JPH0566402B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The purpose of the present invention is to provide a new synthetic wax that has excellent transparency and a high glass transition temperature, is fluidized with a small amount of heat, and is convenient to handle. 5,8-dimethano-1,2,3,
The purpose of this invention is to provide a new synthetic wax containing 4,4a,5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs) as a monomer component. [Prior Art] Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins with excellent transparency. For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as transparency. However, there is a problem that it is easily attacked by strong alkalis and has poor chemical resistance. Therefore, low molecular weight polycarbonate (wax-like) naturally has poor chemical resistance. Polymethyl methacrylate has problems in that it is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has the problem of being weak against strong acids and alkalis and being susceptible to hydrolysis. Therefore, these low molecular weight polymers also have similar properties. On the other hand, many of the low molecular weight polymers of polyolefins, which are famous as general-purpose resins, have excellent chemical and solvent resistance, but many have poor heat resistance.
Since they are crystalline resins, most of them have poor transparency. [Problems to be Solved by the Invention] Therefore, the present inventors have developed a material that has transparency, has a high glass transition temperature, and has a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties. As a result of repeated research into whether a synthetic wax could be obtained, the researchers discovered that a low-molecular-weight polymer containing a specific bulky monomer component in a specific structure in the polymer chain could achieve the objective. As for copolymers of ethylene and bulky comonomers, for example, U.S. Pat. No. 2,883,372 discloses copolymers of ethylene and 2,3-dihydrocyclopentadiene. However, this copolymer has a glass transition temperature of around 100°C and is poor in heat resistance. A copolymer of ethylene and ethylidenenorbornene also exhibits similar properties. However, the polymers found by the present inventors using DMONs as monomers have excellent transparency, chemical resistance, solvent resistance, and dielectric properties, and generally have glass transition temperatures of 100°C or higher, so they have poor heat resistance. It also has excellent long-term heat aging resistance because it has no unsaturated bonds. The monomers used by the inventors are
It has already been disclosed in Japanese Patent Publication No. 46-14910 or Japanese Unexamined Patent Publication No. 58-127728 that DMONs can be used as monomers for polymers. The former concerns homopolymers of DMONs or copolymers of DMONs with comonomers of the norbornene type, while the latter teaches the use of linear olefins as molecular weight modifiers for the homopolymers or copolymers of DMONs. However, since they are all targeted at ring-opened polymers, they have a structure with unsaturated bonds in the polymer main chain, as shown in the general formula (a) below, and have poor heat aging resistance. You can only get something inferior. On the other hand, the polymer of the present invention has a structure as shown in the following general formula () as its main structure, and has substantially no unsaturated bonds, or even if it does, has very few unsaturated bonds. It is considered to be chemically stable and has excellent heat aging resistance.

【formula】 [Means to solve the problem]

That is, the present invention provides (A) 1,4,5,8 represented by the following general formula ()
-dimethano-1,2,3,4,4a,5,8,
8a-Octahydronaphthalenes (hereinafter referred to as DMON)
A homopolymer of DMONs and a random copolymer of ethylene, (Here, R ₁ and R ₂ are hydrogen, an alkyl group, and a halogen, and each may be the same or different.) (B) In the case of a random copolymer, ethylene/
DMONs (molar ratio) is 5/95 to 95/5, and (C) DMONs units are mainly of the following general formula ()
Take the structure shown by (D) Intrinsic viscosity [η] measured in decalin at 135℃
0.005 to less than 0.3 dl/g, as defined by: [Function] The novel synthetic wax of the present invention substantially
Consists of DMONs alone or DMONs and ethylene. However, within a range that does not impair the purpose of the present invention, a small amount of other copolymerizable monomer components may be copolymerized, for example, in a range of less than 5 mol% in the case of a homopolymer and 20 mol% or less in the case of a copolymer. It's okay. Examples of such copolymerizable monomer components include propylene, 1-butene, 1-
α-olefins having 3 or more carbon atoms such as pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene (including ethylene in the case of a homopolymer), cyclopentene ,
Cycloolefins such as cyclohexene and 3-methylcyclohexene, styrenes such as styrene and α-methylstyrene, 2,3,3a,7a-tetrahydro-4,7-methano-1H-indene, 3a,5,
6,7a-tetrahydro-4,7-methano-1H-
Examples include norbornene compounds other than DMONs such as indene. The synthetic wax of the present invention is a homopolymer of DMON represented by the above general formula () or a copolymer with ethylene. These DMONs can be easily produced by condensing norbornenes and cyclopentadiene as shown in the following formula. Specific examples of DMONs include 1,
4,5,8-dimethano-1,2,3,4,4a,
In addition to 5,8,8a-octahydronaphthalene,
2-methyl-1,4,5,8-dimethano-1,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro Naphthalene, 2-propyl-1,4,5,
8-dimethano-1,2,3,4,4a,5,8,
8a-octahydronaphthalene, 2-hexyl-
1,4,5,8-dimethano-1,2,3,4,
4a,5,8,8a-octahydronaphthalene, 2
-stearyl-1,4,5,8-dimethano-1,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-
Dimethano-1,2,3,4,4a,5,8,8a-
Octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene,
2-chloro-1,4,5,8-dimethano-1,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro Naphthalene, 2-fluoro-1,4,5,
8-dimethano-1,2,3,4,4a,5,8,
8a-Octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene,
2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,
8-dimethano-1,2,3,4,4a,5,8,
Examples include 8a-octahydronaphthalene.
Among these, preferred are those in which either R ₁ or R ₂ is substituted with an alkyl group having 1 to 20 carbon atoms. When the synthetic wax is a random copolymer of ethylene and DMONs, the content ratio of both (ethylene/DMON molar ratio) is 5/95 to 95/5,
The ratio is preferably 10/90 to 90/10, particularly preferably 20/80 to 85/15. And DMONs are mainly found in copolymers and homopolymers. It is polymerized with the following structure. This structure is
It can be confirmed by ^C13 -NMR. Since DMONs mainly have the above structure,
The iodine value of the synthetic wax of the present invention is usually 5 or less, and most of them are 1 or less. Therefore, it has a chemically stable structure and excellent heat aging resistance. The synthetic wax has an intrinsic viscosity [η] of 0.005 to less than 0.3 dl/g, measured in decalin at 135°C.
Furthermore, 0.01dl/g to less than 0.3dl/g, especially 0.05
A range of 0.2 to 0.2 dl/g is preferred. The novel synthetic waxes of the present invention are generally amorphous or low-crystalline, preferably amorphous. Therefore, it has good transparency. In general, the degree of crystallinity measured by X-rays is 10% or less, often 0%, and in many cases the melting point cannot be observed using a differential scanning calorimeter (DSC). The synthetic wax of the present invention usually has a glass transition temperature of 80 to 220°C by DSC, and many have a glass transition temperature of 100 to 220°C.
Measured in the range of 200℃. Other properties of the synthetic wax of the present invention are as follows:
The ^viscosity at
10 ⁴ cp, with a softening temperature measured using a penetrometer (TMA) (measured with a load of 49 g and a 0.1 mm penetration using a 0.025 inch diameter quartz needle) of 70 to 240 °C, and many of them have a softening temperature of 90 to 240 °C. Measured in the range of 220℃. In addition, the pyrolysis temperature is usually 350 to 420, which is the temperature at which weight loss starts when the temperature is raised at a rate of 10°C/min under a nitrogen stream using a thermobalance (TGA: manufactured by Rigaku Denki Co., Ltd.).
℃ Most are in the range of 370-410℃. Density is determined using the density gradient tube method (ASTM D
1505) and usually 0.86 to 1.10 g/cm ³ Most of them are 0.88 to 1.10 g/cm3
It is within the range of 1.08g/ ^cm3 . Refractive index (ASTM D
542) is 1.47 to 1.58, and most of them are in the range of 1.48 to 1.56. As the electrical properties of the present invention, ASTM D 150
The dielectric constant (1KHz) is usually 1.5~3.0, often
1.7~2.6, ASTA D 150 dielectric loss tangent is 5x
10 ⁻³ to 5×10 ⁻⁵ , often in the range of 5×10 ⁻⁴ to 8×10 ⁻⁵ . The synthetic wax of the present invention has an excellent balance of transparency, heat resistance, heat aging resistance, dielectric properties, chemical resistance, and solvent resistance, and by taking advantage of these characteristics, it can be used in all fields where wax is normally used. can be used. Examples of such fields of use include candle applications, pine wood impregnation agents, paper processing agents, sizing agents, rubber anti-aging agents, cardboard waterproofing agents, chemical fertilizer slowing agents, heat storage materials, ceramic binders, paper condensers, Electrical insulation materials for electric wires and cables, neutron moderators, textile processing aids, water repellents for building materials, paint protection materials, polishing agents, thixotropic additives, lead hardening agents for pencils and crayons, carbon ink bases, electrostatic charges Examples include toners for copying, lubricants for synthetic resin molding, mold release agents, resin coloring aids, hot melt adhesives, and lubricating greases. The synthetic wax of the present invention may be used by mixing various known waxes. Examples of such waxes include plant-based waxes such as candelilla wax, carnauba wax, wood wax, and jojoba oil, animal-based waxes such as beeswax, lanolin, and spermaceti, montan wax, ozokerite, and ceresin. Mineral waxes, paraffin waxes, microcrystalline waxes, petroleum waxes such as petrolatum, synthetic hydrocarbon waxes such as fissure tropism waxes, polyethylene waxes, polypropylene waxes, poly4-methyl-1-pentene waxes, Examples include modified waxes such as montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives, hydrogenated waxes such as hydrogenated castor oil and hydrogenated castor oil derivatives, fatty acids, fatty acid amides, ketones, amines, imides, and esters. . The synthetic wax of the present invention can also be used in combination with various known non-waxy polymers. Examples of such polymers include (a) polymers derived from hydrocarbons having one or two unsaturated bonds, specifically polyolefins such as polyethylene, polypropylene, which may have a crosslinked structure, Polyisobutylene, polymethylbutene
1. Poly-4-methylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, or copolymers of monomers constituting the above-mentioned polymers, such as ethylene-propylene copolymer, propylene-butene-1-copolymer. Polymer, propylene/isobutylene copolymer, styrene/
Isobutylene copolymers, styrene-butadiene copolymers, ethylene and propylene and dienes such as hexadiene, cyclopentadiene,
(b) Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, etc. , polyvinyl fluoride, polychloroprene,
chlorinated rubber, etc. (c) Polymers derived from α,β-unsaturated acids and their derivatives, specifically polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or monomers constituting the above polymers. Copolymers with other copolymerizable monomers such as acrylonitrile/butadiene/styrene copolymers, acrylonitrile/styrene copolymers, acrylonitrile/styrene/acrylic acid ester copolymers, (d)unsaturated alcohols and polymers derived from amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine , or a copolymer of the monomer constituting the polymer with other copolymerizable monomers, such as ethylene/vinyl acetate copolymer, (e) a polymer derived from epoxide, specifically polyethylene oxide or Polymers derived from bisglycidyl ether, (f) Polyacetals, specifically polyoxymethylene, polyoxyethylene, polyoxymethylene containing ethylene oxide as a comonomer, (g) Polyphenylene oxide, (h) Polycarbonates, polysulfones, polyurethanes and urea resins, polyamides and copolyamides derived from diamines and dicarboxylic and/or aminocarboxylic acids or corresponding lactams, in particular nylon 6, nylon 66 , nylon 11, nylon 12, etc., (wo) dicarboxylic acids and dialcohols and/or
or polyesters derived from oxycarboxylic acids or the corresponding lactones, in particular polyethylene terephthalate, polybutylene terephthalate, poly1,4-dimethylol cyclohexane terephthalate, etc. (iv) polyesters derived from aldehydes and phenols, urea or melamine Polymers with a crosslinked structure, specifically phenol/formaldehyde resin, urea/formaldehyde resin, melamine/
Formaldehyde resins, etc. (f) Alkyd resins, specifically glycerin phthalate resins, etc. (b) Derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, using vinyl compounds as crosslinking agents. unsaturated polyester resins and halogen-containing modified resins obtained by Ru. To produce the novel synthetic wax of the present invention,
DMONs alone or DMONs and ethylene,
Polymerization may be carried out using a well-known Ziegler catalyst. The Ziegler catalyst used in the present invention is a titanium compound supported on a magnesium compound, which is known as a highly active catalyst, or a catalyst consisting of a vanadium compound and a reducing agent such as an alkyl aluminum compound. The titanium compound supported on the magnesium compound is preferably a complex containing at least magnesium, titanium and halogen, and is preferably a compound obtained by bringing a magnesium compound and a titanium compound into close contact by means such as heating or co-pulverization. refers to a composite in which the molar ratio of halogen/titanium contained in the composite exceeds about 4, and the titanium compound is not substantially eliminated by hexane washing at room temperature. A good complex is
The halogen/titanium (molar ratio) is greater than about 4, preferably about 5 or more, more preferably about 8 or more, the magnesium/titanium (molar ratio) is about 3 or more, preferably about 5 to about 50, and the composite has an electron If a donor is included, the electron donor/titanium (molar ratio) is approximately
0.2 to about 6, preferably about 0.4 to about 3, more preferably about 0.8 to about 2, and the specific surface area is about 3 m ² /g or more, more preferably about 40
m ² /g or more, more preferably about 100 m ² /g or more. In addition, the X-ray spectrum of the composite may be amorphous regardless of the starting magnesium compound, or may be in a highly amorphous state compared to that of ordinary commercially available magnesium dihalides. desirable. Examples of means for producing composites include JP-A-48-16986, JP-A-50-108385, and JP-A-Sho 50.
−126590, JP-A-51-20297, JP-A-51-
No. 28189, JP-A-51-92885, JP-A-51-127185
No., JP-A-51-136625, JP-A-52-87489,
JP-A-52-100596, JP-A-52-104593, JP-A-52-147688, JP-A-53-2580, November 1975
Examples include the means described in the Italian patent application dated 21st. Vanadium compounds include VCl ₄ , VBr ₄ ,
Vanadium halides such as VCl ₃ and VBr ₃ ,
Vanadium oxyhalide such as VOOCl ₃ , VBr ₃ , VOCl ₂ , VOBr ₂ or VO(OR) _o X _3-o (However, R hydrocarbon group, X is halogen, 0<n≦
3) A vanadium compound represented by the formula: Among these, hydrocarbon-soluble vanadium compounds, especially oxyhalogenated vanadium or
Compounds represented by VO(OR) _o X _3-o are preferred.
In _the compound represented by VO(OR) _o , especially those with numbers 1 to 3 are good. Further, n<n≦3, preferably 1≦n≦1.5. Examples of such vanadium compounds include VO( _OCH3 ) _Cl2 , VO( _OCH3 ) _2Cl , VO
( _OCH3 ) _{3 ,} VO _{( OC2H5} ) _{Cl2 ,} VO( _OC2H5 ) _1.5
Cl ₁ . ₅ , VO (OC ₂ H ₅ ) ₂ Cl, VO (OC ₂ H ₅ ) ₃ , VO
(OC ₂ H ₅ ) _1.5 Br _1.5 , VO ( _{OC 3} H ₇ ) _{Cl 2} , VO
(OC ₃ H ₇ ) _1.5 Cl _1.5 , VO ( _{OC 3} H ₇ ) _{2 Cl} , VO
(OC ₃ H ₇ ) ₃ , VO(On−C ₄ H ₉ )Cl ₂ , VO(On−
C ₄ H ₉ ) ₂ Cl, VO (O iso C ₄ H ₉ ) ₂ Cl, VO (O sec
_Examples include C ₄ H _{9 ) 3} , VO(OC ₅ H ₁₁ ) _1.5 Cl _1.5 or a mixture thereof. these are
Reacting VOCl ₃ with alcohol, or
It can be easily obtained by reacting VOCl3 and VO(OR _{)3 .} Alkylaluminum compounds have the general formula
It is represented by R′mAlX′ _3-n (where R′ is a hydrocarbon group, X′ is a halogen, and 0<m≦3). Examples of the alkyl aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, any mixture thereof, or a mixture of these and aluminum trihalide. Polymerization takes place in a hydrocarbon medium. For example, aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene may be used alone or in combination as a solvent. I can do it. Polymerization occurs in the reaction medium, for example in the case of a titanium compound and an alkyl aluminum compound, the former being
Adjust the concentration to 0.0001 to 10 mmol/, preferably 0.01 to 1 mmol/,
The latter has an Al/Ti (molar ratio) of 1 or more, preferably
It is adjusted to 1000 or less, particularly preferably 10 to 500. In addition, in the case of vanadium compounds and alkyl aluminum compounds, the former is 0.001
from 100 mmol/, preferably from 0.01 to 100 mmol/, preferably from 0.01 to 100 mmol/
The latter is adjusted so that the Al/V (molar ratio) is 1 or more, preferably 100 or less, and particularly preferably 3 to 50. Among these catalyst systems, the latter one using a vanadium system is particularly preferred. When polymerizing a copolymer of DMONs and ethylene, the charging ratio varies depending on the composition of the desired copolymer, type of reaction medium, polymerization temperature, polymerization pressure, type of catalyst, etc., but in general, the reaction The molar ratio of ethylene/DMONs in the medium is 20 or more.
It is adjusted to 0.01, preferably 15 to 0.05. Polymerization temperature is -50 to 300℃, preferably -30 to 200℃, polymerization pressure is 0 to 100Kg/
cm ² ·G, preferably 0 to 50 Kg/cm ² ·G. For controlling the molecular weight of the polymer, a molecular weight controlling agent such as hydrogen may be present as appropriate. [Examples] Hereinafter, the content of the present invention will be explained in more detail using Examples, but the content of the present invention is not limited to these Examples, and can be modified in any manner as long as the purpose is not impaired. It is possible. Example 1 A stirring blade, a gas blowing pipe, a thermometer, and a dropping funnel were attached to a sufficiently dried separable flask No. 3, and the flask was sufficiently purged with nitrogen. Toluene 1, which had been dehydrated and dried using a molecular sieve, was placed in this flask. 10 mmol of dichloroethoxyoxyvanadium (VO(OC ₂ H ₅ ) Cl ₂ ) was added to the dropping funnel under nitrogen flow, and DMONs (2-methyl-1,4,
5,8-dimethano-1,2,3,4,4a,5,
60 g of 8,8a-octahydronaphthalene (compound (a) in Table 1) and _{100 mmol of ethylaluminum sesquichloride (Al(C 2 H 5 ) 1.5 Cl 1.5 ) were added .} A mixed gas of 320/hr of dry ethylene and 280/hr of hydrogen was passed through the gas blowing pipe into the flask controlled at 30°C for 30 minutes. The copolymerization reaction was started by dropping dichloroethoxyoxyvanadium from the dropping funnel, and the copolymerization reaction was carried out at 30° C. for 30 minutes while passing the mixed gas. The solution during the copolymerization reaction was homogeneous and transparent, and no copolymer precipitation was observed. The copolymerization reaction was stopped by adding 10 ml of methanol to the polymerization solution. After the reaction had been terminated, the polymerization solution was poured into a large amount of methanol-acetone to precipitate a copolymer, which was further washed with acetone and vacuum-dried at 60° C. for one day to obtain 17.2 g of a copolymer. The copolymer ethylene content measured by ^C13 NMR is
The intrinsic viscosity [η] measured in 60 mol% decalin at 135°C was 0.1 dl/g, and the iodine value was 0.9. In addition, in order to measure the physical properties, molded sheets with a thickness of 1 mm or 2 mm were prepared by hot pressing at 230°C. When X-ray diffraction was performed using these sheets, no scattering due to crystals was observed, indicating the degree of crystallinity.
Wc was 0%. In addition, when measurements were made in the range of -120°C to 400°C at a heating rate of 5°C/min using a differential scanning calorimeter model 990 (DSC) manufactured by DuPont, no melting peak (Tm) was observed, and the glass transition The temperature (Tg) was 128°C. In addition, a Dupont penetrometer (TMA) was used to measure the diameter at a load of 49 g.
The softening temperature measured using a 0.025 inch quartz needle at a heating rate of 10°C/min was 126°C. Also,
The transparency of the 1 mm sheet was measured with a haze meter in accordance with ASTM D 1003-52 and was found to be 11%. Emiller rotational viscometer (manufactured by Yagami)
When measured at 750 rpm and 280°C, it was 2200 cp. Furthermore, to examine chemical resistance, the press sheet was immersed in sulfuric acid (97%), aqueous ammonia (20%), acetone, and ethyl acetate for 20 hours at room temperature and its appearance was observed. No deformation, dissolution, cracking, or other properties were observed. Examples 2 to 10 The same operations as in Example 1 were performed, except that the types of DMONs, the amount of ethylene feed, and the reaction conditions were changed as shown in Table 2, and the results shown in Table 3 were obtained. Examples 11 and 12 The same operations as in Example 1 were carried out except that the solvent used was changed to cyclohexane, the polymerization temperature was changed to 10°C, and the types of DMONs and reaction conditions were changed as shown in Table 2. 3 results were obtained.

【table】

【table】

〔Effect of the invention〕

The synthetic wax of the present invention has an excellent balance of transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, and dielectric properties, and can be widely used in various industrial applications.

Claims (1)

[Claims] 1 (A) 1.4.5.8-dimethano-1,2,3,4,4a,5,8,8a- represented by the following general formula ()
A homopolymer of octahydronaphthalenes (hereinafter abbreviated as DMONs) or a random copolymer of DMONs and ethylene, (Here, R ₁ and R ₂ are hydrogen, an alkyl group, and a halogen, and each may be the same or different.) (B) In the case of a random copolymer, ethylene/
DMONs (molar ratio) is 5/95 to 95/5, and (C) DMONs units are mainly of the following general formula ()
Take the structure shown by (D) Intrinsic viscosity [η] measured in decalin at 135℃
A new synthetic wax defined as 0.005 to less than 0.3 dl/g.