties, and has better heat resistance than TDI type, MDI type and PPDI type polyurethane materials, so that the NDI type polyurethane material prepared by the invention can meet special market demands.
In the present invention, NDI was selected to be produced by Bayer, germany, and the polyol of the 1, 5-naphthalene diisocyanate prepared had a molecular weight average of 210.
Preferably, the polyurethane material is mainly prepared from the following raw materials in parts by weight:
22-28 parts of 1, 5-naphthalene diisocyanate, 58-65 parts of polyol and 11-18 parts of chain extender.
Preferably, the polyurethane material is mainly prepared from the following raw materials in parts by weight:
25 parts of 1, 5-naphthalene diisocyanate, 62 parts of polyol and 16 parts of chain extender;
the polyol is one of PTMEG and PCL, and the chain extender is 1, 4-butanediol.
In the invention, the polyol is selected as one of PTMEG and PCL, wherein PTMEG is fully called tetrahydrofuran, has excellent physical and chemical properties, has inertia and high stability, is easy to recycle and reuse, can meet certain solubility and reactivity, and can be reduced when the molecular weight is increased, and the average molecular weight of PTMEG is 2000, and the PTMEG is used as a polyurethane material prepared by a soft segment together with 1, 5-naphthalene diisocyanate and a chain extender, has the characteristics of wear resistance, good flexibility, aging resistance, hydrolysis resistance, good elasticity and the like, is suitable for hydrolysis-resistant environment, has good anticoagulation property and can be used as a medical polymer material.
The PCL is fully called as polycaprolactone, is an organic high polymer, has good biocompatibility, good organic high polymer compatibility and good biodegradability, has the molecular weight of 2000, and is used as a soft segment, and the polyurethane material prepared by the 1, 5-naphthalene diisocyanate and a chain extender has excellent performances of oil resistance, acid and alkali resistance and printing and dyeing reagent resistance.
In the actual use process, the applicant refers to a polyurethane material prepared from NDI, a chain extender and a polyol as YB-B2000, the whole process is YongBand-B2000, the polyurethane material is a novel polyurethane material developed by Beijing Yongbang chemical industry products limited company, and the YB-B2000 which is suitable for hydrolysis-resistant environment is referred to as YB-M-B2000 according to different use environments and is prepared from NDI, the chain extender and PTMEG; the YB-B2000 suitable for oil resistance and acid and alkali resistance is called YB-Z-B2000, and is prepared from NDI, a chain extender and PCL. In the use process, YB-M-B2000 or YB-Z-B2000 can be selected according to the mechanical properties and the use environment of the material so as to meet the stability, reliability, safety and environmental protection of the material in the use process.
The invention also provides a preparation method of the polyurethane formula, which comprises the following steps:
dehydrating polyol, adding 1, 5-naphthalene diisocyanate, stirring, cooling to obtain a prepolymer, mixing the dehydrated chain extender with the prepolymer, vulcanizing, and curing to obtain the polyurethane material.
Preferably, the preparation method further comprises sampling and testing the obtained product after cooling, and defoaming to obtain a prepolymer when the-NCO content is detected to reach a design value;
the sampling test comprises the following steps:
comparing the-NCO content in the tested product with the design value, and if the-NCO content is greater than or equal to the design value, defoaming;
the calculation method of the design value comprises the following steps:
NCO％＝((V 0 -V)×84)/(M×(V 0 +V 1 ))×100％；
wherein V is 0 The unit of the additive amount of the 1, 5-naphthalene diisocyanate is g; v is the consumption of 1, 5-naphthalene diisocyanate in g; m is the molecular weight of 1, 5-naphthalene diisocyanate; v (V) 1 The unit of the added amount of the polyol is g.
The present invention requires control of the-NCO (isocyanate group) content in the prepolymer because the highly unsaturated structure of the isocyanate group determines that it has high reactivity, the content of which directly affects the properties of polyurethane, when the content of the isocyanate group is too high, the hardness and brittleness of polyurethane are increased, the elasticity and toughness are reduced, conversely, when the content of the isocyanate group is too low, the hardness and strength of polyurethane are reduced, the elasticity and toughness are increased, and when the content of the isocyanate group is too high, the long-term contact is harmful to human body, so that strict control of the content of the isocyanate group is required.
Preferably, the temperature of the dehydration is 110-120 ℃, the pressure of the dehydration is 0.10-0.20KPa, and the time of the dehydration is 1.5-3h;
preferably, the temperature of the dehydration is 118 ℃, the pressure of the dehydration is 0.13KPa, and the time of the dehydration is 2h.
Preferably, the stirring time is 30-60min, and the stirring rotating speed is 600-750r/min;
preferably, the stirring time is 45min, and the stirring rotating speed is 700r/min.
Preferably, the temperature of the cooling is 80-90 ℃, and the time of the cooling is 5-9h;
preferably, the temperature of the cooling is 85 ℃, and the time of the cooling is 7h.
Preferably, the vulcanization comprises the steps of:
firstly, placing the prepolymer into a die preheated to 120 ℃ for vacuum vulcanization for 20-60min, and then, vulcanizing again for 6-10h at the temperature of 100-120 ℃.
Preferably, the curing temperature is 22-28 ℃, and the curing time is 6-8 days;
preferably, the curing temperature is 25 ℃, and the curing time is 7 days.
In the present invention, since the reaction rate varies with the temperature, in order to obtain a product of constant quality, it is necessary to perform good control of the temperature, and at the same time, in order to obtain more powerful and good tearing properties, the synthesis temperature should not exceed 100 ℃, and in order to have high rebound resilience, the synthesis temperature should be maintained at 120 ℃ or more all the time, and at the same time, the synthesis temperature is controlled below 120 ℃, and it is also possible to reduce the occurrence of reversible reactions, and to increase the yield.
Preferably, in the actual use process, the coupling agent can be added according to the requirement to increase the bonding strength and the wet heat resistance, the coupling agent is added to increase the oxygen index, the antioxidant, the light stabilizer and the hydrolysis stabilizer are added to relieve the conditions of thermal oxidation, photo aging, hydrolysis and the like, the filler is added to improve the mechanical property, reduce the shrinkage stress and the thermal stress, enhance the stability to thermal damage, reduce the thermal expansion coefficient, improve the viscosity of the resin and reduce the cost, and the antistatic agent is added to ensure that static electricity and the like are not easy to generate on the surface.
In the actual use process, the novel polyurethane material YB-B2000 can be used for manufacturing bars, plates, missile dragging seats, shield machine wheels, conveyor line rollers, roller coaster wheels, monorail cranes, rubber rollers, protective covers, valves, gears, pig and anti-explosion tire supports, is wide in application, can adapt to the actual use requirements of various working conditions, and meets the market requirements.
Compared with the prior art, the invention has at least the following advantages:
(1) When the polyurethane material is prepared, isocyanate is selected as NDI with higher physical properties, NDI is used as a hard segment, PTMEG and PCL are used as soft segments, and micromolecular polyol is used as a chain extender, so that the novel polyurethane material-YB-B2000 is prepared, has good stability, is more environment-friendly and energy-saving compared with the traditional polyurethane or rubber, has particularly outstanding comprehensive mechanical properties such as shock absorption, bearing property, wear resistance, small internal heat generation, tear resistance and the like, and can meet the market special requirements of people.
(2) The invention ensures that the prepared polyurethane material has good physical and mechanical properties by controlling the reaction temperature and the like, adjusts the reaction rate, reduces the occurrence of reversible reaction and improves the yield.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a polyurethane formula with excellent mechanical properties, which comprises the following steps:
(1) Preparation of YB-Z-B2000 prepolymer:
weighing 62 parts of PCL by mass, dehydrating for 2 hours at 118 ℃ under 0312KPa, adding 25 parts of 1, 5-naphthalene diisocyanate, stirring for 45 minutes at a rotating speed of 700r/min, cooling to 85 ℃, and standing for 7 hours to obtain a reaction product;
(2) Testing of the-NCO content in the reaction product:
1) Extracting appropriate amount of reaction product, placing into a triangular flask with a grinding port, adding appropriate amount of di-n-butylamine-toluene solution with a pipette, shaking to mix them uniformly, standing at 25deg.C for 20min, adding ethanol and bromocresol green indicator, titrating with 0.5mol/L hydrochloric acid standard solution until the sample has blue color disappeared and yellow color appears, keeping for 15s as end point, and measuring NCO Measuring 。
NCO Measuring (％)＝((V 0 -V+V 1 )×V+42.02)/(m×1000)×100％；
Wherein V is 0 The volume of hydrochloric acid standard solution is consumed for blank, and the unit is ml; v is the volume of hydrochloric acid standard solution consumed in sample titration, and the unit is ml; v (V) 1 The volume of the hydrochloric acid standard solution consumed for triethylamine contained in the sample is in ml.
2) Design value NCO Is provided with The calculation formula of (2) is as follows:
NCO is provided with (％)＝((V 0 -V)×84)/(M×(V 0 +V 1 ))×100％；
Wherein V is 0 The unit of the additive amount of the 1, 5-naphthalene diisocyanate is g; v is the consumption of 1, 5-naphthalene diisocyanate in g; m is the molecular weight of 1, 5-naphthalene diisocyanate, V 1 The unit of the added amount of the polyol is g.
The calculated NCO Measuring And design value NCO Is provided with For comparison, when NCO Measuring ≥NCO Is provided with At the moment, defoaming is carried out for 20min to obtain YB-Z-B2000 prepolymer;
(3) Preparing YB-Z-B2000;
the obtained prepolymer and 16 parts of dehydrated 1, 4-butanediol are stirred uniformly, injected into a die preheated to 120 ℃, vulcanized in vacuum for 40min on a vacuum machine, then the temperature of an oven is adjusted to 110 ℃, the prepolymer is preheated and vulcanized again for 8h, and then the prepolymer is taken out from the oven and cured for 7 days at 25 ℃ to obtain the polyurethane material.
And the physical and mechanical properties are tested by adopting a universal testing machine, and the physical and mechanical properties are excellent through the test.
Example 2
The specific embodiment corresponds to example 1, with the only difference that the PCL was replaced by PTMEG and the polyurethane material prepared was YB-M-B2000. Through testing, the physical and mechanical properties are excellent.
Examples 3 to 6
The specific embodiment corresponds to example 1, except that the following table 1 shows:
TABLE 1 different raw material ratios
Examples 7 to 8
The specific embodiment corresponds to example 1, except that the following table 2 shows:
TABLE 2 variation of reaction conditions
Example 9
The specific embodiment corresponds to example 1, with the only difference that the chain extender is selected as diethylene glycol. Through testing, the physical and mechanical properties are excellent.
Comparative example 1
The specific embodiment corresponds to example 1, with the only difference that the 1, 5-naphthalene diisocyanate is replaced by diphenylmethane diisocyanate and the polyurethane prepared is an MDI-based polyurethane material. The physical and mechanical properties are poor through testing.
Comparative example 2
The specific embodiment corresponds to example 1, with the only difference that the 1, 5-naphthalene diisocyanate is used in an amount of 10 parts. The physical and mechanical properties are poor through testing.
Comparative example 3
The specific embodiment corresponds to example 1, with the sole difference that the amount of chain extender is chosen to be 5 parts. The physical and mechanical properties are poor through testing.
As is evident from the analysis of the physical and mechanical properties of examples 1 to 9 and comparative examples 1 to 3, the amount of 1, 5-naphthalene diisocyanate used in comparative example 2 was reduced, resulting in a reduction in the content of isocyanate groups, the elasticity and toughness thereof were reduced, resulting in a reduction in the overall physical and mechanical properties thereof, and the amount of chain extender used in comparative example 3 was reduced, resulting in an imperfect expansion of the molecular chains of 1, 5-naphthalene diisocyanate, and thus in poor physical and mechanical properties thereof.
Therefore, when the scheme is adopted to prepare the polyurethane material, the selection and the proportion of raw materials are ensured to be as much as possible in the scheme, so that the polyurethane material with excellent mechanical properties can be prepared.
Experimental example 1
The polyurethane materials prepared in example 1 and comparative example 1 were subjected to a physical and mechanical property comparison, and a physical and mechanical property test was performed using a universal tester model 1185 of Instron, UK, and the test results are shown in Table 3 below:
TABLE 3 physical and mechanical Property test results
As can be seen from the data in Table 3, the polyurethane material YB-B2000 of the NDI system prepared in example 1 of the present invention has better wear resistance, tensile strength, temperature resistance range, compression set, elongation at break, tear strength and other comprehensive physical and mechanical properties and retention rate than the polyurethane material of the MDI system prepared in comparative example 1, and can meet the special market demands.
Finally, it is to be understood that the above embodiments are merely exemplary embodiments employed for the purpose of illustrating the principles of the present invention, however, the present invention is not limited thereto. Various modifications and improvements may be made by those skilled in the art without departing from the principles and spirit of the invention, and such modifications and improvements are also considered within the scope of the invention.
Claims (10)
1. The polyurethane formula with excellent comprehensive physical parameters is characterized by being mainly prepared from the following raw materials in parts by weight:
20-30 parts of 1, 5-naphthalene diisocyanate, 50-70 parts of polyol and 10-20 parts of chain extender;
the polyol is one of PTMEG and PCL, and the chain extender is one or a combination of more of 1, 4-butanediol, 2, 3-butanediol and diethylene glycol.
2. The polyurethane formulation according to claim 1, characterized in that it is mainly prepared from the following raw materials, in parts by weight:
22-28 parts of 1, 5-naphthalene diisocyanate, 58-65 parts of polyol and 11-18 parts of chain extender.
3. The polyurethane formulation according to claim 1, characterized in that it is mainly prepared from the following raw materials, in parts by weight:
25 parts of 1, 5-naphthalene diisocyanate, 62 parts of polyol and 16 parts of chain extender;
the chain extender is 1, 4-butanediol.
4. A process for the preparation of a polyurethane formulation as claimed in any one of claims 1 to 3, comprising the steps of:
dehydrating polyol, adding 1, 5-naphthalene diisocyanate, stirring, cooling to obtain a prepolymer, mixing the dehydrated chain extender with the prepolymer, vulcanizing, and curing to obtain the polyurethane material.
5. The method according to claim 4, wherein the obtained product is subjected to sampling test after cooling, and when the-NCO content is detected to reach a design value, the prepolymer is obtained by deaeration;
the sampling test comprises the following steps:
comparing the-NCO content in the tested product with the design value, and if the-NCO content is greater than or equal to the design value, defoaming;
the calculation method of the design value comprises the following steps:
NCO％＝((V 0 -V)×84)/(M×(V 0 +V 1 ))×100％；
wherein V is 0 The unit of the additive amount of the 1, 5-naphthalene diisocyanate is g; v is the consumption of 1, 5-naphthalene diisocyanate in g; m is the molecular weight of 1, 5-naphthalene diisocyanate; v (V) 1 The unit of the added amount of the polyol is g.
6. The method according to claim 4, wherein the dehydration temperature is 110-120 ℃, the dehydration pressure is 0.10-0.20KPa, and the dehydration time is 1.5-3h;
preferably, the temperature of the dehydration is 118 ℃, the pressure of the dehydration is 0.13KPa, and the time of the dehydration is 2h.
7. The method according to claim 4, wherein the stirring time is 30-60min, and the stirring rotation speed is 600-750r/min;
preferably, the stirring time is 45min, and the stirring rotating speed is 700r/min.
8. The method according to claim 4, wherein the temperature of the cooling is 80-90 ℃, and the cooling time is 5-9 hours;
preferably, the temperature of the cooling is 85 ℃, and the time of the cooling is 7h.
9. The method of preparing as claimed in claim 4, wherein the vulcanization comprises the steps of:
firstly, placing the prepolymer into a die preheated to 120 ℃ for vacuum vulcanization for 20-60min, and then, vulcanizing again for 6-10h at the temperature of 100-120 ℃.
10. The method according to claim 4, wherein the curing temperature is 22-28 ℃, and the curing time is 6-8 days;
preferably, the curing temperature is 25 ℃, and the curing time is 7 days.
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| US20060047058A1 (en) * | 2004-09-01 | 2006-03-02 | Songwei Lu | Process for making polymers having nanostructures incorporated into the matrix of the polymer |
| DE102007054003A1 (en) * | 2007-11-13 | 2009-05-14 | Bayer Materialscience Ag | Polyurethane-elastomer obtained by reacting 1,5-naphthalene diisocyanate and polysuccinate polyol and converting the obtained isocyanate-prepolymer with chain elongator, useful as polyurethane molded part or coating |
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| CN111961186A (en) * | 2020-08-27 | 2020-11-20 | 栖霞市兴邦新材料科技有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN115124693A (en) * | 2022-07-25 | 2022-09-30 | 黎明化工研究设计院有限责任公司 | Foamed polyurethane elastomer and preparation method and application thereof |
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| US20060047058A1 (en) * | 2004-09-01 | 2006-03-02 | Songwei Lu | Process for making polymers having nanostructures incorporated into the matrix of the polymer |
| DE102007054003A1 (en) * | 2007-11-13 | 2009-05-14 | Bayer Materialscience Ag | Polyurethane-elastomer obtained by reacting 1,5-naphthalene diisocyanate and polysuccinate polyol and converting the obtained isocyanate-prepolymer with chain elongator, useful as polyurethane molded part or coating |
| CN110684174A (en) * | 2019-10-24 | 2020-01-14 | 山东一诺威聚氨酯股份有限公司 | Low-hardness 1, 5-naphthalene diisocyanate-based polyurethane elastomer and preparation method thereof |
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