WO2004067590A1

WO2004067590A1 - Cyclized rubber and process for producing the same

Info

Publication number: WO2004067590A1
Application number: PCT/JP2004/000421
Authority: WO
Inventors: Shizuo Kitahara; Yasushi Tanaka; Atsushi Hayashi
Original assignee: Zeon Corporation
Priority date: 2003-01-31
Filing date: 2004-01-20
Publication date: 2004-08-12

Abstract

A cyclized rubber which contains polar groups and can significantly improve adhesion between a molding of a nonpolar polymer, such as polypropylene or polyethylene, and a coating material; and a process for producing the rubber. The cyclized rubber is either a product of the cyclization of a conjugated diene polymer or a derivative thereof, gives a multi-modal molecular-weight distribution curve with two or more peaks, and has a weight-average molecular weight of 1,000 to 1,000,000. The cyclized rubber is incorporated into polypropylene as a feed material or is used as an adhesive ingredient for a primer for polypropylene moldings. Thus, the desired adhesion improvement is attained.

Description

Description Cyclic rubber and its manufacturing method

The present invention relates to a cyclized rubber and a method for producing the same, and more particularly, to a multimodal molecular weight distribution capable of remarkably improving the adhesion between a molded article made of a nonpolar polymer such as polypropylene and polyethylene and a coating composition. The present invention relates to a cyclized rubber having a curve and a method for producing the same. Background art

Molded articles made of polyolefins such as polyethylene and polypropylene are often used with their surfaces painted with paints in order to improve aesthetics and durability. However, polyolefin has a low polarity and, as it is, is inferior in adhesion to the paint, so that there is a problem that the coating film is easily peeled off.

It is known that a coating containing a cyclized product of a conjugated diene polymer such as polyisoprene adheres well to polyolefin (Japanese Patent Application Laid-Open (JP-A) No. 51-128287). In order to improve the conjugated conjugated polymer obtained by adding maleic anhydride to a low molecular weight conjugated polymer having a cis-1,4 bond amount of 70% or more and then performing a cyclization reaction, Its use has been proposed (Japanese Unexamined Patent Publication No. 57-145103).

However, although the use of the cyclized conjugated diene polymer as described above provides a coating material having improved adhesion to a polyolefin molded product to some extent, the degree of improvement was insufficient. Disclosure of the invention

The present invention has been made in view of the above circumstances, and provides a cyclized rubber capable of significantly improving the adhesion between a molded article made of a nonpolar polymer such as polypropylene and polyethylene and a paint, and a method for producing the same. The purpose is to: The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, after starting the polymerization of the conjugated gen monomer using the organic active metal catalyst, the organic active metal The polymerization is continued by adding a polymerization terminator in an amount that inactivates a part of the active metal in the catalyst, and the polymerization is continued to cyclize the obtained conjugated diene polymer having a multimodal molecular weight distribution curve. It has been found that the above object can be achieved by using a cyclized rubber having a modal molecular weight distribution curve and a weight average molecular weight in a specific range, and based on this finding, the present invention has been completed.

According to the present invention, the following inventions 1 to 26 are provided.

I. A cyclized conjugated polymer or a derivative thereof, wherein the molecular weight distribution curve is multimodal having a plurality of peaks, and the weight average molecular weight is from 1,000 to

Cyclic rubber that is 1,000,000.

2. The cyclized rubber having a cyclization ratio of 10% or more.

3. The cyclized rubber having a gel amount of 10% by weight or less.

4. The above-mentioned cyclized rubber wherein the ratio (Pmw-L / Pmw_S) of the minimum peak top molecular weight (Pmw-S) to the maximum peak top molecular weight (Pmw_L) is 1.5 or more.

5. The above-mentioned cyclized rubber having a minimum peak top molecular weight (Pmw_S) of 10,000 or more. '

6. Said cyclized rubber having a maximum peak top molecular weight (Pmw-L) of 1,000,000 or less.

7. Said cyclized rubber whose molecular weight distribution curve is pi-modal.

8. The cyclized rubber as described above, wherein the weight ratio of the low molecular weight component to the high molecular weight component is 95Z5 to 10Z90.

9. The above cyclized rubber, wherein the derivative of the cyclized conjugated polymer is a derivative obtained by introducing a polar group into the cyclized conjugated polymer by a modification reaction using a polar group-containing compound.

10. The polar group is at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen. The cyclized rubber as described above.

I I. The polar group is selected from the group consisting of acid anhydride group, carboxyl group and hydroxyl group. The above-mentioned cyclized rubber, which is at least one group that is removed.

12. The polymerization is completed after starting the polymerization of the conjugated gen monomer or the conjugated gen monomer and a monomer copolymerizable with the conjugated gen monomer using an organic active metal catalyst. Before the polymerization, the polymerization is continued by adding a polymerization terminator in an amount that inactivates a part of the active metal in the organic active metal catalyst, and the polymerization is continued to form a conjugated gen-polymer having a multimodal molecular weight distribution curve. Forming,

Cyclizing the conjugated polymer using a cyclization catalyst to form a cyclized conjugated polymer having a multimodal molecular weight distribution curve;

A method for producing a cyclized rubber having a multimodal molecular weight distribution curve having

13. When polymerizing a conjugated diene monomer or a monomer that can be copolymerized with a conjugated diene monomer and a conjugated diene monomer using an organic active metal catalyst, an organic active metal used for the polymerization is used. After the polymerization is started using a part of the catalyst and before the polymerization is completed, the remaining part of the organic active metal catalyst is added to continue the polymerization to form a conjugated polymer having a multimodal molecular weight distribution curve. The process of

14. The conjugated diene monomer or a monomer that can be copolymerized with the conjugated diene monomer and the conjugated diene monomer is polymerized using an organic active metal catalyst to form an active metal at the polymer chain end. Forming an active conjugated polymer having

The active conjugated polymer is reacted with an amount of a polyfunctional coupling agent that reacts with a part of the active metal in the active conjugated polymer to form a conjugated polymer having a multimodal molecular weight distribution curve. The process of

15. After forming a cyclized conjugated polymer having a multimodal molecular weight distribution curve, a step of introducing a polar group by reacting a compound containing a polar group with the cyclized conjugated polymer is provided. Production method. 16. A modifier for a polymer molding material containing the above-mentioned cyclized rubber as an active ingredient.

17. A polymer composition obtained by blending the above-mentioned modifier for a polymer molding material with the polymer molding material.

18. The polymer composition as described above, wherein the polymer molding composition is non-polar.

19. The above polymer composition, wherein the content of the polymer-forming material modifier is 0.1 to 50 parts by weight per 100 parts by weight of the polymer.

20. A coating agent containing the above cyclized rubber.

2 1. The above-mentioned coating agent for non-polar polymer molding materials.

22. The above coating agent which is a primer for a polymer molding material.

23. Powder particles containing the above cyclized rubber.

24. The above powder particles having an average particle diameter of 1 to 200 µm.

25. The above powder particles further containing a colorant.

26. The powder particles as described above, wherein the amount of the colorant used is 0.1 to 50 parts by weight based on 100 parts by weight of the cyclized rubber.

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 paint made of a nonpolar polymer such as polypropylene and polyethylene and a paint. Is done. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The cyclized rubber of the present invention is a cyclized conjugated polymer or a derivative thereof, the molecular weight distribution curve of which is multimodal having a plurality of peaks, and the weight average molecular weight of which is 1,000 to 1,000, 0 0 0, 0 0 0.

In the present invention, a multi-modal molecular weight distribution curve having a plurality of peaks means that there are a plurality of maximum peaks in a molecular weight distribution curve obtained by gel 'permeation' chromatography (GPC) measurement. means. It is sufficient that there are two or more peaks. Usually, when the peak has more than 20, it is difficult to identify the peak as a maximum peak in the molecular weight distribution curve. Among them, the preferred number of peaks is in the range of 2-5. The cyclized rubber of the present invention has the smallest (minimum peak top molecular weight (Pmw-) among the molecular weights (peak top molecular weights) in terms of standard polystyrene corresponding to the observed peak tops in the molecular weight distribution curve. S)) and the largest one (the maximum peak top molecular weight (Pmw-L)) (Pmw-LZPmw-S) is 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more. Preferably, there is. 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.

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. If the molecular weight is too low, the adhesion tends to decrease. 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 the molecular weight is too high, the adhesion tends to decrease.

When the cyclized rubber of the present invention has a molecular weight distribution curve of a pi-modal (having two peaks) (hereinafter sometimes abbreviated as a bimodal cyclized rubber), the cyclized rubber on the low molecular weight side The weight ratio of the component to the component on the high molecular weight side is preferably 95/5 to 1090, preferably 85Zl 5 to 30/70, and more preferably 80/20 to 50/50. When the ratio is in the above range, the adhesion is further improved. The weight average molecular weight of the cyclized rubber of the present invention is from 1,000 to 1,000,000, preferably from 10,000 to 500,000, more preferably from 30,000 to 300,000, particularly preferably from 50,000 to 50,000. 300,000. If the molecular weight is low, the adhesiveness of the paint is poor, and if it is high, it is difficult to handle the cyclized rubber during production and use. This weight average molecular weight is a standard polystyrene equivalent value measured by GPC.

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 will be poor, and conversely, a cyclized rubber with a high cyclization rate In addition to the difficulty in producing the cyclized rubber solution, gelation is likely to proceed, which may cause a problem in the step of applying the cyclized rubber solution.

The cyclization rate was as follows: — NMR analysis was performed to measure the peak areas of the protons derived from the double bond before and after the cyclization reaction of the conjugated gen polymer used as the raw material, and the value was set to 100 before the cyclization reaction The ratio of the double bond remaining in the cyclized product after the cyclization reaction is determined, and is a value (%) represented by a calculation formula (100—the ratio of the double bond remaining in the cyclized product).

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 150 to 200 ° C, preferably 0 to 100 ° C, more preferably The temperature is 20 to 90 ° C, particularly preferably 30 to 70 ° C.

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. Gel quantity of cyclized rubber is usually 1 0 weight ^_0/0 or less, preferably but 5 wt ^_0/0 or less, and particularly preferably those having substantially no gel. If the amount of gel is large, problems may occur in the application process in a solution state.

The method for producing the cyclized rubber of the present invention includes the following five methods.

(First manufacturing method)

In the first production method, after starting the polymerization of a conjugated gen monomer, or a conjugated gen monomer and a monomer copolymerizable with the conjugated gen monomer using an organic active metal catalyst, Before the polymerization is completed, the polymerization is continued by adding an amount of a polymerization terminator that inactivates a part of the active metal in the organic active metal catalyst, and the polymerization is continued. A step of forming a unity (111);

A step of cyclizing the conjugated polymer using a cyclization catalyst to form a cyclized conjugated polymer having a multimodal molecular weight distribution curve (1-2).

[Process (1-1)]

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethinolene 1,3-butadiene, 2-pheninolene 1,3-butadiene, 1,3-pentadiene, 1,3-pentagenene, and 2-methylenol, 3-pentagen, 1,3-hexadiene, 4,5-getinolene 1,3-octadiene, 3 butyl-1,3-octadiene And the like. Among them, 1,3-butadiene and isoprene are preferred, and isoprene can be more preferably used. These monomers may be used alone or in combination of two or more.

Although the amount of the conjugated gen monomer used is not particularly limited, the content of the conjugated gen monomer unit in the conjugated gen polymer is usually at least 40 mol%, preferably at least 60 mol%, more preferably The amount is 80 mol% or more. If this content is small, it is difficult to increase the cyclization rate, and the intended effect of improving physical properties tends to be hardly obtained.

Monomers copolymerizable with the conjugated diene monomer include, for example, styrene, α-methinolestyrene, ρ-isopropinolestyrene, ρ-pheno-nostyrene, ρ-methoxystyrene, ρ-methoxymethylstyrene. Aromatic vinyl monomers such as p-tert-butoxystyrene, chloromethinolestyrene, 2-fluorostyrene, 3-phenylenostyrene, pentaphenylenostyrene, vinyltonolene, vinylinolephthalene, and vinylinoleanthracene; ethylene, And olefin monomers such as propylene and isobutylene; Of these, aromatic vinyl monomers are preferred, and styrene and α-methylstyrene can be more preferably used.

The organic active metal catalyst is not particularly limited as long as it is a catalyst capable of polymerizing the above monomer in a living manner. Specific examples include, for example, organic alkali metal compounds, organic alkaline earth metal compounds, and the like. Among them, organic alkali metal compounds can be preferably used.

Examples of the organic alkali metal compound include organic monolithium compounds such as η-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, 1,4- Organic polyvalent lithium compounds such as dilithobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these, an organolithium compound is preferred, and an organomonolithium compound can be more preferably used.

The organic metal compound can also be used as an organic metal compound obtained by reacting a secondary amine with the organic metal compound.

Secondary amines include, for example, dimethylamine, methylethylamine, methyl Propylamine, Methylbutylamine, Methylamylamine, Amylhexylamine, Jethylamine, Ethylpropylamine, Ethynolebutynoleamine, Ethylhexylamine, Dipropylamine, Diisopropylamine, Propylbutylamine, Dibutylamine, Aliphatic secondary amines such as diamylamine, dihexylamine, diheptylamine, dioctylamine, methylcyclopentylamine, ethylethylpentinoleamine, methylcyclohexylamine, dicyclopentinoleamine, dicyclohexinoleamine, etc .; diphenylamine, N-methylaniline Aromatic secondary amines such as N-ethylaniline, dibenzylamine, N-methylbenzylamine, N-ethylphenethylamine; aziridine, acetidine, pylori , Piperidine, 2-methylpiperidine, 3-methinoleviperidine, 4-methylpiperidine, 3,5-dimethylbiperidine, 2-ethylbiperidine, hexamethyleneimine, heptamethyleneimine, dodecamethyleneimine, Examples include cyclic imines such as coniine, monoreforin, oxazine, pyrroline, pyrrole, and azepine. These secondary amines are used alone or in combination of two or more.

The amount of the secondary amine used is usually 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents, and more preferably 1 to 1.2 equivalents, based on the metal in the organic alkali metal compound. .

Examples of the organic alkaline earth metal compound include, for example, JP-A-51-115590, JP-A-52-9090, JP-A-52-17591, JP-A-52-30543. Barium, strontium, and calcium disclosed in JP-A-52-48910, JP-A-52-98077, JP-A-56-112916, and JP-A-57-100146. Compounds having a metal such as are exemplified. Specific examples include, for example, n-butylmagnesium bromide, n-hexyl / lemagnesium bromide, ethoxycanolesum, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethyl mercapto-norium, t-butoxybarium, phenoxyvalium, getylaminovalium, ethylparium, and the like.

The above-mentioned organic active metal catalysts can be used alone or in combination of two or more. The amount used depends on the type of the above catalyst or the required weight of the produced polymer. Although it is appropriately selected depending on the average molecular weight, it is usually 0.01 to 100 mmol, preferably 0.05 to 20 mmol, more preferably 0.1 to 10 mmol per 100 g of the monomer. In the millimolar range.

The polymerization using the above 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, iso-octane; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic saturated hydrocarbons; aromatic hydrocarbons such as benzene and toluene; and the like. Among them, n-hexane, cyclohexane, toluene and the like are preferable. If necessary, unsaturated hydrocarbons having extremely low polymerizability, such as 1-butene, cis-1-butene, and 2-hexene, can be used in combination. These polymerization solvents can be used alone or in combination of two or more.

The amount of the polymerization solvent to be used is not particularly limited, but is such that the concentration of the monomer used in the polymerization is usually in the range of 1 to 50% by weight, preferably 10 to 40% by weight. In the polymerization reaction, a polar compound can be used to adjust the bonding structure of the conjugated gen monomer unit. The polar compound is not particularly limited as long as it is one used in normal ion polymerization using an organic active metal catalyst.

Examples of the polar compound include ether compounds such as dibutyl ether, ethylene dalicol dibutyl ether, and tetrahydrofuran; tertiary amines such as tetramethylethylene diamine, trimethylamine, triethylamine, pyridine, and quinutalizine; alkali metal alkoxides such as t-butyloxide; phosphine derivatives such as triphenylphosphine; and the like. Of these, tertiary amines and ether compounds are preferred, tertiary amines are more preferred, and tetramethylethylenediamine can be used particularly preferably. These polar compounds can be used alone or in combination of two or more.

When a polar compound is used, the amount of the polar compound to be used is generally 200 mol or less, preferably 0.1 to 100 mol, more preferably ◦0.5 mol, per mol of the organic active metal catalyst. 550 mol, particularly preferably 0.8-20 mol.

After the initiation of the polymerization 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 inactivate the active metal in the organic active metal catalyst. Examples thereof include alcohols such as methanol, ethanol, isopropanol, n-butanol and t-butanol; Phenoenoles, such as methylphenol and 2,6-tert-ptinolehidroxytonolene; water. Of these, methanol, t-butanol, and 2,6-tert-butyl-hydroxytoluene can be preferably used.

The amount of the polymerization terminator to be used is usually 0.1 to 0.95 equivalent, preferably 0.3 to 0.9 equivalent, and more preferably 0.1 to 0.95 equivalent to the active metal in the organic active metal catalyst used for the polymerization. Or in the range of 0.5 to 0.9 equivalents.

By adjusting the amount of the polymerization terminator added before the completion of the polymerization, the amount of the conjugated gen polymer whose polymerization has been stopped at the time of adding the polymerization terminator can be adjusted. The timing of addition of the polymerization terminator added before the completion of the polymerization is not particularly limited, but is usually 5 to 95% by weight, preferably 20 to 100% by weight in terms of the polymerization conversion rate based on the total amount of the monomers used for the polymerization. 9 0 weight ^_0/0, more preferably 4 0-9 0% by weight. By adjusting the time of this addition, the peak top molecular weight of the conjugated gen polymer whose polymerization has been stopped when the polymerization terminator is added can be adjusted.

In addition, before the polymerization is completed, the polymerization terminator in the above range may be added in portions, and the timing of the addition may 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. By adjusting the amount of each addition, the polymerization was stopped when the polymerization terminator was added. The proportion of the amount of coalescence can be adjusted.

The polymerization reaction is usually carried out in a polymerization mode such as a batch system or a continuous system in the range of −78 to 150 ° C. The polymerization time is not particularly limited, but is preferably performed until the polymerization reaction is almost completed.

After the polymerization reaction is almost completed, the polymerization reaction is stopped by adding a polymerization terminator. As the polymerization terminator, those described above can be used. The total amount of the metal in the organic active metal catalyst and the polymerization terminator added before the completion of the polymerization reaction is usually 1 to 10 equivalents, preferably 1 to 5 equivalents, more preferably 1 to 10 equivalents. The amount is in the range of ~ 1.5 equivalents.

As described above, a conjugated diene polymer having a multimodal molecular weight distribution curve can be obtained. The obtained conjugated diene polymer may be obtained as a solid by removing the polymerization solvent by a conventional method, or may be transferred to the next step as it is as the polymer solution.

[Process (1 _ 2)]

As the cyclization catalyst, generally known ones can be used.

Examples of the cyclization catalyst include sulfuric acid; monofluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, alkylbenzenesnolephonic acid having an anolequinole group having 2 to 16 carbon atoms, and the like. Organic sulfonic acid compounds such as anhydrides or alkyl esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, getyl aluminum monochloride, aluminum bromide, antimony pentachloride And metal halides such as tungsten hexachloride and iron chloride; These cyclization catalysts can be used alone or in combination of two or more.

Among these cyclization catalysts, an organic sulfonic acid conjugate is preferable, and p-toluenesulfonic acid can be more preferably used.

The amount of the cyclization catalyst to be used is appropriately selected depending on the type of the cyclization catalyst and the required cyclization ratio. However, it is usually 0.05 to 10 g per 100 g of the conjugated diene polymer. Parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight.

The cyclization reaction proceeds when the conjugated polymer is brought into contact with the cyclization catalyst, 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 them, those having a boiling point of 70 ° C. or more can be preferably used.

The amount of inert solvent is not particularly limited, step (1 _ 1) conjugate obtained in Jen concentration of the polymer is preferably 5-6 0 weight ^_0/0, more preferably 2 0-4 0 fold It is the amount that becomes the amount%. The reaction temperature in the L2 cyclization reaction is usually 50 to 150 ° C, preferably 80 to 110 ° C, and the reaction time is generally 0.5 to 10 hours, preferably 2 to 10 hours. 5 hours. As described above, a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve can be obtained.

The obtained cyclized rubber is generally obtained as a solid by removing the cyclization catalyst residue and the inert solvent after inactivating the cyclization catalyst by a conventional method.

(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 when polymerizing using an organic active metal catalyst. After the polymerization is started using a part of the organic active metal catalyst, and before the polymerization is completed, the remaining part of the organic active metal catalyst is added to continue the polymerization, and the conjugated agent having a multimodal molecular weight distribution curve is obtained. Forming a polymer (2-1); cyclizing the conjugated diene polymer using a cyclization catalyst to form a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve And (2-2).

[Process (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 ⁰ , based on the total amount of the organic active metal catalyst used for the polymerization. / _0, more preferably in an amount in the range of 1 0-5 0 mol ^_0/0. If the amount is too small or too large, the intended effect of improving physical properties may not be obtained. By adjusting this amount, the content of the conjugated gen polymer on the high molecular weight side can be adjusted.

After the initiation of the polymerization, before the polymerization is completed, the remaining organic active metal catalyst is added to carry out the polymerization. The time of addition is not particularly limited, but is usually 5 to 90% by weight, preferably 10 to 70% by weight, more preferably 10 to 100% by weight based on the total amount of the monomers used for the polymerization. ~ 50% by weight. By adjusting the timing of the addition, the peak top molecular weight of the conjugated gen polymer formed by the remaining organic active metal catalyst added after the start of the polymerization can be adjusted.

Also, the remaining organic active metal catalyst added after the start of the polymerization will complete the polymerization. Can be added in portions before the addition, and the timing of their addition 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. By adjusting the amount of each addition, the peak is formed by the organic active metal catalyst added after the start of polymerization. The proportion of each conjugated polymer can be adjusted.

The polymerization method and conditions in the step (2-1) are as described above. The conditions are the same as those in the step (11-1), except that the polymerization is continued by adding the agent.

After the polymerization reaction is almost completed, the polymerization reaction is stopped by adding a polymerization terminator. 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, based on the metal in the organic active metal catalyst used for the polymerization. It is the amount that becomes.

As described above, a conjugated diene polymer having a multimodal molecular weight distribution curve can be obtained. The obtained conjugated gen polymer may be obtained as a solid by removing the polymerization solvent by a conventional method, or may be transferred to the next step as it is as the polymer solution.

[Process (2-2)]

The conjugated diene polymer obtained in the step (2-1) is cyclized using a cyclization catalyst to form a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve. The conditions of the method in this step are the same as those in step (1-2).

(Third manufacturing method) ''

In the third 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 to obtain a polymer. (3-1) forming an active conjugated polymer having an active metal at the chain end; and reacting the active conjugated gen polymer with a part of the active metal in the active conjugated gen polymer. Reacting the multifunctional coupling agent to form a conjugated diene polymer having a multimodal molecular weight distribution curve (3-2);

Cyclizing the conjugated polymer using a cyclization catalyst to form a cyclized conjugated polymer having a multimodal molecular weight distribution curve (3-3); L4.

[Process (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 (2-11).

(1) After the polymerization reaction is almost completed, stop the polymerization reaction.

(2) After the polymerization is started and before the polymerization is completed, the polymerization is continued by adding a polymerization terminator in an amount that inactivates a part of the active metal in the organic active metal catalyst.

(3) After the polymerization is started using a part of the organic active metal catalyst used for the polymerization, before the polymerization is completed, the remaining part of the organic active metal catalyst is added and the polymerization is continued. As described above, an active conjugated polymer having an active metal at a polymer chain terminal is formed.

[Process (3_2)]

The active conjugated polymer obtained in the step (3-1) is reacted with a multifunctional coupling agent in an amount that reacts with a part of the active metal in the active conjugated polymer to obtain a multimodal molecular weight distribution. A conjugated gen polymer having a curve is formed.

The polyfunctional coupling agent is a compound having two or more sites that react with the active metal at the polymer terminal of the active conjugated polymer and bond to the polymer molecule.

Examples of the bifunctional coupling agent include difunctional silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; difunctional silanes such as diphenyldimethoxysilane and diphenylethoxysilane; difunctional alkoxysilanes such as dichloroethane; Difunctional molybdenum salts such as dipromoethane, methylene chloride, and dipromomethane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethynoresichlorotin, cetinoresichlorotin, monobutyldichlorotin, dibutyldichlorotin Bifunctional tin halides such as rosin; benzoic acid, CO, and 2-chloropropene.

Examples of trifunctional cappuri agents include: trifunctional silanes such as trichloroethane and trichlorobutane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; Trifunctional alcohols such as methyltrimethoxysilane, phenyltrimethoxysilane, and phenoltriethoxysilane Coxysilane; and the like.

Examples of the tetrafunctional coupling agent include tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional silanes such as tetrachlorosilane and tetrabromosilane; tetramethoxysilane and tetraethoxysilane Tetrafunctional alkoxysilanes such as silane; tetrafunctional tin halides such as tetrachlorotin and tetrabutyl motin; and the like.

Examples of the coupling agent having five or more functionalities include 1,1,1,2,2-pentanochloroethane, cyclopentane, pentachlorobenzene, / chlorobenzene, octabromodipheninoleether, deca Bromodieninoleetanore and the like.

When an n-functional coupling agent (where n is an integer of 3 or more) is used, the number of branched polymer chains is n for a straight-chain polymer chain. — 2 A coupling type conjugated gen polymer can be formed.

By reacting the active conjugated diene polymer with the n-functional force-pulling agent, a force-coupled product having a molecular weight approximately n times that of the active conjugated diene polymer is produced.

The amount of the polyfunctional coupling agent used was such that the active conjugated polymer remained after the reaction of the active conjugated polymer and the polyfunctional coupling agent, and was used in the polymerization. The amount of the functional group in the polyfunctional coupling agent is usually 0.1 to 0.9 equivalent, preferably 0.1 to 0.7 equivalent, relative to the total amount of the active metal in the organic active metal catalyst. More preferably, the amount is in the range of 0.1 to 0.5 equivalent. If the amount is too small or too large, the intended effect of improving physical properties may not be obtained.

The reaction temperature of the active conjugated diene polymer and the polyfunctional coupling agent is usually room temperature to 120 ° C., preferably 40 to 100 ° C., and the reaction time is usually 1 to 100 ° C. Minutes 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 hardly occur.

Thereafter, a polymerization terminator is added to stop the polymerization reaction. As the polymerization terminator, those described above can be used, and the amount used is based on the metal in the organic active metal catalyst used in the polymerization. The range is usually 0.1 to 10 equivalents, preferably 0.2 to 5 equivalents, and more preferably 0.5 to 1.5 equivalents.

[Process (3-3)]

The conjugated diene polymer obtained in the step (3-2) is cyclized using a cyclization catalyst to form a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve. The method and conditions in this step are the same as those in step (1-2).

(Fourth manufacturing method)

In the fourth production method, a mixture of two or more conjugated diene polymers having different peak top molecular weights in the molecular weight distribution curve is cyclized using a cyclization catalyst to form a multi-modal molecular weight distribution curve. This is a method of forming a cyclized product of a conjugated gen polymer having the same.

In advance, two or more conjugated gen polymers having different peak top molecular weights in the molecular weight distribution curve are separately prepared. Each of these conjugated diene polymers can be prepared by a conventional method.

These conjugated diene polymers are mixed in 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 those in the step (1-2).

As described above, a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve can be obtained.

(Fifth manufacturing method)

The fifth production method is a method of mixing two or more cyclized conjugated diene polymers having different peak top molecular weights in the molecular weight distribution curve.

In advance, two or more kinds of conjugated gen polymer cyclized compounds having different peak top molecular weights in the molecular weight distribution curve are prepared. Each of these cyclized conjugated polymer can be prepared by a conventional method.

These cyclized conjugated polymers are mixed in a desired ratio to form a multimodal A cyclized product of a conjugated diene polymer having a suitable molecular weight distribution curve is obtained. Examples of the mixing method include a method in which the solution is removed after kneading or mixing in a solution state. As described above, a cyclized conjugated diene polymer having a multimodal molecular weight distribution curve can be obtained.

Among the above production methods, the first to third production methods are preferred in terms of production efficiency, and further, 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 the ratio (Pmw-LZPmw-S) can be arbitrarily adjusted.

In the present invention, the cyclized conjugated polymer having a multimodal molecular weight distribution curve can be subjected to a modification reaction with a polar group-containing compound, if necessary.

The polar group-containing compound used in the modification reaction is not particularly limited as long as the compound can introduce a polar group into the cyclized conjugated polymer, and examples thereof include an acid anhydride group, a carboxyl group, a hydroxyl group, Examples include ethylenically unsaturated compounds having a polar group such as a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen.

The polar group is preferably an acid anhydride group, a carboxyl group, a hydroxyl group, an ester group, an epoxy group, or an amino group, and more preferably an acid anhydride group, a carboxyl group, or a hydroxyl group, from the viewpoint of excellent effect of improving the adhesiveness.

Examples of the compound having an acid anhydride group or a carboxyl group include, for example, ethylenically unsaturated compounds such as maleic anhydride, itaconic anhydride, aconitic anhydride, norponenedicarboxylic anhydride, acrylic acid, methacrylic acid, and maleic acid. Compounds are mentioned, and among them, maleic anhydride is awarded for its reactivity and economy.

Examples of the ethylenically unsaturated compound having a hydroxyl group include, for example, hydroxyalkyl esters of unsaturated acids such as 2-hydroxyhexyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; —Methylol (meth) acrylamide, N— (2-Hydroxitytyl) (meth) Unsaturated acid amides having a hydroxyl group such as acrylamide; polyethylene glycol mono (meth) attarile-K polypropylene glycol mono (Meta) atalilate, poly (ethylene glycol) Poly (propylene glycol)) polyalkylene glycol monoesters of unsaturated acids such as mono (meth) acrylate; polyhydric alcohol monoesters of unsaturated acids such as glycerone mono (meth) atalylate; Of these, hydroxyalkyl esters of unsaturated acids are preferred, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferred.

Examples of other ethylenically unsaturated compounds containing a polar group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl ( Examples thereof include (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, and (meth) acrylonitrile.

The method for introducing the polar group-containing compound into the cyclized conjugated polymer is not particularly limited.However, when an ethylenically unsaturated compound is added, a known reaction generally called an ene addition reaction or a graft polymerization reaction is used. It is good to follow.

This addition reaction is carried out by reacting the cyclized conjugated polymer and the polar group-containing compound in the presence of a radical generator as required. Examples of the radical generator include peroxides such as di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxide benzoate, methylethyl ketone peroxide; Bisisoptyronitrile and the like; kunitrile; and the like.

The addition reaction may be performed in a solid state or in a solution state, but is preferably performed in a solution state because the reaction can be easily controlled. As the solvent to be used, for example, the same as the above-mentioned hydrocarbon-based solvent in the cyclization reaction can be mentioned. 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 g per 100 g of the modified cyclized rubber. 1100 mmol, more preferably 5-50 mmol. The reaction for introducing a polar group can be carried out under any of pressurized, depressurized and atmospheric pressures.However, it is desirable to carry out the reaction under atmospheric pressure in terms of simplicity of operation. When the reaction is performed in an atmosphere of dry nitrogen or dry argon, side reactions derived from moisture can be suppressed. The reaction temperature and the reaction time may be in accordance with a conventional method, and the reaction temperature is usually 30 to 250 ° C, preferably 60 to 200 ° C, and the reaction time is usually 0. 5 to 5 hours, preferably 1 to 3 hours.

The cyclized rubber of the present invention is used by adding a coloring agent such as a pigment and a dye; and a compounding agent such as an antioxidant, a filler, a softener, and a wax, if necessary. The compounding agent may be any commonly used one.

Examples of the antioxidants include 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl-t-butylphenol), tetrakis [methylene-3- (3 ′, 5′-g-t) —Phthyl-14'-hydroxyphenyl) propionone] Phenol anti-aging agents such as methane; phenyl-α-naphthylamine, diphenyl-ρ-phenylenediamine, Ν-1,3-dimethylbutyl-1-Ν —Aphenyl-based anti-aging agents such as phenyl-ρ-phenylenediamine; phosphorus-based anti-aging agents such as tris (nonylphenyl) phosphite.

Examples of the filler include calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, barium sulfate, myriki, silica, carbon black, tanolek, clay , Titanium dioxide, zinc oxide, glass fiber, carbon fiber and the like.

The amount of the compounding agent can be appropriately selected depending on the purpose of the compounding and the type of the compounding agent.

The shape of the cyclized rubber can be appropriately selected depending on the application, but is usually in the form of a pellet or powder. In order to make it into a powder, the solid cyclized rubber, together with the above-mentioned compounding agents, which are added as necessary, is cooled and crushed using a crusher such as a bantam mill, jet mill, disk mill, ball mill, or colloid mill. You only need to grind it.

The average particle diameter of the powder particles thus obtained is usually 1! 2200 μπι, preferably 3 μm ：: L 00 m, 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. The content of cyclized rubber in the powder particles, typically 5 weight ^_0/0 or more, preferably 1 0 % By weight, more preferably at least 20% by weight, particularly preferably at least 30% by weight. The cyclized rubber of the present invention obtained in this manner does not generate a gel even during long-term storage, and is useful in many applications utilizing the properties of the cyclized rubber. For example, the above-mentioned powder particles can be used as a powder coating by making use of excellent adhesion to a resin or a metal. In the case of a powder coating, a coloring agent is blended, and if necessary, an antioxidant, a filler, a softener, a wax and the like are appropriately blended according to a conventional method.

The content of the cyclized rubber in the powder particles is usually at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight, particularly preferably at least 30% by weight.

The shape of the powder particles is not particularly limited, and examples thereof include a spherical shape and an irregular shape.

The powder particles made of the cyclized rubber of the present invention can be used as a powder coating, for example, by taking advantage of their excellent adhesion to resins and metals. In the case of a powder coating, a coloring agent is blended, and if necessary, an antioxidant, a filler, a softener, a wax, and the like are appropriately blended according to a conventional method.

When a pigment is used as a colorant, benzidine, azo, and isodoline 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. For black coloring, carbon black is usually used. Examples of the carbon black include thermal black, acetylene black, channel black, furnace black, lamp black and the like.

When dyes are used as colorants, yellow-colored azo, nitro-, quinoline-, quinophthalone-, and methine-based dyes, magenta-colored anthraquinone-, azo-, and xanthene-based dyes and cyan-colored Anthraquinone type, phthalocyanine type and indooriline type dyes are preferably used.

The amount of the colorant to be used may be appropriately selected depending on the desired hue, density, and the like.

It is 1 to 20 parts by weight. The powder coating can be usually obtained by mixing a cyclized rubber, a colorant and, if necessary, an additive contained therein, pulverizing the mixture, and classifying the mixture.

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 mixer roll, a single-screw or twin-screw extruder.

The above-mentioned method may be used as the pulverizing method.

Examples of the classification method include methods such as air classification, centrifugal classification, and sieve classification.

Further, the cyclized rubber of the present invention is used as a modifier for a polymer molding material, and is blended with various polymer molding materials including a thermoplastic resin, a thermosetting resin, an elastomer, etc. It is suitable for improving the adhesiveness of the resin. In addition, the dispersibility of different polymers constituting the polymer molding material is used as a modifier for the polymer molding material to improve the dispersibility of compounding agents such as fillers and pigments in the polymer molding material. Is also useful.

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 Thermoplastic resins such as fats, polycarbonate resins, polyvinyl butylate resins, polyarylate resins, and fluorine resins.

2. Thermosetting resins such as phenolic resin, tarezol resin, urea resin, melamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin and urethane resin.

3. Natural rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-vulcanized rubber such as butadiene rubber; olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer Elastomers such as one.

Among them, polyethylene, polypropylene, polypentene-1 etc. When added to a hydrocarbon thermoplastic resin such as a chain-like olefin resin; an addition copolymer of ethylene and norpolenenes, a ring-opened polymer of norbornene, or a cyclic olefin resin; Great reforming effect.

The above polymers can be used alone or in combination of two or more. Also, if necessary, coloring agents such as pigments and dyes; antioxidants, fillers, softeners, waxes, antistatic agents, stabilizers, lubricants, crosslinkers, antiblocking agents, light blocking agents, ultraviolet light absorbers A compounding agent such as an agent can also be appropriately compounded.

In the polymer composition obtained by blending the polymer molding material modifier with the polymer molding material, the amount of the polymer molding material modifier is appropriately determined according to the type of the polymer molding material and the required performance. As selected, usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the polymer in the polymer molding material. Parts, particularly preferably 2 to 5 parts by weight. Further, the cyclized rubber of the present invention is used as an adhesive component such as a vehicle component for a primer or a binder component for a paint in a coating agent such as a primer or a paint for the polymer molding material described above, whereby the polymer molding material is obtained. Adhesion between paint and paint can be significantly improved. In this case, the cyclized rubber is at least 2% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, based on the total solids in the coating agent such as a primer or paint. / ₀ or more is preferable.

When used as a coating agent, the cyclized rubber may be blended with other adhesive components and various additives as necessary.

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 when other adhesive components are blended is appropriately selected according to the type and purpose of blending, but is usually 100: 0 to 5: 5 by weight ratio of cyclized rubber to other adhesive components. 95, preferably 80: 20 to 30: 70, more preferably 70: 30 to 50: 50.

Examples of the additive include the same additives as those for the polymer exemplified in the section of the modifier. The coating agent containing the cyclized rubber is usually obtained by dissolving or dispersing the cyclized rubber or a mixture of the cyclized rubber and other components in a solvent. The solvent to be used may be appropriately selected, for example, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ether solvent, a halogen solvent. Solvents, aqueous solvents and the like can be mentioned. The amount of the solvent used is such that the solid content of the coating agent is usually 5 to 95% by weight, preferably 15 to 60% by weight.

The coating agent containing the cyclized rubber of the present invention can also be used as a surface treatment agent for a dispersed material such as various fillers and pigments. Surface treatment of the dispersing material with the coating agent improves the dispersibility of the dispersing material in various polymers. As the filler and pigment to be subjected to the surface treatment, those described above can be used. The amount of the cyclized rubber to be used is appropriately selected according to the type of the dispersing material and the type of the polymer in which the cyclized rubber is dispersed, but usually 0.1 to 100 parts by weight per 100 parts by weight of the dispersing material. It is preferably used in a proportion of 5 to 20 parts by weight.

The cyclized rubber of the present invention can also be used as an adhesive for firmly bonding different materials to each other. In this case, examples of the combination of different materials include OPP (extended polypropylene), ZC PP (crystalline polypropylene), polypropylene / polyethylene terephthalate, polypropylene / ethylene-vinyl acetate copolymer, and polypropylene Z aluminum. The shape is not particularly limited, but a film shape or a sheet shape is preferable. Examples of the bonding method include, for example, a method in which a cyclized rubber preliminarily formed into a film is sandwiched between different kinds of materials and then heated and bonded, or a coating agent containing the cyclized rubber is applied to one surface of the material. After that, a method of bonding with the other material surface can be adopted.

The above embodiment is an exemplification, and any configuration having substantially the same configuration as the technical idea of the present invention and exerting the same effect is included in the technical scope of the present invention. Is done. Example

Hereinafter, the present invention will be described more specifically with reference to examples. The following description In the above, "parts" and "%" are based on weight unless otherwise specified.

The evaluation was performed as follows.

(1) Gel permeation 'chromatography (GPC) analysis of polymer GPC analysis of polymer was performed under the following conditions. All molecular weights are standard polystyrene equivalents.

Measuring device: HLC-8220 (manufactured by Tosoh Corporation)

Column: G5000HXL, G4000HXL and G2000HXL manufactured by Tosoh Corporation were connected in series.

Detector: Differential refractometer

Eluent: tetrahydrofuran (lm 1 Z)

Column temperature: 40 ° C

From the obtained molecular weight distribution curve, the number of the maximum peak, the peak top molecular weight of each peak, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in each peak (Mw / Mn), and each peak The peak area ratio (corresponding to the weight ratio of the polymer component constituting each peak) was determined.

(2) Glass transition temperature of polymer

The glass transition temperature of the polymer is measured by a differential scanning calorimeter (Seiko Electronics Co., Ltd .:

The measurement was performed using a SSC 5200) under the conditions of a starting temperature of 100 ° C and a heating rate of 10 ° C / min.

(3) Cyclization rate of cyclized conjugated polymer

The proton NMR analysis measures the peak areas of the protons derived from the double bond before and after the cyclization reaction of the conjugated gen polymer, and the ratio of the double bond remaining in the cyclized product when the value before the cyclization reaction is set to 100. I asked. Then, the cyclization rate (%) was determined by the following formula: (100—the proportion of the double bond remaining in the cyclized product).

(4) Measurement of the amount of polar group (carboxyl group) in the modified polymer

The acid value of the modified polymer was measured according to the method described in "Standard Oil and Fat Analysis Test Method" (Japan Oil Chemicals Association) 2, 4, 1-83, and converted to the amount of carboxyl groups in the polymer. .

(5) Spray applicability The primer was painted, the condition of the painted surface was observed, and judgment was made based on the following criteria. 〇: The painting surface is smooth and the painting is fine.

X: Stringing phenomenon occurs during spray coating, resulting in poor smoothness of the coated surface.

(6) Peel strength

Using a cutter blade, a cut was made on the surface of the molded body to which the paint was applied using a cutter blade until the blade reached the substrate with a width of 1 cm, and the coating film at the end was peeled off. The end of the peeled coating film was pulled in a direction of 180 ° at a speed of 5 Omm / mi η, and the peel strength (unit: kgf / cm) was measured.

(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 maintained at 60 ° C. 487 g of isoprene was continuously added to the reactor for 15 minutes, and the internal temperature was controlled so as not to exceed 75 ° C. Thereafter, the reaction was carried out at 70 ° C for 1 hour, and it was confirmed that the polymerization conversion was almost 100%.

Then, after adding 10 mmol of methanol (toluene solution), 113 g of isoprene was continuously added to the reactor at 70 ° C for 15 minutes, and further reacted at 70 ° C for 1 hour. It was confirmed that the polymerization conversion was almost 100%.

Thereafter, 1.4 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 a. GPC analysis of polymer a was performed, and the results are shown in Table 1.

After terminating the polymerization reaction, the temperature was raised to 80 ° C, and 4.24 g of p-toluenesulfonic acid was added. Then, while maintaining the temperature at 80 ° C, a cyclization reaction was performed for 3 hours. 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 µπι.

Toluene was distilled off from the obtained reaction solution at 160 ° C, and when the solid content concentration became 80 to 85%, 15 g of maleic anhydride was added to the solid solution. Next, after reacting at 160 ° C for 1 hour, unreacted maleic anhydride and toluene were distilled off. After adding 0.6 g of 1010 (manufactured by Chipa Specialty Chemicals), the mixture was poured into a metal pad covered with tetrafluoroethylene 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.

(Example 2)

In a pressure-resistant reactor equipped with a stirrer, 1400 g of dehydrated toluene and 1.1 mmol of n-butyllithium (1.56 mol Z liter: hexane solution) were charged, and the internal temperature was maintained at 60. 77 g of isoprene was continuously added to the reactor over a period of 15 minutes, and the internal temperature was controlled so as not to exceed 75 ° C. Thereafter, the reaction was carried out at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion was almost 100%.

Then, after adding 7.4 mmol of n-butyllithium (1.56 mol / l: hexane solution), while maintaining 70 ° C, 523 g of isoprene was continuously added to the reactor for 15 minutes. And further reacted at 70 ° C. for 1 hour. Further, the reaction was carried out at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion was almost 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. GPC analysis of polymer b was performed, and the results are shown in Table 1.

After terminating the polymerization reaction, the temperature was raised to 80 ° C, and 4.68 g of p_toluenesulfonic acid was added. Then, while maintaining the temperature at 80 ° C, a cyclization reaction was performed for 3 hours. Thereafter, an aqueous solution obtained by dissolving 1.90 g of sodium carbonate in 5.76 g of water was added thereto to stop the cyclization reaction. After stirring at 80 ° C for 30 minutes, a catalyst residue was removed using a glass fiber filter having a pore size of 1 μηι.

Toluene was distilled off from the obtained reaction solution at 160 ° C., and when the solid content concentration became 75 to 80%, 18 g of maleic anhydride was added to the mixture. Then, after reacting at 160 for 1 hour, unreacted maleic anhydride and toluene were distilled off, and 0.6 g of Irganox 1010 (Chipa Specialty Chemicals) was added. The mixture was poured into a metal vat coated with a modified titanium resin. It was dried under reduced pressure at 75 ° C. to obtain a modified cyclized rubber B. Analysis of modified cyclized rubber B See Table 1.

(Example 3)

A pressure-resistant reactor equipped with a stirrer was charged with 6100 g of toluene and 45.2 mmol of n-butyllithium (a hexane solution having a concentration of 1.56 mol / liter), and the internal temperature was raised to 60 ° C. Then, while controlling the internal temperature not to exceed 75 ° C, 260 g of isoprene in 60 minutes! : Continuously added to the reactor. After the addition of isoprene was completed, the mixture was further reacted at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion reached 100%. The weight average molecular weight of the polymer produced at this time was 92,000.

Next, 3.5 mmol of tetramethoxysilane was added to the mixture and reacted at 70 ° C. for 120 minutes. Thereafter, 32.5 mmol of methanol was added as a polymerization terminator to terminate the polymerization reaction, and a conjugated diene polymer c was obtained.

A part of the obtained conjugated diene polymer c was sampled and subjected to GPC analysis. The conjugated gen polymer c contained 25% of the three-branched polymer and the four-branched polymer, and the weight average molecular weight of both of them was 305,000. Further, the conjugated diene polymer c contained 75% of a linear polymer having a weight average molecular weight of 92,000.

After terminating the polymerization reaction, the temperature was raised to 80 ° C, 31.2 g of p-toluenesulfonic acid was added, and the cyclization reaction was performed for 3 hours while maintaining the internal temperature at 80 ° C. Thereafter, the reaction was stopped by adding a 25% aqueous solution of sodium carbonate containing 11.9 g of sodium carbonate, and the mixture was stirred at 80 ° C for 30 minutes, and then reacted using a glass fiber filter having a pore size of 1 im. The solution was filtered to remove the catalyst residue.

From the filtered reaction solution, toluene was distilled off at 160 ° C., and when the solid content concentration reached 80 to 85% by weight, 65 g of maleic anhydride was added thereto, and the mixture was added at 16 °. The reaction was performed at C for 1 hour. Thereafter, unreacted maleic anhydride and toluene were distilled off, and 0.6 g of Irganox 110 (manufactured by Ciba Specialty Chemicals) was added, followed by coating with ethylene tetrafluoride resin. Poured into metal bat. This was dried under reduced pressure at 75 ° C. to obtain a modified cyclized rubber C. The modified cyclized rubber C was analyzed, and the results are shown in Table 1. ,

28

(Example 4)

A pressure-resistant reactor equipped with a stirrer was charged with 6100 g of toluene and 56.3 mmol of n-butyllithium (hexane solution having a concentration of 1.56 mol Z liter), and the internal temperature was raised to 60 ° C. Thereafter, 2600 g of isoprene was continuously added to the reactor for 60 minutes while controlling the internal temperature not to exceed 75 ° C. After the addition of isoprene was completed, the reaction was carried out at 70 ° C. for 1 hour, and it was confirmed that the polymerization conversion reached 100%. The weight average molecular weight of the polymer produced at this point was 73,000.

Next, 4.1 mmol of tetrachlorosilane was added and reacted for 120 minutes. After the reaction, 38.2 mmol of methanol was added as a terminator to obtain a conjugated diene polymer d.

A part of the obtained polymer d was sampled and subjected to GPC analysis. The conjugated diene polymer d consisted of 30% of a four-branched polymer having a weight average molecular weight of 241,000 and a linear polymer having a weight average molecular weight of 73,000 as 70%.

After terminating the polymerization reaction, the mixture was heated to 80 ° C., 31.2 g of p-toluenesulfonic acid was added, and the cyclization reaction was performed for 3 hours while maintaining the internal temperature at 80 ° C. Thereafter, the reaction was stopped by adding a 25% aqueous solution of sodium carbonate containing 11.9 g of sodium carbonate, and the mixture was stirred at 80 ° C for 30 minutes, and then the reaction solution was filtered using a glass fiber filter having a pore size of 1 / m. The residue was removed by filtration.

Toluene was distilled off from the filtered reaction solution at 160 ° C, and when the solid content concentration reached 80 to 85% by weight, 65 g of maleic anhydride was added and reacted at 160 ° C for 1 hour. Was. Thereafter, unreacted maleic anhydride and toluene were distilled off, 0.6 g of Irganox 1010 (Chipa Specialty Chemicals) was added, and the mixture was covered with ethylene tetrafluoride resin. Poured into metal bat. This was dried under reduced pressure at 75 ° C. to obtain a modified cyclized rubber D. The modified cyclized rubber D was analyzed, and the results are shown in Table 1.

(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 e cut into 1 O mm squares (consisting of 73% of cis-1,4-monomeric isoprene units, 22% of 1,4-trans-isoprene units, and 5% of 3,4-isoprene units, 100 parts of polyisoprene having a weight-average molecular weight of 159,000 and a molecular weight distribution of 1.15, and 157 parts of toluene were charged. After the atmosphere in the flask was replaced with nitrogen, the temperature was raised to 80 ° C., and the polyisoprene was dissolved in toluene. Thereafter, 2.5 parts of maleic anhydride was added, and the addition reaction of maleic anhydride was performed at 180 ° C for 1 hour. The obtained reaction solution was poured into 30000 parts of 2,6-di-tert-butylphenol 1% acetone solution to collect a precipitate, which was dried under reduced pressure, and polyisoprene modified with maleic anhydride. Got.

Dissolve 100 parts of the modified polyisoprene in 730 parts of toluene, add 3.6 parts of p-toluenesulfonic acid to the solution, and cyclize for 5 hours while maintaining the solution temperature at 85 ° C. The reaction was performed. After cooling to room temperature, 400 parts of ion-exchanged water was added to stop the cyclization reaction, and the mixture was allowed to stand for 30 minutes to separate the separated oil layer. After washing the oil layer three times with 400 parts of ion-exchanged water, the oil layer is poured into 100 parts of a 2,6-di-tert-butylphenol 1% methanol solution, and the precipitate is collected. Was dried under reduced pressure to obtain a modified cyclized rubber E. The modified cyclized rubber E was analyzed, and the results are shown in Table 1.

Note that none of the obtained modified cyclized rubbers A to E contained any components insoluble in toluene.

Actual £ example Comparative example

1 2 3 4 1 Polymer abcde Maximum number of peaks 2 2 2 2 1 Minimum peak top molecular weight 68,000 89,000 92,000 73,000 One Minimum peak Mw Mn 1.04 1.03 1.03 1.03 ― Maximum peak top molecular weight 250 , 000 251, 000 295, 000 241,000 159, 000 Maximum peak MwZMn 1.06 1.04 1.10 1.08 1.15 Peak area ratio between maximum peak and minimum peak 26/74 20/80 25/75 30/70 ― Modified cyclized rubber ABCDE Cyclization ratio (%) 68 73 74 73 76 Amount of carboxyl group (millimono 10Og) 22 25 25 24 21 Glass transition temperature (° c) 31 46 43 46 48 Maximum number of peaks 2 2 2 2 1 Minimum peak top molecular weight (Pmw— S) 58,000 71,000 73,000 57,000-MwZMn of minimum peak 1.13 1.15 1.09 1.08-Maximum peak top molecular weight (Pmw_L) 213,000 200,800 244,000 192,000 127,000 MwZMn of maximum peak 1.18 1.19 1.16 1.15 1.31

(Pmw—L) (Pmw—S) ratio 3.67 2.83 3.34 3.37 Peak area ratio of maximum peak to minimum peak 26/74 20/80 10/90 15/85 ―

(Example 5)

After mixing 20 parts of the modified cyclized rubber A, 15 parts of titanium oxide, and 80 parts of xylene with a high-speed stirrer (Dispar) for 10 minutes, dilute the primer with thinner so that the flowability becomes 13 to 14 seconds in the flow time. Prepared. The above-mentioned fluidity means the flow time at 20 ° C according to the Ford Cup No. 4 method specified in JIS K 5400.

Three types of molded plates X to Z (5 OmmX 80 mmX 3 mm) were prepared by injection molding the resin materials shown in Table 2. In addition, Y was prepared by mixing the respective components with a Hensile mixer, then melt-kneading with a twin-screw extruder and pelletizing. Table 2

After the molded plates X to Z are thoroughly washed with water and dried, the film thickness becomes 10 / im on the molded plates using a spray gun with a diameter of 1. Omm and a spray pressure of 3.5 to 5. OMPa. Thus, the primer was spray painted. The spray applicability was confirmed, and the results are shown in Table 3. After drying for 5 minutes, two-part curable urethane-based metallic paint RB-212 (trade name) and RB—288 (tary paint), manufactured by Bee Chemical Co., Ltd., the same as above so that the film thickness of the entire coating film is 80 μιη. Two coats were applied using a spray gun. After drying at 23 ° C for 15 minutes, it was dried at 80 ° C for 30 minutes in a non-circulating drier and allowed to stand at room temperature for 3 days to obtain a coated test piece. The peel strength of the coating film was measured, and the results are shown in Table 3.

(Examples 6 to 8 and Comparative Example 2)

A primer was prepared in the same manner as in Example 5, except that the modified cyclized rubber A, B, C, D or E was used instead of the modified cyclized rubber A, respectively, to obtain a coated test piece. The peel strength of these coatings was measured, and the results are shown in Table 3.

(Comparative Example 3)

A coated test piece was obtained in the same manner as in Example 5, except that no primer was applied. The peel strength of the coating film was measured, and the results are shown in Table 3. Table 3

Table 3 shows the following. The modified cyclized rubbers A, B, C, and D of the present invention, whose molecular weight distribution curves have a plurality of maximum peaks, are used for the adhesive property of the primer. When used as a fraction, the adhesion of the painted film is significantly improved.

(Example 9)

95 parts of polypropylene resin (J 3050HP: manufactured by Idemitsu Petrochemical Co., Ltd.), 5 parts of modified cyclized rubber A and 0.1 part of Ilganox 1010 (manufactured by Ciba Specialty Chemicals) are mixed with a Henschel mixer, and then mixed. Using a twin-screw extruder, the mixture was kneaded at a melting temperature of 200 ° C to obtain pellets of the resin composition. This pellet was injection molded to obtain a molded plate (thickness 3 mm × width 5 Omm × length 80 mm).

Using a spray gun with a diameter of 1. Omm and a spray pressure of 3.5 to 5 OMPa, a two-part curable urethane metallic paint (Nippon Bee Chemical Co., Ltd., trade name RB-212 ( Base coat) and trade name RB-288 (Tarry paint)) were coated in two coats so that the total thickness of the coating film was 8 μμπι. After drying at 23 ° C for 15 minutes, it was dried at 80 ° C for 30 minutes in a non-circulating dryer 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.

(Examples 10 to 12)

A molded plate was prepared in the same manner as in Example 9, except that the modified cyclized rubber B, C or D was used instead of the modified cyclized rubber A, and a coated test piece was prepared using the molded plate. The peel strength of this coating film was measured, and the results are shown in Table 4.

(Comparative Example 4)

Polypropylene resin (J 305 OHP: Idemitsu Petrochemicals Co., Ltd.) without using modified cyclized rubber 100 parts Oyirganox 1010 (Ciba Specialty Chemicals) 0.1 part resin A molded plate was prepared in the same manner as in Example 9 except that the composition was used, and a coated test piece was prepared using the molded plate. The peel strength of this coating film was measured, and the results are shown in Table 4. Table 4

Table 4 shows the following.

The molded article made of the polypropylene resin blended with the modified cyclized rubber of the present invention has remarkably improved adhesion to a coating film.

(Example 13)

In a pressure-resistant reactor equipped with a stirrer, 6100 g of toluene and 56.3 mmol of n-butyllithium (a hexane solution having a concentration of 1.56 mol) were charged, and the internal temperature was raised to 60 ° C. Thereafter, 2600 g of isoprene was continuously added to the reactor for 60 minutes while controlling the internal temperature not to exceed 75 ° C. After completion of the isoprene addition, the reaction was carried out at 70 ° C for 1 hour, and it was confirmed that the polymerization conversion reached 100%. The weight average molecular weight of the polymer produced at this point was 73,000.

Next, 4.1 mmol of tetrachlorosilane was added and reacted for 120 minutes. After the reaction, 38.2 mmol of methanol was added as a terminator to obtain a conjugated diene polymer f.

A part of the obtained polymer f was sampled and subjected to GPC analysis. The conjugated diene polymer f was composed of 30% of a 4-branched polymer having a weight average molecular weight of 241,000, and 70% of a linear polymer having a weight average molecular weight of 73,000.

After terminating the polymerization reaction, the temperature was raised to 80 ° C, 31.2 g of p-toluenesulfonic acid was added, and the cyclization reaction was performed for 3 hours while maintaining the internal temperature at 80 ° C. Then charcoal The reaction was stopped by adding a 25% aqueous solution of sodium carbonate containing 11.9 g of sodium acid, stirred at 80 ° C for 30 minutes, and then filtered using a glass fiber filter with a pore size of 1 μπι. The catalyst residue was removed.

From the reaction solution after filtration, the toluene was distilled off at 160 ° C, when the solid concentration became 80-8 5 wt ^_0/0, Iruganokkusu 1010 (manufactured by Ciba Su Bae rice tea 'Chemicals) 0 After adding 6 g, the mixture was poured into a metal pad covered with tetrafluoroethylene resin. This was dried under reduced pressure at 75 ° C. to obtain a cyclized rubber F.

Analysis of cyclized rubber F gave the following results.

Cyclization ratio 73%, glass transition temperature = 46 ° C, maximum number of peaks = 2, minimum peak top molecular weight (Pmw-S) = 57,000, minimum peak top Mw / Mn = 1 · 08, maximum peak Top molecular weight (Pmw-L) = 192,000, maximum peak top Mw / Mn = 1.15, (Pmw-L) / (Pmw-S) = 3.37, maximum and minimum peak Area ratio = 15/85

The obtained cyclized rubber F did not contain any components insoluble in toluene. 100 parts of the cyclized rubber F and 5 parts of a copper phthalocyanine cyan pigment (Helogen Blue S7004: manufactured by BASF) were melt-kneaded with a plast mill, and then the solidified product was pulverized at 25 ° C. using a jet mill. . The pulverized material was subjected to air classification to obtain a cyan powder coating material having an average particle diameter of 30 / m. The obtained powder coating was applied on a zinc phosphate-treated steel sheet so as to have a thickness of 50 to 60 μπι, and was baked by heating in an oven at 200 ° C for 20 minutes.

The obtained coating film was uniform, and the adhesion of the coating film was 100/100 as measured by a grid test, indicating that the adhesion was excellent.

The powder coating using the cyclized rubber of the present invention formed a uniform coating film having excellent adhesion to a substrate. Industrial applicability

The cyclized rubber of the present invention can be used as a modifier for improving adhesion between a polymer molding material and a coating material, a primer vehicle component added to a coating material such as a primer for a polymer molding material or a coating material, or a binder for a coating material. For various uses as an adhesive component such as a component Applicable. It is particularly useful in that the adhesiveness between the non-polar polymer molding material and the paint can be significantly improved.

Claims

The scope of the claims

I. A cyclized conjugated polymer or a derivative thereof, wherein the molecular weight distribution curve is multimodal having a plurality of peaks, and the weight average molecular weight is from 1,000 to 1,000,000.

2. The cyclized rubber according to claim 1, wherein the cyclization rate is 10% or more.

3. The cyclized rubber according to claim 1 or 2, wherein the gel amount is 10% by weight or less.

4. The ratio of the minimum peak top molecular weight (Pmw_S) to the maximum peak top molecular weight (Pmw—L) (Pmw_L / Pmw—S) is 1.5 or more.

4. The cyclized rubber according to any one of items 1 to 3.

5. The cyclized rubber according to claim 4, wherein the minimum peak top molecular weight (Pmw-S) is 10,000 or more.

6. The cyclized rubber according to claim 4 or 5, wherein the maximum peak top molecular weight (Pmw-L) is 1,000,000 or less.

7. The cyclized rubber according to any one of claims 1 to 6, wherein the molecular weight distribution curve is bimodal.

8. The cyclized rubber according to claim 7, wherein the weight ratio between the low molecular weight component and the high molecular weight component is 95/5 to 10/90.

9. The cyclized product of claim 1, wherein the derivative of the cyclized conjugated polymer is a derivative obtained by introducing a polar group into the cyclized conjugated polymer by a modification reaction using a polar group-containing compound. The cyclized rubber according to any one of the above items.

10. The polar group is at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen. 10. The cyclized rubber according to claim 9.

I I. The cyclized rubber according to claim 9, wherein the polar group is at least one group selected from the group consisting of an acid anhydride group, a carboxyl group and a hydroxyl group.

12. Conjugated gen monomer or conjugated gen monomer and copolymerized with conjugated gen monomer An amount of a polymerization terminator that deactivates a part of the active metal in the organic active metal catalyst after the polymerization is started using the organic active metal catalyst and before the polymerization is completed is completed. To continue polymerization and form a conjugated gen polymer having a multimodal molecular weight distribution curve,

13 3. Organic activity used in the polymerization of conjugated gen monomer or conjugated gen monomer and a monomer copolymerizable with conjugated gen monomer using an organic active metal catalyst. After the polymerization is started using a part of the metal catalyst, and before the polymerization is completed, the polymerization is continued by adding the remainder of the organically active metal catalyst, and the conjugated dimer having a multimodal molecular weight distribution curve is obtained. Forming a coalescence,

14. Polymerization of a conjugated diene monomer, or a conjugated diene monomer and a monomer copolymerizable with a conjugated diene monomer using an organic active metal catalyst, to form an active gold at the polymer chain end. Forming an active conjugated polymer having a genus,

The active conjugated diene polymer is reacted with an amount of a polyfunctional coupling agent that reacts with a part of the active metal in the active conjugated diene polymer to form a conjugated diene polymer having a multimodal molecular weight distribution curve. Forming,

15. The method according to the above claim, wherein a step of introducing a polar group by reacting a conjugated polymer cyclized product having a multimodal molecular weight distribution curve with a polar group-containing compound to the conjugated polymer cyclized product is provided. The production method according to any one of the ranges 12 to 14.

16. The cyclized rubber according to any one of claims 1 to 11 is effective. Modifier for polymer molding materials as a component.

17. A polymer composition comprising the polymer molding material and the modifier for a polymer molding material according to claim 16 blended therein.

18. The polymer composition according to claim 17, wherein the polymer molding material is non-polar.

19. The polymer according to claim 17 or 18, wherein the content of the modifier for a polymer molding material is from 0 :! to 50 parts by weight per 100 parts by weight of the polymer. Composition.

20. A coating agent comprising the cyclized rubber according to any one of the above-mentioned claims 1 to 11.

21. The coating agent according to claim 20, which is used for a nonpolar polymer molding material.

22. The coating agent according to claim 2 which is a primer for a polymer molding material.

23. Powder particles comprising the cyclized rubber according to any one of claims 1 to 11 above.

24. The powder particle according to claim 23, wherein the powder particle has an average particle diameter of 1 to 200 µm.

25. The powder particles according to claim 23 or 24, further comprising a colorant.

26. The powder particles according to claim 25, wherein the amount of the colorant used is 0.1 to 50 parts by weight based on 100 parts by weight of the cyclized rubber.