Polymer containing fluorene skeleton

Abstract

The invention relates to a polymer containing a fluorene skeleton. A polymer having a silicon phenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain, and having a polyol structure in the side chain.

Description

Technical Field

[0001] The present invention relates to a polymer containing a fluorene skeleton. Background Art

[0002] It is known that polymers containing a fluorene skeleton are excellent in heat resistance and electrical properties. An example of a polymer containing a fluorene skeleton is disclosed in Patent Document 1, which is a functional epoxy resin having the formula (X). Since the epoxy resin has no flexible site on the main chain, it is presumed that the epoxy resin cracks during curing.

[0003]

[0004] Meanwhile, a fluorene skeleton-containing resin in which a divalent hydrocarbon group or a polysiloxane structure is introduced as a flexible site has been proposed (Patent Documents 2 and 3), and it is known that the fluorene skeleton-containing resin exhibits good flexibility. In addition, a fluorene skeleton-containing resin in which a polysiloxane structure and a silylphenylene structure are introduced has been proposed (Patent Document 4), and it has been found that the fluorene skeleton-containing resin is excellent not only in flexibility but also in film properties and chemical resistance.

[0005] However, in recent years, semiconductor vehicle-mounted materials still require higher heat resistance, and a new type of resin containing a fluorene skeleton is desired.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: JP 4873223

[0009] Patent Document 2: JP-A 2014-047207

[0010] Patent Document 3: JP-A 2014-062055

[0011] Patent Document 4: JP-A 2008-184571 Summary of the invention

[0012] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel fluorene skeleton-containing polymer that provides a film having better heat resistance than a film obtained from a conventional fluorene skeleton-containing polymer including a siloxane structure.

[0013] The present inventors have conducted repeated studies to achieve the above object and have found that a polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain and a polyol structure in the side chain provides a film having better heat resistance than a film obtained from a conventional fluorene skeleton-containing polymer, thereby completing the present invention.

[0014] That is, the present invention provides the following polymers containing a fluorene skeleton.

[0015] 1. A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyol structure in the side chain.

[0016] 2. The polymer according to item 1, which contains a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further contain a repeating unit having the formula (A3) and a repeating unit having the formula (A4):

[0017]

[0018] wherein R 1 to R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms and may contain a heteroatom, m is each independently an integer from 1 to 600, and when m is an integer of 2 or more, R 3 may be the same as or different from each other, R 4 may be the same as or different from each other, a, b, c, and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1, X 1 is a divalent group having the formula (X1), and X 2 is a divalent group having the formula (X2):

[0019]

[0020] wherein n 1 and n 2 are each independently an integer from 1 to 7, R 11 and R 12 are each independently a hydrogen atom or a methyl group, and L 1 to L 4 are each independently a saturated alkylene group having 1 to 15 carbon atoms, a part of -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO-, or -CONH-, and a part or all of the hydrogen atoms of the saturated alkylene group may be replaced by a hydroxyl group, and the dashed line indicates a bonding end; and

[0021]

[0022] wherein R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k 1 and k 2Each independently is an integer from 0 to 7, p is an integer from 0 to 600, and the dashed line represents the bonding end.

[0023] 3. The polymer according to item 2, wherein L 1 and L 3 both have 1 carbon atom.

[0024] 4. The polymer according to item 2 or 3, wherein L 2 and L 4 both have 1 carbon atom.

[0025] 5. The polymer according to any one of items 2 to 4, wherein n 1 and n 2 are both 1.

[0026] 6. The polymer according to any one of items 2 to 5, wherein R 11 and R 12 are both hydrogen atoms.

[0027] 7. The polymer according to any one of items 2 to 6, wherein R 21 and R 22 are both hydrogen atoms.

[0028] Advantages of the Invention

[0029] The polymer of the present invention can provide a film with more excellent heat resistance compared to the film obtained from the conventional polymer containing a fluorene skeleton with a siloxane structure. Detailed Description of the Invention

[0030] Polymer Containing Fluorene Skeleton

[0031] The polymer containing a fluorene skeleton of the present invention is a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain, and containing a polyol structure in the side chain.

[0032] Such a polymer is preferably a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further contain a repeating unit having the formula (A3) and a repeating unit having the formula (A4).

[0033]

[0034] In the formulas (A1) to (A4), a, b, c, and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1, preferably numbers satisfying 0.1 < a < 0.8, 0.1 < b < 0.8, 0 ≤ c < 0.15, 0 ≤ d < 0.15, and a + b + c + d = 1.

[0035] In formulas (A2) and (A4), R 1 To R 4 Each is independently a hydrocarbon group having 1 to 20 carbon atoms and may contain heteroatoms. m is independently an integer of 1 to 600, preferably an integer of 8 to 100. When m is an integer of 2 or more, R 3 can be the same or different from each other, R 4 Can be the same as or different from each other.

[0036] In formula (A2) and (A4), when there are two or more siloxane units (i.e., when m is an integer of 2 or more), all the siloxane units may be the same or different from each other, or the repeating unit of formula (A2) or (A4) may contain two or more types of different siloxane units. When the repeating unit of formula (A2) or (A4) contains two or more types of different siloxane units, the siloxane units may be randomly bonded or alternately bonded, or the repeating unit of formula (A2) or (A4) may contain a block of a plurality of siloxane units of the same type.

[0037] In formulas (A1) and (A2), X 1 It is a divalent group having the formula (X1). The divalent group having the formula (X1) is a group having a fluorene skeleton.

[0038]

[0039] In the formula, the dotted line represents the bonding end (bond).

[0040] In formula (X1), n 1 and n 2 Each is independently an integer from 1 to 7, and each is preferably 1.

[0041] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group, R 11 and R 12 Both are preferably hydrogen atoms.

[0042] In formula (X1), L 1 To L 4 Each independently is a saturated alkylene group having 1 to 15 carbon atoms, a portion of the saturated alkylene group -CH2- can be substituted by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms of the saturated alkylene group can be substituted by a hydroxyl group. The -CH2- of the saturated alkylene group can be located at its end.

[0043] The saturated alkylene group may be linear, branched, or cyclic, and specific examples thereof include alkanediyl groups having 1 to 15 carbon atoms, such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, and pentadecane-1,15-diyl; and cyclic saturated alkylene groups having 3 to 15 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl.

[0044] Preferred L 1 and L 3 All have 1 carbon atom, and L is more preferred 2 and L 4 All have 1 carbon atom.

[0045] In formulas (A3) and (A4), X 2 is a divalent group having the formula (X2).

[0046]

[0047] In the formula, the dotted line represents the bonding end (bond).

[0048] In formula (X2), R 21 and R 22 Each is independently a hydrogen atom or a methyl group, and each is preferably a hydrogen atom.

[0049] In formula (X2), R 23 and R 24 Each is independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0050] In formula (X2), k 1 and k 2 Each is independently an integer from 0 to 7, and each is preferably 0.

[0051] In formula (X2), p is an integer of 0 to 600, preferably an integer of 0 to 100, and more preferably an integer of 0 to 30. When p is an integer of 2 or more, R 23 can be the same or different from each other, R 24 Can be the same as or different from each other.

[0052] The polymer containing a fluorene skeleton of the present invention preferably has a weight average molecular weight (Mw) of 2,000 to 500,000, and more preferably has a weight average molecular weight (Mw) of 8,000 to 100,000. The polymer having Mw within the above range can be obtained in a solid form and can ensure film-forming properties. In the present invention, Mw is a polystyrene conversion measurement value based on gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0053] The fluorene skeleton-containing polymer of the present invention may be a polymer in which repeating units of formula (A1), repeating units of formula (A2), repeating units of formula (A3) and repeating units of formula (A4) are randomly or alternately bonded, or may be a polymer containing blocks of a plurality of these units.

[0054] Method for producing polymer containing fluorene skeleton

[0055] The method for producing a polymer containing a fluorene skeleton is not particularly limited. For example, a polymer containing a fluorene skeleton can be produced by addition polymerization of a compound having formula (1), a compound having formula (2), a compound having formula (3), and, if necessary, a compound having formula (4) in the presence of a metal catalyst.

[0056]

[0057] In the formula, R 1 To R 4 and m are as defined above.

[0058]

[0059] In the formula, R 11 and R 12 、n 1 、n 2 and L 1 To L 4 As defined above.

[0060]

[0061] In the formula, R 21 To R 24 , k 1 , k 2 and p are as defined above.

[0062] As the metal catalyst, the following catalysts can be used: a single substance of a platinum group metal, such as platinum (including platinum black), rhodium and palladium; platinum chloride, chloroplatinic acid and chloroplatinates, such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2 and Na2HPtCl4·xH2O (wherein x is preferably an integer from 0 to 6, particularly preferably 0 or 6); ); alcohol-modified chloroplatinic acid, such as that described in US3220972; complexes of chloroplatinic acid and olefins, such as those described in US3159601, US3159662 and US3775452; platinum group metals (such as platinum black and palladium) supported on a carrier (such as alumina, silica or carbon); rhodium-olefin complexes; tris(triphenylphosphine)rhodium chloride (the so-called Wilkinson catalyst); and complexes of platinum chloride, chloroplatinic acid or chloroplatinates and vinyl-containing siloxanes (especially vinyl-containing cyclosiloxanes).

[0063] The amount of the catalyst used is a catalytic amount, and generally, as a platinum group metal, it is preferably 0.001 to 0.1 weight percent relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent can be used as needed. The solvent is preferably a hydrocarbon solvent, such as toluene or xylene. As for the polymerization conditions, from the viewpoint of suppressing the deactivation of the catalyst and completing the polymerization in a short time, the polymerization temperature is preferably 40 to 150° C., particularly preferably 60 to 120° C. The polymerization time depends on the type and amount of the polymer, and in order to suppress the interference of moisture in the polymerization system, it is preferably about 0.5 to 100 hours, particularly preferably 0.5 to 30 hours. After the polymerization reaction is completed, the solvent is evaporated and removed in the case of using a solvent, thereby obtaining a polymer.

[0064] The reaction method is not particularly limited. It is preferred to first mix and heat a compound having formula (2), a compound having formula (3), and, if necessary, a compound having formula (4), then add a metal catalyst to the resulting mixed solution, and then dropwise (add dropwise) a compound having formula (1) to the mixed solution over a period of 0.1 to 5 hours.

[0065] These raw material compounds are preferably blended so that the total amount of hydrosilyl groups in the compound having formula (1) and the compound having formula (2) is 0.67 to 1.67, more preferably 0.83 to 1.25 in molar ratio relative to the total amount of alkenyl groups in the compound having formula (3) and the compound having formula (4). The Mw of the polymer of the present invention can be controlled by using a monoallyl compound (e.g., o-allylphenol), or a monohydrosilane or a monohydrosiloxane (e.g., triethylhydrosilane) as a molecular weight regulator.

[0066] In the polymerization reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor used include various phenols, hydroquinone (hydroquinone), benzoquinone, catechol (catechol), hydroxylamine and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, relative to the compound having formula (3).

[0067] After the reaction is completed, a solvent is optionally added and washed with water. Then, the organic layer is heated under reduced pressure to distill off the solvent, thereby producing a polymer containing a fluorene skeleton of the present invention. When washing with water, an aqueous solution of a metal hydroxide (e.g., sodium hydroxide or potassium hydroxide), or a metal carbonate or metal bicarbonate (e.g., sodium carbonate, sodium bicarbonate, or potassium carbonate) can be optionally used.

[0068] Another example of a method for producing a polymer containing a fluorene skeleton of the present invention is to react a polymer containing repeating units having formula (B1) and repeating units having formula (B2), which may further contain repeating units having formula (B3) and repeating units having formula (B4) (hereinafter, the polymer is also referred to as "polymer B") with a compound having formula (5).

[0069]

[0070] In the formula, R 1 To R 4 , m, a, b, c, d, and X 2 As defined above.

[0071]

[0072] In formula (B1) and (B2), X 3 It is a divalent group having the formula (X3). The divalent group having the formula (X3) is a group having a fluorene skeleton.

[0073]

[0074] In the formula, R 11 , R12 、n 1 and n 2 As defined above. Dashed lines represent bonded ends.

[0075] In formula (5), L 5 is a saturated alkylene group having 1 to 14 carbon atoms, a portion of -CH2- in the saturated alkylene group may be substituted by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms in the saturated alkylene group may be substituted by hydroxyl groups. 5 The saturated alkylene group represented may be linear, branched or cyclic and preferably has 1 to 7 carbon atoms.

[0076] In formula (5), L 6 is a saturated alkylene group having 1 to 14 carbon atoms, a portion of -CH2- in the saturated alkylene group may be substituted by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms in the saturated alkylene group may be substituted by hydroxyl groups. 6 The saturated alkylene group represented may be linear, branched or cyclic and preferably has 1 to 7 carbon atoms.

[0077] Specific examples of the compound having the formula (5) include glycidol (Epiol ), but are not limited to them.

[0078] The reaction conditions are not particularly limited, and it is generally preferred to mix and heat the polymer B and the compound having the formula (5) in a solvent. From the viewpoint of accelerating the reaction, it is preferred to use a polar solvent as the solvent, and it is particularly preferred to use an alcohol-based solvent such as propylene glycol monomethyl ether. From the viewpoint of suppressing side reactions and completing the reaction in a short time, the reaction temperature is, for example, preferably 35 to 130° C., particularly preferably 45 to 100° C. The reaction time depends on the type and amount of the reaction substrate, and is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0079] In the above reaction, the raw material compounds are blended so that the compound having the formula (5) and the X in the polymer B 3 The molar ratio is preferably 1.0 to 8.0, more preferably 4.0 to 6.0. As for the compound having the formula (5), one type may be used alone or two or more types may be used in combination.

[0080] In the above reaction, a catalyst may be used optionally. Examples of the catalyst include: amines such as triethylamine, triethylenediamine, bis(2-dimethylaminoethyl)ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole; pyridine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; organic tin compounds such as tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercapto, dibutyltin maleate, dibutyltin dilaurate (dibutyltin dilaurate (IV)), dibutyltin dineodecanoate, dioctyltin dimercapto, dilauric acid (dilauryl ate) dioctyltin, and dibutyltin dichloride; organic lead compounds such as lead octoate, and lead naphthenate; organic nickel compounds such as nickel naphthenate; organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octoate; organic bismuth compounds such as bismuth octoate, and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0081] The amount of catalyst used is usually a catalytic amount relative to X in polymer B. 3 , preferably 0.1 to 20 mol%. The catalyst may be used alone or in combination of two or more types.

[0082] In the above reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor used include various phenols, hydroquinone (hydroquinone), benzoquinone, catechol (catechol), hydroxylamine and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, relative to the compound having formula (5).

[0083] After the reaction is completed, a solvent is optionally added and washed with water. Then, the organic layer is heated under reduced pressure to distill off the solvent, thereby producing the polymer containing the fluorene skeleton of the present invention. When washing with water, an aqueous solution of a metal hydroxide (such as sodium hydroxide or potassium hydroxide), or a metal carbonate or metal bicarbonate (such as sodium carbonate, sodium bicarbonate, or potassium carbonate) can be optionally used.

[0084] By making the polymer of the present invention into a composition containing the polymer and a curing agent, and applying the composition to a substrate and then heating it, a cured film having excellent heat resistance can be obtained.

[0085] The curing agent used may be an isocyanate curing agent. Examples of the isocyanate curing agent include: aliphatic isocyanates such as methyl isocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; aromatic isocyanates such as toluene diisocyanate, diphenylmethane diisocyanate and metaphenylene diisocyanate; and modified products of the above compounds.

[0086] The content of the curing agent in the composition is preferably 5 to 50 parts by weight, more preferably 5 to 45 parts by weight, per 100 parts by weight of the polymer of the present invention. The curing agent may be used alone or in combination of two or more types.

[0087] As required, the composition may contain a solvent. Examples of solvents include: ketones, such as cyclohexanone, cyclopentanone and methyl-2-n-pentanone; alcohols, such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol; ethers, such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; and esters, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate and gamma-butyrolactone. These can be used alone or in combination of two or more. The content of the solvent in the composition is preferably 50 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, and further preferably 50 to 100 parts by weight per 100 parts by weight of the polymer of the present invention. The solvent may be used alone or in combination of two or more.

[0088] The composition can be applied to the substrate by a known method. For example, methods such as dipping, spin coating and roller coating can be used. The amount of application can be appropriately selected according to the purpose, preferably an amount that allows the film to have a thickness of 0.1 to 100 μm.

[0089] By heating and curing the applied composition, a film excellent in heat resistance can be provided. The heating conditions are appropriately selected according to the type of curing agent and fluorene skeleton-containing polymer used, and heating is usually preferably performed at 50 to 250° C. for about 10 minutes to 6 hours.

[0090] Example

[0091] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following Examples, Mw was measured by GPC method using monodisperse polystyrene as standard, under the analysis conditions of flow rate 0.6 mL / min, THF as dissolution solution, column temperature 40° C., using TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as GPC column.

[0092] The compounds used for synthesizing the polymer are shown below.

[0093]

[0094]

[0095] Example 1

[0096] Synthetic polymer 1

[0097] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4g (0.235mol) of a compound having the formula (S-2a) and 430.5g (1.00mol) of a compound having the formula (S-4a) were added, and then 1,500g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by weight) was charged into the flask, and 142.9g (0.735mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90°C and aged (ripened) for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 444.5 g (6.00 mol) of the compound having the formula (S-5a) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure, thereby producing polymer 1. The Mw of polymer 1 was 8,000. Mw was measured by a polystyrene conversion measurement value based on gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0098] pass 1 H-NMR (manufactured by Bruker Corporation) confirmed that Polymer 1 was a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2).

[0099] Example 2

[0100] Synthetic polymer 2

[0101] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 530.5g (0.18mol) of a compound having the formula (S-2b), 387.5g (0.90mol) of a compound having the formula (S-4a), and 18.64g (0.10mol) of a compound having the formula (S-3) were added, and then 1,500g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by weight) was charged into the flask, and 153.6g (0.79mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90°C and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 400.0 g (5.40 mol) of the compound having the formula (S-5a) and 9.11 g (0.09 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure, thereby producing polymer 2. The Mw of polymer 2 was 80,000. 1 H-NMR (manufactured by Bruker Corporation) confirmed that Polymer 2 was a polymer containing a repeating unit having formula (A1), a repeating unit having formula (A2), a repeating unit having formula (A3) and a repeating unit having formula (A4).

[0102] Example 3

[0103] Synthetic polymer 3

[0104] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4g (0.235mol) of a compound having the formula (S-2a) and 430.5g (1.00mol) of a compound having the formula (S-4a) were added, and then 1,500g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5 wt%) was charged into the flask, and 142.9g (0.735mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the addition was completed, the resulting mixture was heated to 90°C and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 528.6 g (6.00 mol) of the compound having the formula (S-5b) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure, thereby producing polymer 3. The Mw of polymer 3 was 8,500. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that Polymer 3 was a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2).

[0105] Example 4

[0106] Synthetic polymer 4

[0107] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4g (0.235mol) of a compound having the formula (S-2a) and 430.5g (1.00mol) of a compound having the formula (S-4a) were added, and then 1,500g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5 wt%) was charged into the flask, and 142.9g (0.735mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90°C and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 696.7 g (6.00 mol) of the compound having the formula (S-5c) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure, thereby producing polymer 4. The Mw of polymer 4 was 9,000. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that Polymer 4 was a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2).

[0108] Comparative Example 1

[0109] Synthesis of comparative polymer 1

[0110] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 401 g (0.50 mol) of a compound having the formula (S-2a), 488 g (0.90 mol) of a compound having the formula (S-4b), and 18.6 g (0.10 mol) of a compound having the formula (S-3) were added, and then 1,100 g of toluene was added to the flask, and the resulting mixture was heated to 80°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5 wt%) was charged into the flask, and 95.3 g (0.49 mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.99:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing a comparative polymer 1. The Mw of Comparative Polymer 1 was 12,000.

[0111] Comparative Example 2

[0112] Synthesis of comparative polymer 2

[0113] To a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 362g (0.45mol) of a compound having the formula (S-2b), 215g (0.50mol) of a compound having the formula (S-4a), and 271g (0.50mol) of a compound having the formula (S-4b) were added, and then 2,100g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Then, 2.0g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by weight) was charged into the flask, and 105g (0.54mol) of a compound having the formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.99:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 100°C and aged for 12 hours, and then toluene was distilled off from the reaction solution under reduced pressure, thereby producing Comparative Polymer 2. The Mw of Comparative Polymer 2 was 14,000.

[0114] Heat resistance test

[0115] 20 parts by weight of DURANATETMA-100 (manufactured by Asahi Kasei Corporation) were added to 100 parts by weight of polymers 1 to 4 and comparative polymers 1 and 2, respectively, as an isocyanate curing agent, and 55 parts by weight of cyclopentanone were further added to dissolve the components until the resulting solution became uniform. Each solution was applied to a silicon wafer by spin coating, pre-baked at 120°C for 2 minutes, and then thermally cured at 180°C for 4 hours to form a film (thickness: 20 μm) on the silicon wafer. The sample was heated at 150°C for 300 hours, and then the weight loss rate was measured to evaluate heat resistance. When the weight loss rate was less than 1%, the heat resistance was evaluated as "good"; when the weight loss rate was 1% or more, the heat resistance was evaluated as "poor". The results are shown in Table 1.

[0116] Table 1

[0117]

[0118] The above results show that the film obtained from the polymer of the present invention has excellent heat resistance.

Claims

1. A polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in a main chain and containing a polyol structure in a side chain.

2. The polymer according to claim 1, comprising a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further comprise a repeating unit having the formula (A3) and a repeating unit having the formula (A4): wherein R 1 to R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms and may contain a heteroatom, m are each independently an integer from 1 to 600, and when m is an integer of 2 or greater, R 3 may be the same as or different from each other, R 4 may be the same as or different from each other, a, b, c and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1 and a + b + c + d = 1, X 1 is a divalent group having the formula (X1), X 2 is a divalent group having the formula (X2): where n 1 and n 2 are each independently an integer from 1 to 7, R 11 and R 12 are each independently a hydrogen atom or a methyl group, L 1 To L 4 Each is independently a saturated alkylene group having 1 to 15 carbon atoms, a portion of -CH2- in the saturated alkylene group may be substituted by -O-, -S-, -SO2-, -CO- or -CONH-, a portion or all of the hydrogen atoms in the saturated alkylene group may be substituted by hydroxyl groups, and the dotted line indicates a bonding end; and Where R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k 1 and k 2 Each is independently an integer from 0 to 7, p is an integer from 0 to 600, and the dotted line represents a bonding end.

3. The polymer according to claim 2, wherein L 1 and L 3 All have 1 carbon atom.

4. The polymer according to claim 2, wherein L 2 and L 4 All have 1 carbon atom.

5. The polymer according to claim 2, wherein n 1 and n 2 Both are 1.

6. The polymer according to claim 2, wherein R 11 and R 12 All are hydrogen atoms.

7. The polymer according to claim 2, wherein R 21 and R 22 All are hydrogen atoms.

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