JP3016561B2 - Heat resistant resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hydrogenated polymer composition having excellent heat resistance.

[Prior art] Conventionally, as a transparent resin, polymethyl methacrylate,
Polycarbonate, polystyrene, 3-methylpentene resin and the like are known. These resins are produced in large quantities industrially, and are utilized in various fields in various fields by taking advantage of their good transparency.

However, these resins do not always have sufficient heat resistance, for example, polycarbonate, which is the most heat-resistant resin among the above resins, has a glass transition temperature of about 150 ° C., which is an index of its heat resistance, Development of a resin having high heat resistance has been desired.

As a resin having excellent transparency and higher heat resistance, a ring-opened polymer of a norbornene derivative having polar substitution has been proposed. However, ring-opened polymers of norbornene derivatives have carbon-carbon double bonds in the main chain, so they undergo severe oxidative degradation at high temperatures, and are practically used as heat-resistant polymers despite having a high glass transition temperature. Had not been. Therefore, by hydrogenating the ring-opening polymer,
An attempt to improve the oxidative deterioration property has been proposed (Japanese Patent Publication No. 57-8815). This improvement in oxidative deterioration by hydrogenation can greatly increase the oxidative deterioration resistance compared to conventional unhydrogenated polymers. However, in the case of a high heat-resistant resin having a high glass transition temperature, it is inevitable. Therefore, it was necessary to raise the processing temperature, and deterioration during processing, especially yellowing, was still a problem.

[Problems to be Solved by the Invention] Such a ring-opened (co) polymer of a norbornene derivative,
In addition, in order to suppress the oxidative deterioration of the hydrogenated product at a high temperature, various attempts have been made to add an antioxidant to prevent the coloring at the high temperature.

However, simply adding a commonly used antioxidant such as a hindered phenol antioxidant, and a phosphorus antioxidant or a sulfur antioxidant to the aforementioned polymer still causes yellowing during processing. At present, coloring occurs, and the effect of the addition is not sufficiently seen.

In view of the current situation, the present inventors have conducted intensive studies with the aim of obtaining a resin composition having excellent heat resistance and transparency, and also having excellent oxidation resistance, and as a result, it has a polar substituent. In producing a hydrogenated product of a ring-opened polymer of a norbornene derivative, only when a non-aromatic double bond present in a polymer is hydrogenated to a high hydrogenation ratio far exceeding a conventionally considered level, That is, the addition of a specific phenolic antioxidant and a specific phosphorus antioxidant has a very effective effect only when 99 mol% or more as measured by 60 MHz NMR has been hydrogenated, The inventors have found that sufficient oxidation deterioration resistance is obtained, and have reached the present invention.

[Means and Actions for Solving the Problem] That is, the present invention provides: (a) a ring-opened polymer of at least one compound represented by the following general formula (I), and / or another copolymerization of the compound with the compound; Ring-opening copolymer obtained by ring-opening copolymerization with an aromatic monomer, obtained by hydrogenating at least 99 mol% of non-aromatic carbon-carbon double bonds present in the (co) polymer. 100 parts by weight of hydrogenated tetracyclododecene resin, (b) 0.01 to 10 parts by weight of at least one kind of hindered phenolic antioxidant having a molecular weight of 350 or more, and (c) structural unit of general formula (II) A heat-resistant resin composition comprising 0.01 to 10 parts by weight of at least one phosphorus-based antioxidant having at least one of the following.

[In the formula, A and B represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a carbon atom substituted with a halogen atom. 10 hydrocarbon _{group, - (CH 2) n COOR} 1, - (CH 2) n O
COR ¹ ,-(CH ₂ ) _n CN,-(CH ₂ ) _n CONR ² R ³ ,-(CH ₂ ) _n C
_{OOZ, - (CH 2) n} OCOZ, - (CH 2) n OZ, - (CH 2) composed of _n W or X and Y Wherein at least one of X and Y is a group other than a group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms, m
Is 0 or 1. R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen atom, W is SiR ⁵ _p D _3-p ( R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁶
Or -OR ⁶ (R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms), p is an integer of 0 to 3), n is an integer of 0. ] [In the formula, R _{1 to} R ₅ are a hydrogen atom, an alkyl group or an aryl group, and two or more of R _{1 to} R ₅ are an alkyl group or an aryl group having 2 to 10 carbon atoms. As a method for producing the hydrogenated norbornene resin in the present invention, at least one compound represented by the above general formula (I) is ring-opened in the presence of a mono- or other copolymerizable monomer and a metathesis catalyst. (Co) polymerized and obtained (co)
It is obtained by subjecting the polymer to a hydrogenation reaction in the presence of a hydrogenation catalyst, and hydrogenating at least 99 mol% of the non-aromatic double bonds present in the molecule.

In the compound represented by the general formula (I), at least one of the substituents X and Y must be a group other than a group selected from a hydrogen atom and a hydrocarbon group in order to obtain a high glass transition temperature. However, preferably, one of the substituents X and Y is a hydrogen atom or a hydrocarbon group in that the obtained polymer exhibits low hygroscopicity, and the other obtained polymer has a high glass transition temperature and In view of showing low hygroscopicity and hardly changing by hydrogenation reaction, the formula-(CH
₂₎ it is preferably a carboxylic acid ester group represented by _n COOR ^1.

Further, among the carboxylic acid ester groups represented by the formula — (CH ₂ ) _n COOR ¹ , those having a smaller n are preferable because the glass transition temperature of the obtained polymer is higher. In addition,
In the formula-(CH ₂ ) _n COOR ¹ , n = 0 is preferable in terms of synthesizing the monomer and from the viewpoint of the stability of the obtained polymer. R ¹ is an aliphatic or alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which is preferable in that the larger the number of carbon atoms, the lower the water absorption of the obtained polymer is. Generally, the higher the number of carbon atoms, the higher the number. Therefore, in order to maximize the characteristics of the present polymer, a chain hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 or more carbon atoms, or a phenyl group or substituted phenyl group is preferable, and, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene is particularly preferred.

The ring-opening polymer is obtained by converting the compound represented by the general formula (I) to 2
Copolymers can be used by using more than one kind. For example, 8
-Methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene and 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] also out copolymerizing 2-heptene. This combination is 5-methyl-
5-methoxycarbonyl-bicyclo [2.2.1] -2-heptene is 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene order obtained as intermediates in the preparation Particularly preferred.

Other monomers copolymerized with compound (I) include cyclopentene, cyclohexene, cycloheptene, cyclooctene, dicyclopentadiene, bicyclo [2.2.1] heptene, and tricyclo [5.2.1.0 ^2,6 ] -8. −
Decene, tricyclo [5.2.1.0 ^2,6] -3- decene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] -4-pentadecene, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -11- pentadecene, pentacyclo [7.4.0.1 ^3.4 .0 ^10,13 .0 ^2,7]
4-pentadecene, Pentakuro [6.6.1.1 ^3,6 .0 ^2,7 .0
Cycloalkanes such as ^9,13 ] -4-hexadecene, and alkyl-substituted products thereof. Among these copolymerizable monomers, particularly preferred is dicyclopentadiene, which is readily available.

When a copolymer with the compound represented by the general formula (I) is obtained using a copolymerizable monomer, if the amount of the compound represented by the general formula (I) is small, the obtained polymer has a high glass transition temperature. Therefore, the proportion of the monomer of the general formula (I) needs to be 5 mol% or more, preferably 20% or more, and more preferably 50% or more. is there.

The compound represented by the general formula (I) has a carbon-carbon double bond in the main chain of polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-non-conjugated diene copolymer, polynorbornene, or the like. Can be polymerized in the presence of an unsaturated hydrocarbon-based polymer containing, in this case, the impact resistance of the resin is generally improved. Of these unsaturated copolymerized hydrocarbon-based polymers, butadiene-styrene copolymer and isoprene-styrene copolymer are obtained by changing the ratio of diene and styrene.
It is preferable because the copolymer of the present invention having good transparency can be easily obtained. In this case, the copolymer of diene and styrene may be a random copolymer or a block copolymer. Upon polymerization in the presence of an unsaturated hydrocarbon polymer, the polymer is 1 to 90%, preferably 3 to 70%, more preferably 5 to 90% of the compound represented by the general formula (I).
~ 40% used.

The metathesis catalyst used for ring-opening polymerization is usually
(A) at least one compound selected from compounds of W, Mo and Re, and (b) periodic table IA, IIA, IIB, III
A, IV A or IV B group compound with at least 1
The catalyst comprises at least one combination selected from those having one of the two element-carbon bonds or the element-hydrogen bond, and may be one to which an additive (c) for enhancing the catalytic activity is added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ , MoCl ₅ and ReOCl ₃ .
The compounds shown in Japanese Patent Application No. 3884 can be used.

Specific examples of the component (b) include n-BuLi, (C
_{2 H 5) 3 Al, (} C 2 H 5) 2 AlCl, there are such LiH, No. Sho 62
The compound shown in -288528 can also be used.

As typical examples of the component (c), alcohols, aldehydes, ketones, amines and the like can be suitably used, and in addition, the compounds shown in Japanese Patent Application No. 62-288528 can also be used.

The use ratio of the component (a) to the component (b) is such that the metal atom ratio (a) :( b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:25.

The molar ratio of component (c) to component (a) is (c) :( a) 0.005: 1 to 10: 1, preferably 0.05: 1 to
Used in the range of 2: 1.

The molecular weight of the polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but more preferably, α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene are reacted. It is advisable to coexist in the system and adjust the amount by changing the amount.

The hydrogenation reaction of the (co) polymer obtained by the metathesis ring-opening polymerization is carried out by a usual method. As the catalyst used in this hydrogenation reaction, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

For example, examples of the heterogeneous catalyst include a solid catalyst in which a catalytic substance such as palladium, platinum, ruthenium, rhodium, and nickel is supported on a carrier such as carbon, silica, alumina, and titania.

Further, as a homogeneous catalyst, nickel naphthenate, titanocene dichloride, organic solvent-soluble nickel such as cobalt acetylacetonate, cobalt, titanium, vanadium compound and triethylaluminum, triisobutylaluminum, organic aluminum such as diethylaluminum monochloride, Alternatively, a catalyst in combination with an organic lithium such as butyllithium can be used. Also, a noble metal complex catalyst such as chlorotris (triphenylphosphine) rhodium can be used.

The hydrogenation reaction is carried out under a hydrogen gas atmosphere at normal pressure to 300 atm, preferably 3 to 150 atm, at a temperature of 0 to 200 ° C., preferably 20 to 200 atm.
It can be performed at ~ 180 ° C. The hydrogenation rate is measured by 60 MHz NMR, and it is essential that the hydrogenation rate is 99 mol% or more, calculated from the decrease in the peak in the range of δ = 4.5 to 6.0 ppm due to the hydrogenation reaction. If the degree of hydrogenation is less than 99 mol%, even if the antioxidant of the present invention is added, a composition having good resistance to oxidation deterioration cannot be obtained, and the object of the present invention will not be achieved. The higher the degree of hydrogenation, the more pronounced the effect of the addition of the antioxidant is preferred,
In that sense, the hydrogenation ratio needs to be 99 mol% or more.

The hindered phenolic antioxidant that can be used in the present invention has a molecular weight of 350 or more, preferably 500 or more, more preferably 600 or more, and particularly preferably 650 to 1,500.

Preferred examples thereof include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- [3- (3-
t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] 2,4,8,10
-Tetraoxaspiro [5,5] undecane.

The phosphorus antioxidant used in the present invention, [In the formula, R _{1 to} R ₅ are a hydrogen atom, an alkyl group or an aryl group, and two or more of R _{1 to} R ₅ are an alkyl group or an aryl group having 2 to 10 carbon atoms. And a phosphorus-based antioxidant having at least one structural unit represented by the following formula in the molecule.
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t
-Butylphenylphosphite), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester. Other commonly used phosphorus antioxidants which do not have the above structural units cannot provide a composition having good thermal stability.

The amount of the hindered phenol-based antioxidant and the phosphorus-based antioxidant is 0.01 to 10 parts by weight and 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer hydrogenated product. Parts by weight, 0.1 to 5 parts by weight. If the amount is less than 0.01 parts by weight, a sufficient oxidation deterioration preventing effect cannot be obtained,
If added in an amount of 10 parts by weight or more, the mechanical strength of the resin is undesirably reduced.

The composition of the present invention may contain an ultraviolet absorber, a lubricant, a coloring agent, and a pigment according to the purpose.

The method of adding these antioxidants to the hydrogenated norbornene-based compound includes, for example, a method of adding it to the polymer solution after hydrogenation and a method of adding it during pelletization, and is not particularly limited.

The heat-resistant resin composition of the present invention can be used for window glass, glass for automobiles, films, sheets, and general molded products, in addition to optical materials such as lenses, optical disk substrates, and optical fibers.

[Examples] Hereinafter, the present invention will be specifically described with reference to examples.

The measuring method used in the examples is as follows.

Hue: Powder polymer composition before pelletization in which each antioxidant is dry-blended, pellets obtained by melt-kneading them with an extruder, and a molded plate obtained by injection molding the pellets are each in a 15% methylene chloride solution. JIS-K-7
According to 103, the yellowness (YI1 value) was measured by transmitted light.

Reference Example 1 (Production of Hydrogenated Norbornene-Based Resin M-1) Under a nitrogen atmosphere, a monomer 8-methyl-8 represented by the structural formula (1) was placed in a nitrogen-substituted 50 reaction vessel.
-Methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene 5 kg, toluene 20, molecular weight regulator 1-hexene 650 g, catalyst WCl ₆ concentration 0.05
86 ml of a 0 M / chlorobenzene solution, 34 ml of a toluene solution having a concentration of 0.1 M / paraaldehyde, and 205 ml of a toluene solution having a concentration of 0.5 M / diethylaluminum monochloride were added and reacted at 80 ° C. for 4 hours to obtain a polymer. Unreacted monomers and catalyst were removed by adding 1.0 kg of triethanolamine and methanol 16 to the polymer solution, and after thoroughly stirring, discarding the upper layer. After adding 0.05% of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] to the obtained lower layer solution with respect to the polymer, a steam strip was dried. The polymer was recovered. This polymer was dissolved in tetrahydrofuran, charged into a high-pressure reactor, and 1 kg of a 5% palladium / alumina catalyst was added as a hydrogenation catalyst.
The hydrogenation reaction was performed at a temperature of 150 ° C. and a hydrogen pressure of 100 kg / cm ² for 5 hours. After removing the catalyst by passing the obtained polymer, steam strip and drying were performed to obtain polymer M-1.
Was recovered. The intrinsic viscosity (η _inh ) of the obtained polymer is
At 0.75 dl / g, substantially no olefin peak was recognized on the NMR chart, and the hydrogenation rate was 99 mol% or more.

Reference Example 2 (preparation of hydrogenated norbornene resin M-2) reference in Example 1, a monomer 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5} .1 represented monomer with structural formula (1) ^7,10 ] -3-dodecene, 4.5kg
And the monomer 5-methyl-5 represented by the structural formula (2)
Polymerization, hydrogenation and the like were carried out in the same manner as in Reference Example 1 except that 0.5 kg of -methoxycarbonylbicyclo [2.2.1] -2-heptene was used, to obtain a polymer M-2. The intrinsic viscosity (η _inh ) of the obtained polymer was 0.90 dl / g, substantially no olefin peak was recognized on the NMR chart, and the hydrogenation ratio was 99 mol% or more.

Reference Example 3 (preparation of hydrogenated norbornene resin M-3) reference in Example 1, a monomer 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5} .1 represented monomer with structural formula (1) ^7,10 ] -3-dodecene, 4.5kg
Then, polymerization and hydrogenation were carried out in the same manner as in Reference Example 1 except that 0.5 kg of the monomeric dicyclopentadiene represented by the structural formula (3) was used, to obtain a polymer M-3. The intrinsic viscosity (η _inh ) of the obtained polymer was 0.85 dl / g, virtually no olefin peak was observed on the NMR chart, and the hydrogenation rate was
It was 99 mol% or more.

Reference Example 4 (Production of hydrogenated norbornene resin M-4) Polymerization and hydrogenation were performed in the same manner as in Reference Example 1 except that the amount of the hydrogenation catalyst and the hydrogenation time were changed. Polymers M-4, M-5 and M-6 having different ratios were obtained.
The degree of hydrogenation of the polymer was 99, 95, and 97%, respectively.

Example The hydrogenated polymer obtained in Reference Example and various antioxidants were dry-blended in the amounts shown in Table 1, and pelletized by an extruder. Injection molding the obtained pellets under the following conditions,
The heat distortion temperature and oxidation resistance were measured.

(Pelletization) Extruder: VSK40 (Nakaya Machine) 40mm Screw rotation speed: 150 rpm Temperature: 280 ° C (Injection molding) Injection molding machine: IS80A (Toshiba Machine) 5 oz Injection pressure: 900 kg / cm ² Screw rotation speed: 80 rpm Back pressure: 60 kg / cm ² cycles: 45 seconds Mold temperature: 80 ° C Note) A: Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] B: 1,3,5-trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene C: 3,9- Bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-
1,1-dimethylethyl] 2,4,8,10-tetraoxospiro [5,5] undecane E: 1,3,5-tris (4-t-butyl-3-hydroxy-
2,6-dimethylbenzyl) isocyanurate F: bis- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite G: tris (2,4-di-t-butylphenyl phosphite) H) 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester I: 2,2'-methylenebis (4-methyl-6-t-butylphenol) J: trinonylphenyl phosphite

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hitoshi Oka 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-63-317520 (JP, A) JP-A Sho 59-108795 (JP, A) JP-A-53-58558 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 65/00

Claims (1)

(57) [Claims] (A) a ring-opening polymer of at least one compound represented by the following general formula (I) and / or a compound obtained by ring-opening copolymerizing the compound with another copolymer monomer; 100 parts by weight of a hydrogenated tetracyclododecene resin obtained by hydrogenating at least 99 mol% of the non-aromatic carbon-carbon double bonds present in the (co) polymer. (B) 0.01 to 10 parts by weight of at least one kind of a hindered phenolic antioxidant having a molecular weight of 350 or more; and (c) a phosphorus-based antioxidant having at least one structural unit of the general formula (II). A heat-resistant resin composition comprising at least one of 0.01 to 10 parts by weight. [In the formula, A and B represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a carbon atom substituted with a halogen atom. 10 hydrocarbon _{group, - (CH 2) n COOR} 1, - (CH 2) n OCOR 1, - (CH 2) n CN, - (CH 2) n CONR 2 R 3, - (CH 2) n _{COOZ, - (CH 2) n} OCOZ, - (CH 2) n OZ, - (CH 2) composed of _n W or X and Y Wherein at least one of X and Y is a group other than a group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen atom, W is SiR ⁵ _p D _3-p ( R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom,
—OCOR ⁶ or —OR ⁶ (R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms), p represents an integer of 0 to 3), and n represents an integer of 0 to 10. ] [In the formula, R _{1 to} R ₅ are a hydrogen atom, an alkyl group or an aryl group, and two or more of R _{1 to} R ₅ are an alkyl group or an aryl group having 2 to 10 carbon atoms. ]