JPS6049051A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent heat deformation resistance and high stability to heat and light, by compounding a vinyl chloride polymer with a hydrogenated product of a ring-opened polymer of 5-cyanobicyclo [2.2.1]heptene-2. CONSTITUTION:The objective composition is produced by compounding (A) 70-5wt% vinyl chloride polymer with (B) 30-95wt% polymer obtained by the hydrogenation reaction of a ring-opened polymer of 5-cyanobicyclo[2.2.1]heptene- 2 to a hydrogenation ratio of >=50%. The component B can be produced by hydrogenating a polymer obtained by the ring-opening polymerization of a monomer of formula (R is H, 1-5C alkyl or cyano) or a mixture composed mainly of the monomer and containing other norbornene derivative or cycloalkene, by a process for the polymerization of a cyclic olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinyl chloride polymer and 5-cyanobicyclo[2
・2.1] The present invention relates to a resin composition having particularly excellent heat resistance, which is characterized by being similar to a hydrogenated product of a hebutene-dicyclic polymer.

Vinyl chloride polymer (PVC) has tensile strength, hardness,
Although it has excellent properties such as transparency, chemical resistance, and flame retardancy, its heat distortion temperature is about 70C, and there is a limit to its use at higher temperatures. Therefore, in order to improve the heat distortion temperature of p'va, a polymer having a heat distortion temperature higher than that of PVC and showing good compatibility with PVO is generally mixed. Such polymers include, for example, polymethyl methacrylate, acrylonitrile-styrene copolymer,
Acrylonitrile mediene-styrene copolymer, methyl methacrylate-styrene copolymer.

Examples include methyl methacrylate-acrylonitrile-styrene copolymer. However, the deformation temperature of these polymers is 1000C or less in the case of polymethyl methacrylate, and about 100C even in the case of other polymers. Therefore, even if these polymers are mixed with PVA, it is difficult to significantly improve the PVCQ heat distortion temperature.

In addition, cyanonorbornene-based ring-opening polymers have good compatibility with PVO and are effective as impact modifiers;
The improvement effect on heat distortion temperature is not so large;
Moreover, since it is easily deteriorated by heat and light, there are problems in processing and use, such as discoloration during heat molding, discoloration and deterioration due to long-term ultraviolet irradiation.

However, since cyanonorbornene-based ring-opening polymers have a relatively high heat deformation temperature, we focused on this polymer and created a composition that maintains the above-mentioned characteristics of PVC, has excellent heat deformation resistance, and is stable against heat and light. As a result of repeated research to develop the product, we found that vinyl chloride polymer 70-5 Jusuman and 5-cyanobicyclo[2
, 2, 13 hebutene-2-based ring-opening polymer 60 ~ obtained by hydrogenating a butene-2 ring-opening polymer so that the hydrogenation rate becomes 50 ~
The present invention was achieved based on the discovery that a resin composition comprising 95% by weight achieved the initial objective.

The PVC used in the present invention may be a homopolymer of vinyl chloride, or a copolymer or graft polymer in which vinyl chloride is the main proportion.

5- which is the raw material for the other component used in the present invention
Cyanovincro [2.2.1] Hebutene-2-based open polymers are monomers represented by the general formula (R is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an ano group) or The main proportion is monomer (usually .

is 50 moles or more) and a monomer mixture of this and other norbornene derivatives or ncroalkenes is prepared using a conventional cyclic olefin polymerization method, for example, a tungsten compound and/or molybdenum compound and an organoaluminum compound, or a combination of them and an activator. Open with a combined catalyst system]
, 'i't'N Derivatives such as menooctahydronaphthalene, etc. are used as monoolefin compounds (e.g., cyclopentene, cycloheptene, cyclopentene, cyclononene, cyclodecene, etc.).
, non-conjugated cyclic polyene compounds (1,5-7 chlorooctadiene, 1,5,9-cyclododecatriene, etc.).

In the present invention, a hydrogenated polymer can be obtained by subjecting this Kaeseng polymer to a hydrogenation reaction using a conventional method. Any hydrogenation catalyst that is commonly used in the hydrogenation of olefin compounds can be used.
For example, examples of heterogeneous catalysts include solid catalysts in which nickel, palladium, platinum, or these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, nickel/diatomaceous earth, etc. , palladium/carbon, palladium/silica, palladium/silica, palladium/alumina, etc. In addition, homogeneous catalysts include compounds of metals from group Ⅰ of the periodic table and compounds of metals from groups 1 to 1+1;
For example, naphthene e nickel/triethylaluminum,
Cobalt octenoate/yL-phthyllithium, nickel acetylacetonate/triethylaluminum, etc.
Alternatively, Rh compounds may be mentioned.

The hydrogenation reaction is carried out homogeneously or heterogeneously using a catalyst under a hydrogen pressure of 1 to 150 atmospheres and at a reaction temperature of 0 to 180C, preferably 20 to 100C. The hydrogenation rate can be adjusted arbitrarily by changing the hydrogen pressure, reaction time, catalyst concentration, etc., but the hydrogenated product shows excellent heat deformation resistance, light deterioration resistance, and heat deterioration resistance. In order to achieve this, the hydrogenation rate of the main chain double bonds in the polymer must be 50%.
Above, preferably 80% or more is required. Surprisingly, the heat distortion temperature of the ring-opened polymer increases as the hydrogenation rate increases. For example, a ring-opened polymer (5-cyanovinculo[2.2.1]hebutene-2'v) (
In the case of [polyanonorbornene], at a hydrogenation rate of 0%, it is 12
0C, but at 50% hydrogenation rate it is 140C, hydrogenation rate 10
At 0%, it becomes 160C. In order to improve heat resistance in this way, it is necessary to increase the hydrogenation rate.

The proportion of each component in the resin composition of the present invention is 70 to 5% by weight of the PVA polymer, preferably 50 to 5% by weight;
60 to 95% by weight of hydrogenated product of 5-cyanobicyclo[2.2.1]hebutene-2 ring-opening polymer, preferably 50% by weight
The content is between 95% and 95% by weight. When the blending amount of the hydrogenated ring-opening polymer is less than 30% by weight, iJ: the heat distortion temperature of the composition is 90
If it is less than C, it is not practical, and if it exceeds 95%, the advantages of PVC will be lost, and it will become particularly flammable.
Undesirable.

In the present invention, the PVC and the hydrogenated ring-opening polymer are mixed by a conventional method using, for example, a roll, a calender, a Bamba IJ-mixer, an extruder, or the like.

The resin composition of the present invention needs to contain a stabilizer or an ultraviolet absorber in order to prevent decomposition or oxidative deterioration of PVC during mixing, as in the case of ordinary PVC compacts. Stabilizers include, for example, gold-hexachloride-based stabilizers, organotin-based stabilizers,
Usual stabilizers such as lead-based and epoxy-based stabilizers are used, but organic tin-based stabilizers are preferable in order to maintain transparency.

Other ordinary PVC compounding agents can also be used as appropriate.

The resin composition of the present invention can be molded by a conventional method to produce molded products with excellent heat deformation resistance, light deterioration resistance, heat deterioration resistance, solvent resistance, transparency, etc. It is expected to be used in container tongues for lighting equipment, lenses, housing materials, display panels, automobile parts, tableware, etc.

The present invention will be explained in more detail with reference to Examples below.

Example 1 5-cyanobicyclo[2.2.1] Hebutene-2 to 2
By dissolving in twice the amount of toluene, using 3 moles of tungsten hexachloride and 9 moles of diethylaluminium chloride (both based on monomers) as polymerization catalysts, reacting at 20C for 10 hours, and then purifying in methanol. ,
Polycyanonorbornene was prepared.

Next, the obtained polycyanonorbornene 60y.
A solution of 6 g of diatomaceous earth containing 1% palladium dissolved in 0 mg of tetrahydrofuran was added to 1
2 was placed in an autoclave, and the temperature was maintained at 200℃. After replacing the air in the autoclave with nitrogen, it was further replaced with hydrogen, and then the hydrogen pressure was raised to 5 ok/cm'a2.
After stirring at 0C for 60 minutes, the temperature of the autoclave was raised to 50G, and the mixture was stirred for 5 hours to perform a hydrogenation reaction. The solution after the hydrogenation reaction was filtered through a 1μ filter to remove the hydrogenation catalyst, and then an appropriate amount of tetrahydrofuran was added to precipitate the hydrogenated product of polyanonorbornene in methanol, followed by drying and purification. The hydrogenation rate of this purified product was 100% as determined by the NMR spectrum.

In addition, hydrogenated chloride (1% palladium-supported diatomaceous earth) was added to
．． When 81y of the hydrogenation catalyst was added, the hydrogenation rate was 80%, and when 6.2y of the hydrogenation catalyst was added, the hydrogenation rate was 60%. - Mix these hydrogenated or unhydrogenated products with polyvinyl chloride (Zeon 105F, P manufactured by Nippon Zeon (Φ)) at the compounding ratio shown in Table 1, and then add diptyl to 100N parts of polyvinyl chloride. A compound containing 3 parts by weight of tin maleate, 1 part by weight of ptylsdaleate, and 0.5 part by weight of liquid paraffin was mixed with a roll at 190 C to prepare a sample.The heat distortion temperature of these samples (ASTM D-64
8, 18, 6 (kya! TI) load), photodegradability and thermal deterioration properties are shown in Table 1. It can be seen that Experiments Nos. 7 to 12 are extremely useful as resin compositions with improved heat resistance and light and heat deterioration resistance.

Table 1 *1 Comparative example *2 A 0.01m thick cast film was irradiated with a carbon arc lamp for 100 hours *s O,01m thick cast film was heated in air at v2oac for 20 minutes Example 2 Polymer used in Example 1 ) The same procedure as in Example 1 was used, except that a cold-type combination consisting of 280 moles of 5-ananobicyclo[2.2.1]hebdene and 20 moles of cycloheptene was used for the cyanoturbo J/N/. We conducted an experiment. However, L/PvO/ 17; 1 ring offshore hydrogenation ratio is 30
/ 70. The results are shown in Table 2.

Table 2 * Comparative example

Claims (1)

[Scope of Claims] Vinyl chloride polymer 70-5-fold metal and 5-cyanobicyclo [2.2.1] hebutene-2 intersystem ring polymer are hydrogenated at a hydrogenation rate of 50% or more. A heat-resistant resin composition characterized by comprising 30 to 95% by weight of a polymer obtained by hydrogenation reaction.