WO2010010685A1 - 脂肪族ポリエステル樹脂及びその製造方法 - Google Patents
脂肪族ポリエステル樹脂及びその製造方法 Download PDFInfo
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- WO2010010685A1 WO2010010685A1 PCT/JP2009/003399 JP2009003399W WO2010010685A1 WO 2010010685 A1 WO2010010685 A1 WO 2010010685A1 JP 2009003399 W JP2009003399 W JP 2009003399W WO 2010010685 A1 WO2010010685 A1 WO 2010010685A1
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- aliphatic polyester
- polyester resin
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- organophosphorus compound
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6922—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the present invention relates to an aliphatic polyester resin mainly composed of a polyhydroxy acid skeleton in which the activity of a polymerization catalyst is reduced by copolymerizing a specific organophosphorus compound, and a method for producing the same.
- the aliphatic polyester resin mainly composed of a polyhydroxy acid skeleton is composed of a polymer of lactic acid or lactide (polylactic acid), or a copolymer of lactic acid or lactide and another monomer. Since these resins have a polyhydroxy acid skeleton exhibiting excellent biodegradability, in recent years, extensive research has been actively conducted to use them from the viewpoint of environmental problems.
- aliphatic polyester resins mainly composed of a polyhydroxy acid skeleton are obtained by melt-mixing lactide, which is a dimer of hydroxy acid, and, if desired, other hydroxy acid, polyol, lactone, etc. under heating to form a known ring-opening. It is produced by a method in which a ring-opening polymerization is performed under a nitrogen atmosphere using a polymerization catalyst.
- This polymerization catalyst needs to have activity during the polymerization reaction, but if it remains in the resin while maintaining the activity after the completion of the polymerization reaction, the resin is heated by heating in the purification step to remove unreacted monomers. Is partially depolymerized to return to the raw material monomer lactide.
- Patent Documents 1 to 3 As this method, it has been proposed to add a specific phosphorus compound to the reaction system after completion of the polymerization reaction to reduce the activity of the polymerization catalyst (Patent Documents 1 to 3). As these phosphorus compounds, phosphoric acid compounds or phosphorous acid compounds are used in Patent Documents 1 and 2, and alkyl phosphates and / or alkylphosphonates are used in Patent Document 3.
- the activity of the polymerization catalyst remaining in the resin after completion of the polymerization reaction can be reduced to some extent, and the production of monomer lactide by heating after polymerization or after production is prevented to some extent.
- the degree of prevention is insufficient to sufficiently prevent the strength deterioration of the resin, and further improvement has been demanded.
- the present invention was devised in view of the current state of the prior art described above, and its purpose is that the activity of the polymerization catalyst contained in the resin after polymerization is sufficiently reduced, and heating after polymerization or after production. It is another object of the present invention to provide an aliphatic polyester resin that hardly produces lactide and a method for producing the same.
- the present invention is as follows (1) to (7).
- An aliphatic polyester resin having a polyhydroxy acid skeleton as a main component and produced using a polymerization catalyst, and an organic phosphorus compound represented by the following general formula [I] is copolymerized in the resin Aliphatic polyester resin characterized by: In the formula, R 1 , R 2 , R 3 and R 4 represent hydrogen or an alkyl group, which may be the same or different, and n represents an integer of 1 or more.
- R 1 , R 2 , R 3 and R 4 represent hydrogen or an alkyl group, which may be the same or different, and n represents an integer of 1 or more.
- a method for producing an aliphatic polyester resin having a polyhydroxy acid skeleton as a main component by carrying out a ring-opening polymerization reaction in the presence of a polymerization catalyst, the organophosphorus compound represented by the following general formula [I] A method comprising reducing the activity of a polymerization catalyst by adding to the reaction system:
- R 1 , R 2 , R 3 and R 4 represent hydrogen or an alkyl group, which may be the same or different
- n represents an integer of 1 or more.
- the aliphatic polyester resin of the present invention contains a specific organophosphorus compound that is more effective in reducing the activity of the polymerization catalyst than the conventional one, the polymerization catalyst is activated by heating after polymerization or after production. Monomer lactide is hardly formed in it. Therefore, the molded body, coating, and adhesive produced using the aliphatic polyester resin of the present invention can exhibit good heat resistance, durability, and adhesion over a long period of time.
- the aliphatic polyester resin of the present invention has a polyhydroxy acid skeleton as a main component.
- a typical example of a hydroxy acid is lactic acid.
- Examples of hydroxy acids (derivatives) other than lactic acid include glycolic acid, 2-hydroxyisobutyric acid, 3-hydroxybutyric acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-2-methylbutyric acid, 12-hydroxystearic acid, malic acid, Examples include citric acid and gluconic acid.
- intramolecular esters of hydroxy acids such as caprolactone and cyclic dimers of ⁇ -hydroxy acids such as lactide are also used.
- examples of the aliphatic polycarboxylic acid that can be used as a raw material in addition to lactic acid (lactide) include succinic acid, adipic acid, and sebacic acid.
- examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, and polyglycerin.
- the aliphatic polyester resin of the present invention desirably contains 50% by mass or more of a polyhydroxy acid skeleton. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. When the content of the polyhydroxy acid skeleton is less than the above range, sufficiently good biodegradability, moldability, durability, and adhesion may not be obtained.
- the aliphatic polyester resin of the present invention can be produced based on a conventionally known method using a polymerization catalyst.
- a polymerization catalyst for example, lactide, which is a dimer of hydroxy acid, and other hydroxy acid, polyol, lactone, etc. described above are melt-mixed under heating, and heat-opening polymerization is performed in a nitrogen atmosphere using a known ring-opening polymerization catalyst. Can be adopted.
- the ring-opening polymerization reaction of lactide has a simple process, and a high-purity product is easily obtained.
- the organophosphorus compound represented by the general formula [I] is added to the reaction system at the time of production for the purpose of reducing the amount of lactide produced as a by-product after polymerization and after production. It is characterized by.
- the timing of adding the organophosphorus compound is not particularly limited, but in order to effectively reduce the amount of by-produced lactide, it is preferable to add the organophosphorus compound before the end of the ring-opening polymerization, and before the start of the ring-opening polymerization. It is more preferable to add.
- the polymerization catalyst used in the method for producing the aliphatic polyester resin of the present invention is not particularly limited, and examples thereof include tin compounds such as tin octylate and tin dibutylate, aluminum compounds such as aluminum acetylacetonate and aluminum acetate, tetra Conventionally known catalysts suitable for lactic acid polymerization, such as titanium compounds such as isopropyl titanate and tetrabutyl titanate, zirconium compounds such as zirconium isoprooxide, and antimony compounds such as antimony trioxide, can be mentioned.
- the optimum amount of the polymerization catalyst may be appropriately adjusted depending on the type of the catalyst. For example, when tin octylate is used as the catalyst, 0.005 to 0.5% by weight, preferably 0. 01 to 0.1% by weight. When aluminum acetylacetonate is used as a catalyst, it is 0.01 to 0.8% by weight, preferably 0.01 to 0.1% by weight, based on 100% by weight of the raw material monomer.
- the aliphatic polyester resin of the present invention can be produced by subjecting the raw material monomer to a heat polymerization reaction for 0.5 to 10 hours in the presence of a catalyst. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or in an air stream.
- the reaction system After completion of the polymerization reaction, if necessary, the reaction system is depressurized to distill off unreacted monomers.
- the temperature of the distillation step is usually 150 to 200 ° C.
- the pressure is usually 0.05 to 10 Torr
- the time is usually 0.2 to 2 hours.
- a lactide ring-opening polymerization initiator may be used.
- the ring-opening polymerization initiator is not particularly limited, and may be, for example, any of mono-, di- or polyhydric alcohols of aliphatic alcohols, and may be saturated or unsaturated.
- monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol and other dialcohols, glycerol, polyglycerol, sorbitol, xylitol, ribitol, erythritol, etc.
- Alcohol methyl lactate, ethyl lactate and the like can be used. Of these, ethylene glycol, lauryl alcohol, glycerol, and polyglycerol are particularly preferably used.
- the boiling point of the alcohol used is lower than the polymerization temperature, it is necessary to carry out the reaction under pressure.
- the amount of alcohol varies depending on the purpose, but if it is too large, the molecular weight tends to be difficult to increase.
- it is used at a ratio of 0.01 to 1 mol% with respect to 100 mol% of the total monomer amount.
- the organophosphorus compound used in the method for producing an aliphatic polyester resin of the present invention is represented by the following general formula [I].
- R 1 , R 2 , R 3 and R 4 represent hydrogen or an alkyl group, which may be the same or different, and n represents an integer of 1 or more.
- n represents an integer of 1 or more.
- the activity of the polymerization catalyst decreases as the proportion of hydrogen in R 1 , R 2 , and R 3 increases, the polymerization failure occurs when the organophosphorus compound is added before ring opening polymerization or at the beginning of ring opening polymerization, resulting in a molecular weight. It tends to be difficult to go up. Therefore, in producing the aliphatic polyester resin of the present invention, it is preferable to select an organic phosphorus compound depending on the timing of addition of the organic phosphorus compound.
- R 1 , R 2 and R 3 of the organophosphorus compound have a small proportion of hydrogen if the reaction product has a weight average molecular weight of 10,000 or less. In particular, it is preferable that the number of hydrogen is 1 or less. Further, if the organophosphorus compound is added after the ring-opening polymerization is completed, it is preferable that R 1 , R 2 , and R 3 of the organophosphorus compound have a large proportion of hydrogen from the viewpoint of reducing by-product lactide. It may be.
- the addition amount of the organophosphorus compound is preferably 0.5 to 30 times by mole, particularly preferably 0.5 to 10 times by mole, relative to the amount of catalyst used for the polymerization. If the amount is less than the above range, it may be difficult to obtain the effect of reducing lactide, and even if it is added more than the above range, there is a tendency that the effect does not vary.
- the method for adding the organophosphorus compound to the reaction system is not particularly limited. You may add with a raw material monomer, and you may add after raising the temperature of a reaction liquid and melt
- R 4 is hydrogen as shown in the following general formula [II] in order to increase the reaction efficiency.
- R 1 , R 2 and R 3 represent hydrogen or an alkyl group, which may be the same or different, and n represents an integer of 1 or more.
- R 1 , R 2 and R 3 are all alkyl groups include methyl dimethoxyphosphinyl acetate, ethyl diethoxyphosphinyl acetate, ethyl 2- (diethoxyphosphinyl) propanoate, 3- (di Ethoxyphosphinyl) ethyl propanoate.
- Examples of the compound in which only one of R 1 and R 2 is hydrogen and R 3 is an alkyl group include methyl methoxyphosphinyl acetate, ethyl ethoxyphosphinyl acetate, 2- (ethoxyphosphinyl) propane And ethyl 3- (ethoxyphosphinyl) propanoate.
- Compounds in which R 1 , R 2 of both R 1 , R 2 and R 3 are hydrogen and R 3 is an alkyl group include methyl phosphonoacetate, ethyl phosphonoacetate, ethyl 2-phosphonopropanoate, 3 -Ethyl phosphonopropanoate.
- R 1 of R 2, R 3, R 2 , R 3 is hydrogen compounds, phosphonoacetic acid, 2-phosphono propanoic acid, 3-phosphono propanoic acid.
- These organic phosphorus compounds may be dissolved in an organic solvent and added to the polymerization reaction system.
- the solvent to be used may be the same as or different from the ring-opening polymerization initiator, and examples thereof include methanol, ethanol, propanol, xylene, toluene, ethylene glycol, and lauryl alcohol.
- the aliphatic polyester resin of the present invention is characterized in that the organophosphorus compound represented by the general formula [I] is copolymerized in the resin, but the bonding mode is not particularly limited.
- the polyhydroxy acid as the main component is preferably polylactic acid as described above.
- the polylactic acid segment is bonded to at least one of R 1 , R 2 and R 3 of the organophosphorus compound, particularly to R 3 of the organophosphorus compound. preferable.
- this bonding mode is not particularly limited, it is preferable that the terminal hydroxyl group of the polylactic acid segment reacts with the carboxyl group or phosphate group site to which R 1 , R 2 , or R 3 is bonded and is bonded by an ester bond. .
- the aliphatic polyester resin of the present invention was formed by forming a complex between the organophosphorus compound of the formula [I] and a polymerization catalyst. It has been found that the activity of the polymerization catalyst is reduced and the by-production of monomer lactide due to heating after polymerization or after production is suppressed. Since the polyester resin of the present invention is copolymerized with an organophosphorus compound, it is unreacted after volatilization of the organophosphorus compound due to heat during ring-opening polymerization or after completion of the ring-opening polymerization, compared to a simple blend as in the prior art.
- the organic phosphorus compound to add can reduce the activity of a polymerization catalyst efficiently, and can suppress the byproduct of a lactide.
- the organophosphorus compound represented by the general formula [I] a portion of R 1 , R 2 and R 3 which is hydrogen interacts with the polymerization catalyst to reduce the activity of the catalyst, As a result, by-production of lactide after polymerization can be suppressed, and further, the production of lactide can be suppressed when the obtained aliphatic polyester resin is subjected to heat processing such as molding, adhesion, and coating.
- the aliphatic polyester resin back-by-back is obtained.
- the production of lactide due to the Bing reaction can be suppressed, and when the resulting aliphatic polyester resin is subjected to heat processing such as molding, adhesion, coating, etc., a by-product of lactide due to the back biting reaction can also be suppressed.
- any one of R 1 , R 2 and R 3 is It is considered that the lactic acid segment is bonded to the hydroxyl group and copolymerized.
- any of R 1 , R 2 and R 3 is an alkyl group, at least one of R 1 , R 2 and R 3 not bonded to the polylactic acid segment is undergoing ring-opening polymerization. Further, it is preferable from the viewpoint of suppressing the production of lactide that the alkyl group is eliminated and becomes hydrogen.
- a structure in which a polylactic acid segment is bonded to R 3 of the general formula [I] can be exemplified, and can be represented by the following general formula [III], for example.
- R 1 and R 2 represent hydrogen or an alkyl group
- n is an integer of 1 or more
- m is an integer of 3 or more.
- the aliphatic polyester resin of the present invention may include those in which all of R 1 , R 2 , and R 3 in the general formula [I] are substituted with polylactic acid segments, but has such a structure.
- R 1 , R 2 and R 3 are a polylactic acid segment and the others are hydrogen or an alkyl group
- R 3 is a polylactic acid segment, and the others are hydrogen or an alkyl group. More preferably.
- R 1 , R 2 and R 3 which are not polylactic acid segments are particularly preferably hydrogen.
- the molar ratio of the phosphorus element (A) derived from the organophosphorus compound and the metal element (B) derived from the polymerization catalyst in the resin is 1 ⁇ (A) / (B) ⁇ 30, particularly 3 It is preferable that ⁇ (A) / (B) ⁇ 9 is satisfied.
- the polymerization temperature in producing the aliphatic polyester resin of the present invention is preferably a temperature that can dissolve the raw material monomer and is lower than the boiling point of the organic phosphorus compound to be added. If the polymerization is carried out at a temperature higher than the boiling point of the organophosphorus compound, even if a cooling pipe is provided, the organophosphorus compound is distilled off during the reaction, and the activity of the catalyst cannot be lowered and the residual lactide may not be reduced. is there. If the polymerization temperature is high, the structural change of the organophosphorus compound is quick and the activity of the polymerization catalyst can be reduced in a short time. However, since the racemization of lactide proceeds, the polymerization temperature is preferably 230 ° C. or lower. . In particular, the polymerization temperature is preferably in the range of 100 to 230 ° C.
- the aliphatic polyester resin of the present invention contains an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, a fragrance, and an antibacterial agent as necessary. Further, various additives such as a dispersing agent and a polymerization inhibitor can be contained within a range not impairing the object of the present invention.
- the aliphatic polyester resin of the present invention can be used in conventionally known fields such as molding materials, films, fibers, adhesives, coating agents, paint binders and ink binders.
- adhesives since the lactide in the resin is small, even if it is stored for a long time under high temperature and high humidity, the adhesive strength is unlikely to decrease.
- the organophosphorus compound in which the polylactic acid segment is bonded to R 3 and the organophosphorus compound in which R 1 , R 2 and R 3 in the general formula [I] are not changed from the structure before addition are divided.
- NMR nuclear magnetic resonance spectrum
- Adhesive strength as heat seal adhesive The synthesized polylactic acid resin was dissolved in ethyl acetate at a solid content concentration of 40%. The obtained solution was applied to a biaxially stretched polylactic acid film, and then dried under reduced pressure at 35 ° C. overnight to remove the solvent to prepare two coating films. The application surfaces of the two coating films obtained were overlapped and heat laminated at 100 ° C. and 3 kgf / cm 2 to prepare a peel test sample. Two test pieces were cut out to a width of 10 mm from this sample. One test piece was immediately (on day 0) measured for adhesive strength. Another test piece was allowed to stand for 20 days under the conditions of 40 ° C. and 85% RH, and then the adhesive strength on the 20th day was measured. The adhesive strength was measured by subjecting the test piece to a T peel test with a tensile speed of 10 mm / min using a tensile tester.
- Example 1 In a 2 liter SUS304 reaction kettle equipped with a stirrer, thermometer and nitrogen inlet, 400 g of L-lactide and 100 g of D-lactide as raw monomers were placed, and the raw monomers were stirred at a temperature of 120 ° C. while stirring in a nitrogen atmosphere. After melting, 0.14 g of tin octylate as a polymerization catalyst, 0.5 g of ethylene glycol as a ring-opening polymerization initiator, and 0.22 g of ethyl diethoxyphosphinyl acetate as an organic phosphorus compound were added.
- Example 2 A polylactic acid resin was synthesized in the same manner as in Example 1 except that the amount of ethyl diethoxyphosphinyl acetate was changed to 0.66 g. Table 1 shows the details of the resin production method and the physical properties of the obtained resin.
- Example 3 A polylactic acid resin was synthesized in the same manner as in Example 1 except that the amount of ethyl diethoxyphosphinyl acetate was changed to 1.98 g. Table 1 shows the details of the resin production method and the physical properties of the obtained resin.
- Example 4 A polylactic acid resin was synthesized in the same manner as in Example 1 except that 0.22 g of ethyl diethoxyphosphinyl acetate was changed to 0.54 g of methyl dimethoxyphosphinyl acetate. Table 1 shows the details of the resin production method and the physical properties of the obtained resin.
- Example 5 A polylactic acid resin was synthesized in the same manner as in Example 1 except that 0.22 g of ethyl diethoxyphosphinyl acetate was changed to 0.71 g of ethyl 2- (diethoxyphosphinyl) propanoate. Table 1 shows the details of the resin production method and the physical properties of the obtained resin.
- Example 6 A polylactic acid resin was synthesized in the same manner as in Example 1 except that 0.22 g of ethyl diethoxyphosphinyl acetate was changed to 0.70 g of ethyl 3- (diethoxyphosphinyl) propanoate. Table 1 shows the details of the resin production method and the physical properties of the obtained resin.
- Example 7 In a 2 liter SUS304 reaction kettle equipped with a stirrer, thermometer and nitrogen inlet, 400 g of L-lactide and 100 g of D-lactide as raw monomers were placed, and the raw monomers were stirred at a temperature of 120 ° C. while stirring in a nitrogen atmosphere. After melting, 0.14 g of tin octylate as a polymerization catalyst and 0.5 g of ethylene glycol as a ring-opening polymerization initiator were added. Thereafter, the temperature of the reaction system was raised to 180 ° C., and polymerization was carried out for 1.5 hours.
- ⁇ Comparative example 2> In a 2 liter SUS304 reaction kettle equipped with a stirrer, thermometer and nitrogen inlet, 400 g of L-lactide and 100 g of D-lactide as raw monomers were placed, and the raw monomers were stirred at a temperature of 120 ° C. while stirring in a nitrogen atmosphere. After melting, 0.14 g of tin octylate as a polymerization catalyst, 0.5 g of ethylene glycol as a ring-opening polymerization initiator, and 0.28 g of trimethyl phosphate as an organic phosphorus compound were added. Thereafter, the temperature of the reaction system was raised to 180 ° C., and polymerization was carried out for 1.5 hours.
- the aliphatic polyester resin of the present invention was produced by using the aliphatic polyester resin of the present invention because the polymerization catalyst is activated by heating after polymerization or after production, and monomer lactide is hardly generated in the resin. Molded bodies, coatings and adhesives can exhibit good heat resistance, durability and adhesion over a long period of time.
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Abstract
Description
(1)重合触媒を使用して製造された、ポリヒドロキシ酸骨格を主成分とする脂肪族ポリエステル樹脂であって、下記一般式[I]で表される有機リン化合物が樹脂中に共重合されていることを特徴とする脂肪族ポリエステル樹脂:
式中、R1、R2、R3、R4は水素またはアルキル基を表し、それぞれ同一でも異なっていても良く、nは1以上の整数を表す。
(2)ポリヒドロキシ酸がポリ乳酸であり、前記ポリ乳酸が有機リン化合物のR1、R2およびR3のうち少なくとも一箇所に結合していることを特徴とする(1)に記載の脂肪族ポリエステル樹脂。
(3)ポリ乳酸が有機リン化合物のR3に結合していることを特徴とする(2)に記載の脂肪族ポリエステル樹脂。
(4)樹脂中の、有機リン化合物由来のリン元素(A)と重合触媒由来の金属元素(B)のモル比が以下の関係を満足することを特徴とする(1)~(3)のいずれかに記載の脂肪族ポリエステル樹脂。
(5)(1)~(4)のいずれかに記載の脂肪族ポリエステル樹脂を用いたことを特徴とする接着剤。
(6)重合触媒の存在下で開環重合反応することによってポリヒドロキシ酸骨格を主成分とする脂肪族ポリエステル樹脂を製造する方法であって、下記一般式[I]で表される有機リン化合物を反応系に添加して重合触媒の活性を低下させることを特徴とする方法:
式中、R1、R2、R3、R4は水素またはアルキル基を表し、それぞれ同一でも異なっていても良く、nは1以上の整数を表す。
(7)有機リン化合物を開環重合反応の開始前に反応系に添加することを特徴とする(6)に記載の方法。
式中、R1、R2、R3、R4は水素またはアルキル基を表し、それぞれ同一であっても異なっていても良く、nは1以上の整数を表す。特にR1、R2、R3の水素の割合が高くなるほど重合触媒の活性が低下するため、開環重合前若しくは開環重合初期に上記有機リン化合物を添加した場合に重合不良を起こし分子量が上がりにくくなる傾向にある。従って、本発明の脂肪族ポリエステル樹脂を製造するにあたっては、有機リン化合物の添加時期によって有機リン化合物を選択することが好ましい。
式中、R1、R2、R3は水素またはアルキル基を表し、それぞれ同一でも異なっていても良く、nは1以上の整数を表す。
式中、R1、R2は水素またはアルキル基を表し、nは1以上の整数であり、mは3以上の整数である。
もちろん、本発明の脂肪族ポリエステル樹脂には、一般式[I]においてR1、R2、R3の全てをポリ乳酸セグメントに置換したものが含まれても良いが、そのような構造であると、重合触媒の活性を低下させるための相互作用部位を有さないためラクチドの副生を抑制する効果が小さくなる傾向にある。そのため、R1、R2、R3のうち少なくとも一つがポリ乳酸セグメントであり、それ以外は水素またはアルキル基であることが好ましく、R3がポリ乳酸セグメントであり、それ以外は水素またはアルキル基であることがさらに好ましい。ポリ乳酸セグメントでないR1、R2、R3は水素であることが特に好ましい。
テトラヒドロフランを移動相とした島津製作所製島津液クロマトグラフProminenceを用いて、カラム温度30℃、流量1mL/分にて、合成したポリ乳酸樹脂のGPC測定を行なった。その結果から計算して、ポリスチレン換算した値を樹脂の重量平均分子量とした。カラムとしては昭和電工(株)Shodex KF-802、804、806を用いた。
合成したポリ乳酸樹脂をクロロホルム-dに溶解し、得られた溶液を用いて400MHzの核磁気共鳴スペクトル(NMR)装置で、ポリ乳酸に由来するプロトンの積分値とラクチドに由来するプロトンの積分値を測定した。重合後の副生ラクチド量は、これらの比から算出した。
合成したポリ乳酸樹脂40mgをクロロホルム-d/DMSO-d=1/1(体積比)混合溶媒0.6mlに溶解し、リン酸5μlを添加後、室温で1時間放置し、500MHzの核磁気共鳴スペクトル(NMR)装置を用い、1H-NMRを測定した。
1H-NMRの結果に基づいて、有機リン化合物に由来するピークの積分比とポリ乳酸に由来するピークの積分比との対比から一般式[I]のR1、R2が添加前の構造から変化しておらずR3にポリ乳酸セグメントが結合した有機リン化合物と、一般式[I]のR1、R2、R3共に添加前の構造から変化していない有機リン化合物とに分けて有機リン化合物の量を算出した。
更に、合成したポリ乳酸樹脂500mgをクロロホルム-d/DMSO-d=1/1(体積比)混合溶媒2.5mlに溶解し、リン酸約80mgを添加後、室温で1時間放置し、500MHzの核磁気共鳴スペクトル(NMR)装置を用い、31P-NMRを測定した。31P-NMRの結果より、1H-NMRではピークが見えなかった有機リン化合物の存在が明らかになった。
先に1H-NMR測定から算出した有機リン化合物の量と31P-NMR測定の結果から、ポリ乳酸中に含まれる有機リン化合物のうちポリ乳酸に共重合されている有機リン化合物の量を算出した。
算出した共重合されている有機リン化合物の量(mol%)は、ポリ乳酸を構成するラクチドに対する量を表す。
合成したポリ乳酸樹脂0.2gに硝酸3mLを添加し、密閉性高圧湿式分解法により測定液を調整した。測定液からICP発光法により、リン元素量及び重合触媒由来の金属元素量を定量した。
合成したポリ乳酸樹脂を酢酸エチルに固形分濃度40%で溶解した。得られた溶液を二軸延伸ポリ乳酸フィルムに塗布した後、35℃で一晩減圧乾燥して溶剤を除去してコーティングフィルムを二枚作成した。得られた二枚のコーティングフィルムの塗布面同士を重ねて100℃、3kgf/cm2でヒートラミネート接着を行って剥離試験サンプルを作成した。このサンプルから二枚の試験片を10mm幅に切り出した。一枚の試験片は、直ちに(0日目に)接着強度を測定した。もう一枚の試験片は、40℃、85%RHの条件下に20日間放置した後、20日目の接着強度を測定した。接着強度は、試験片を引張り試験機にて引張速度10mm/分のT剥離試験に供することによって測定した。
攪拌機、温度計、窒素吹き込み口を備えた2リットルのSUS304製反応釜に、原料モノマーとしてのL-ラクチド400g、D-ラクチド100gを入れ、窒素雰囲気下で攪拌しながら温度120℃で原料モノマーを溶融した後、重合触媒としてのオクチル酸スズ0.14g、開環重合開始剤としてのエチレングリコール0.5g、有機リン化合物としてのジエトキシホスフィニル酢酸エチル0.22gを添加した。その後、反応系を180℃まで昇温し、重合を1.5時間行った。重合反応終了後、180℃、0.1Torrで0.5時間減圧して未反応モノマーを留去し、ポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
ジエトキシホスフィニル酢酸エチルの量を0.66gに変更した以外は実施例1と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
ジエトキシホスフィニル酢酸エチルの量を1.98gに変更した以外は実施例1と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
ジエトキシホスフィニル酢酸エチル0.22gをジメトキシホスフィニル酢酸メチル0.54gに変更した以外は実施例1と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
ジエトキシホスフィニル酢酸エチル0.22gを2-(ジエトキシホスフィニル)プロパン酸エチル0.71gに変更した以外は実施例1と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
ジエトキシホスフィニル酢酸エチル0.22gを3-(ジエトキシホスフィニル)プロパン酸エチル0.70gに変更した以外は実施例1と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
攪拌機、温度計、窒素吹き込み口を備えた2リットルのSUS304製反応釜に、原料モノマーとしてのL-ラクチド400g、D-ラクチド100gを入れ、窒素雰囲気下で攪拌しながら温度120℃で原料モノマーを溶融した後、重合触媒としてのオクチル酸スズ0.14g、開環重合開始剤としてのエチレングリコール0.5gを添加した。その後、反応系を180℃まで昇温し、重合を1.5時間行った。重合反応終了後、有機リン化合物としてのジエトキシホスフィニル酢酸エチル0.66gを添加して30分攪拌した後、180℃、0.1Torrで0.5時間減圧して未反応モノマーを留去し、ポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
攪拌機、温度計、窒素吹き込み口を備えた2リットルのSUS304製反応釜に、原料モノマーとしてのL-ラクチド400g、D-ラクチド100gを入れ、窒素雰囲気下で攪拌しながら温度120℃で原料モノマーを溶融した後、重合触媒としてのオクチル酸スズ0.14g、開環重合開始剤としてのエチレングリコール0.5gを添加した。その後、反応系を180℃まで昇温し、重合を1.5時間行った。重合反応終了後、180℃、0.1Torrで0.5時間減圧して未反応モノマーを留去し、ポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
攪拌機、温度計、窒素吹き込み口を備えた2リットルのSUS304製反応釜に、原料モノマーとしてのL-ラクチド400g、D-ラクチド100gを入れ、窒素雰囲気下で攪拌しながら温度120℃で原料モノマーを溶融した後、重合触媒としてのオクチル酸スズ0.14g、開環重合開始剤としてのエチレングリコール0.5g、有機リン化合物としてのリン酸トリメチル0.28gを添加した。その後、反応系を180℃まで昇温し、重合を1.5時間行った。重合反応終了後、180℃、0.1Torrで0.5時間減圧して未反応モノマーを留去し、ポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
リン酸トリメチル0.28gをリン酸トリエチル0.38gに変更した以外は比較例2と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
リン酸トリメチル0.28gをフェニルホスホン酸ジメチル0.38gに変更した以外は比較例2と同様の方法でポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
攪拌機、温度計、窒素吹き込み口を備えた2リットルのSUS304製反応釜に、原料モノマーとしてのL-ラクチド400g、D-ラクチド100gを入れ、窒素雰囲気下で攪拌しながら温度120℃で原料モノマーを溶融した後、重合触媒としてのオクチル酸スズ0.14g、開環重合開始剤としてのエチレングリコール0.5gを添加した。その後、反応系を180℃まで昇温し、重合を1.5時間行った。重合反応終了後、有機リン化合物としてのリン酸トリメチル0.28gを添加して30分攪拌した後、180℃、0.1Torrで0.5時間減圧して未反応モノマーを留去し、ポリ乳酸樹脂を合成した。樹脂の製造方法の詳細、及び得られた樹脂の物性を表1に示す。
Claims (7)
- ポリヒドロキシ酸がポリ乳酸であり、前記ポリ乳酸が有機リン化合物のR1、R2およびR3のうち少なくとも一箇所に結合していることを特徴とする請求項1に記載の脂肪族ポリエステル樹脂。
- ポリ乳酸が有機リン化合物のR3に結合していることを特徴とする請求項2に記載の脂肪族ポリエステル樹脂。
- 請求項1~4のいずれかに記載の脂肪族ポリエステル樹脂を用いたことを特徴とする接着剤。
- 有機リン化合物を開環重合反応の開始前に反応系に添加することを特徴とする請求項6に記載の方法。
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JP2013527778A (ja) * | 2010-03-31 | 2013-07-04 | アボット カーディオヴァスキュラー システムズ インコーポレイテッド | 分解速度の調節可能なポリ(l−ラクチド)ステントの作製方法 |
US9889238B2 (en) | 2009-07-21 | 2018-02-13 | Abbott Cardiovascular Systems Inc. | Biodegradable stent with adjustable degradation rate |
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JP6787897B2 (ja) | 2014-12-22 | 2020-11-18 | スリーエム イノベイティブ プロパティズ カンパニー | ポリ乳酸ポリマーとポリ酢酸ビニルポリマーと可塑剤とを含む組成物及びフィルム |
EP3458505B1 (en) | 2016-05-20 | 2021-04-28 | 3M Innovative Properties Company | Oriented polylactic acid polymer based film |
WO2017222824A1 (en) | 2016-06-21 | 2017-12-28 | 3M Innovative Properties Company | Graphic articles comprising semicrystalline polylactic acid based film |
EP3548250A4 (en) | 2016-12-05 | 2020-11-25 | 3M Innovative Properties Company | ADHESIVE ARTICLES INCLUDING A POLYLACTIC ACID POLYMERIC FILM AND METHOD OF MANUFACTURING |
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CN102105509B (zh) | 2014-04-23 |
EP2305733A4 (en) | 2015-01-28 |
US20110086998A1 (en) | 2011-04-14 |
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JP5645122B2 (ja) | 2014-12-24 |
US20130041127A1 (en) | 2013-02-14 |
US8642717B2 (en) | 2014-02-04 |
EP2305733A1 (en) | 2011-04-06 |
JPWO2010010685A1 (ja) | 2012-01-05 |
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