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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3237—Polyamines aromatic
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
  • F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor

Definitions

• the present invention relates to a casting polyurethane elastomer-forming composition and a method for producing a polyurethane elastomer using the forming composition. More specifically, 2,4'-diphenylmethane diisocyanate (hereinafter referred to as 2,4'-MDI) isocyanate using diphenylmethane diisocyanate with high isomer content.
• 2,4'-MDI 2,4'-diphenylmethane diisocyanate
• a polyurethane elastomer for casting made of a base terminal polymer and an aromatic diamine as a curing agent, and the resulting polyurethane elastomer has excellent mechanical strength and heat resistance.
• Patent Document 1 exists as a prior art document regarding a thermosetting polyurethane elastomer using a chlorine-containing aromatic diamine such as (2,6-decylaniline).
• TD monomer has a high vapor pressure and is designated as a specified chemical substance as a highly volatile substance. For this reason, substances that use TDI are strictly regulated in terms of production and use, and it is necessary to thoroughly remove residual monomers from Prevolima. Therefore, extra steps and costs are required.
• thermosetting resin obtained is limited, and the elastic modulus decreases at high temperatures. There are also problems.
• Patent Document 2 an isocyanate group-terminated polymer using 95% by mass of 2,4'_MDI isomer is used as a moisture curing sealant
• the present invention is different from the present invention which is a two-component type in which a polyurethane elastomer for casting is obtained by reacting an isocyanate group-terminated prepolymer with an aromatic diamine as a curing agent.
• the invention in Patent Document 2 cannot satisfy the characteristics required for the roll member.
• Patent Document 1 Special Table 7-7 5 0 9 2 7 4
• Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 6 _ 3 7 0 9 9
• the first object of the present invention is to have both high hardness and high mechanical strength, and durability (mechanical properties ⁇ heat resistance) that can be used for a long period of time as a component (particularly roll) constituting an industrial machine. Providing a molded polyurethane elastomer product with excellent properties
• the present invention is the following I to V I.
• a cast polyurethane elastomer-forming composition comprising an isocyanate group-terminated polymer (A) and a curing agent (B),
• (B) is an aromatic diamine
• Isocyanate group-terminated prepolymer (A) force NCO content is 2.0-10.0 mass 0 / o and viscosity is 75-3 ° C 100-3, OO Om m2 / s And the residual monomer content of diphenylmethane diisocyanate is
• the polyurethane elastomer-forming composition for casting according to the above I which is 5% by mass or less.
• Curing agent (B) force 4 _ with black mouth 3,5 diaminobenzoate A casting polyurethane elastomer-forming composition as described in I or II above.
• the molar ratio of isocyanate group / active hydrogen group of component (A) and component (B) is set to 0.
• V I I I A mouthpiece member obtained from the polyurethane elastomer-forming composition for casting according to any one of I to V I above.
• an isocyanate group-terminated polymer having a low viscosity and excellent reactivity can be obtained. Furthermore, when chlorine-containing aromatic diamines such as 4,4'-methylenebis (2-chloroaniline) (hereinafter abbreviated as MOCA) are not used as curing agents, Excellent effect.
• MOCA 4,4'-methylenebis (2-chloroaniline
• the polyurethane elastomer obtained by the present invention has high hardness (80 or more, especially 90 or more according to JIS_A) required for engineering applications, such as parts and components constituting industrial machines, and excellent mechanical properties. It has both heat resistance and excellent balance of physical properties (tensile strength, elongation-tear strength). Therefore, the molded product of the present invention can be suitably used as a component (1) or member constituting various industrial machines such as a papermaking roll, an ironmaking roll, and a paper feeding roll. Further, the molded product of the present invention having excellent heat resistance is less likely to sag even when used at high temperatures, and is excellent in durability as a part (part) constituting an industrial machine that tends to become high temperature.
• a polyurethane elastomer forming composition having high hardness, excellent mechanical properties, and heat resistance can be reliably produced. Can be built.
• the isocyanate group-terminated urethane prepolymer (A) in the present invention has a diphenylmethane diisocyanate (a 1) containing at least 95% by mass of 2,4′-diphenylmethane diisocyanate isomer. And a hydroxyl group-containing compound (a 2).
• the content of (a 1) used in the isocyanate group-terminated urethane prepolymer (A) is at least 95% by mass, more preferably 97% by mass or more, and optimally 98% by mass or more.
• Examples of the hydroxyl group-containing compound (a2) in the present invention include one or a mixture of two or more of polyether polyol, polyester polyol, polycarbonate diol and the like. These hydroxyl group-containing compounds (a2) have a number average molecular weight of 300 to 5,000, among which a number average molecular weight of 400 to 3,000 is preferable, and a number average molecular weight of 500 to 2,000 is more preferable. It is a hydroxyl group-containing compound. Of these, polyether polyol is preferred.
• polyether glycols examples include poly (ethylene ether) glycol, poly (propylene ether) glycol, and poly (tetramethylene ether) glycol (hereinafter abbreviated as “PTMG”). These include ethylene glycol (hereinafter abbreviated as “EG”), 1,3_butanediol (hereinafter abbreviated as “1,3_BD”), 1,4_butanediol (hereinafter abbreviated as “1,4—BDJ”) Initiators of short chain diols such as diethylene glycol, dipropylene glycol, 1,2_propylene glycol (hereinafter abbreviated as “1,2_PG”), 1,3-propylene glycol (hereinafter abbreviated as “1,3_PG”) As a polyether polyol from one or more of polyethers such as polyether produced by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide, trimethylene oxide and tetrahydro
• Polyester polyols include ethylene glycol, propylene glycol, 1,3_BD, 1,4_butanediol, 1,5_pentanediol, 3_methyl_1,5_pentanediol, 1,6 —One or more of hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, etc., malonic acid, maleic acid, succinic acid Acid, adipic acid, glutaric acid, pimelic acid, sebacic acid, citric acid, phthalic acid, isophthalic acid
• polystrength monoponate diol examples include the short chain diols described above, low molecular strength such as diphenylstrength monoponate, jetyl carbonate, ethylene strength-ponate, etc.
• the isocyanate group-terminated urethane prepolymer (A) in the present invention is composed of 2, 4'-MD I (a 1) and a hydroxyl group-containing compound (a 2) having a number average molecular weight of 300 to 5,000. In an isocyanate group / hydroxyl group (molar ratio) of 1.6 to 20, and this system is reacted at a temperature of 50 to 100 ° C. for 1 to 5 hours.
• a catalyst for promoting the N 2 CO / OH reaction can be added during the production of the isocyanate group-ended prepolymer.
• Suitable catalysts include known amine compounds or organometallic compounds or quaternary ammonium salts.
• the following compounds can be used as catalysts: triethylamine, triptylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, ⁇ , ⁇ , ⁇ ', ⁇ ' -tetramethyl Rudiaminojetyl ether, bis (dimethylaminopropyl) urea, N-methyl- and N-ethylmorpholine, ⁇ , ⁇ '-dimorpholinojetyl ether
• DMDEE ⁇ -Cyclohexylmorpholine
• ⁇ , ⁇ , ⁇ ', ⁇ ' -tetramethylethylenediamine ⁇ , ⁇ , ⁇ ', ⁇ ' -tetramethylbutanediamine
• Pentamethyljetylenetriamine Dimethylbiperazine, ⁇ -Dimethyl-aminoethyl-piberidine, 1,2_Dimethylimidazole, ⁇ -Hydroxypropyl Imidazol, 1-Mazak Mouth [2. 2.0] Octane, 1,4-Diazak Mouth Mouth [2. 2.
• Octane (Dabco) and Alkanol Lumamine Compounds eg, Triethanolamine, Triisopropanol Lumamine) , N-methyl- and N-ethylethanolamine), dimethylaminoethanol, 2_ (N, N-dimethylaminoethoxy) ethanol, ⁇ , ⁇ ', ⁇ -tris (dialkylaminoalkyldialkylaminoal) (Kill) hexahydrotriazine (eg, ⁇ , ⁇ ', ⁇ -tris (dimethylaminopropyl) -s-hexahydrotriazine), iron (II) chloride, zinc chloride, lead octate and, preferably, a tin salt ( For example, tin dioctate, tin jetyl hexate, dibutyltin dilaurate and / or dibutyl dilauryltin mercaptide), 2,3-di
• antioxidants can be added during the production of the isocyanate group-terminated polymer.
• the NCO content of the isocyanate group-terminated polymer is preferably 2.0 to 10.0 mass%, more preferably 3.0 to 8.0 mass%, and most preferably 3 5 to 6.0% by mass.
• An isocyanate group-terminated polymer having an NCO content of less than 2.0% by mass has high viscosity and poor fluidity, and it is difficult to perform a casting operation of a composition containing this as a main component.
• isocyanate group-terminated polymer having an NCO content exceeding 10.0 mass% is excessively reactive with an active hydrogen compound (curing agent), and a composition comprising this as a main component (mixture with a curing agent). ), The fluidity drops rapidly, making casting difficult.
• the isocyanate group-terminated polymer obtained by the present invention preferably has a dynamic of 75 to 3,000 mm2 / s, more preferably 200 to 1,50 Omm2 / s at 75 ° C. Has viscosity. If the viscosity is 50 mm 2 / s or less, the resin will enter the gap of the mold during casting, making it difficult to release after curing.
• the isocyanate group-terminated polymer having a viscosity of more than 3,000 mm2 / s has a high initial viscosity, and its fluidity rapidly decreases due to the reaction with the active hydrogen compound (curing agent), making the casting operation difficult.
• the isocyanate group-terminated polymer (A) obtained by the present invention is MD
• Residual monomer content is 2.5% or less.
• the reaction between the residual monomer and the curing agent is quick during the curing reaction, the initial viscosity of mixing increases, and casting becomes difficult.
• thin film distillation or the like may be performed in order to make the residual monomer content 2.5% or less.
• Examples of the curing agent (B) include 3,5_bis (methylthio) -1,2,4-toluenediamine, 3,5-bis (methylthio) -1,2,6_toluenedia 4, 4-Methylenebis (2,6_dimethylaniline), 4,4-Methylenebis (2_isopropyl_6-methylaniline), 4,4-Methylenebis (2,6-isopropylaniline) ), 2, 4-toluenediamine,
• aromatic diamine containing one chlorine element in the molecule preferred is an aromatic diamine containing no chlorine element.
• the aromatic diamine containing elemental chlorine is preferably 4_chlorodione 3,5 diaminobenzoic acid isobutyl, and the most preferable aromatic diamine not containing elemental chlorine is 3,5_bis (methylthio) 2,4_toluenediamine and 3,5_bis (methylthio) -1,6_toluenediamine or a mixture of the two components.
• the mixing ratio of the isocyanate group-terminated polymer (A) and the curing agent (B) is the isocyanate group and curing agent (B) of the isocyanate component constituting the main agent (A).
• ) Is preferably in such a ratio that the molar ratio (isocyanate group / active hydrogen group, R value) with the active hydrogen group of the polyol component constituting is 0.8 to 1.2, particularly preferably 0.2.
• the ratio is 9 to 1.1.
• the above-mentioned catalyst, existing antioxidant, defoaming agent, ultraviolet absorber, reaction modifier and the like can be added in advance.
• the catalyst is preferably added to the curing agent (B).
• the molded product after demolding may be post-heated.
• Table 1 shows the measurement results of the NCO content, viscosity at 75 ° C, and residual monomer content of P_1 to P_5.
• 2, 4'-MD I 2, 4 '— Diphenylmethane diisocyanate containing 98% or more of diphenylmethane diisocyanate isomer (manufactured by Nippon Polyurethane Industry Co., Ltd.)
• T-100 2, 4_ Tolylene Diisocyanate (Millionate T-1100, manufactured by Nippon Polyurethane Industry Co., Ltd.)
• MOCA 4, 4'—Diamino 1,3'—dichlorodiphenylmethane (Iharacamine MT, manufactured by Ihara Chemical Industry Co., Ltd.)
• Etacure 300 3, 5_bis (methylthio) -1,2,6_toluenediamine and 3,5_bis (methylthio) 1,2,4_toluenediamine (Ethyl Corporation)
• CDAB 4_Kuroguchi 1,3,5-Diaminobenzoic acid isobutyl (Waisuke 1 Co., Ltd.)
• the 4,4′_MD I prepolymer had a fast reaction, and the 2,4′-M D I prepolymer had a low mixing viscosity and a long pot life.
• a polyurethane elastomer for casting was obtained by the production method. Hardness and tensile strength of the obtained resin (modulus [M 1 0 0, M300], TB), elongation (EB), tear strength (TR), and rebound resilience (Re).
• Prebolimer P_ 1 prepared beforehand by heating to 80 ° C and Etcure 300 of the curing agent were mixed and stirred, and 120 ° C. Then, it was poured into a molding die provided with a roll core preheated at 120 ° C. and cured at 120 ° C. for 5 hours. Thereafter, by cooling to near room temperature and demolding, a roll in which the surface of the roll core was coated with a cured product (elastic member) was produced. As a result of measuring the height of the obtained roll, the J I S_A hardness was 90, and the Short_D hardness was 40.
• the prepolymer P_2 prepared by heating to 80 ° C in advance and CDAB as a curing agent were mixed and stirred, and the temperature was adjusted to 120 ° C. It was poured into a molding die provided with a preheated roll core and cured by heating at 120 ° C. for 5 hours. Thereafter, the roll was cooled to near room temperature and demolded to produce a roll whose surface was covered with a cured product (elastic member). As a result of measuring the height of the obtained roll, it was 93 in J I 3_8 hardness and 41 in Shore-D hardness.
• Example 1 1 In accordance with the formulation shown in Example 7 in Table 3 below (mixing ratio), prepolymer P _ 1 heated to 80 ° C in advance and CDAB as a curing agent were mixed and stirred, and then 120 ° C. Then, it was poured into a molding die provided with a roll core preheated to 120 ° C. and cured by heating at 120 ° C. for 5 hours. Thereafter, the roll was cooled to near room temperature and demolded to produce a roll whose surface was covered with a cured product (elastic member). As a result of measuring the height of the obtained roll, the JIS_A hardness was 90 and the Shore_D hardness was 38.
• the number average molecular weight of the hydroxyl group-containing compound described in the present invention was calculated by the value described in the manufacturer's results sheet or by the terminal hydroxyl group quantification method.
• the isocyanate group-terminated polymer obtained was measured by gas chromatography, and the residual diphenylmethane diisocyanate was quantified by an internal standard method. (Measuring instrument: Hewlett-Packard, HP 68 90 S er e e s and Sy s te m)
• the pot life was measured as shown below.
• Etacure_300 is a liquid at room temperature and does not need to be heated.
• C (A) and (B) are mixed with agitator for 30 seconds at the specified mixing ratio.
• d. Pour the mixture into a measuring bottle and soak it in an oil bath at 1 20 ° C.
• d. Viscosity measurement with B type viscometer H_7 rotor at 40 rpm.
• e. The time when the mixed viscosity reaches 100 000 mP a s is defined as the pot life.
• a cured body constituting the elastomer composition was molded and measured to 50 mm ⁇ 5 mm ⁇ 2 mm to prepare a sample. Next, this sample was set so that the gap between the chucks of the tension jig was 38 mm. Excitation amplitude _ 25; Um to 10 25 m, minimum weight amplitude 0 gf, pre-mouth load 50.
• the E ′ value measured by the above measurement method is the storage elastic modulus, Reflect gender.
• the molded product according to the present invention can be suitably used as a component part of various industrial devices that require elasticity (flexibility) and mechanical strength, and is capable of forming polyurethane for casting according to the present invention.
• the composition By using the composition, the durability of the part can be remarkably improved.
• the polyurethane-forming composition for casting according to the present invention can be mounted on industrial equipment as a component used under high-temperature conditions, which could not be handled by a conventionally known molded product. New performance can be given to industrial equipment that performs high-speed processing (industrial equipment that requires the use of elastic parts under high-temperature conditions).

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• 2006
  • 2006-11-28 JP JP2006319666A patent/JP2008133343A/ja active Pending
• 2007
  • 2007-08-20 CN CNA2007800439835A patent/CN101547952A/zh active Pending
  • 2007-08-20 WO PCT/JP2007/000886 patent/WO2008065733A1/ja active Application Filing
  • 2007-08-20 KR KR1020097010528A patent/KR20090082249A/ko not_active Application Discontinuation

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