JP4207586B2 - Cyclized rubber and method for producing the same - Google Patents

Description

【０１２２】
（実施例３）
変性環化ゴムＡ２０部、酸化チタン１５部およびキシレン８０部を高速攪拌機（ディスパー）で１０分間混合した後、流動性を流下時間で１３〜１４秒になるようにシンナーで希釈してプライマーを調製した。なお、上記の流動性は、ＪＩＳ Ｋ ５４００に規定されたフォードカップＮｏ．４法に準じて、２０℃における流下時間を意味する。
【０１２３】
表２に示す樹脂材料を射出成形して３種類の成形板Ｘ〜Ｚ（５０ｍｍ×８０ｍｍ×３ｍｍ）を作成した。なお、Ｙは、各配合成分をヘンシェルミキサーで混合した後、二軸押出機によって溶融混練してペレット化したものを使用した。
【０１２４】
【表２】

【０１２５】
成形板Ｘ〜Ｚを水でよく洗浄して乾燥した後、口径１．０ｍｍ、スプレー圧３．５〜５．０ＭＰａのスプレーガンを用いて、成形板上に膜厚が１０μｍになるように、前記のプライマーをスプレー塗装した。スプレー塗布性を確認し、その結果を表３に示す。５分間乾燥した後、二液硬化型ウレタン系メタリック塗料（日本ビーケミカル社製、商品名ＲＢ−２１２（ベース塗料）および商品名ＲＢ−２８８（クリアー塗料））を、塗膜全体の膜厚が８０μｍになるように上記と同じスプレーガンを用いて２コート塗装した。１５分間、２３℃で乾燥した後、８０℃で３０分間、非循環式乾燥器にて乾燥し、３日間室温で静置して、塗装試験片を得た。この塗膜の剥離強度を測定し、その結果を表３に示す。
【０１２６】
（実施例４および比較例２）
変性環化ゴムＡの代わりに、それぞれ、変性環化ゴムＢまたはＣを用いる以外は、実施例３と同様に、プライマーを調製し、塗装試験片を得た。これらの塗膜の剥離強度を測定し、その結果を表３に示す。
【０１２７】
【表３】

【０１２８】
表３から、以下のようなことがわかる。その分子量分布曲線が複数の極大ピークを有する本発明の変性環化ゴムＡおよびＢを、プライマーの接着性成分として用いると、塗装された塗膜の密着性が著しく改善されている。
【０１２９】
（実施例５）
ポリプロピレン樹脂（Ｊ３０５０ＨＰ：出光石油化学社製）９５部、変性環化ゴムＡ５部およびイルガノックス１０１０（チバ・スペシャリティー・ケミカルズ社製）０．１部を、ヘンシェルミキサーで混合後、二軸押出機を用いて、溶融温度２００℃で混練して、樹脂組成物のペレットを得た。このペレットを射出成形して、成形板（厚さ３ｍｍ×幅５０ｍｍ×長さ８０ｍｍ）を得た。
この成形板上に、口径１．０ｍｍ、スプレー圧３．５〜５．０ＭＰａのスプレーガンを用いて、二液硬化型ウレタン系メタリック塗料（日本ビーケミカル社製、商品名ＲＢ−２１２（ベース塗料）および商品名ＲＢ−２８８（クリアー塗料））を、塗膜全体の膜厚が８０μｍになるように２コート塗装した。１５分間、２３℃で乾燥した後、８０℃で３０分間、非循環式乾燥器にて乾燥し、３日間室温で静置して、塗装試験片を得た。この塗膜の剥離強度を測定し、その結果を表４に示す。
【０１３０】
（実施例６）
変性環化ゴムＡの代わりに、変性環化ゴムＢを用いる以外は、実施例５と同様に、成形板を作製し、それを用いて、塗装試験片を作製した。この塗膜の剥離強度を測定し、その結果を表４に示す。
【０１３１】
（比較例３）
変性環化ゴムを使用せず、ポリプロピレン樹脂（Ｊ３０５０ＨＰ：出光石油化学社製）１００部およびイルガノックス１０１０（チバ・スペシャリティー・ケミカルズ社製）０．１部からなる樹脂組成物を用いる以外は、実施例５と同様に、成形板を作製し、それを用いて、塗装試験片を作製した。この塗膜の剥離強度を測定し、その結果を表４に示す。
【０１３２】
【表４】

【０１３３】
表４から以下のようなことがわかる。
本発明の変性環化ゴムを配合したポリプロピレン樹脂からなる成形体は、塗膜との密着性が著しく改善されている。
【発明の効果】
本発明によれば、ポリプロピレン、ポリエチレンなどの非極性の重合体からなる成形体と塗料との密着性を著しく向上できる、マルチモーダルな分子量分布曲線を有する環化ゴムおよびその製造方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cyclized rubber and a method for producing the same, and more specifically, has a multimodal molecular weight distribution curve that can remarkably improve the adhesion between a molded body made of a nonpolar polymer such as polypropylene and polyethylene and a paint. The present invention relates to a cyclized rubber and a method for producing the same.
[0002]
[Prior art]
Molded articles made of polyolefins such as polyethylene and polypropylene are often used by coating their surfaces with paints in order to improve cosmetics and durability. However, since polyolefin has low polarity and is inferior in adhesion to a coating as it is, there is a problem that the coating film is easily peeled off.
[0003]
It is known that a paint containing a cyclized product of a conjugated diene polymer such as polyisoprene adheres well to a polyolefin (see Patent Document 1). In order to further improve the adhesion, a cis-1,4 bond is used. It has been proposed to use a modified conjugated diene polymer cyclized product obtained by adding a maleic anhydride to a conjugated diene polymer having a low molecular weight of 70% or more and then performing a cyclization reaction (see Patent Document 2). .)
However, by using the conjugated diene polymer cyclized product as described above, a coating material having improved adhesion to the polyolefin molded body to some extent can be obtained, but the improvement degree is insufficient.
[0004]
[Patent Document 1]
Japanese Patent Laid-Open No. 51-12827
[Patent Document 2]
JP-A-57-145103
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a cyclized rubber capable of remarkably improving the adhesion between a molded body made of a nonpolar polymer such as polypropylene and polyethylene and a paint, and a method for producing the same.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have started the polymerization of a conjugated diene monomer using an organic active metal catalyst, and before the polymerization is completed, the organic active metal catalyst Multimodal molecular weight obtained by adding a polymerization terminator to inactivate a part of the active metal in the polymer and continuing the polymerization to cyclize the resulting conjugated diene polymer having a multimodal molecular weight distribution curve The present inventors have found that the above object can be achieved by using a cyclized rubber having a distribution curve and having a weight average molecular weight in a specific range, and based on this finding, the present invention has been completed.
[0007]
  Thus, according to the present invention, the following invention1-2Is provided.
  1.A conjugated diene monomer, or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer, using an organic active metal catalyst, before the polymerization is completed, Adding a polymerization terminator in an amount that inactivates part of the active metal in the active metal catalyst and continuing the polymerization to form a conjugated diene polymer having a multimodal molecular weight distribution curve;
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve;
A process for producing a cyclized rubber having a multimodal molecular weight distribution curve comprising:
A ring comprising a step of introducing a polar group by forming a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve and then reacting the conjugated diene polymer cyclized product with a polar group-containing compound. A method for producing synthetic rubber.
2.Part of an organic active metal catalyst used for polymerization when a conjugated diene monomer or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer is polymerized using an organic active metal catalyst And after the polymerization is started, before the polymerization is completed, the remainder of the organic active metal catalyst is added to continue the polymerization to form a conjugated diene polymer having a multimodal molecular weight distribution curve; and Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve;
A process for producing a cyclized rubber having a multimodal molecular weight distribution curve comprising:
A ring comprising a step of introducing a polar group by forming a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve and then reacting the conjugated diene polymer cyclized product with a polar group-containing compound. A method for producing synthetic rubber.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The cyclized rubber of the present invention is a conjugated diene polymer cyclized product or a derivative thereof, the molecular weight distribution curve is multimodal having a plurality of peaks, and the weight average molecular weight is 1,000 to 1,000,000. belongs to.
[0012]
In the present invention, the molecular weight distribution curve being multimodal having a plurality of peaks means that there are a plurality of maximum peaks in the molecular weight distribution curve obtained by gel permeation chromatography (GPC) measurement. To do.
It is sufficient that two or more peaks exist. Usually, when there are more than 20 peaks, it is difficult to confirm as a maximum peak in the molecular weight distribution curve. Especially, the number of preferable peaks is in the range of 2-5.
[0013]
The cyclized rubber of the present invention has the smallest molecular weight (peak top molecular weight (Pmw−)) in the molecular weight distribution curve of the standard polystyrene equivalent molecular weight (peak top molecular weight) corresponding to the peak top of each observed peak. S)) and the largest (maximum peak top molecular weight (Pmw-L)) (Pmw-L / Pmw-S) is 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more It is preferable that If this ratio is too small, the desired physical properties may not be obtained. The maximum value of this ratio is usually about 20, and preferably 10 or less.
[0014]
The minimum peak top molecular weight (Pmw-S) of the cyclized rubber of the present invention is preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 50,000 or more. When this molecular weight is too low, the adhesion tends to be lowered.
[0015]
The maximum peak top molecular weight (Pmw-L) of the cyclized rubber of the present invention is preferably 1,000,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less. If this molecular weight is too high, the adhesion tends to decrease.
[0016]
When the cyclized rubber of the present invention has a molecular weight distribution curve of bimodal (having two peaks) (hereinafter sometimes abbreviated as bimodal cyclized rubber), The weight ratio with respect to the high molecular weight component is 95/5 to 10/90, preferably 85/15 to 30/70, more preferably 80/20 to 50/50. When the ratio is within the above range, the adhesion is further improved.
[0017]
The weight average molecular weight of the cyclized rubber of the present invention is 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 30,000 to 300,000. If the molecular weight is low, the adhesion of the paint is inferior. On the other hand, if the molecular weight is high, it becomes difficult to handle the cyclized rubber during production or use. This weight average molecular weight is a standard polystyrene conversion value measured by GPC.
[0018]
The cyclization rate of the cyclized rubber of the present invention is not particularly limited, but is usually 10% or more, preferably 40 to 95%, more preferably 60 to 90%, and particularly preferably 70 to 85%. If the cyclization rate is too low, the adhesion of the paint is inferior, and conversely, it becomes difficult to produce a cyclized rubber having a high cyclization rate, and gelation tends to proceed. It may cause problems.
The cyclization rate is¹By H-NMR analysis, the peak areas of protons derived from double bonds before and after the cyclization reaction of the conjugated diene polymer used as a raw material were measured, respectively, and the ring after the cyclization reaction when the pre-cyclization reaction was taken as 100 The ratio of the double bond remaining in the fluoride is determined, and is a value (%) represented by the calculation formula = (100−the ratio of the double bond remaining in the cyclized compound).
[0019]
The glass transition temperature of the cyclized rubber of the present invention is not particularly limited and can be appropriately selected depending on the application, but is usually −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 90 ° C., and particularly preferably. Is 30-70 ° C.
[0020]
Further, the degree of cyclization (n) of the cyclized rubber, that is, the connection of the rings is usually in the range of n = 1 to 3. The gel amount of the cyclized rubber is usually 10% by weight or less, preferably 5% by weight or less, but it is particularly preferable that the gel has substantially no gel. If the amount of gel is large, there may be a problem in the application process in a solution state.
[0021]
The following five methods are mentioned as a manufacturing method of the cyclized rubber of this invention.
(First manufacturing method)
In the first production method, a conjugated diene monomer or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer is polymerized using an organic active metal catalyst. Before completion of the process, a polymerization terminator is added to inactivate a part of the active metal in the organic active metal catalyst and polymerization is continued to form a conjugated diene polymer having a multimodal molecular weight distribution curve. Step (1-1) to perform,
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve (1-2);
Consists of.
[0022]
[Step (1-1)]
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and the like. Of these, 1,3-butadiene and isoprene are preferable, and isoprene can be more preferably used. These monomers may be used alone or in combination of two or more.
[0023]
The amount of the conjugated diene monomer used is not particularly limited, but the conjugated diene monomer unit content in the conjugated diene polymer is usually 40 mol% or more, preferably 60 mol% or more, more preferably 80 mol%. This is the amount. When this content is small, it becomes difficult to increase the cyclization rate, and the desired effect of improving physical properties tends to be difficult to obtain.
[0024]
Examples of the monomer copolymerizable with the conjugated diene monomer include styrene, α-methylstyrene, p-isopropylstyrene, p-phenylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-tert- Aromatic vinyl monomers such as butoxystyrene, chloromethylstyrene, 2-fluorostyrene, 3-fluorostyrene, pentafluorostyrene, vinyltoluene, vinylnaphthalene and vinylanthracene; olefin monomers such as ethylene, propylene and isobutylene; Etc. Among these, aromatic vinyl monomers are preferable, and styrene and α-methylstyrene can be more preferably used.
[0025]
The organic active metal catalyst is not particularly limited as long as it is a catalyst capable of livingly polymerizing the monomer. Specific examples include organic alkali metal compounds and organic alkaline earth metal compounds. Of these, organic alkali metal compounds can be preferably used.
[0026]
Examples of the organic alkali metal compound include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4 -Organic polyvalent lithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic lithium compound is preferable, and an organic monolithium compound can be more preferably used.
[0027]
The organic alkali metal compound can also be used as an organic alkali metal amide compound obtained by reacting the organic alkali metal compound with a secondary amine.
[0028]
Secondary amines include, for example, dimethylamine, methylethylamine, methylpropylamine, methylbutylamine, methylamylamine, amylhexylamine, diethylamine, ethylpropylamine, ethylbutylamine, ethylhexylamine, dipropylamine, diisopropylamine, propylbutylamine , Dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, methylcyclopentylamine, ethylcyclopentylamine, methylcyclohexylamine, dicyclopentylamine, dicyclohexylamine, and other aliphatic secondary amines; diphenylamine, N-methylaniline, N -Ethylaniline, dibenzylamine, N-methylbenzylamine, N-ethylphenethylamine, etc. Group secondary amines; aziridine, acetylidine, pyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, heptamethyleneimine, dodecamethylene Examples thereof include cyclic imines such as imine, coniine, morpholine, oxazine, pyrroline, pyrrole and azepine. These secondary amines are used alone or in combination of two or more.
The amount of secondary amine used is usually 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the metal in the organic alkali metal compound. .
[0029]
Examples of the organic alkaline earth metal compound include JP-A-51-115590, JP-A-52-9090, JP-A-52-17591, JP-A-52-30543, JP-A-52-30543. Compounds having metals such as barium, strontium, calcium and the like disclosed in Japanese Patent Publication Nos. 52-48910, 52-98077, 56-1112916, 57-10016, etc. Is exemplified. Specific examples include, for example, n-butylmagnesium bromide, n-hexylmagnesium bromide, ethoxycalcium, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethyl mercaptobarium, t-butoxybarium, phenoxybarium, diethylaminobarium, ethyl Examples include barium.
[0030]
Said organic active metal catalyst can be used individually or in combination of 2 or more types. The amount used is appropriately selected depending on the type of the catalyst or the required weight average molecular weight of the produced polymer, but is usually 0.01 to 100 mmol, preferably 0.05 to 20 mmol, per 100 g of the monomer. More preferably, it is the range of 0.1-10 mmol.
[0031]
The polymerization using the catalyst is usually performed in a polymerization solvent. The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization.
Examples of the polymerization solvent include aliphatic saturated hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; alicyclic rings such as cyclopentane, cyclohexane, and methylcyclopentane. Formula saturated hydrocarbons; aromatic hydrocarbons such as benzene and toluene; Among these, n-hexane, cyclohexane, toluene and the like are preferable. Moreover, unsaturated hydrocarbons with extremely low polymerizability, such as 1-butene, cis-2-butene, and 2-hexene, can be used in combination as necessary. These polymerization solvents can be used alone or in combination of two or more.
Although the usage-amount of a polymerization solvent is not specifically limited, The density | concentration of the monomer used for superposition | polymerization is 1-50 weight% normally, Preferably it is the quantity used as the range of 10-40 weight%.
[0032]
In the polymerization reaction, a polar compound can be used to adjust the bond structure of the conjugated diene monomer unit. The polar compound is not particularly limited as long as it is used in normal anionic polymerization using an organic active metal catalyst.
Examples of the polar compound include ether compounds such as dibutyl ether, ethylene glycol dibutyl ether, and tetrahydrofuran; tertiary amines such as tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, and quinuclidine; potassium-t-amyl oxide, potassium-t-butyl. Alkali metal alkoxides such as oxide; phosphine derivatives such as triphenylphosphine; and the like. Among these, tertiary amines and ether compounds are preferable, tertiary amines are more preferable, and tetramethylethylenediamine can be particularly preferably used. These polar compounds can be used alone or in combination of two or more.
When using a polar compound, the amount used is usually 200 mol or less, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, particularly preferably 1 mol of the organic active metal catalyst. 0.8 to 20 mol.
[0033]
After the polymerization is started as described above, before the polymerization is completed, an amount of a polymerization terminator that inactivates a part of the active metal in the organic active metal catalyst is added.
The polymerization terminator is not particularly limited as long as it can deactivate the active metal in the organic active metal catalyst. For example, alcohols such as methanol, ethanol, isopropanol, n-butanol, and t-butanol; phenol, Phenols such as methylphenol and 2,6-tert-butyl-hydroxytoluene; water. Of these, methanol, t-butanol, and 2,6-tert-butyl-hydroxytoluene can be preferably used.
The amount of the polymerization terminator used is usually 0.1 to 0.95 equivalent, preferably 0.3 to 0.9 equivalent, more preferably 0, relative to the active metal in the organic active metal catalyst used for the polymerization. The range is from 0.5 to 0.9 equivalents.
[0034]
By adjusting the amount of the polymerization terminator added before the polymerization is completed, the amount of the conjugated diene polymer that has terminated the polymerization at the time when the polymerization terminator is added can be adjusted.
[0035]
The addition timing of the polymerization terminator to be added before the completion of the polymerization is not particularly limited, but is usually 5 to 95% by weight, preferably 20 to 90% by weight, based on the polymerization conversion ratio with respect to the total amount of monomers used for the polymerization. More preferably, it is 40 to 90% by weight. By adjusting this addition time, the peak top molecular weight of the conjugated diene polymer that has been polymerized when the polymerization terminator is added can be adjusted.
[0036]
In addition, before the polymerization is completed, an amount of the polymerization terminator in the above range can be added in portions, and the timing for adding them can be appropriately selected within the above range. By adjusting the number of divisions, the number of peaks in the molecular weight distribution curve can be adjusted, and by adjusting the amount of each added, the polymerization was stopped at the time when the polymerization terminator was added, for each conjugated diene polymer. The amount ratio can be adjusted.
[0037]
The polymerization reaction is usually carried out in a polymerization mode such as batch or continuous in the range of −78 to 150 ° C. The polymerization time is not particularly limited, but it is preferable to carry out until the polymerization reaction is almost completed.
[0038]
After the polymerization reaction is almost completed, a polymerization terminator is further added to stop the polymerization reaction. As the polymerization terminator, those described above can be used, and the amount used is the total amount of the metal in the organic active metal catalyst used for the polymerization and the polymerization terminator added before the completion of the polymerization reaction. In general, the amount is 1 to 10 equivalents, preferably 1 to 5 equivalents, more preferably 1 to 1.5 equivalents.
[0039]
As described above, a conjugated diene polymer having a multimodal molecular weight distribution curve is obtained. The obtained conjugated diene polymer may be obtained as a solid product by removing the polymerization solvent by a conventional method, or may be transferred to the next step as the polymer solution.
[0040]
[Step (1-2)]
As the cyclization catalyst, a conventionally known catalyst can be used.
Examples of the cyclization catalyst include sulfuric acid; organic sulfonic acid compounds such as monofluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, their anhydrides or alkyl esters; boron trifluoride, boron trichloride, four And metal halides such as tin chloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, and iron chloride. These cyclization catalysts can be used alone or in combination of two or more.
Among these cyclization catalysts, organic sulfonic acid compounds are preferable, and p-toluenesulfonic acid can be more preferably used.
[0041]
The amount of the cyclization catalyst used is appropriately selected according to the type of cyclization catalyst and the required cyclization rate, but is usually 0.05 to 10 parts by weight, preferably 100 parts by weight based on 100 g of the conjugated diene polymer. 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight.
[0042]
The cyclization reaction proceeds when the conjugated diene polymer and the cyclization catalyst are brought into contact with each other, but is usually performed in an inert solvent. The inert solvent is not particularly limited as long as it does not inhibit the cyclization reaction.
As the inert solvent, those described above as the polymerization solvent can be used. Among these, those having a boiling point of 70 ° C. or higher can be preferably used.
The amount of the inert solvent used is not particularly limited, but the amount of the conjugated diene polymer obtained in step (1-1) is preferably 5 to 60% by weight, more preferably 20 to 40% by weight. is there.
[0043]
The reaction temperature in the cyclization reaction is usually 50 to 150 ° C., preferably 80 to 110 ° C., and the reaction time is usually 0.5 to 10 hours, preferably 2 to 5 hours.
[0044]
As described above, a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve is obtained.
The obtained cyclized rubber is usually obtained as a solid by inactivating the cyclization catalyst by a conventional method, then removing the cyclization catalyst residue and removing the inert solvent.
[0045]
(Second manufacturing method)
In the second production method, a conjugated diene monomer, or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer is used for polymerization using an organic active metal catalyst. After the polymerization is started using a part of the organic active metal catalyst, before the polymerization is completed, the remainder of the organic active metal catalyst is added to continue the polymerization, and the conjugated diene polymer having a multimodal molecular weight distribution curve is obtained. A step of forming a coalescence (2-1);
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve (2-2);
Consists of.
[0046]
[Step (2-1)]
The amount of the organic active metal catalyst used for initiating the polymerization is usually 5 to 90 mol%, preferably 10 to 70 mol%, more preferably the total amount of the organic active metal catalyst used for the polymerization. The amount is in the range of 10 to 50 mol%. If the amount used is too small or too large, the desired effect of improving physical properties may not be obtained. By adjusting this amount, the content of the conjugated diene polymer on the high molecular weight side can be adjusted.
[0047]
After the polymerization is started, before the polymerization is completed, the remainder of the organic active metal catalyst is added for polymerization. Although the addition time is not particularly limited, it is usually 5 to 90% by weight, preferably 10 to 70% by weight, more preferably 10 to 50% by weight, based on the polymerization conversion rate with respect to the total amount of monomers used for the polymerization. . By adjusting this addition time, the peak top molecular weight of the conjugated diene polymer formed by the remaining organic active metal catalyst added after the start of polymerization can be adjusted.
[0048]
Further, the remaining organic active metal catalyst to be added after the polymerization is started can be added in a divided manner before the polymerization is completed, and the addition timing can be appropriately selected within the above range. By adjusting the number of divisions, the number of peaks in the molecular weight distribution curve can be adjusted, and by adjusting the amount of each added, each conjugated diene formed by the organoactive metal catalyst added after the start of polymerization. The ratio of the polymer amount can be adjusted.
[0049]
The polymerization method and conditions in the step (2-1) are as described above, and after the polymerization is started, before the polymerization is completed, the polymerization is stopped in such an amount as to deactivate a part of the active metal in the organic active metal catalyst. Except for the point that the polymerization is continued by adding an agent, the conditions are the same as those in the step (1-1).
[0050]
After the polymerization reaction is almost completed, a polymerization stopper is added to stop the polymerization reaction. As the polymerization terminator, those described above can be used. The amount of the polymerization terminator used is usually in the range of 1 to 10 equivalents, preferably 1 to 5 equivalents, more preferably 1 to 1.5 equivalents, relative to the metal in the organic active metal catalyst used for the polymerization. Amount.
[0051]
As described above, a conjugated diene polymer having a multimodal molecular weight distribution curve is obtained. The obtained conjugated diene polymer may be obtained as a solid product by removing the polymerization solvent by a conventional method, or may be transferred to the next step as the polymer solution.
[0052]
[Step (2-2)]
The conjugated diene polymer obtained in step (2-1) is cyclized using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve. The method and conditions in this step are the same as in step (1-2).
[0053]
(Third production method)
The third production method comprises polymerizing a conjugated diene monomer, or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer using an organic active metal catalyst, and A step (3-1) of forming an active conjugated diene polymer having an active metal on the active conjugated diene polymer, and a bifunctional amount of the active conjugated diene polymer that reacts with a part of the active metal in the active conjugated diene polymer. A step (3-2) of forming a conjugated diene polymer having a multimodal molecular weight distribution curve by reacting an ionic coupling agent;
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve (3-3);
Consists of.
[0054]
[Step (3-1)]
The polymerization method and the conditions in the step (3-1) are the same as described above except for the following three points in the steps (1-1) and (2-1).
(1) After the polymerization reaction is almost completed, the polymerization reaction is stopped.
(2) After the polymerization is started, before the polymerization is completed, an amount of a polymerization terminator that inactivates a part of the active metal in the organic active metal catalyst is added to continue the polymerization.
(3) After the polymerization is started using a part of the organic active metal catalyst used for the polymerization, the remainder of the organic active metal catalyst is added and the polymerization is continued before the polymerization is completed.
As described above, an active conjugated diene polymer having an active metal at the end of the polymer chain is formed.
[0055]
[Step (3-2)]
The active conjugated diene polymer obtained in step (3-1) is reacted with a bifunctional coupling agent in an amount that reacts with a part of the active metal in the active conjugated diene polymer, so that a multimodal molecular weight is obtained. A conjugated diene polymer having a distribution curve is formed.
[0056]
The bifunctional coupling agent is a compound having two sites that react with the active metal at the end of the polymer chain of the active conjugated diene polymer and bind to the polymer molecule.
Examples of the bifunctional coupling agent include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional alkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; dichloroethane and dibromoethane. Difunctional tin halides such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, dibutyldichlorotin, etc. Benzoic acid, CO, 2-chloropropene and the like.
[0057]
By reacting the active conjugated diene polymer with a bifunctional coupling agent, a coupled product having a molecular weight approximately twice that of the active conjugated diene polymer is produced.
[0058]
The amount of the bifunctional coupling agent used is such that the active conjugated diene polymer remains even after reacting the active conjugated diene polymer with the bifunctional coupling agent. The amount of the functional group in the bifunctional coupling agent is usually 0.1 to 0.9 equivalent, preferably 0.1 to 0.7 equivalent, based on the total amount of active metal in the organic active metal catalyst. More preferably, the amount is in the range of 0.1 to 0.5 equivalents. If the amount used is too small or too large, the desired effect of improving physical properties may not be obtained.
[0059]
The reaction temperature of the active conjugated diene polymer and the bifunctional coupling agent is usually room temperature to 120 ° C., preferably 40 to 100 ° C., and the reaction time is usually 1 minute to several hours, preferably 10 minutes to 2 hours. Within this range, the reaction proceeds sufficiently and problems such as gelation due to side reactions are unlikely to occur.
[0060]
Thereafter, a polymerization stopper is added to stop the polymerization reaction. As the polymerization terminator, those described above can be used, and the amount used is usually 0.1 to 10 equivalents, preferably 0.2 to 5 equivalents, relative to the metal in the organic active metal catalyst used for the polymerization. More preferably, it is the range of 0.5-1.5 equivalent.
[0061]
As described above, a conjugated diene polymer having a multimodal molecular weight distribution curve is obtained. The obtained conjugated diene polymer may be obtained as a solid product by removing the polymerization solvent by a conventional method, or may be transferred to the next step as the polymer solution.
[0062]
[Step (3-3)]
The conjugated diene polymer obtained in step (3-2) is cyclized using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve. The method and conditions in this step are the same as in step (1-2).
[0063]
(Fourth manufacturing method)
The fourth production method has a multimodal molecular weight distribution curve by cyclizing a mixture of two or more conjugated diene polymers having different peak top molecular weights in the molecular weight distribution curve using a cyclization catalyst. This is a method of forming a conjugated diene polymer cyclized product.
[0064]
Two or more kinds of conjugated diene polymers having different peak top molecular weights in the molecular weight distribution curve are prepared in advance. Each of these conjugated diene polymers can be prepared by a conventional method.
[0065]
These conjugated diene polymers are mixed at a desired ratio and cyclized using a cyclization catalyst to form a conjugated diene polymer cyclized product.
The method and conditions for the cyclization reaction are the same as in step (1-2).
As described above, a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve is obtained.
[0066]
(Fifth manufacturing method)
The fifth production method is a method in which two or more conjugated diene polymer cyclized products having different peak top molecular weights in the molecular weight distribution curve are mixed.
[0067]
Two or more kinds of conjugated diene polymer cyclized products having different peak top molecular weights in the molecular weight distribution curve are prepared in advance. Each of these conjugated diene polymer cyclized products can be prepared by a conventional method.
[0068]
These conjugated diene polymer cyclized products are mixed at a desired ratio to obtain a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve. Examples of the mixing method include a method of removing the solution after kneading or mixing in a solution state. As described above, a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve is obtained.
[0069]
Among the above production methods, the first to third production methods are preferable from the viewpoint of production efficiency, and the ratio (Pmw−) between the minimum peak top molecular weight (Pmw-S) and the maximum peak top molecular weight (Pmw-L). The first and second production methods are more preferable in that L / Pmw-S) can be arbitrarily adjusted.
[0070]
In the present invention, a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve can be subjected to a modification reaction with a polar group-containing compound, if necessary.
[0071]
The polar group-containing compound used for the modification reaction is not particularly limited as long as it is a compound that can introduce a polar group into the conjugated diene polymer cyclized product. For example, an acid anhydride group, a carboxyl group, a hydroxyl group, Examples thereof include ethylenically unsaturated compounds having polar groups such as thiol groups, ester groups, epoxy groups, amino groups, amide groups, cyano groups, silyl groups, and halogens.
As the polar group, an acid anhydride group, a carboxyl group, a hydroxyl group, an ester group, an epoxy group, and an amino group are preferable, and an acid anhydride group, a carboxyl group, and a hydroxyl group are more preferable in terms of excellent adhesive improvement effect.
[0072]
Examples of the compound having an acid anhydride group or carboxyl group include ethylenically unsaturated compounds such as maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, acrylic acid, methacrylic acid and maleic acid. Among them, maleic anhydride is used in terms of reactivity and economy.
[0073]
Examples of the ethylenically unsaturated compound containing a hydroxyl group include hydroxyalkyl esters of unsaturated acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylol (meth) Unsaturated acid amides having hydroxyl groups such as acrylamide and N- (2-hydroxyethyl) (meth) acrylamide; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) Polyalkylene glycol monoesters of unsaturated acids such as mono (meth) acrylate; polyhydric alcohol monoesters of unsaturated acids such as glycerol mono (meth) acrylate; among these, Hi B alkoxyalkyl esters are preferred, particularly 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylic acid.
[0074]
Examples of other ethylenically unsaturated compounds containing polar groups include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethyl Aminopropyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, etc. are mentioned.
[0075]
The method for introducing the polar group-containing compound into the conjugated diene polymer cyclized product is not particularly limited, but when adding an ethylenically unsaturated compound, a known reaction generally called an ene addition reaction or a graft polymerization reaction is used. Just follow.
This addition reaction is performed by reacting the conjugated diene polymer cyclized product and the polar group-containing compound in the presence of a radical generator, if necessary. Examples of radical generators include peroxides such as di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxide benzoate, and methyl ethyl ketone peroxide; azobisisobutyronitrile. Azonitriles; and the like.
[0076]
The addition reaction may be performed in a solid phase state or a solution state, but is preferably performed in a solution state from the viewpoint of easy reaction control. Examples of the solvent used include those similar to the hydrocarbon solvent in the cyclization reaction as described above.
[0077]
The amount of the polar group-containing compound used is appropriately selected, but the ratio of the introduced polar group is usually 0.1 to 200 mmol, preferably 1 to 100 mmol, per 100 g of the cyclized rubber after modification. The range is preferably 5 to 50 mmol.
[0078]
The reaction for introducing a polar group can be performed under pressure, reduced pressure, or atmospheric pressure, but is preferably performed under atmospheric pressure from the viewpoint of ease of operation. When carried out in an atmosphere of nitrogen or dry argon, side reactions derived from moisture can be suppressed.
Moreover, reaction temperature and reaction time should just follow a conventional method, Reaction temperature is 30-250 degreeC normally, Preferably it is 60-200 degreeC, and reaction time is 0.5 to 5 hours normally, Preferably it is 1 ~ 3 hours.
[0079]
The cyclized rubber of the present invention is used by adding colorants such as pigments and dyes; and compounding agents such as anti-aging agents, fillers, softeners, and waxes, as necessary. The compounding agent should just be generally used.
[0080]
Examples of the antioxidant include 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl-t-butylphenol), tetrakis [methylene-3- (3 ′, 5′-di-t. -Butyl-4'-hydroxyphenyl) propionate] phenolic antioxidants such as methane; phenyl-α-naphthylamine, diphenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylene Examples include amine-based anti-aging agents such as diamines; phosphorus-based anti-aging agents such as tris (nonylphenyl) phosphite.
[0081]
Examples of the filler include calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, barium sulfate, mica, silica, carbon black, talc, clay, titanium dioxide. Zinc oxide, glass fiber, carbon fiber and the like.
[0082]
The usage-amount of a compounding agent can be suitably selected with the objective of a mixing | blending and the kind of compounding agent.
[0083]
The shape of the cyclized rubber can be appropriately selected according to the use, but is usually a pellet or powder. In order to obtain a powder form, the solid cyclized rubber may be pulverized with a pulverizer such as a bantam mill, a jet mill, a disk mill, a ball mill, or a colloid mill under cooling.
[0084]
The average particle diameter of the powder particles is usually 1 μm to 200 μm, preferably 3 μm to 100 μm, and more preferably 5 μm to 50 μm. The average particle diameter is a particle diameter corresponding to a 50% number-based integrated value in a number-based integral curve with respect to the particle diameter, which is measured by a laser diffraction / scattering method.
[0085]
The content of the cyclized rubber in the powder particles is usually 5% by weight or more, preferably 10% by weight, more preferably 20% by weight or more, and particularly preferably 30% by weight or more.
[0086]
The shape of the powder particles is not particularly limited, and examples thereof include a spherical shape and an indefinite shape.
[0087]
The powder particles made of the cyclized rubber of the present invention can be used, for example, as a powder coating by taking advantage of excellent adhesion to resins and metals. In the case of a powder coating material, a colorant is blended, and an anti-aging agent, a filler, a softening agent, a wax and the like are blended as necessary according to a conventional method.
[0088]
When pigments are used as colorants, benzidine, azo, and isoindoline pigments are used for yellow coloring, and azo lake, rhodamine lake, quinacridone, naphthol, and diketopyrrolopyrrole pigments are used for magenta coloring. However, phthalocyanine pigments and indanthrene pigments are preferably used for cyan coloring. Carbon black is usually used for black coloring. Examples of carbon black include thermal black, acetylene black, channel black, furnace black, and lamp black.
[0089]
When dyes are used as colorants, azo, nitro, quinoline, quinophthalone, and methine dyes are used for yellow coloring, anthraquinone, azo, and xanthene dyes are used for magenta coloring, and anthraquinone is used for cyan coloring. , Phthalocyanine and indoaniline dyes are preferably used.
[0090]
The amount of the colorant to be used may be appropriately selected depending on the desired hue, density, etc., and is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the cyclized rubber. .
[0091]
The powder coating material can be usually obtained by mixing a cyclized rubber with a colorant and, if necessary, an additive, pulverizing and classifying the mixture.
[0092]
The mixing method is not particularly limited, and for example, there is a method of melt-mixing using a kneader such as a Banbury mixer, a kneader, a mixing roll, a single screw or a twin screw extruder.
[0093]
What is necessary is just to follow the above-mentioned method as a grinding | pulverization method.
Examples of classification methods include air classification, centrifugal classification, and sieve classification.
[0094]
In addition, the cyclized rubber of the present invention can be used as a modifier for polymer molding materials by blending it with various polymer molding materials composed of thermoplastic resins, thermosetting resins, elastomers, etc. It is suitable for improving the property. Furthermore, it is also useful as a modifier for polymer molding materials to improve the dispersibility of different types of polymers that make up the polymer molding materials and the dispersibility of fillers, pigments, and other compounding agents in polymers. is there.
[0095]
Examples of the polymer used for the polymer molding material to be modified include the following.
1. Hydrocarbon resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polycarbonate resin, polyvinyl Thermoplastic resins such as butyrate resins, polyarylate resins, and fluorine resins.
2. Thermosetting resins such as phenolic resin, cresol resin, urea resin, melamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin, urethane resin.
[0096]
3. Vulcanized rubbers such as natural rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber; elastomers such as olefin thermoplastic elastomer, styrene thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer.
[0097]
Among these, hydrocarbons such as chain olefin resins such as polyethylene, polypropylene and polypentene-1; cyclic copolymers such as addition copolymers of ethylene and norbornene, ring-opening polymers of norbornenes; When blended with a thermoplastic resin, the effect of modification by cyclized rubber is great.
[0098]
The above polymers can be used alone or in combination of two or more, and if necessary, colorants such as pigments and dyes; anti-aging agents, fillers, softeners, waxes, antistatic agents A compounding agent such as an agent, a stabilizer, a lubricant, a cross-linking agent, an antiblocking agent, a light blocking agent, and an ultraviolet absorber can be appropriately blended.
[0099]
The blending amount as the modifier is appropriately selected according to the type of polymer molding material and the required performance, but is usually 0.1 to 50 parts by weight, preferably 100 parts by weight per 100 parts by weight of the polymer in the polymer molding material. Is 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and particularly preferably 2 to 5 parts by weight.
[0100]
Furthermore, the cyclized rubber of the present invention is used as an adhesive component such as a primer component or a binder component for a paint in a coating agent such as a primer or a paint for the above-described polymer molding material, thereby Adhesiveness with paint can be remarkably improved. In this case, the cyclized rubber is preferably contained in an amount of 2% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more based on the total solid content in the coating agent such as primer or paint.
[0101]
When used as a coating agent, other adhesive components and various additives are blended with the cyclized rubber as necessary.
[0102]
Examples of other adhesive components include acrylic resin, urethane resin, polyester resin, epoxy resin, melamine resin, alkyd resin, chlorinated olefin resin, and silicone rubber.
The ratio in the case of blending other adhesive components is appropriately selected according to the type and blending purpose, but is usually a weight ratio between the cyclized rubber and the other adhesive components, and is usually 100: 0 to 5:95. Preferably it is 80: 20-30: 70, More preferably, it is 70: 30-50: 50.
[0103]
Moreover, as an additive, the thing similar to the case where it mix | blends with a polymer as mentioned above in the term of a modifier is illustrated.
[0104]
A coating agent comprising a cyclized rubber is usually obtained by dissolving or dispersing a cyclized rubber or a mixture of the cyclized rubber and other components in a solvent. The solvent to be used may be appropriately selected, and examples thereof include an aliphatic solvent, an alicyclic solvent, an aromatic hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ether solvent, a halogen solvent, and an aqueous solvent. Can be mentioned. The amount of the solvent used is in such a range that the solid content concentration of the coating agent is usually 5 to 95% by weight, preferably 15 to 60% by weight.
[0105]
The coating agent containing the cyclized rubber of the present invention can also be used as a surface treatment agent for dispersion materials such as various fillers and pigments. When the dispersion material is surface-treated with the coating agent, the dispersibility of the dispersion material with respect to various polymers is improved.
As the filler and pigment to be surface-treated, those described above can be used. The amount of the cyclized rubber used is appropriately selected according to the type of the dispersing material and the type of the polymer in which it is dispersed, but is usually 0.1 to 100 parts by weight, preferably 5 to 100 parts by weight of the dispersing material. It is used at a ratio of 20 parts by weight.
[0106]
【Example】
The present invention will be described more specifically with reference to the following examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.
[0107]
Evaluation was performed as follows.
(1) Analysis of polymer gel permeation chromatography (GPC) GPC analysis of the polymer was carried out under the following conditions. All molecular weights are standard polystyrene equivalent values.
Measuring instrument: HLC-8220 (manufactured by Tosoh Corporation)
Column: Tosoh G5000HXL, G4000HXL and G2000HXL connected in series were used.
Detector: Differential refractometer
Eluent: Tetrahydrofuran (1 ml / min)
Column temperature: 40 ° C
From the obtained molecular weight distribution curve, the number of maximum peaks, the peak top molecular weight of each peak, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in each peak, and the peak of each peak The area ratio (corresponding to the weight ratio of the polymer components constituting each peak) was determined.
[0108]
(2) Glass transition temperature of polymer
The glass transition temperature of the polymer was measured using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd .: SSC5200) under the conditions of a starting temperature of −100 ° C. and a heating rate of 10 ° C./min.
[0109]
(3) Cyclization rate of cyclized product of conjugated diene polymer
By proton NMR analysis, the peak areas of protons derived from double bonds before and after the cyclization reaction of the conjugated diene polymer were measured, respectively, and the ratio of double bonds remaining in the cyclized product was defined as 100 before the cyclization reaction. Asked. And the cyclization rate (%) was calculated | required by calculation formula = (100-ratio of the double bond which remains in a cyclization thing).
[0110]
(4) Measurement of the amount of polar groups (carboxyl groups) in the modified polymer
The acid value of the modified polymer was measured according to the method described in “Reference Oil Analysis Test Method” (Japan Oil Chemicals Association) 2, 4, 1-83, and converted to the amount of carboxyl groups in the polymer.
[0111]
(5) Spray applicability
The primer was painted, the state of the painted surface was observed, and judged according to the following criteria.
○: The painted surface is smooth and can be painted neatly.
X: A stringing phenomenon occurs during spray coating, and the smoothness of the coating surface is poor.
(6) Peel strength
Using a cutter blade, a cut was made on the surface of the molded body to which the paint had been applied until the blade reached the substrate with a width of 1 cm, and the coating film at the end was peeled off. The edge part of the peeled coating film was pulled in the direction of 180 ° at a speed of 50 mm / min, and the peel strength (unit: kgf / cm) was measured.
[0112]
Example 1
A pressure-resistant reactor equipped with a stirrer was charged with 1400 g of dehydrated toluene and 11.4 mmol of n-butyllithium (1.56 mol / liter: hexane solution), and the internal temperature was kept at 60 ° C. 487 g of isoprene was continuously added to the reactor over 15 minutes, and the internal temperature was controlled not to exceed 75 ° C. Thereafter, the mixture was reacted at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion was almost 100%.
Next, after adding 10 mmol of methanol (toluene solution), 113 g of isoprene was continuously added to the reactor at 70 ° C. over 15 minutes, and further reacted at 70 ° C. for 1 hour. It was confirmed that it was 100%.
Thereafter, 1.4 mmol of methanol was added as a polymerization terminator to terminate the polymerization reaction.
A small amount of polymerization solution was collected to obtain polymer a. The polymer a was subjected to GPC analysis, and the results are shown in Table 1.
[0113]
After stopping the polymerization reaction, the temperature was raised to 80 ° C., 4.24 g of p-toluenesulfonic acid was added, and then the cyclization reaction was performed for 3 hours while maintaining the temperature at 80 ° C. Thereafter, an aqueous solution in which 1.70 g of sodium carbonate was dissolved in 5.1 g of water was added to stop the cyclization reaction. After stirring at 80 ° C. for 30 minutes, the catalyst residue was removed using a glass fiber filter having a pore size of 1 μm.
[0114]
From the resulting reaction solution, toluene was distilled off at 160 ° C., and 15 g of maleic anhydride was added when the solid content concentration reached 80 to 85%. Next, after reacting at 160 ° C. for 1 hour, unreacted maleic anhydride and toluene were distilled off, and after adding 0.6 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals), ethylene tetrafluoride Poured into a metal vat coated with resin. It was dried under reduced pressure at 75 ° C. to obtain a modified cyclized rubber A.
The modified cyclized rubber A was analyzed, and the results are shown in Table 1.
[0115]
(Example 2)
A pressure-resistant reactor equipped with a stirrer was charged with 1400 g of dehydrated toluene and 1.1 mmol of n-butyllithium (1.56 mol / liter: hexane solution), and the internal temperature was kept at 60 ° C. 77 g of isoprene was continuously added to the reactor over 15 minutes, and the internal temperature was controlled so as not to exceed 75 ° C. Thereafter, the mixture was reacted at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion was almost 100%.
Then, 7.4 mmol of n-butyllithium (1.56 mol / liter: hexane solution) was added, and then 523 g of isoprene was continuously added to the reactor over 15 minutes while maintaining 70 ° C. The mixture was further reacted at 70 ° C. for 1 hour. Furthermore, it reacted at 70 degreeC for 1 hour, and confirmed that the polymerization conversion rate was about 100%. Thereafter, 8.5 mmol of methanol was added as a polymerization terminator to terminate the polymerization reaction.
A small amount of the polymerization solution was collected to obtain a polymer b. The polymer b was subjected to GPC analysis, and the results are shown in Table 1.
[0116]
After stopping the polymerization reaction, the temperature was raised to 80 ° C., 4.68 g of p-toluenesulfonic acid was added, and a cyclization reaction was performed for 3 hours while maintaining the temperature at 80 ° C. Thereafter, an aqueous solution in which 1.90 g of sodium carbonate was dissolved in 5.76 g of water was added to stop the cyclization reaction. After stirring at 80 ° C. for 30 minutes, the catalyst residue was removed using a glass fiber filter having a pore size of 1 μm.
[0117]
Toluene was distilled off at 160 ° C. from the resulting reaction solution, and 18 g of maleic anhydride was added when the solid content concentration became 75 to 80%. Next, after reacting at 160 ° C. for 1 hour, unreacted maleic anhydride and toluene were distilled off, and after adding 0.6 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals), ethylene tetrafluoride Poured into a metal vat coated with resin. It was dried under reduced pressure at 75 ° C. to obtain a modified cyclized rubber B.
The modified cyclized rubber B was analyzed, and the results are shown in Table 1.
[0118]
(Comparative Example 1)
This comparative example was carried out with reference to JP-A-57-145103.
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, polymer c (73% cis-1,4-structure isoprene unit, trans-1,4- 100 parts of polyisoprene comprising 22% structural isoprene units and 5% 3,4-structure isoprene units, having a weight average molecular weight of 159,000 and a molecular weight distribution of 1.15) and 1570 parts of toluene were charged. After the atmosphere in the flask was replaced with nitrogen, the temperature was raised to 80 ° C., and polyisoprene was dissolved in toluene. Thereafter, 2.5 parts of maleic anhydride was added, and maleic anhydride addition reaction was performed at 180 ° C. for 1 hour. The obtained reaction solution was put into 3000 parts of a 2,6-di-tert-butylphenol 1% acetone solution to collect a precipitate, which was dried under reduced pressure to obtain polyisoprene modified with maleic anhydride. .
[0119]
100 parts of the modified polyisoprene was dissolved in 730 parts of toluene, 3.6 parts of p-toluenesulfonic acid was added to the solution, and a cyclization reaction was performed for 5 hours while maintaining the solution temperature at 85 ° C. After cooling to room temperature, 400 parts of ion-exchanged water was added to stop the cyclization reaction, and the oil layer was separated by standing for 30 minutes. This oil layer was washed three times with 400 parts of ion-exchanged water, and then the oil layer was put into 1000 parts of a 2,6-di-tert-butylphenol 1% methanol solution to recover a precipitate, which was dried under reduced pressure. Modified cyclized rubber C was obtained. The modified cyclized rubber C was analyzed, and the results are shown in Table 1.
[0120]
Note that none of the obtained modified cyclized rubbers A to C contained a component insoluble in toluene.
[0121]
[Table 1]

[0122]
(Example 3)
20 parts of modified cyclized rubber A, 15 parts of titanium oxide and 80 parts of xylene were mixed with a high-speed stirrer (disper) for 10 minutes, and then diluted with thinner so that the flowability would be 13 to 14 seconds in the flow-down time to prepare a primer did. The above fluidity is measured by the Ford Cup No. specified in JIS K 5400. According to Method 4, it means the flow time at 20 ° C.
[0123]
The resin material shown in Table 2 was injection molded to produce three types of molded plates X to Z (50 mm × 80 mm × 3 mm). In addition, after mixing each compounding component with a Henschel mixer, Y used the thing melt-kneaded with the twin-screw extruder and pelletized.
[0124]
[Table 2]

[0125]
After thoroughly washing the molded plates X to Z with water and drying, using a spray gun with a caliber of 1.0 mm and a spray pressure of 3.5 to 5.0 MPa, the film thickness is 10 μm on the molded plate. The primer was spray painted. The spray coatability was confirmed, and the results are shown in Table 3. After drying for 5 minutes, the two-component curable urethane-based metallic paint (product name RB-212 (base paint) and trade name RB-288 (clear paint) manufactured by Nippon Bee Chemical Co., Ltd.)) Two coats were applied using the same spray gun as described above to a thickness of 80 μm. After drying at 23 ° C. for 15 minutes, it was dried in a non-circulating dryer at 80 ° C. for 30 minutes, and allowed to stand at room temperature for 3 days to obtain a coated test piece. The peel strength of this coating film was measured, and the results are shown in Table 3.
[0126]
(Example 4 and Comparative Example 2)
A primer was prepared in the same manner as in Example 3 except that the modified cyclized rubber B or C was used in place of the modified cyclized rubber A, and a coated test piece was obtained. The peel strengths of these coating films were measured, and the results are shown in Table 3.
[0127]
[Table 3]

[0128]
Table 3 shows the following. When the modified cyclized rubbers A and B of the present invention whose molecular weight distribution curve has a plurality of maximum peaks are used as the adhesive component of the primer, the adhesion of the coated film is remarkably improved.
[0129]
(Example 5)
95 parts of polypropylene resin (J3050HP: manufactured by Idemitsu Petrochemical Co., Ltd.), 5 parts of modified cyclized rubber A and 0.1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) were mixed with a Henschel mixer, and then a twin screw extruder. Was used and kneaded at a melting temperature of 200 ° C. to obtain resin composition pellets. This pellet was injection-molded to obtain a molded plate (thickness 3 mm × width 50 mm × length 80 mm).
On this molded plate, using a spray gun having a caliber of 1.0 mm and a spray pressure of 3.5 to 5.0 MPa, a two-component curable urethane-based metallic paint (trade name RB-212 manufactured by Nippon Bee Chemical Co., Ltd. (base paint) ) And trade name RB-288 (clear paint)) were applied in two coats so that the film thickness of the entire coating film was 80 μm. After drying at 23 ° C. for 15 minutes, it was dried in a non-circulating dryer at 80 ° C. for 30 minutes, and allowed to stand at room temperature for 3 days to obtain a coated test piece. The peel strength of this coating film was measured, and the results are shown in Table 4.
[0130]
(Example 6)
A molded plate was produced in the same manner as in Example 5 except that the modified cyclized rubber B was used instead of the modified cyclized rubber A, and a coating test piece was produced using the molded plate. The peel strength of this coating film was measured, and the results are shown in Table 4.
[0131]
(Comparative Example 3)
Except for using a resin composition comprising 100 parts of polypropylene resin (J3050HP: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) without using a modified cyclized rubber, In the same manner as in Example 5, a molded plate was produced, and a coating test piece was produced using the molded plate. The peel strength of this coating film was measured, and the results are shown in Table 4.
[0132]
[Table 4]

[0133]
Table 4 shows the following.
A molded body made of a polypropylene resin containing the modified cyclized rubber of the present invention has remarkably improved adhesion to the coating film.
【The invention's effect】
According to the present invention, there is provided a cyclized rubber having a multimodal molecular weight distribution curve and a method for producing the same, which can remarkably improve the adhesion between a molded body made of a nonpolar polymer such as polypropylene and polyethylene and a paint. .

Claims (2)

A conjugated diene monomer, or a monomer that can be copolymerized with a conjugated diene monomer and a conjugated diene monomer, is polymerized using an organic active metal catalyst and before the polymerization is completed. Adding a polymerization terminator in an amount that inactivates a part of the active metal in the active metal catalyst and continuing the polymerization to form a conjugated diene polymer having a multimodal molecular weight distribution curve;
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve;
A process for producing a cyclized rubber having a multimodal molecular weight distribution curve comprising:
A ring comprising a step of introducing a polar group by forming a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve and then reacting the conjugated diene polymer cyclized product with a polar group-containing compound. A method for producing synthetic rubber . Part of an organic active metal catalyst used for polymerization when a conjugated diene monomer or a monomer copolymerizable with a conjugated diene monomer and a conjugated diene monomer is polymerized using an organic active metal catalyst And after the polymerization is started, before the polymerization is completed, the remainder of the organic active metal catalyst is added to continue the polymerization to form a conjugated diene polymer having a multimodal molecular weight distribution curve; and
Cyclizing the conjugated diene polymer using a cyclization catalyst to form a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve;
A process for producing a cyclized rubber having a multimodal molecular weight distribution curve comprising:
A ring comprising a step of introducing a polar group by forming a conjugated diene polymer cyclized product having a multimodal molecular weight distribution curve and then reacting the conjugated diene polymer cyclized product with a polar group-containing compound. A method for producing synthetic rubber.