JPH0551421A - Production of modified hydrogenated polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent heat resistance and moldability and useful for automotive exteriors, automotive interiors, etc., by polymerizing a vinylic monomer in the presence of a specific hydrogenated polymer, etc. CONSTITUTION:A vinylic monomer (e.g. methyl methacrylate or styrene) is polymerized in the presence of a hydrogenated polymer obtained by further hydrogenating a ring-opened polymer with hydrogen preferably in an amount of >=80% to obtain the objective polymer, which the rind-opened polymer has been produced by subjecting a monomer (preferably a tetracyclododecene derivative wherein m is 1) consisting of a norbornene derivative of the formula (A, B are H, 1-10C hydrocarbon; X, Y are H, halogen, monovalent organic group; one of X and Y is H or a polar group except the hydrocarbon; m is 0, 1) or a mixture of the monomer with a copolymerizable monomer (e.g. polybutadiene) to a ring-opening polymerization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified hydrogenated polymer having excellent heat resistance, chemical resistance and moldability.

[0002]

2. Description of the Related Art A ring-opening polymer obtained by ring-opening polymerization of a monomer comprising a norbornene derivative having a specific polar substituent and a copolymerizable monomer copolymerizable therewith is further hydrogenated. Since the obtained hydrogenated polymer has excellent optical performance and high heat resistance, it has been attempted to be adopted in many fields such as optical parts and vehicles, electric / electronic parts and building materials. It is also used as a material for improving the heat resistance of other thermoplastic resins.

[0003]

However, the hydrogenated polymer is low in chemical resistance and has a difficulty in molding processability, so that the field of use is limited. Further, compatibility with alloying with other resins is not sufficient, and it may be difficult to improve heat resistance to a target by alloying.

[0004]

As a result of intensive studies on the above problems, the present invention has revealed that a monomer comprising at least one norbornene derivative represented by the following general formula (I) or the monomer and the monomer In the presence of a hydrogenated polymer (a) obtained by further hydrogenating a ring-opening polymer obtained by ring-opening polymerization of a copolymerizable copolymerizable monomer, a vinyl-based monomer (b) Method for producing modified hydrogenated polymer characterized by polymerizing general formula (I)

[Chemical 2] [In Formula (I), A and B are a hydrogen atom or C1-C1.
10 hydrocarbon groups, X and Y are hydrogen atoms, halogen atoms or monovalent organic groups, at least one of X and Y is a hydrogen atom and a polar group other than a hydrocarbon group, m is 0 or 1. ], It was found that excellent heat resistance, chemical resistance, and molding processability are surely exhibited. Hereinafter, the present invention will be specifically described. In the present invention, the hydrogenated polymer (a) component is
A monomer composed of the norbornene derivative represented by the above general formula (I) (hereinafter referred to as “specific monomer”) is
Alternatively, a hydrogenated polymer obtained by further hydrogenating a ring-opening polymer obtained by ring-opening copolymerization of a specific monomer with a copolymerizable monomer copolymerizable therewith using a metathesis polymerization catalyst And is hereinafter also referred to as "hydrogenated polymer (a)". The molecular weight of this hydrogenated polymer (a) is 2 in terms of polystyrene-equivalent weight average molecular weight.
It is preferably from 50,000 to 700,000, particularly preferably from 30,000 to 500,000. In the present invention, as the hydrogenated polymer (a), for example, JP-A-1-
A polymer obtained by hydrogenating a ring-opening (co) polymer of a compound having a norbornene ring described in Japanese Patent No. 132626 can be mentioned. Among these specific monomers, X or Y in the above general formula (I) is represented by the formula- (C
The specific monomer which is a group represented by H ₂ ) nCOOR ¹ is
It is preferable in that the obtained polymer has a high glass transition temperature and a low hygroscopicity, and it is particularly preferable that one polymer is contained per molecule of the specific monomer to obtain the hygroscopicity of the modified hydrogenated polymer obtained. Is preferable in that In addition, the formula- (CH
₂ ) Among the groups represented by nCOOR ¹ , the smaller the value of n, the higher the glass transition temperature of the obtained polymer, which is preferable, and the specific monomer in which n is 0 is easy to synthesize. And is preferable in that good properties can be obtained in the obtained polymer.

In the above formula, R ¹ has 1 to 20 carbon atoms.
However, it is preferable that the number of carbon atoms increases as the hygroscopicity of the resulting polymer decreases. But,
From the viewpoint of the balance with the glass transition temperature of the polymer obtained, a chain alkyl group having 1 to 4 carbon atoms or 5 carbon atoms
The above (poly) cyclic alkyl group is preferable, and a methyl group is particularly preferable. Furthermore,-(C
The specific monomer in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the group represented by H ₂ ) nCOOR ¹ is bonded is a glass transition of the obtained modified hydrogenated polymer. It is preferable because it lowers the hygroscopicity without lowering the temperature. And, in particular, the specific monomer in which the substituent is a methyl group is preferable in that the synthesis thereof is easy. The ring-opening polymer of the hydrogenated polymer (a) used in the present invention may be a ring-opening polymerized of a specific monomer alone, but the specific monomer and the copolymerizable monomer It may be a compound obtained by ring-opening copolymerization with the body. When the copolymerizable monomer is used as described above, the proportion of the specific monomer in the ring-opening polymer is 5 mol% or more, preferably 20 mol% or more. As the copolymerizable monomer used, a monomer that can be ring-opening polymerized by a metathesis polymerization catalyst, and a partially polymerized low degree of polymerization having a carbon-carbon double bond in the main chain of the polymer. Can be mentioned.

Among the above-mentioned specific monomers, the tetracyclododecene derivative in which m is 1 in the above general formula (I) is preferable in that a polymer having a high glass transition point can be obtained. In the general formula (I), among the tetracyclododecene derivatives in which m is 1, a preferred compound is 8-
Carboxymethyl tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 5-carboxymethyl-bicyclo [2.
2.1] -2-heptene and the like can be mentioned.

The specific monomer can also be copolymerized with a cyclic olefin compound. Specific examples of the cyclic olefin compound include cyclopentene, cyclooctene, 1,
Cycloolefins such as 5-cyclooctadiene and 1,5,9-cyclododecatriene; bicyclo [2.2.
1] -2-heptene, tricyclo [5.2.1.
0 ^2,6 ] -8-decene, tricyclo [5.2.1.0]
^2,6 ] -3-decene, tricyclo [6.2.1.
0 ^1,8 ] -9-undecene, tricyclo [6.2.1.
0 ^1,8 ] -4-undecene, tetracyclo [4.4.
0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,8 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [6.6.1.1 ^3,6. 0 ^2,7 .
0 ^9,14 ] -4-Hexadecene, pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -11-pentadecene,
Dicyclopentadiene, pentacyclo [6.5.1.1
^3,6 . 0 ^{2, 7} . 0 ^9,13] - pentadeca -4.11- poly cycloalkenes diene may be mentioned.

Further, as the copolymerizable monomer copolymerizable with the specific monomer, polybutadiene, polyisoprene,
An unsaturated hydrocarbon polymer containing a carbon-carbon double bond in the main chain of a polymer such as styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, polypentenamer can also be mentioned. .. A method of ring-opening polymerization of a specific monomer and a copolymerizable monomer copolymerizable therewith and a method of hydrogenation are disclosed in JP-A-1-132.
A method similar to the method described in Japanese Patent No. 626 can be mentioned.

The hydrogenation rate of the resulting hydrogenated polymer (a) is usually 50% or more, preferably 70% or more, more preferably 80% or more. A polymer having a hydrogenation rate of less than 50% is not preferable because the thermal stability becomes low due to the low hydrogenation rate. Next, as the vinyl-based monomer used in the present invention, there are α, β-unsaturated carboxylic acid ester, aromatic vinyl, vinyl cyanide, and a mixture of two or more kinds thereof may be used. Examples of the α, β-unsaturated carboxylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, allyl methacrylate,
Examples include phenyl methacrylate. Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene and the like. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. The modified hydrogenated polymer is mainly composed of a graft product obtained by grafting a vinyl-based monomer on the hydrogenated polymer (a) and a polymer of the vinyl-based monomer. It may contain a hydrogenated polymer which is not present.

An example of the method for producing the modified hydrogenated polymer is shown below. The hydrogenated polymer (a) is dissolved in a solvent in a reaction vessel, the inside of the vessel is replaced with nitrogen, and the temperature is kept constant. Next, put a predetermined amount of catalyst, then drop vinyl monomer,
The reaction is performed at a constant temperature for a predetermined time. The ratio of the vinyl-based monomer graft-bonded to the hydrogenated polymer to the hydrogenated polymer (grafting rate) is the amount of catalyst, the reaction time,
It can be changed depending on the temperature. The chemical resistance of the modified hydrogenated polymer itself and the compatibility with the thermoplastic resin are influenced by the graft ratio of the graft polymer. The hydrogenated polymer (a) is used in an amount of usually 3 to 90% by weight, preferably 5 to 85% by weight, more preferably 10% by weight.
To 80% by weight, the vinyl monomer is 97 to 10% by weight, preferably 95 to 15% by weight, more preferably 9% by weight.
It is 0 to 20% by weight. When the amount of the hydrogenated polymer (a) used is less than 3% by weight, the heat resistance improving effect is not seen. Further, if it exceeds 90% by weight, the chemical resistance is lowered. The graft ratio of the vinyl-based monomer is 3 to 200% by weight, preferably 5 to 150% by weight, more preferably 10 to 10%.
It is 0% by weight. If it is less than 3% by weight, the chemical resistance is not improved. On the other hand, if it exceeds 200% by weight, the moldability becomes poor.

The graft ratio of the graft polymer is calculated by dissolving the reaction product in a solvent of the vinyl monomer polymer and then centrifuging to obtain a precipitate. This precipitate is extracted and the insoluble matter is used as a graft polymer, which is represented by the following formula. Graft ratio = (weight of graft-polymerized vinyl compound) / (weight of charged hydrogenated polymer) × 100% The modified hydrogenated polymer is mainly a vinyl polymer grafted to the hydrogenated polymer (a). And a vinyl-based polymer (matrix) not grafted, and the content of the matrix is usually 5% by weight or more, preferably 10% by weight or more. The intrinsic viscosity (30 ° C.) of the methyl ethyl ketone soluble component in the modified hydrogenated polymer is 0.3 to 1.2 deciliter / g, preferably 0.35.
~ 1.0 deciliter / g, more preferably 0.4 ~
It is 0.9 deciliter / g. 0.3 deciliters /
If it is less than g, the mechanical strength of the modified hydrogenated polymer will be low. When it exceeds 1.2 deciliter / g, the fluidity becomes low and the moldability becomes poor.

Next, other thermoplastic resins which can be blended with the modified hydrogenated polymer obtained in the present invention include:
There is no particular limitation as long as it is thermoplastic, for example, polystyrene, styrene-acrylonitrile copolymer, polyethylene, polypropylene, polymethyl methacrylate, polyethyl methacrylate, styrene-methyl methacrylate copolymer, polycarbonate, polyamide, polybutylene terephthalate. , Polyethylene terephthalate, polysulfone, polyphenyl ether, polyphenyl sulfite, ABS, AES, high impact polystyrene,
Examples include AAS and MBS. In addition, you may mix and use these 2 or more types. In addition, as the thermoplastic resin, in the presence of a hydrogenated diene polymer obtained by hydrogenating a block copolymer composed of a conjugated diene and an aromatic vinyl compound, an aromatic vinyl compound, a (meth) acrylic acid alkyl ester, a cyanide A rubber-modified thermoplastic resin obtained by graft-copolymerizing a monomer such as vinyl chloride may also be used. From the viewpoint of the compatibility between the modified hydrogenated polymer and the thermoplastic resin, the thermoplastic resin is most preferably a vinyl monomer polymer similar to the graft component of the modified hydrogenated polymer. The blend ratio of the modified hydrogenated polymer to the thermoplastic resin is 5/95 to 95/5 (weight ratio), preferably 10/90 to 90/10 (weight ratio). When the modified hydrogenated polymer is less than 5% by weight, the heat resistance is not improved. The thermoplastic resin composition of the present invention can be obtained, for example, by kneading the modified hydrogenated polymer and the thermoplastic resin with various extruders, Banbury mixers, kneader rolls and the like. Further, the modified hydrogenated polymer obtained in the present invention,
Antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl)-
4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), tris (di-nonylphenylphosphite); UV absorber,
For example, p-t-butylphenyl salicylate, 2,2 '
-Dihydroxy-4-methoxy-benzophenone, 2-
(2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole; lubricants such as paraffin wax, stearic acid, hardened oil, stearamide, methylenebis stearamide, m-butyl stearate, ketone wax, octyl alcohol, Hydroxystearic acid triglyceride, silicone oil; flame retardants such as antimony oxide, aluminum hydroxide, zinc borate,
Chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as stearoamidopropyldimethyl-β-hydroxyethyl, ammonium urate; fillers such as calcium oxide, clay, silica, glass fibers, If necessary, glass spheres, carbon fibers, colorants such as titanium oxide, carbon black, pigments, dyes, plasticizers, etc. can be added.

The modified hydrogenated polymer and the thermoplastic resin composition obtained by the present invention are injection molding method, sheet extrusion method, vacuum molding method, modified foam molding method, press molding method, stampable molding method, cast molding method. It is possible to obtain various molded products by the above. The various molded products obtained here can be used for exterior members / interior members of automobiles, various electric / electronic-related parts, housings, optical materials, etc. by utilizing their excellent properties.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, parts and% mean parts by weight and% by weight unless otherwise specified. Example 1 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene 500 g, 1,2-dicycloloethane 2000 ml, and a molecular weight regulator 1
-3.8 g of hexene and 9 chlorobenzene solution of tungsten hexachloride with a concentration of 0.05 M / l as catalyst
1.6 ml and paraaldehyde concentration 0.1M
/8.7 liter of a solution of 1,2-dicycloloethane and a concentration of triisomethylaluminum of 0.
Add 37 ml of 5 M / liter toluene solution and react at 60 ° C. for 10 hours to give an intrinsic viscosity (η _inh ) of 0.56 deciliter / g (in chloroform, 30 ° C., concentration 0.5 g / deciliter). 450 g of a ring polymer was obtained. The ring-opened polymer was dissolved in 9,000 ml of tetrahydrofuran, and 45 g of a palladium-alumina catalyst having a palladium concentration of 5% by weight was added,
Charge hydrogen gas to a pressure of 100 kg / cm ² ,
Hydrogenation reaction was carried out at 150 ° C. for 5 hours. After the hydrogenation reaction, the catalyst was filtered off, and the filtrate was poured into a large excess of hydrochloric acid-acidified methanol to produce hydrogenated polymer a-1. (Hydrogenation rate 100%) Polymer a-1, 22 parts by weight, 64.4 parts by weight of methacrylate, 9.6 parts by weight of styrene, and 4 parts by weight of acrylonitrile were dissolved in 130 parts by weight of toluene in a reaction vessel. After adding a catalyst (t-butylperoxide isopropylcarbonate), a reaction was carried out at 95 ° C. for 6 hours to synthesize a modified hydrogenated polymer. The graft ratio with acetone was 41%, and the matrix [η] was 0.43. 29 using injection molding machine
It was molded at 0 ° C. and the physical properties were measured (Table 1). Examples 2-5, Comparative Examples 1-2 Hydrogenated polymers; vinyl monomers, amount and reaction temperature,
Modified hydrogenated polymers as shown in Table 1 were synthesized at different times.
In Comparative Example 1, only the hydrogenated polymer a-1 was used. In Comparative Example 2, a vinyl monomer was polymerized separately from the hydrogenated polymer, and the physical properties of the mixture mixed with the hydrogenated polymer were measured. did. The physical property results are shown in Table 1. Physical properties HDT (ASTM D648) Thickness 1/2,
264 psi Chemical resistance 1% or more, gasoline soaked, no cracking for 24 hours ○ MFR (JIS K7210) 220 ° C, 10 kg TS (ASTM) Tensile strength

[0015]

[Table 1]

Examples 6 to 9 and Comparative Examples 6 and 7 Production of Rubber-Modified Thermoplastic Resin (G-1) A stainless steel autoclave with a ribbon-type stirring blade and an internal volume of 10 liters was used as a base rubber which was previously made into a uniform solution. Hydrogenated diene polymer KRATON G-1650 (SEBS manufactured by Shell Chemical Co., Ltd.) 30 parts by weight, styrene 4
9 parts by weight, 120 parts by weight of toluene, and 0.1 part by weight of tertiary decyl mercaptan were charged, the temperature was raised with stirring, and 21 parts by weight of acrylonitrile and 0.5 parts by weight of benzoyl peroxide were added at 50 ° C.
After adding 0.1 part by weight of digyl peroxide and further raising the temperature to 80 ° C., the polymerization reaction is carried out at a stirring rotation speed of 100 rpm while keeping the temperature constant at 80 ° C. It took 1 hour from the 6th hour after the disclosure of the reaction to raise the temperature to 120 ° C., and the reaction was further performed for 2 hours to complete the reaction. Polymerization rate is 9
It was 7%. After cooling to 100 ° C., 2.2'-methylenebis (4-methyl-6-t-butylphenol) 0.2.
After adding 2 parts by weight, the reaction mixture was taken out from the autoclave, and the powder reaction monomer and the solvent were distilled off by steam distillation, and after finely pulverizing, 40 mmφ vent extruder (22
At 0 ° C. and 700 mmHg vacuum), the volatile matter was substantially distilled off and the polymer was pelletized to obtain a rubber-modified thermoplastic resin (G-1). The modified hydrogenated polymer of Example 1 and the above-mentioned (G-1) were blended at the ratio shown in Table 2 and the physical properties were measured. The physical property results are shown in Table 2.

[0017]

[Table 2]

[0018]

The modified hydrogenated polymer and the thermoplastic resin composition thereof obtained by the present invention have excellent heat resistance, chemical resistance and good processability, and are suitable for exterior and interior members of automobiles and It can be suitably used for various electric and electronic parts, housings and the like.

Claims (2)

[Claims] 1. Obtained by ring-opening polymerization of a monomer comprising at least one norbornene derivative represented by the following general formula (I) or this monomer and a copolymerizable monomer copolymerizable therewith. A method for producing a modified hydrogenated polymer, which comprises polymerizing a vinyl monomer (b) in the presence of a hydrogenated polymer (a) obtained by further hydrogenating the obtained ring-opening polymer. General formula (I): [In Formula (I), A and B are a hydrogen atom or C1-C1.
10 hydrocarbon groups, X and Y are hydrogen atoms, halogen atoms or monovalent organic groups, at least one of X and Y is a hydrogen atom and a polar group other than a hydrocarbon group, m is 0 or 1. ] 2. A thermoplastic resin composition comprising (a) the modified hydrogenated polymer obtained in claim 1 and (b) a thermoplastic resin other than the component (a).