WO2013180006A1 - ポリウレタン - Google Patents
ポリウレタン Download PDFInfo
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- WO2013180006A1 WO2013180006A1 PCT/JP2013/064355 JP2013064355W WO2013180006A1 WO 2013180006 A1 WO2013180006 A1 WO 2013180006A1 JP 2013064355 W JP2013064355 W JP 2013064355W WO 2013180006 A1 WO2013180006 A1 WO 2013180006A1
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- polyurethane
- polymer polyol
- polybutadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4275—Valcrolactone and/or substituted valcrolactone
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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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
- C08G18/65—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
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/694—Polymers of conjugated dienes containing carboxylic ester groups
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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
- C08G18/70—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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
Definitions
- the present invention relates to polyurethane. More particularly, the present invention relates to a polyurethane having good mechanical properties and excellent water resistance.
- This application claims priority based on Japanese Patent Application No. 2012-122744 for which it applied to Japan on May 30, 2012, and uses the content here.
- Thermoplastic polyurethane (hereinafter sometimes referred to as TPU) is used in various fields as various elastomer molded products, synthetic leather, artificial leather, adhesives, shoe soles, spandex, and the like.
- TPU is produced by reacting a polyol, an organic polyisocyanate, and, if necessary, a chain extender (Patent Document 3, Patent Document 4, etc.). By changing the types of polyol and organic diisocyanate used as raw materials, TPU having various characteristics can be obtained.
- Patent Document 1 is obtained by reacting a block copolymer consisting of a block composed of a hydrocarbon polymer having a substantially saturated main chain and a block obtained by ring-opening polymerization of ⁇ -caprolactone with diphenylmethane diisocyanate.
- a transparent cured product sheet is disclosed.
- Patent Document 2 discloses a lactone polymer obtained by ring-opening polymerization of lactones using polybutadiene polyol as an initiator. Patent Document 2 states that this lactone polymer can be used for thermoplastic urethane elastomers, thermosetting urethane elastomers, urethane foams, adhesives, sealing agents, paints, and the like.
- JP 55-152720 A Japanese Patent Laid-Open No. 60-23418 JP 2005-133030 A JP 2011-46912 A
- An object of the present invention is to provide a polyurethane having good mechanical properties and excellent water resistance.
- the present invention includes the following aspects. ⁇ 1> A polyurethane obtained by reacting a polymer polyol represented by the formula (I), an asymmetric diisocyanate, and a chain extender. HO-X 1 -YX 2 -OH (I) In the formula (I), X 1 and X 2 each independently represent a polyester component, and Y represents a polybutadiene component.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group
- n represents the number of repeating units in parentheses and is an integer of 3 to 7.
- polyurethane according to ⁇ 1> or ⁇ 2> wherein the polymer polyol is a polymer obtained by a reaction between a polybutadiene having a hydroxyl group at a terminal and a lactone compound represented by the formula (III).
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group
- n represents the number of repeating units in parentheses, and is an integer of 3 to 7.
- ⁇ 4> The polyurethane according to ⁇ 1>, wherein the polybutadiene component has a molar ratio of 1,2-structure / 1,4-structure of 55/45 to 95/5.
- ⁇ 5> The polyurethane according to any one of ⁇ 1> to ⁇ 4>, wherein the chain extender is an aliphatic glycol.
- the polyurethane of the present invention has good mechanical properties and excellent water resistance.
- the present inventors have made it possible to react a polymer polyol having a specific block structure, an asymmetric diisocyanate, and a chain extender, thereby obtaining good mechanical properties and excellent water resistance. It has been found that a polyurethane having properties can be obtained.
- the present invention has been completed by further studies based on these findings.
- the polyurethane according to the present invention is obtained by reacting a polymer polyol, an asymmetric diisocyanate, and a chain extender.
- Polymer polyol The polymer polyol used in the present invention has the formula (I): HO-X 1 -YX 2 -OH (I) It is the polymer polyol represented by these.
- X 1 and X 2 represent a polyester component, and Y represents a polybutadiene component.
- X 1 and X 2 may be polyester components having the same structure, or may be polyester components having different structures.
- the polybutadiene component is a polymer component in which repeating units derived from butadiene are connected.
- the repeating unit derived from butadiene includes a repeating unit represented by the formula (IVa) or (IVb) (hereinafter sometimes referred to as a 1,4-structure), and a formula (Va) or (Vb). Repeating units (hereinafter, sometimes referred to as 1,2-structure).
- the polybutadiene component those containing a 1,4-structure and a 1,2-structure are preferable.
- the double bond in the formula (IVb) includes a trans bond or a cis bond.
- the polybutadiene component has a molar ratio of 1,2-structure / 1,4-structure of preferably 55/45 to 95/5, more preferably 70/30 to 95/5.
- the molar ratio of 1,2-structure / 1,4-structure can be calculated, for example, by measurement with 1 H-NMR.
- the method for adjusting the molar ratio of the 1,2-structure / 1,4-structure can be performed by a known method.
- the molar ratio of 1,2-structure / 1,4-structure can be controlled by selecting the type of catalyst used for polymerizing butadiene and the polymerization auxiliary material.
- the number average molecular weight (Mn) of the polybutadiene component is preferably 500 to 10,000, more preferably 1000 to 7000.
- the number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- the measurement conditions are mobile phase THF (tetrahydrofuran), mobile phase flow rate 1 mL / min, column temperature 40 ° C., sample injection amount 40 ⁇ L, and sample concentration 2% by weight.
- the polyester component is not particularly limited as long as repeating units are connected by an ester bond.
- a component containing at least one repeating unit represented by the formula (II) is preferable.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom.
- n represents the number of repeating units in parentheses and is an integer from 3 to 7, preferably 5.
- the alkyl group in R 1 and R 2 preferably has 1 to 6 carbon atoms, more preferably 1 to 4, more preferably 1 to 2 carbon atoms.
- Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, and n-hexyl group. it can. Among these, a methyl group or an ethyl group is preferable.
- the polyester component may be one in which repeating units having the same structure are connected, or may be one in which repeating units having different structures are connected.
- the ratio of the mass of X 2 to the mass of X 1 in the polymer polyol represented by the formula (I) is preferably 1/99 to 99/1.
- the ratio of the mass of Y to the total mass of X 1 and X 2 in the polymer polyol represented by the formula (I) is preferably 0.1 to 10, more preferably 0.2 to 5, and still more preferably 0.3 to 3.5.
- the ratio of the mass of Y to the total mass of X 1 and X 2 can be adjusted, for example, by changing the charged mass ratio in the reaction between the polybutadiene having a hydroxyl group at the terminal and the lactone compound.
- the ratio of the mass of Y to the total mass of X 1 and X 2 can be calculated, for example, by measuring with 1 H-NMR.
- the structure of the bonding portion between X 1 or X 2 and Y is not particularly limited, and can be appropriately selected within a range that does not impair the effects of the present invention.
- the polymer polyol represented by the formula (I) is not particularly limited by the production method.
- the polymer polyol is preferably produced by reacting a polybutadiene having a hydroxyl group at a terminal with a lactone compound.
- a commercially available product can be used as the polybutadiene having a hydroxyl group at the terminal.
- Nissan-PB-G-1000 (manufactured by Nippon Soda Co., Ltd.), Nissan-PB-G-2000 (manufactured by Nippon Soda Co., Ltd.), Nissan-PB-G-3000 (manufactured by Nippon Soda Co., Ltd.), Nissan-PB-GI- 1000 (Nippon Soda Co., Ltd.), Nisso-PB-GI-2000 (Nippon Soda Co., Ltd.), Nissan-PB-GI-3000 (Nippon Soda Co., Ltd.), PoIy bd R45HT (Idemitsu Kosan Co., Ltd.) it can. These can be used alone or in combination of two or more.
- lactone compound examples include a 3-membered ring lactone such as ⁇ -acetolactone; a 4-membered ring lactone such as ⁇ -propiolactone; a 5-membered ring lactone such as ⁇ -butyrolactone and ⁇ -laurolactone; and ⁇ -valerolactone.
- lactones examples include 6-membered ring lactones; 7-membered ring lactones such as ⁇ -caprolactone, and 9-membered ring lactones such as ⁇ -caprolactone. These can be used alone or in combination of two or more. Of these, a compound represented by the formula (III) is preferable, a 7-membered ring lactone is more preferable, and ⁇ -caprolactone is most preferable.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom.
- n represents the number of repeating units in parentheses and is an integer from 3 to 7, preferably 5.
- a catalyst can be used in the reaction between the polybutadiene having a hydroxyl group at the terminal and the lactone compound.
- the catalyst is not particularly limited.
- organic titanium compounds such as tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate; dibutyltin oxide, dibutyltin laurate, tin (II) 2-ethylhexanoate, stannous octylate
- organic tin compounds such as mono-n-butyltin fatty acid salts; stannous halides such as stannous chloride, stannous bromide and stannous iodide.
- the amount of the catalyst used is 0.05 to 2% by weight with respect to the total weight of the polybutadiene and the lactone compound.
- the amount of the catalyst used is preferably 0.01 mol% to 2 mol%, more preferably 0.02 mol% to 1.2 mol%, based on the hydroxyl groups in the reaction raw material.
- the reaction between the polybutadiene and the lactone compound can be carried out by raising the temperature of the reaction raw material until the viscosity becomes such that the reaction raw material can be sufficiently stirred, but the reaction raw material volatilizes or the catalyst decomposes. It is preferable to avoid raising the temperature to such a level.
- the specific temperature during the reaction is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 150 ° C.
- the reaction time can be appropriately selected according to the scale of the reaction, the reaction temperature, the type and mass ratio of polybutadiene and lactone compounds, the type and amount of catalyst used, and the like.
- the reaction may be performed by a continuous flow method or a batch method.
- the method for charging the polybutadiene having a hydroxyl group at the terminal and the lactone compound into the reactor is not particularly limited.
- the polybutadiene and lactone compound may be mixed and then added to the reactor all at once, continuously or intermittently, or each of the polybutadiene and lactone compound may be added to the reactor at once. You may add continuously or intermittently.
- one type of lactone compound may be added to the reactor at a time, and then another type of lactone compound may be added continuously or intermittently.
- the polymer polyol used in the present invention has a hydroxyl value of preferably 20 to 350 mgKOH / g, more preferably 20 to 200 mgKOH / g. When the hydroxyl value is in the above range, a polyurethane having an excellent balance between mechanical strength and water resistance can be obtained.
- the polymer polyol used in the present invention has a number average molecular weight (Mn) of 1,000 to 100,000, preferably 3,000 to 30,000, more preferably 5,000 to 15,000.
- the molecular weight distribution (Mw / Mn) is preferably 1.01 to 5, more preferably 1.1 to 2.2.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured by gel permeation chromatograph (GPC) using polystyrene as a standard substance, as described above.
- the asymmetric diisocyanate used in the present invention is an organic compound having two isocyanato groups in one molecule.
- the two isocyanato groups in the asymmetric diisocyanate exhibit different reactivities to the OH group due to differences in steric and electronic environments due to the asymmetric nature of the compound.
- a polyurethane having good mechanical properties and excellent water resistance can be obtained.
- Asymmetric diisocyanates include aromatic asymmetric diisocyanates such as 2,4-triylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-2,4′-diisocyanate; 1-isocyanatomethyl-3-isocyanato-1,5, Alicyclic asymmetric diisocyanates such as 5-trimethyl-cyclohexane (isophorone diisocyanate), 1-methyl-2,4-diisocyanato-cyclohexane and hydrides of the above aromatic diisocyanates; 1,6-diisocyanato-2,2,4- Aliphatic asymmetric diisocyanates such as trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane and lysine diisocyanate can be mentioned, and 2,4-triylene diisocyanate and / or isophorone diisocyanate.
- Anates are particularly
- Aromatic asymmetric diisocyanates and alicyclic asymmetric diisocyanates are preferred from the viewpoint of superiority and the viewpoint of excellent mechanical strength of the resulting polyurethane.
- the amount of asymmetric diisocyanate used in the reaction is set so that the R ratio value is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2.1 to 3.8.
- the R ratio is the ratio of the number of moles of isocyanate groups derived from asymmetric diisocyanate to the number of moles of hydroxyl groups derived from the polymer polyol.
- the chain extender used in the present invention is mainly a low molecular polyol or a low molecular polyamine, preferably a low molecular polyol.
- Low molecular polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-2- Propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2,2, 4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,6-he Sundiol,
- an aliphatic glycol or an alicyclic glycol is preferable, an aliphatic glycol is more preferable, and an aliphatic glycol having 2 to 5 carbon atoms. Is more preferred, butanediol is particularly preferred.
- low molecular weight polyamine examples include aromatic diamines such as 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, and 4,4′-diphenylmethanediamine; ethylenediamine, 1,2-propylenediamine, 2, 2-dimethyl-1,3-propanediamine, 1,3-pentanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine , 2,2,4- or 2,4,4-trimethylhexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine and the like; 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane, 4,4'-dicyclohexylmethanediamine, isopropylidenecyclo Hexyl-4,4'-diamine, 1,4-d
- the amount of chain extender used during the reaction is such that the NCO index value is preferably 0.2 to 10, more preferably 0.5 to 1.25, and even more preferably 0.9 to 1.1. Set.
- the NCO index is the ratio of the number of moles of isocyanate groups derived from asymmetric diisocyanate to the total number of moles of hydroxyl groups derived from the polymer polyol and hydroxyl groups derived from the chain extender.
- the polyurethane according to the present invention is not particularly limited in its production method, and can be produced, for example, by a prepolymer method or a one-shot method, but is preferably produced by a prepolymer method.
- a polymer polyol and an asymmetric diisocyanate are first reacted to obtain a urethane prepolymer having a terminal isocyanato group, and a chain extender is reacted with this to obtain a polyurethane.
- the one-shot method is a method of obtaining a polyurethane by adding a polymer polyol, an asymmetric diisocyanate, and a chain extender to a reactor and reacting them almost simultaneously.
- the reaction can be carried out by raising the temperature of the reaction raw material until the viscosity becomes such that the reaction raw material can be sufficiently stirred.
- the specific temperature during the reaction is preferably room temperature to 200 ° C, more preferably 50 to 100 ° C. If the temperature during the reaction is too low, the progress of the reaction is slow and the time required for production tends to be long. If the temperature during the reaction is too high, side reactions may occur or the pot life may be shortened, making the molding process difficult.
- This reaction can be carried out without a solvent or in a solvent. It is preferable to use a solvent inert to the reaction. Examples of the solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, dimethylformamide, tetrahydrofuran and the like.
- a catalyst can be used.
- the catalyst include tertiary amines such as dimethylethanolamine, triethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, and dimethylcyclohexylamine, metal catalysts such as stannous octate, potassium octylate, and dibutyltin dilaurate. And so on.
- the amount of the catalyst used is preferably 1 to 1000 ppm, more preferably 5 to 800 ppm, based on the total amount of the polymer polyol, the asymmetric diisocyanate and the chain extender.
- the reaction is slowed down and the time required for production becomes long. If the amount of the catalyst used is too large, the heat generation is intense and the reaction is difficult to control, and a gelled product may be formed or a colored polyurethane may be obtained.
- additives can be appropriately added to the polyurethane of the present invention as long as the effects of the present invention are not impaired.
- examples of other additives include flame retardants, deterioration inhibitors, and plasticizers.
- polymer polyol A is a number average
- Mn was 5900
- Mw weight average molecular weight
- Mw / Mn was 1.30
- the 1 H-NMR spectrum of polymer polyol A was measured.
- the mass ratio of polybutadiene component / polycaprolactone component (Y / (X 1 + X 2 )) was 67.4 / 32.6.
- Polymer polyol B has a number average molecular weight (Mn) of 7600, a weight average molecular weight (Mw) of 9400, a molecular weight distribution (Mw / Mn) of 1.23, and a mass ratio of polybutadiene component / polycaprolactone component (Y / (X 1 + X 2)) was 43.7 / 56.3.
- Polymer polyol C has a number average molecular weight (Mn) of 9900, a weight average molecular weight (Mw) of 12200, a molecular weight distribution (Mw / Mn) of 1.23, and a mass ratio of polybutadiene component / polycaprolactone component (Y / (X 1 + X 2 )) was 25.0 / 75.0.
- the polymer polyol D has a number average molecular weight (Mn) of 7400, a weight average molecular weight (Mw) of 9500, a molecular weight distribution (Mw / Mn) of 1.28, and a mass ratio of polybutadiene component / polycaprolactone component (Y / (X 1 + X 2)) was 55.5 / 44.5.
- the polymer polyol E has a number average molecular weight (Mn) of 9600, a weight average molecular weight (Mw) of 14400, a molecular weight distribution (Mw / Mn) of 1.51, and a mass ratio of polybutadiene component / polycaprolactone component (Y / (X 1 + X 2 )) was 60.8 / 39.2.
- Polymer polyol F has a number average molecular weight (Mn) of 7200, a weight average molecular weight (Mw) of 9800, a molecular weight distribution (Mw / Mn) of 1.36, and a mass ratio of polybutadiene component / polyvalerolactone component (Y / (X 1 + X 2 )) was 51.3 / 48.7.
- 2,4-tolylene diisocyanate Cosmonate T-100, manufactured by Mitsui Chemicals, Inc., containing 98% or more of 2,4-tolylene diisocyanate
- the NCO content was measured as follows. About 3 g of the reaction solution was placed in a conical stoppered Erlenmeyer flask in which dry air was allowed to flow, and 20 ml of toluene and 20 ml of dibutylamine / toluene solution were added thereto, followed by stirring for 15 minutes. Thereafter, 100 ml of 2-propanol and a few drops of bromophenol blue indicator were added, titrated with 0.5M hydrochloric acid, and quantitative analysis of isocyanato (NCO) groups was performed.
- Example 2 Polyurethane B was obtained in the same manner as in Example 1 except that polymer polyol B was used instead of polymer polyol A. The appearance of polyurethane B was light yellow and transparent.
- Example 3 Polyurethane C was obtained in the same manner as in Example 1 except that polymer polyol C was used instead of polymer polyol A. The appearance of polyurethane C was light yellow and transparent.
- Example 4 Polyurethane D was obtained in the same manner as in Example 1 except that polymer polyol D was used instead of polymer polyol A. The appearance of polyurethane D was light yellow and transparent.
- Example 5 Polyurethane E was obtained in the same manner as in Example 1 except that polymer polyol E was used instead of polymer polyol A. Polyurethane E was colored orange.
- diphenylmethane diisocyanate Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd., containing
- urethane prepolymer G 1.1 g of 1,4-butanediol was added to 53.9 g of urethane prepolymer G at 50 to 60 ° C., and degassed for 10 minutes under reduced pressure while stirring. Nitrogen was introduced into the system to return to normal pressure. This was immediately poured into a glass plate that had been treated with a release agent to a thickness of 2 mm. In addition, 2 mm-thick silicon rubber was installed as a wall on the edge of the glass plate. This was reacted at 100 ° C. for 2 hours and at 110 ° C. for 15 hours. The obtained sheet was peeled from the glass plate and annealed at 100 ° C. for 14 hours to obtain polyurethane G. Polyurethane G exhibited very brittle physical properties.
- VESTANET IPDI isophorone diisocyanate
- the NCO content was measured as follows. About 3 g of the reaction solution was placed in a conical stoppered Erlenmeyer flask in which dry air was allowed to flow, 20 ml of toluene and 20 ml of dibutylamine / toluene solution were added thereto, and the mixture was stirred for 15 minutes. Thereafter, 100 ml of 2-propanol and a few drops of bromophenol blue indicator were added, titrated with 0.5M hydrochloric acid, and quantitative analysis of isocyanato (NCO) groups was performed.
- m-xylylene diisocyanate manufactured by Tokyo Chemical Industry Co., Ltd.
- ⁇ Tensile test> In accordance with JIS K 7312, a No. 5 dumbbell test piece was prepared, and using a tester (manufactured by Shimadzu Corporation, Autograph AGS-J (5 kN), modulus at 100% elongation (M100), 200% elongation The modulus at time (M200), modulus at 300% elongation (M300), tensile strength (TB, stress at break), and elongation at break (EB) were measured.
- a tester manufactured by Shimadzu Corporation, Autograph AGS-J (5 kN
- M100 modulus at 100% elongation
- M200 modulus at time
- M300 modulus at 300% elongation
- TB tensile strength
- EB elongation at break
- the polyurethane G obtained in Comparative Example 2 exhibited a break elongation of 111% in the tensile test, and M200 and M300 could not be measured.
- the polyurethanes A to E and H obtained in Examples 1 to 6 had good mechanical properties and low water absorption.
- the polyurethane of the present invention has good mechanical properties and excellent water resistance.
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Abstract
Description
本願は、2012年5月30日に日本に出願された特願2012-122744号に基づき優先権を主張し、その内容をここに援用する。
〈1〉式(I)で表されるポリマーポリオールと、非対称ジイソシアネートと、鎖延長剤とを反応させて得られるポリウレタン。
HO-X1-Y-X2-OH (I)
前記式(I)中、X1およびX2は、各々独立して、ポリエステル成分を示し、Yはポリブタジエン成分を示す。
〈5〉鎖延長剤が、脂肪族グリコールである〈1〉~〈4〉のいずれかひとつに記載のポリウレタン。
本発明に用いられるポリマーポリオールは、式(I):
HO-X1-Y-X2-OH (I)
で表されるポリマーポリオールである。
ポリエステル成分は、同一構造の繰り返し単位が繋がったものであってもよいし、異なる構造の繰り返し単位が繋がったものであってもよい。
また、前記式(I)で示されるポリマーポリオール中におけるX1とX2の合計質量に対するYの質量の比は、好ましくは0.1~10、より好ましくは0.2~5、さらに好ましくは0.3~3.5である。X1とX2の合計質量に対するYの質量の比は、例えば、末端に水酸基を有するポリブタジエンとラクトン化合物との反応における仕込み質量比を変えることによって調整することができる。また、X1とX2の合計質量に対するYの質量の比は、例えば、1H-NMRなどで測定して算出することができる。
X1またはX2とYとの結合部分の構造は特に限定されず、本発明の効果を損なわない範囲で適宜選択することができる。
触媒としては、特に限定されないが、例えば、テトラブチルチタネート、テトライソプロピルチタネート、テトラエチルチタネート等の有機チタン系化合物;ジブチルスズオキシド、ジブチルスズラウレート、2-エチルヘキサン酸スズ(II)、オクチル酸第一スズ、モノ-n-ブチルスズ脂肪酸塩等の有機スズ化合物;塩化第一スズ、臭化第一スズ、ヨウ化第一スズ等のハロゲン化第一スズ等を挙げることができる。触媒の使用量は、前記ポリブタジエンとラクトン化合物との合計重量に対して、0.05重量%~2重量%である。また、触媒の使用量は、反応原料中の水酸基に対して、好ましくは0.01モル%~2モル%、より好ましくは0.02モル%~1.2モル%である。
本発明に用いられる非対称ジイソシアネートは、1分子中に2つのイソシアナト基を有する有機化合物である。非対称ジイソシアネート中の、2つのイソシアナト基は、化合物が非対称であることに起因する立体的および電子的環境の違いにより、OH基に対して異なる反応性を示す。このような非対称ジイソシアネートを用いることにより、良好な機械的物性と優れた耐水性を有するポリウレタンを得ることができる。
非対称ジイソシアネートとしては、2,4-トリイレンジイソシアネート、ナフタレン-1,4-ジイソシアネート、ジフェニルメタン-2,4'-ジイソシアネートなどの芳香族非対称ジイソシアネート;1-イソシアナトメチル-3-イソシアナト-1,5,5-トリメチル-シクロヘキサン(イソホロンジイソシアネート)、1-メチル-2,4-ジイソシアナト-シクロヘキサンおよび上記の芳香族ジイソシアネートの水素化物などの脂環式非対称ジイソシアネート;1,6-ジイソシアナト-2,2,4-トリメチルヘキサン、1,6-ジイソシアナト-2,4,4-トリメチルヘキサンおよびリジンジイソシアネートなどの脂肪族非対称ジイソシアネート等を挙げることができ、2,4-トリイレンジイソシアネート及び/又はイソホロンジイソシアネートが特に好ましく使用される。これらは1種単独でまたは2種以上を組み合わせて用いることができる。また、本発明には、非対称ジイソシアネートと対称ジイソシアネートを組み合わせて用いる態様も包含する。
本発明において用いられる鎖延長剤は、主として、低分子ポリオールまたは低分子ポリアミンであり、好ましくは低分子ポリオールである。
プレポリマー法では、ポリマーポリオールと非対称ジイソシアネートとを先ず反応させて末端イソシアナト基を有するウレタンプレポリマーを得、これに鎖延長剤を反応させてポリウレタンを得る方法である。ワンショット法は、ポリマーポリオールと非対称ジイソシアネートと鎖延長剤とをほぼ同時に反応器に添加して反応させてポリウレタンを得る方法である。
この反応は溶剤無しでも、溶剤中でも行うことができる。溶剤としては反応に不活性なものを用いることが好ましい。溶剤としては、トルエン、酢酸エチル、酢酸ブチル、メチルエチルケトン、ジメチルフォルムアミド、テトラヒドロフランなどを挙げることができる。
合成例1
1Lセパラブルフラスコに、両末端にヒドロキシエチル基を有するポリブタジエン(NISSO-PB G-1000、日本曹達(株)社製、1,2-構造/1,4-構造のモル比=90.4/9.6、数平均分子量(Mn)=2500(ポリスチレンを標準物質として用いたGPC測定)、水酸基価=72.9(KOHmg/g))300.5gと、ε-カプロラクトン(和光純薬工業(株)社製)211.8gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)(和光純薬工業(株)社製)1.8gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン538.3gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール5331gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。デカントにて上澄みを除去し、沈殿物をテトラヒドロフラン508.6gに添加して溶解させた。揮発成分をエバポレーターで減圧留去し、ポリマーポリオールAを得た。
1Lセパラブルフラスコに、両末端にヒドロキシエチル基を有するポリブタジエン(NISSO-PB G-1000、日本曹達(株)社製、1,2-構造/1,4-構造のモル比=90.4/9.6、数平均分子量(Mn)=2500(ポリスチレンを標準物質として用いたGPC測定)、水酸基価=72.9(KOHmg/g))200.0gと、ε-カプロラクトン(和光純薬工業(株)社製)282.7gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)(和光純薬工業(株)社製)1.2gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン508.8gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール5244gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。デカントにて上澄みを除去し、沈殿物をテトラヒドロフラン587.8gに添加して溶解させた。揮発成分をエバポレーターで減圧留去し、ポリマーポリオールBを得た。
ポリマーポリオールBは、数平均分子量(Mn)が7600、重量平均分子量(Mw)が9400、分子量分布(Mw/Mn)が1.23、ポリブタジエン成分/ポリカプロラクトン成分の質量比(Y/(X1+X2))が43.7/56.3であった。
1Lセパラブルフラスコに、両末端にヒドロキシエチル基を有するポリブタジエン(NISSO-PB G-1000、日本曹達(株)社製、1,2-構造/1,4-構造のモル比=90.4/9.6、数平均分子量(Mn)=2500(ポリスチレンを標準物質として用いたGPC測定)、水酸基価=72.9(KOHmg/g))100.1gと、ε-カプロラクトン(和光純薬工業(株)社製)281.7gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)(和光純薬工業(株)社製)0.6gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン736.2gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール7095gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。ろ過にて沈殿物を回収し、減圧乾燥し、ポリマーポリオールCを得た。
ポリマーポリオールCは、数平均分子量(Mn)が9900、重量平均分子量(Mw)が12200、分子量分布(Mw/Mn)が1.23、ポリブタジエン成分/ポリカプロラクトン成分の質量比(Y/(X1+X2))が25.0/75.0であった。
1Lセパラブルフラスコに、両末端にヒドロキシエチル基を有するポリブタジエン(NISSO-PB G-2000、日本曹達(株)社製、1,2-構造/1,4-構造のモル比=90.5/9.5、数平均分子量(Mn)=3600(ポリスチレンを標準物質として用いたGPC測定)、水酸基価=52.6(KOHmg/g))250.0gと、ε-カプロラクトン250.1gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)1.0gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン515.2gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール5062gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。デカントにて上澄みを除去し、沈殿物をテトラヒドロフラン515.6gに添加して溶解させた。揮発成分をエバポレーターで減圧留去し、ポリマーポリオールDを得た。
ポリマーポリオールDは、数平均分子量(Mn)が7400、重量平均分子量(Mw)が9500、分子量分布(Mw/Mn)が1.28、ポリブタジエン成分/ポリカプロラクトン成分の質量比(Y/(X1+X2))が55.5/44.5であった。
1Lセパラブルフラスコに、両末端にヒドロキシエチル基を有するポリブタジエン(PoIy bd R-45HT、出光興産(株)社製、1,2-構造/1,4-構造のモル比=20/80、数平均分子量(Mn)=2500(ポリスチレンを標準物質として用いたGPC測定)、水酸基価=44.9(KOHmg/g))250.0gと、ε-カプロラクトン202.4gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)0.9gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン548.1gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール4979gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。デカントにて上澄みを除去し、沈殿物をテトラヒドロフラン467.5gに添加して溶解させた。揮発成分をエバポレーターで減圧留去し、ポリマーポリオールEを得た。
ポリマーポリオールEは、数平均分子量(Mn)が9600、重量平均分子量(Mw)が14400、分子量分布(Mw/Mn)が1.51、ポリブタジエン成分/ポリカプロラクトン成分の質量比(Y/(X1+X2))が60.8/39.2であった。
0.1Lナスフラスコに、NISSO-PB G-1000を10.0gと、δ-バレロラクトン(東京化成工業(株)社製)14.1gを入れ、60℃に加温し、窒素雰囲気下で均一溶液とした。これに2-エチルヘキサン酸スズ(II)0.1gを加えて100℃に昇温し、100℃で7時間撹拌した。その後、12時間放冷した。これをテトラヒドロフラン37.2gに添加して溶解させた。得られた溶液を、激しく撹拌したメタノール1222gの中に、滴下した。滴下終了後、2時間撹拌し、次いで12時間静置した。デカントにて上澄みを除去し、沈殿物をテトラヒドロフラン89.3gに添加して溶解させた。揮発成分をエバポレーターで減圧留去し、ポリマーポリオールFを得た。
ポリマーポリオールFは、数平均分子量(Mn)が7200、重量平均分子量(Mw)が9800、分子量分布(Mw/Mn)が1.36、ポリブタジエン成分/ポリバレロラクトン成分の質量比(Y/(X1+X2))が51.3/48.7であった。
実施例1
500mLセパラブルフラスコに、ポリマーポリオールA 125.1gを仕込み、系内を減圧した。その後、温度100℃にて撹拌し、系内の水分を除去した。次いで、系内に窒素を導入して常圧とし、温度80℃に下げた。これに2,4-トリレンジイソシアネート(コスモネートT-100、三井化学(株)社製、2,4-トリレンジイソシアネートを98%以上含有する)20.0g(Rレシオ=2.1)を加え、80℃にて1時間撹拌した。NCO含量が理論値(=3.5%)±0.5%の範囲内となるまで反応を進行させ、ウレタンプレポリマーAを得た。
なお、NCO含量は、次のようにして測定した。ドライエアーを流しておいた共栓付き三角フラスコに反応液約3gを入れ、これにトルエン20mlとジブチルアミン/トルエン溶液20mlを加え、15分間撹拌した。その後、2-プロパノール100mlとブロムフェノールブルー指示薬を数滴加え、0.5M塩酸で滴定し、イソシアナト(NCO)基の定量分析を行った。
これを直ちに、離型剤処理を施したガラス板に、厚さ2mmとなるように流涎した。なお、ガラス板の縁に2mm厚のシリコンゴムを壁として設置した。これを100℃にて2時間、110℃にて15時間反応させた。得られたシートをガラス板から剥がし、100℃にて14時間アニール処理を行って、ポリウレタンAを得た。ポリウレタンAの外観は、淡黄色透明であった。
ポリマーポリオールAの代わりにポリマーポリオールBを用いた以外は、実施例1と同じ手法にてポリウレタンBを得た。ポリウレタンBの外観は、淡黄色透明であった。
ポリマーポリオールAの代わりにポリマーポリオールCを用いた以外は、実施例1と同じ手法にてポリウレタンCを得た。ポリウレタンCの外観は、淡黄色透明であった。
ポリマーポリオールAの代わりにポリマーポリオールDを用いた以外は、実施例1と同じ手法いてポリウレタンDを得た。ポリウレタンDの外観は、淡黄色透明であった。
ポリマーポリオールAの代わりにポリマーポリオールEを用いた以外は、実施例1と同じ手法にてポリウレタンEを得た。ポリウレタンEは、オレンジ色に着色していた。
500mLセパラブルフラスコに、ポリマーポリオールB 126.8gを仕込み、系内を減圧した。その後、温度100℃にて撹拌し、系内の水分を除去した。次いで、系内に窒素を導入して常圧とし、温度80℃に下げた。これにジフェニルメタンジイソシアネート(ミリオネートMT、日本ポリウレタン工業(株)製、4,4’-ジフェニルメタンジイソシアネートを99%以上含有する)20.4gを加え、80℃にて1時間撹拌した。NCO含量が理論値(=2.4%)±0.5%の範囲内となるまで反応を進行させ、ウレタンプレポリマーFを得た。
500mLセパラブルフラスコに、ポリマーポリオールB 47.5gを仕込み、系内を減圧した。その後、温度100℃にて攪拌し、系内の水分を除去した。次いで、系内に窒素を導入して常圧とし、温度60℃に下げた。これにジフェニルメタンジイソシアネート(ミリオネートMT、日本ポリウレタン工業(株)製、4,4’-ジフェニルメタンジイソシアネートを99%以上含有する )7.7gを加え、80℃にて1時間攪拌した。NCO含量が理論値(=2.4%)±0.5%の範囲内となるまで反応を進行させ、ウレタンプレポリマーGを得た。
これを直ちに、離型剤処理を施したガラス板に、厚さ2mmとなるように流涎した。なお、ガラス板の縁に2mm厚のシリコンゴムを壁として設置した。これを100℃にて2時間、110℃にて15時間にて反応させた。得られたシートをガラス板から剥がし、100℃にて14時間アニール処理を行って、ポリウレタンGを得た。ポリウレタンGは、非常に脆い物性を示した。
500mLセパラブルフラスコに、ポリマーポリオールBを125.1g仕込み、系内を減圧した。その後、温度100℃にて撹拌し、系内の水分を除去した。次いで、系内に窒素を導入して常圧とし、温度80℃に下げた。これにイソホロンジイソシアネート(商品名VESTANET IPDI、EVONIK社製)18.7g(Rレシオ=2.1)を加え、80℃にて1時間撹拌した。NCO含量が理論値(=2.6%)±0.5%の範囲内となるまで反応を進行させ、ウレタンプレポリマーHを得た。
なお、NCO含量は、次のようにして測定した。ドライエアーを流しておいた共栓付き三角フラスコに反応液約3gを入れ、これにトルエン20mlとジブチルアミン/トルエン溶液20mlを加え、15分間撹拌した。その後、2-プロパノール100mlとブロムフェノールブルー指示薬を数滴加え、0.5M塩酸で滴定し、イソシアナト(NCO)基の定量分析を行った。
これを直ちに、離型剤処理を施したガラス板に、厚さ2mmとなるように流涎した。なお、ガラス板の縁に2mm厚のシリコンゴムを壁として設置した。これを100℃にて2時間、110℃にて15時間反応させた。得られたシートをガラス板から剥がし、100℃にて14時間アニール処理を行って、ポリウレタンHを得た。ポリウレタンHの外観は、淡黄色透明であった。
500mLセパラブルフラスコに、ポリマーポリオールBを130.0gを仕込み、系内を減圧した。その後、温度100℃にて撹拌し、系内の水分を除去した。次いで、系内に窒素を導入して常圧とし、温度80℃に下げた。これにm-キシリレンジイソシアネート(東京化成工業(株)社製)14.9gを加え、80℃にて1時間撹拌した。NCO含量が理論値(=2.4%)±0.5%の範囲内となるまで反応を進行させ、ウレタンプレポリマーIを得た。
ポリウレタンA~E、GおよびHについて、それぞれ以下の硬度試験、引張り試験、および吸水性試験を行った。結果を表1に示す。
2mm厚の成形シートを6枚重ねて、Aタイプ又はDタイプデュロメータを用い、JIS K 7311に準じて硬度を測定した。
JIS K 7312に準じて、5号ダンベル試験片を作成し、試験機(株式会社島津製作所製、オートグラフAGS-J(5kN)を用いて、100%伸長時のモジュラス(M100)、200%伸長時のモジュラス(M200)、300%伸長時のモジュラス(M300)、引張り強さ(TB、破断時の応力)、及び破断伸び(EB)を測定した。
50mm×50mm×2mm厚の試験片を作成して試験片の質量W0を測定した。それを23℃の水に24時間浸漬し、引き上げて表面の水を拭き取り、試験片の質量W1を再度測定した。浸漬前の質量W0に対する浸漬前後の増加質量W1-W0の割合(吸水率)を算出した。
一方、実施例1~6で得たポリウレタンA~EおよびHは、良好な機械的物性と低い吸水率を有するものであった。
Claims (5)
- 式(I):
HO-X1-Y-X2-OH (I)
(式(I)中、X1およびX2は、各々独立して、ポリエステル成分を示し、Yはポリブタジエン成分を示す。)で表されるポリマーポリオールと、
非対称ジイソシアネートと、
鎖延長剤と
を反応させて得られるポリウレタン。 - 前記ポリブタジエン成分は、1,2-構造/1,4-構造のモル比率が55/45~95/5である請求項1に記載のポリウレタン。
- 前記鎖延長剤が、脂肪族グリコールである請求項1に記載のポリウレタン。
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EP3480234A1 (de) * | 2017-11-03 | 2019-05-08 | Evonik Degussa GmbH | Block-copolymere, enthaltend polyester- und polyolefin-struktureinheiten, und deren verwendung |
JP2021050326A (ja) * | 2019-09-20 | 2021-04-01 | 保土谷化学工業株式会社 | ラクトン重合体の製造方法 |
CN110903805B (zh) * | 2019-12-23 | 2021-10-29 | 美瑞新材料股份有限公司 | 一种低极性高回弹的聚氨酯热熔胶、其制备方法及应用 |
EP3919539A1 (de) * | 2020-06-04 | 2021-12-08 | Evonik Operations GmbH | Herstellung von polyurethanschaum |
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