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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment

Definitions

• the present invention relates to a method for producing radically polymerizable organopolysiloxane.
• the technique of applying energy to harden a liquid resin composition is a widely used technique, and is used in many fields for the production of coatings and moldings.
• Heat and radiation such as ultraviolet rays are used as the energy required for this curing.
• thermosetting a heat-activated catalyst is added to the base resin and heat is applied to obtain a cured product.
• radiation curing a composition containing a photoinitiator activated by radiation such as ultraviolet rays is cured by irradiation with radiation.
• Typical functional groups used for radiation curing include (meth)acryloyl groups, mercapto groups, and epoxy groups.
• a (meth)acryloyl group forms a crosslink by a radical polymerization reaction, and a mercapto group undergoes an ene-thiol reaction by a radical in the presence of an alkenyl group.
• Epoxy groups undergo cationic polymerization with acids.
• Silicone is a general term for organopolysiloxanes having continuous siloxane bonds as a main chain and side chains having organic groups such as methyl groups. Silicone has excellent heat resistance, cold resistance, chemical resistance, electrical insulation, mold releasability, etc., and can be made into various forms such as oil, rubber, and resin. , silicone rubber, silicone for release paper, and silicone for hard coating.
• Organopolysiloxanes containing (meth)acryloyl groups as radiation-polymerizable groups are used as release coatings, hard coats, and surface tension modifiers.
• a photopolymerization initiator is added to this base material, and a cured product is obtained by irradiating radiation while purging nitrogen in a chamber in order to efficiently react radicals generated by radiation.
• an organopolysiloxane containing (meth)acryloyl groups is produced by reacting (meth)acrylic acid with an epoxy group using epoxy-modified organopolysiloxane as a raw material.
• hydroxyl groups are generated as a result of the ring-opening of the epoxy, which increases the viscosity of the product, leaving a problem in terms of handling.
• Patent Documents 2 and 3 propose a method of introducing (meth)acryloyl groups into the siloxane main chain by using hydroxyl group-containing organopolysiloxane as a raw material and subjecting (meth)acrylic acid to an esterification reaction.
• the problem with this technique is that the strong acid used for esterification causes not only ester bond formation but also siloxane bond cleavage, making it extremely difficult to control the reaction conditions.
• Patent Documents 4 and 5 a silane material having (meth)acryloyl groups is oligomerized by hydrolytic condensation, and then polymerized together with other silicon oligomers having dimethyl units to synthesize the desired organopolysiloxane.
• the synthesis of the silane having a (meth)acryloyl group as a raw material is complicated, and purification by distillation is required, but there is a problem that the (meth)acryloyl group tends to polymerize unless the conditions are precisely controlled.
• Patent Documents 6 and 7 disclose a method for producing a (meth)acryloyl group-containing organopolysiloxane by transesterification using a Zr catalyst.
• zirconium acetylacetonate Zr(acac) 4
• Zr(acac) 4 zirconium acetylacetonate
• an object of the present invention is to provide a novel transesterification method for producing a (meth)acryloyl group-containing organopolysiloxane that is transparent and has a good appearance while suppressing costs.
• an organopolysiloxane containing a hydroxyl group-containing organic group and a (meth)acrylic acid ester are combined with a zirconium alkoxide and an organic compound having a specific structure as a catalyst.
• a new production method of obtaining a (meth)acryloyl group-containing radically polymerizable organopolysiloxane by transesterification has been found.
• the present invention is a method for producing a (meth)acryloyl group-containing organopolysiloxane, comprising: (A) a hydroxyl group-containing organopolysiloxane represented by the following average formula (1); (In the formula, R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, or a monovalent hydrocarbon group having a terminal hydroxyl group or (poly)oxy an alkylenealkyl group (hereinafter collectively referred to as a hydroxyl group-containing group), at least one of R 1 is a hydroxyl group-containing group, a is a positive number of 2 or more, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and 2 ⁇ a + b + c + d ⁇ 1,000) (B) a (meth)acrylic acid ester represented by the following
• (C) A compound which is represented by the following general formula ( 3 ) and is liquid at 20°C. 3) (Wherein, R 4 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, which may contain a carbonyl group)
• (D) A compound represented by the following general formula (4) or (5), which is liquid at 20°C. (wherein R 5 and R 6 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) (wherein R 7 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms).
• the desired (meth)acryloyl group-containing organopolysiloxane can be efficiently obtained by transesterification using inexpensive raw materials.
• the catalyst used is liquid, it has excellent compatibility with the reaction substrate, and a product with good transparency can be obtained without remaining solid after the completion of the reaction.
• the operation can be simplified because there is no complicated operation such as charging a solid into a reactor.
• the present invention provides a method for producing a (meth)acryloyl group-containing organopolysiloxane.
• the (meth)acryloyl group-containing organopolysiloxane obtained by this production method is particularly represented by the following average formula (5).
• R 8 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, the hydroxyl group-containing group, or a group having a (meth)acryloyloxy group at the end is a valent hydrocarbon group or (poly)oxyalkylenealkyl group (hereinafter collectively referred to as a (meth)acryloyloxy group-containing group), at least one R 8 is the (meth)acryloyloxy group-containing group, l is a positive number of 2 or more, m is 0 or a positive number, n is 0 or a positive number, o is 0 or a positive number, 2 ⁇ l + m + n + o ⁇ 1,000, and a hydroxyl group-containing group is bonded
• the number of silicon atoms to be used is 0 to 30% with respect to the total number of all silicon atoms).
• a hydroxyl group-containing organopolysiloxane represented by the following average formula (1) and
• R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, or a monovalent hydrocarbon group having a terminal hydroxyl group or (poly)oxy an alkylenealkyl group (hereinafter collectively referred to as a hydroxyl group-containing group)
• at least one of R 1 is a hydroxyl group-containing group
• a is a positive number of 2 or more
• b is 0 or a positive number
• c is 0 or a positive number
• d is 0 or a positive number
• 2 a (meth)acrylic acid ester represented by the following general formula (2), and
• R 2 is a hydrogen atom
• (C) a compound represented by the following general formula (3), which is liquid at 20° C. Zr(OR 4 ) 4 3) (Wherein, R 4 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, which may contain a carbonyl group)
• (D) A compound represented by the following general formula (4) or (5), which is liquid at 20°C. (Wherein, R 5 and R 6 are each independently an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms) (wherein R 7 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms).
• R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, or a hydroxyl group-containing group, and at least one of R 1 is a hydroxyl-containing group.
• monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group. be done.
• the number of silicon atoms to which hydroxyl group-containing groups are bonded is 1 to 50%, preferably 2 to 45%, more preferably 3 to 40% of the total number of all silicon atoms. is good. If the number of silicon atoms to which the hydroxyl group-containing group is bonded is less than the above lower limit, the radiation curability may be insufficient. On the other hand, if it is more than the above upper limit, the substrate concentration of (meth)acrylic acid in the reaction system becomes high during the reaction, and there is a possibility that viscosity increase or gelation may occur due to polymerization of (meth)acryloyl groups.
• the monovalent hydrocarbon group having a terminal hydroxyl group is preferably a monovalent hydrocarbon group having 2 to 20 carbon atoms, more preferably 3 to 15 carbon atoms and having one terminal hydroxyl group. More preferably, it is a monovalent hydrocarbon group having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, and having one terminal hydroxyl group.
• a (poly)oxyalkylenealkyl group having a terminal hydroxyl group is a (poly)oxyalkylenealkyl group having one terminal hydroxyl group, preferably having 4 to 25 carbon atoms, more preferably 5 to 16 carbon atoms.
• Examples of the oxyalkylene group include an oxyethylene group, an oxyisopropylene group, an oxy n-propylene group, and an oxybutylene group. Among them, an oxyethylene group and an oxyisopropylene group are preferred, and two or more oxyalkylene groups are used. may have.
• Examples of the hydroxyl group-containing group are represented by the following structures. In the formula below, the points indicated by dotted lines are bonds with the silicon atoms of the organopolysiloxane.
• R2 is a hydrogen atom or a methyl group.
• e is an integer of 1-10, and f and g are each independently an integer of 1-5.
• e is an integer from 1 to 7 and f and g are independently from each other integers from 1 to 3. More preferably, e is an integer from 1 to 4, and f and g are 1 or 2 independently of each other.
• the bonding order of ethylene oxide and propylene oxide shown in parentheses is not limited, and they may be arranged randomly or form a block structure.
• broken lines indicate bonds with silicon atoms of organopolysiloxane. If the proportion of hydroxyl groups in the composition as a whole satisfies the above range, it may contain a compound having both a hydroxyl group-containing organic group and a (meth)acryloyl group, as shown in the above figure.
• a is a positive number of 2 or more
• b is 0 or a positive number
• c is 0 or a positive number
• d is 0 or a positive number, provided that 2 ⁇ a + b + c + d ⁇ 1 , 000.
• the amount of hydroxyl group-containing groups satisfies the above range
• the organopolysiloxane has a viscosity at 25° C. of 5 to 10,000 mPa ⁇ s, more preferably 10 to 5,000 mPa ⁇ s. Just do it. Viscosity is a value measured with a BM type rotational viscometer.
• the upper limits of a, b, c, and d may be any value that satisfies 2 ⁇ a+b+c+d ⁇ 1,000 and the organopolysiloxane has the viscosity described above.
• the upper limit of b is preferably 998 or less, more preferably 798 or less, and even more preferably 598 or less.
• the lower limit of b may be 0, b is preferably 1 or more, more preferably 5 or more, and still more preferably 8 or more. That is, preferably 1 ⁇ b ⁇ 998, more preferably 5 ⁇ b ⁇ 798, and even more preferably 8 ⁇ b ⁇ 598.
• c is preferably 0 ⁇ c ⁇ 5, more preferably 0 ⁇ c ⁇ 4, and still more preferably 0 ⁇ c ⁇ 3.
• d is preferably 0 ⁇ d ⁇ 4, more preferably 0 ⁇ d ⁇ 3, and still more preferably 0 ⁇ d ⁇ 2.
• the organopolysiloxane represented by the average formula (1) more more preferably has a linear structure.
• Examples of the organopolysiloxane represented by the average formula (1) include compounds represented by the following structures.
• Me represents a methyl group and Ph represents a phenyl group.
• h is an integer of 0 to 1,000
• i is an integer of 0 to 800
• j is an integer of 1 to 200
• k is an integer of 0 to 100.
• the above is a number that satisfies 0 ⁇ b ⁇ 998, more preferably a number that satisfies 1 ⁇ b ⁇ 998, more preferably a number that satisfies 5 ⁇ b ⁇ 798, and still more preferably a number that satisfies 8 ⁇ b ⁇ 598 .
• Component (B) is a (meth)acrylic acid ester represented by the following general formula (2), and is a reaction agent for introducing a (meth)acryloyl group into component (A).
• R2 is a hydrogen atom or a methyl group.
• R 3 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 5 carbon atoms. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group. From the viewpoints of industrial cost and progress of transesterification reaction, R 3 is preferably an alkyl group having 1 to 4 carbon atoms, that is, a methyl group, an ethyl group, a propyl group or a butyl group. On the other hand, if R 3 has more than 5 carbon atoms, the boiling point of the alcohol produced during the transesterification reaction becomes high, making it difficult to remove it from the reaction system, making it difficult for the transesterification reaction to proceed.
• the amount of component (B) is 1 to 10 mol, preferably 1.5 to 9 mol, more preferably 2 to 8 mol, relative to 1 mol of hydroxyl groups in organopolysiloxane (A). It is better to react. If the amount of component (B) is less than the above lower limit, the rate of introduction of (meth)acryloyl groups by transesterification will decrease. If it is more than the above upper limit, the rate of introduction of (meth)acryloyl groups by transesterification is high, but the amount of component (B) blended is too large, resulting in a decrease in pot yield.
• Component (C) is represented by the following general formula (3) and is a compound that is liquid at 20°C. Zr(OR 4 ) 4 (3) (Wherein, R 4 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon having 1 to 10 carbon atoms, which may contain a carbonyl group)
• R 4 is an unsubstituted or substituted, linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may contain a carbonyl group in its structure. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and t-butyl group, cycloalkyl groups such as cyclohexyl group, phenyl group and acetyl group.
• a monovalent hydrocarbon group containing a carbonyl group includes an acetyl group and a (meth)acryloyl group.
• Component (C) is particularly preferably a zirconium alkoxide having an alkyl group of 1 to 6 carbon atoms as R 4 , and from the viewpoint of general availability, R 4 is preferably a propyl group or a butyl group.
• the component (C) is the main component of the catalyst for reacting the components (A) and (B).
• the amount of component (C) is 0.001 to 0.1 mol, preferably 0.003 to 0.08 mol, more preferably 0.005 to 0.05, per 1 mol of hydroxyl groups contained in component (A). Mole. If it is less than the above lower limit, the reaction may not proceed sufficiently. If it exceeds the above upper limit, it may become difficult to remove after the reaction.
• the component (C) is liquid at 20°C. Since the component (C) is a liquid catalyst, it can be charged into the reaction vessel in the same manner as liquid compounds such as the components (A) and (B). If the catalyst is a solid, it is necessary to take measures to handle dust, which may complicate the operation. Moreover, in the case of a solid catalyst, since the compatibility varies depending on the structure of the product, the catalyst may not dissolve in the product but may be dispersed as a solid, making the product turbid.
• Component (D) is a compound represented by the following general formula (4) or (5) and liquid at 20°C. (wherein R 5 and R 6 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) (wherein R 7 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms)
• R 5 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms.
• alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group. It is preferably a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 5 is preferably a methyl group.
• hydrogen atoms bonded to these carbon atoms may be substituted with halogen atoms or other groups, exemplified by trifluoromethyl group, 3,3,3-trifluoropropyl group and the like. be.
• R 6 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms.
• alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group. It is preferably a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 6 is preferably a methyl group and an ethyl group.
• hydrogen atoms bonded to these carbon atoms may be substituted with halogen atoms or other groups, exemplified by trifluoromethyl group, 3,3,3-trifluoropropyl group and the like. be.
• compounds represented by the general formula (4) include, for example, methyl acetoacetate, ethyl acetoacetate, and propyl acetoacetate.
• Methyl acetoacetate and ethyl acetoacetate are preferred because of their general availability.
• R 7 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms.
• alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group. It is preferably a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 7 is preferably a methyl group or an ethyl group.
• hydrogen atoms bonded to these carbon atoms may be substituted with halogen atoms or other groups, exemplified by trifluoromethyl group, 3,3,3-trifluoropropyl group and the like. be.
• the compound represented by the general formula (5) includes, for example, acetylacetone.
• the component (D) is a component that functions in concert with the main component (C) of the catalyst for reacting the components (A) and (B). It is considered that the component (D) is coordinated with the component (C) to form a catalyst species that effectively works for transesterification in the present invention.
• the amount of component (D) is such that the molar ratio of component (A) to 1 mol of hydroxyl groups is 0.002 to 0.8 mol, preferably 0.005 to 0.5 mol, more preferably 0.005 to 0.5 mol. 01 to 0.4 mol. If it is less than the above lower limit, the reaction may not proceed sufficiently. If the above upper limit is exceeded, the component (D) itself may act as a substrate for the transesterification reaction, causing side reactions.
• the component (E) is a polymerization inhibitor, and is an additive for suppressing the polymerization of the (meth)acrylic acid ester as the component (B) without reacting with the component (A) during the reaction.
• the polymerization inhibitor is not limited as long as it has the effect of suppressing radical polymerization, and the following alkylphenols are available.
• amine-based polymerization inhibitors can also be used, including the following. Alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine , 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine.
• the amount of the polymerization inhibitor is 0.01 to 1 part by mass, preferably 0.02 to 0.5 part by mass, more preferably 0.03 to 0.3 part by mass, per 100 parts by mass of component (A). department is good. If it is more than the above upper limit, the curability of the obtained radiation-curable organopolysiloxane composition containing the radically polymerizable organopolysiloxane may be lowered. If it is less than the above lower limit, there is a concern that (meth)acrylic acid may polymerize and thicken or gel during production.
• the transesterification reaction of the present invention can be carried out without solvent or in an organic solvent.
• organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, cyclohexane, methylcyclohexane, and isoparaffin, industrial gasoline, petroleum benzine, and hydrocarbon solvents such as solvent naphtha; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; and mixed solvents thereof. . These can be used individually by 1 type or in combination of 2 or more types as appropriate.
• the reaction temperature can be 70 to 150°C, preferably 75 to 145°C, more preferably 80 to 140°C. If it is lower than 70°C, the reaction may not proceed sufficiently because the by-product alcohol may not sufficiently escape from the reaction system, and if it is higher than 150°C, the (B) component (meth)acrylate There is concern about thickening and gelation due to polymerization of
• the reaction time may be in the range of 1 to 72 hours, but is not limited to this.
• the reaction atmosphere may be a nitrogen atmosphere or air, or a mixed gas such as nitrogen containing a small amount of oxygen. The amount of oxygen at this time is 0.1 to 20%, preferably 0.5 to 18%, more preferably 1 to 15% in terms of volume.
• the product can be obtained by distilling off the remaining component (B) under reduced pressure.
• the temperature during distillation may be from 20° C. to 120° C., and the reduced pressure may be from 1 to 200 mmHg, but is not limited thereto.
• the (meth)acryloyl group-containing organopolysiloxane obtained in the present invention is represented by the following average formula (5).
• R 8 is the group defined by R 1 in the average formula (1) above, or a monovalent hydrocarbon group or (poly)oxyalkylene group having a (meth)acryloyl group at the end (hereinafter collectively referred to as (meth) (referred to as an acryloyloxy group-containing group). At least one of R8 is a (meth)acryloyloxy group-containing group.
• the number of silicon atoms to which the (meth)acryloyloxy group-containing group is bonded is 1 to 50%, more preferably 2 to 45%, and still more preferably 3 to 40% of the total number of all silicon atoms. is good.
• the (meth)acryloyloxy group-containing group is a group in which the terminal hydroxyl group of the hydroxyl group-containing group described above is substituted with a (meth)acryloyloxy group. Therefore, unlike a group into which a (meth)acryloyloxy group is introduced by ring opening of an epoxy group, it does not have a hydroxyl group.
• the oxyalkylene group are as described above, preferably an oxyethylene group and an oxyisopropylene group, and may have two or more oxyalkylene groups.
• it is represented by the following structure. In the formula below, the points indicated by the dotted lines are the bonds with the silicon atoms of the polysiloxane.
• R2 is a hydrogen atom or a methyl group.
• e is an integer of 1-10, and f and g are each independently an integer of 1-5.
• e is an integer from 1 to 7 and f and g are independently from each other integers from 1 to 3. More preferably, e is an integer from 1 to 4, and f and g are 1 or 2 independently of each other.
• the bonding order of ethylene oxide and propylene oxide shown in parentheses is not limited, and they may be arranged randomly or form a block structure. In the formula, broken lines indicate bonds with silicon atoms of organopolysiloxane.
• l is a positive number of 2 or more
• m is 0 or a positive number
• n is 0 or a positive number
• o is 0 or a positive number
• the amount of the (meth)acryloyloxy group-containing organic group satisfies the above range
• the organopolysiloxane has a viscosity at 25° C. of 5 to 10,000 mPa ⁇ s, more preferably 10 to 5,000 mPa ⁇ s.
• the (meth)acryloyl group-containing organopolysiloxane obtained by the production method of the present invention can have a low viscosity.
• Preferably 5 to 3,000 mPa s, more preferably 5 to 2,000 mPa s, still more preferably 8 to 1,500 mPa s, further 10 to 1,000 mPa s, particularly 15 to 700 mPa s. can have The viscosity is a value measured by a BM type rotational viscometer.
• the upper limits of l, m, n, and o may be any value that satisfies 2 ⁇ l+m+n+o ⁇ 1,000 and the organopolysiloxane has the viscosity described above.
• the upper limit of m is preferably 998 or less, more preferably 798 or less, and even more preferably 598 or less.
• the lower limit of m may be 0, m is preferably 1 or more, more preferably 5 or more, and still more preferably 8 or more. That is, preferably 1 ⁇ m ⁇ 998, more preferably 5 ⁇ m ⁇ 798, and even more preferably 8 ⁇ m ⁇ 598.
• n is preferably 0 ⁇ n ⁇ 5, more preferably 0 ⁇ n ⁇ 4, and still more preferably 0 ⁇ n ⁇ 3.
• o is preferably 0 ⁇ o ⁇ 4, more preferably 0 ⁇ o ⁇ 3, and still more preferably 0 ⁇ o ⁇ 2.
• the organopolysiloxane represented by the average formula (5) more more preferably has a linear structure.
• the (meth)acryloyl group introduction rate of the transesterification reaction in Examples or Comparative Examples was calculated as follows.
• Example 1 72.91 g of organopolysiloxane represented by the following average formula (A-1), (B-1) ethyl acrylate 47.09 g (the organo 3 moles per 1 mole of hydroxyl groups in polysiloxane (A-1)), 0.18 g of 2,2′-methylenebis(6-tert-butyl-4-methylphenol) monoacrylate as a polymerization inhibitor, (C-1) 0.902 g of an 80% butanol solution of zirconium tetrabutoxide (liquid at 20° C.) (an amount of 0.012 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-1)), ( D-1) 0.979 g of ethyl acetoacetate (liquid at 20° C.) (an amount of 0.048 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-1)) was charged, and the reaction system was
• the unreacted components were removed from the reaction solution by distillation under reduced pressure of 20 mmHg at 85° C. for 2 hours to obtain an organopolysiloxane represented by the following average formula (X-1).
• the target product was yellow and transparent, and the acryloyl group introduction rate was 98%.
• Example 2 72.91 g of organopolysiloxane represented by the following average formula (A-2), (B-1) ethyl acrylate 47.09 g (the organo 3 mol per 1 mol of hydroxyl groups in polysiloxane (A-1)), 0.18 g of 2,2′-methylenebis(6-tert-butyl-4-methylphenol) monoacrylate as a polymerization inhibitor, (C-1) 1.503 g of an 80% butanol solution of zirconium tetrabutoxide (liquid at 20° C.) (an amount of 0.02 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-2)), ( D-1) 1.632 g of ethyl acetoacetate (liquid at 20°C) (0.08 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-2)) was charged, and the reaction system was heated to 85°C.
• A-2
• the mixture was heated and stirred for 24 hours while distilling off ethanol produced as a by-product at a temperature at which the mixture was reacted. Unreacted components were removed from the reaction solution by distillation under reduced pressure of 20 mmHg at 85° C. for 2 hours to obtain a yellow transparent product.
• the product was an organopolysiloxane represented by the following average formula (X-2). The acryloyl group introduction rate was 98%.
• Example 3 In place of (D-1) ethyl acetoacetate in Example 2 above, 1.456 g (D-2) methyl acetoacetate (liquid at 20° C.) (per mole of hydroxyl groups in the organopolysiloxane (A-2) Example 2 was repeated with the exception that 0.08 mol was used to obtain a yellow transparent desired product. The acryloyl group introduction rate was 96%.
• Example 4 instead of (C-1) the 80% butanol solution of zirconium tetrabutoxide in Example 2 above, 3.668 g of (C-2) a 70% propanol solution of zirconium tetrapropoxide (liquid at 20 ° C.) (the organopoly 0.05 mol per 1 mol of hydroxyl groups in the siloxane (A-2)), and the amount of (D-1) ethyl acetoacetate is 4.080 g (the amount of the organopolysiloxane (A-2) Example 2 was repeated except that the amount was adjusted to 0.2 mol per 1 mol of hydroxyl group to obtain a yellow transparent desired product. The acryloyl group introduction rate was 98%.
• Example 5 1.256 g of (D-3) acetylacetone in place of (D-1) ethyl acetoacetate in Example 2 (0.08 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-2)) Example 2 was repeated except that was used to obtain a yellow transparent object.
• the acryloyl group introduction rate was 98%.
• Example 1 was repeated except that (D-1) ethyl acetoacetate was not used in Example 1 to obtain a yellow transparent desired product.
• the acryloyl group introduction rate was 19%.
• Example 1 was repeated except that (C-1) 80% butanol solution of zirconium tetrabutoxide was not used in Example 1 to obtain a yellow transparent target product.
• the acryloyl group introduction rate was 5%.
• Example 3 (C-1) 0.902 g of an 80% butanol solution of zirconium tetrabutoxide in Example 1 (an amount of 0.012 mol per 1 mol of hydroxyl groups in the organopolysiloxane (A-1)), and (D-1) 0.764 g of zirconium acetylacetonate (Zr(acac) 4, melting point 191°C) instead of ethyl acetoacetate (0.01 per mole of hydroxyl group in the organopolysiloxane (A-1))
• Example 1 was repeated, except that molar amounts were used.
• the resulting product was a slightly turbid yellow solution with solids derived from Zr(acac) 4 remaining.
• the acryloyl group introduction rate was 98%.
• Example 2 [Comparative Example 4] In Example 2, (C-1) 0.902 g of an 80% butanol solution of zirconium tetrabutoxide (an amount equivalent to 0.012 equivalents to the hydroxyl groups in the organopolysiloxane (A-1)) was used, and (D -1) 0.764 g of zirconium acetylacetonate (Zr(acac) 4 , melting point 191° C.) instead of ethyl acetoacetate (0.01 mol per 1 mol of hydroxyl group in the organopolysiloxane (A-1)); Example 2 was repeated to obtain a yellow, transparent target product, except that a different amount was used. The acryloyl group introduction rate was 99%.
• the catalyst (Zr(acac) 4 ) used in Comparative Examples 3 and 4 is powder, the operation may be complicated. For example, there is a problem that the powder must be charged directly into the opening/closing type introduction part instead of being charged from the supply line by pressure feeding, which makes the operation time-consuming.
• the production method of the present invention since inexpensive raw materials are used and the operation is simple, it is possible to efficiently obtain the desired organopolysiloxane.
• a liquid catalyst is used, it is possible to improve appearance defects due to undissolved solid catalyst.
• the obtained (meth)acryloyl-modified organopolysiloxane can be used for radiation-curable coating agents, additives, resins, and the like.

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• 2022
  • 2022-10-28 JP JP2023563579A patent/JP7723760B2/ja active Active
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