JPH0344090B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing a modified 4-methyl-1-pentene polymer, which comprises graft copolymerizing an unsaturated carboxylic acid or its acid anhydride to a 4-methyl-1-pentene polymer. Novel modified 4- produced by the method of the present invention
Methyl-1-pentene polymer is 4-methyl-1
- When blended with a pentene polymer, it exhibits an excellent lubricant effect during extrusion molding, and provides the molded product with excellent printing properties, as well as excellent adhesion properties when laminated onto metal and other substrates. I can do it. Moreover, the polymer obtained by further chlorinating the unsaturated carboxylic acid or its acid anhydride graft copolymerized modified 4-methyl-1-pentene polymer of the present invention has excellent solubility in various organic solvents at room temperature. The coating film obtained by applying this solution to a substrate such as metal, drying, and baking exhibits excellent coating properties such as adhesion, coating strength, heat resistance, and rust prevention. . Crystalline 4-methyl-1-pentene homopolymer or 4-methyl-1-pentene and other α-
Copolymers with olefins are generally produced by stereospecific catalysts using titanium catalyst components such as titanium trichloride. 4- produced with this catalyst
The homopolymer or copolymer of methyl-1-pentene is
It is insoluble in many solvents at room temperature, and therefore its use as a solution-type paint or adhesive must be subject to many restrictions. The homopolymer or copolymer has a wide molecular weight distribution and a high melting point. For example, the ratio of weight average molecular weight to number average molecular weight (hereinafter referred to as molecular weight distribution) is often a value of 6 or more. Such 4-methyl-1-pentene polymerization has a lubricant effect,
It is not suitable for practical use in terms of printing characteristics, adhesion, coating suitability, etc. As a result of investigating the properties of 4-methyl-1-pentene polymer when it is used as a coating film-forming element component without modification, the applicant found that
It was previously discovered that a 4-methyl-1-pentene copolymer whose melting point, intrinsic viscosity [η], and molecular weight distribution are within specific ranges exhibits good coating performance, and this was published in JP-A-56-76416. Already suggested. Although these 4-methyl-1-pentene copolymers showed considerably improved film performance when used as a film-forming element component in their unmodified state, they were still not sufficient; - Even if it is blended with a 1-pentene polymer, an excellent lubricant effect cannot be obtained, and the adhesion of the composition to different types of substrates, the printing properties of molded products made of the composition, or the adhesion properties of Lamicoat are not sufficient. do not have. Further, even when the chlorinated 4-methyl-1-pentene copolymer proposed in the above-mentioned publication is used as a coating film-forming component, excellent coating properties are not necessarily obtained. The 4-methyl-1-pentene polymer proposed by the applicant in the above publication has a lower intrinsic viscosity than the 4-methyl-1-pentene polymer obtained by polymerization in the presence of a stereospecific catalyst. It not only has a small [η] but also has a narrow molecular weight distribution, a low melting point, a low softening point, and a low crystallinity. The present inventors investigated the performance of compounding agents added to 4-methyl-1-pentene polymer and
- A more detailed study on improving the performance of coating films made of pentene polymers revealed that a 4-methyl-1-pentene polymer with specific properties was modified by graft copolymerization with an unsaturated carboxylic acid or its acid anhydride. is not only excellent as a lubricant for 4-methyl-1-pentene polymers, but also compositions containing it have excellent adhesion to different types of substrates, and molded articles obtained from the compositions have excellent printing properties. It was discovered that the obtained Lamicort has excellent adhesion, and furthermore, it was discovered that a coating film made of the chlorinated product of the unsaturated carboxylic acid or its acid anhydride has excellent coating properties. Reached. To summarize the present invention, the present invention comprises 4-methyl-
55 to 100% by weight of 1-pentene component units (a), and 0 to 45% by weight of α-olefin component units (b) having a carbon atom number in the range of 2 to 20 other than 4-methyl-1-pentene. range [where (a) and (b)
The sum of
(c) under the reaction temperature of 100℃ to 250℃, (c)
The graft copolymerization is carried out in a range of 0.01 to 20 parts by weight based on 100 parts by weight of the 4-methyl-1-pentene polymer, and the intrinsic viscosity [η] measured at 135°C in a decalin solvent is 0.05 to 10 dl/g, molecular weight distribution expressed as weight average molecular weight/number average molecular weight (w/n) of 1 to 6, melting point measured by differential scanning calorimeter of 150 to 245.
A method for producing a substantially linear modified 4-methyl-1-pentene polymer having a crystallinity of 1 to 45% as measured by differential scanning calorimetry. This is the gist of the invention. The composition of the 4-methyl-1-pentene component unit (a) in the 4-methyl-1-pentene polymer constituting the modified 4-methyl-1-pentene polymer of the present invention is as follows:
It is necessary to range from 55 to 100% by weight, and more preferably from 80 to 100% by weight. In addition, the composition of α-olefin component unit (b), which is a constituent other than 4-methyl-1-pentene, must be in the range of 0 to 45% by weight, and more preferably in the range of 0 to 20% by weight. It is preferable that there be. Here, in both cases, (a) and
The sum with (b) is 100. The α-olefin component unit (b) other than 4-methyl-1-pentene in the 4-methyl-1-pentene polymer constituting the modified 4-methyl-1-pentene polymer of the present invention has 2 carbon atoms. The number of α-olefin component units ranges from 20 to 20, preferably 3 to 18. Specifically, the α-olefin component units include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3
-Component units such as methyl-1-pentene, 2-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, etc. can be mentioned. These component units may be produced by direct copolymerization, or may be produced by cutting off a portion of the originally existing polymerized units during decomposition. Two or more types of unsaturated hydrocarbon component units other than 4-methyl-1-pentene may be present. The component unit of 4-methyl-1-pentene in the 4-methyl-1-pentene polymer constituting the modified 4-methyl-1-pentene polymer of the present invention can be determined by infrared absorption spectrum. For example, the infrared absorption spectra of a solution of the modified product according to the present invention in a suitable solvent and a solution of 4-methyl-1-pentene homopolymer are taken, and the ratio of the absorbance of the maximum absorption band around 1356 cm ^-1 based on the isobutyl group is obtained. The content (a) of the 4-methyl-1-pentene component unit of the copolymer can be determined from the content (a) of the 4-methyl-1-pentene component unit (b) of the copolymer. ) can be found. The unsaturated carboxylic acid or its acid anhydride graft copolymerized modified 4-methyl-1-pentene polymer of the present invention is obtained by grafting an unsaturated carboxylic acid or its acid anhydride onto the 4-methyl-1-pentene polymer. It is a polymerized product, and its base structure is substantially linear, meaning that it does not have a three-dimensional crosslinked structure. It can be confirmed. The unsaturated carboxylic acid or acid anhydride component unit (c) constituting the modified 4-methyl-1-pentene polymer of the present invention is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, maleic acid, or fumaric acid. ,
Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, glutaconic acid, nadiconic acid, methylnadic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, Examples include unsaturated dicarboxylic anhydrides such as allylsuccinic anhydride, glutaconic anhydride, nadic anhydride, methyl nadic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride, and mixtures of two or more of these components. It doesn't matter if it happens. Among these unsaturated carboxylic acids or their acid anhydrides, maleic acid,
Preference is given to using maleic anhydride, nadic acid or nadic anhydride. The grafting ratio of the unsaturated carboxylic acid or its acid anhydride component unit (c) constituting the modified 4-methyl-1-pentene polymer of the present invention is based on 100 parts by weight of the base 4-methyl-1-pentene polymer. It is necessary that the amount is in the range of 0.01 to 20 parts by weight, more preferably in the range of 0.05 to 10 parts by weight, and particularly preferably in the range of 0.1 to 7 parts by weight. When the grafting ratio of the graft modification component (c) is less than 0.01 parts by weight or more than 20 parts by weight, modified 4-methyl-1 obtained by graft copolymerizing the unsaturated carboxylic acid or its acid anhydride.
- The lubricant effect of the pentene polymer, the adhesion of the composition containing the modified product to different substrates, the printing properties of molded articles made of the composition, the adhesion properties of Lamicote and the coating properties of its chlorinated product are reduced. The modified 4-methyl-1-pentene polymer of the present invention has an excellent lubricant effect due to its unsaturated carboxylic acid or its acid anhydride graft copolymerized product, and improves the adhesion of compositions containing it to different types of substrates. In order to exhibit excellent performance in the printing properties of the molded product made of the composition, the adhesion properties of Lamicoat, and the properties of the coating film made of chlorinated substances, the intrinsic viscosity [η] (value measured at 135°C in decalin solvent) is required. is 0.05 or
It is necessary to be in the range of 10 dl/g, and
0.08 to 5 dl/g, especially 0.12 to 3 dl/g
It is preferable that it is in the range of . As the intrinsic viscosity [η] increases, the lubricant effect of the modified product, the adhesion of the composition containing the modified product to different types of substrates, the printing properties of molded products made of the composition, and the adhesion properties of Lamicoat all decrease. In addition, the properties of the coating film made of the chlorinated product of the modified product also deteriorate. Furthermore, if the intrinsic viscosity [η] becomes too small, the aforementioned lubricant effect, adhesiveness of the composition, printing properties of the molded article, adhesion properties of Lamicoat, and coating film properties will be poor. The molecular weight distribution (w/n) expressed as weight average molecular weight/number average molecular weight of the modified 4-methyl-1-pentene polymer of the present invention is measured by gel vermiaction chromatography (GPC).
The molecular weight distribution of the low molecular weight polymer ranges from 1 to 6, preferably from 2 to 5. Measurement of molecular weight distribution by GPC was carried out according to the following method.
That is, using o-dichlorobenzene as a solvent, 0.04 g of polymer per 100 parts by weight of solvent (0.05 g of 2,6-di-tert-butyl-p-cresol was added as a stabilizer per 100 parts by weight of polymer).
is added to form a solution, and then filtered through a 1μ filter to remove insoluble matter such as dust. Thereafter, measurements were performed using a GPC measuring machine set at a column temperature of 135°C and a flow rate of 1.0 ml/min, and numerical ratios were converted on a polystyrene basis. The Mw/Mn of 4-methyl-1-pentene homopolymers or copolymers produced using general stereospecific catalysts exceeds 6 in many cases. The melting point of the modified 4-methyl-1-pentene polymer of the present invention was measured by differential scanning calorimetry (DSC). The melting point of the 4-methyl-1-pentene polymer of the present invention is 150 to 245°C, preferably 180 to 245°C.
It is in the range of 238℃. Note that the melting point here is measured as follows. That is, the sample was placed in a differential scanning calorimeter (du pout 990 model) and heated from room temperature to 20
The temperature is increased at a rate of ℃/min, and when it reaches 250℃,
Raise the temperature at a rate of °C/min, lower it to 25 °C, then raise the temperature again at a rate of 20 °C/min, and read the melting point from the melting peak at this time (in many cases, multiple melting peaks will appear). Therefore, in this case, the value on the high melting point side was adopted). Based on this measurement method, the melting point of a normal homopolymer of 4-methyl-1-pentene obtained by polymerization using a stereospecific catalyst is around 240°C, and The pentene copolymer has a melting point of (3X-60)°C when the 4-methyl-1-pentene content is x% by weight.
Many of them indicate the vicinity. The modified 4-methyl-1-pentene polymer of the present invention needs to have a degree of crystallinity based on DSC in the range of 1 to 45%, and more preferably in the range of 2 to 35%.
% range is preferable. The degree of crystallinity was measured by the following method. That is, using the chart when measuring the melting point by DSC described above,
The melting area (S) of the measurement sample is compared with the melting area (So) on the recording paper corresponding to the melting energy (Po) per unit amount of indium, which is a control sample. Indium Po is a known amount, while 4
Since the melting energy (P) per unit amount of the crystal part of the -methyl-1-pentene polymer is also known as shown below, the degree of crystallinity of the measurement sample can be determined by the following equation. Crystallinity (%) = S/SO
Philosophical Magazine, 4 , 200 (1959)] Even if the crystallinity of the low molecular weight polymer becomes too low or too high, the lubricant properties of the modified product, the adhesive properties of the composition containing the modified product, The printing properties of the molded article of the composition, the adhesion properties of Lamicoat, and the performance of the coating film made of the chlorinated product of the modified product deteriorate. The method for producing the modified 4-methyl-1-pentene heavy body of the present invention is as follows. The graft copolymerization reaction occurs by reacting the 4-methyl-1-pentene polymer with the unsaturated carboxylic acid or its acid anhydride under heating. The graft copolymerization reaction can be carried out in the presence of a solvent in a solution state or in a molten state. It is particularly preferred to carry out the modification reaction in the presence of a radical initiator. The proportion of the radical initiator used is generally 0.01 to 300 parts by weight, preferably 0.1 to 200 parts by weight, based on 100 parts by weight of the 4-methyl-1-pentene polymer. The proportion of the solvent used when carrying out the modification reaction in a solution state is usually 100 to 100,000 parts by weight, preferably 300 to 10,000 parts by weight, based on 100 parts by weight of the 4-methyl-1-pentene polymer. be. The temperature during the modification reaction is usually 100 to 250
℃, preferably in the range of 110 to 200℃, and the reaction time is usually 15 to 360 minutes, preferably
It ranges from 30 to 300 minutes. Solvents used in the modification reaction include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, and kerosene, and alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclododecane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene, chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane , halogenated hydrocarbons such as tetrachloroethylene, and the like. Among these, alkyl aromatic hydrocarbons are particularly preferred. When such a solvent is used, the solvent is often added to the reaction product, and the amount thereof is particularly large when an alkyl aromatic hydrocarbon is used. Furthermore, when the graft modification reaction is carried out in a molten state, the mixture consisting of the 4-methyl-1-pentene polymer, the unsaturated carboxylic acid or its acid anhydride, and the radical initiator is heated in an extruder or the like. It is also possible to cause a modification reaction by melt-kneading the polymer. Typical radical initiators used in the graft modification reaction are organic peroxides, more specifically alkyl peroxides,
These include aryl peroxides, acyl peroxides, aroyl peroxides, ketopene oxides, peroxycarbonates, peroxycarboxylates, hydroperoxides, and the like. As the alkyl peroxide, diisopropyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexine-3, etc.; aryl peroxides such as dicumyl peroxide; acyl peroxides such as dilauroyl peroxide; aroyl peroxides; is dibenzoyl peroxide, ketone peroxides are methyl ethyl ketone hydroperoxide, cyclohexanone peroxide, etc. hydroperoxides are tert.
-butyl hydroperoxide, cumene hydroperoxide and the like. Among these are di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di-tert-butylperoxy-hexyne-3, dicumyl peroxide, dibenzoyl peroxide and the like are preferred. The unsaturated carboxylic acid or its acid anhydride graft copolymer-modified 4-methyl-1-pentene polymer of the present invention provides an excellent lubricant effect during extrusion molding by blending it with a 4-methyl-1-pentene polymer. In addition, the composition has excellent adhesion to different substrates and the surface of a molded product obtained from the composition has excellent printing properties, and furthermore, the lamicoat formed from the composition has excellent adhesion properties to the substrate. . 4
- For use as a lubricant during extrusion molding of methyl-1-pentene polymers, the modified 4-methyl-
The blending ratio of the 1-pentene polymer is the 4-methyl-
The amount is generally 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the 1-pentene polymer. The composition containing the modified 4-methyl-1-pentene polymer may be applied to a different substrate, such as metals such as steel, aluminum, copper, stainless steel, or lead, or nylon, saponified ethylene/vinyl acetate copolymer, epoxy resin, or urethane. In order to adhere to polar plastics such as resins, melamine resins, or paper, the blending ratio of the modified 4-methyl-1-pentene polymer is 0.1 to 0.1 to 100 parts by weight of the 4-methyl-1-pentene polymer. In the range of 50 parts by weight. In addition, the modified 4-methyl-1-pentene polymer is extremely useful as a binder when an inorganic filler or glass fiber is added to the 4-methyl-1-pentene polymer, and in this case, the modified 4-methyl-1-pentene polymer is The blending ratio of the -methyl-1-pentene polymer is in the range of 0.1 to 50 parts by weight per 100 parts by weight of the 4-methyl-1-pentene polymer. Furthermore, in order to use the composition containing the modified 4-methyl-1-pentene polymer by lamicating, it is necessary to use the modified 4-methyl-1-pentene polymer.
- The blending ratio of methyl-1-pentene polymer is 4
-Usually 1 to 50 parts by weight, preferably 2 to 40 parts by weight per 100 parts by weight of the methyl-1-pentene polymer
Parts by weight range. Furthermore, the modified 4-
The chlorine compound of methyl-1-pentene polymer has significantly improved solubility in various organic solvents compared to unmodified 4-methyl-1-pentene polymer, and the chlorinated compound can be used as a film-forming element. The coating film obtained by this process is characterized by excellent coating properties such as adhesion, coating strength, and heat resistance. The rate of chlorination when preparing the chlorinated product of the modified product is carried out until the chlorine content of the chlorinated product after chlorination reaches a range of usually 5 to 80% by weight, preferably 10 to 70% by weight. be done. The modified 4-methyl-1-pentene polymer of the present invention has good solubility in some solvents, and therefore, solutions dissolved in such solvents can be used for various substrates, such as metals, polyolefins, glass, etc. It can be used for coating materials, inorganic fillers, surface treatment agents for glass fibers, adhesives, paints, etc. Solvents used for this purpose include:
Preferred are carbon tetrachloride, halogenated hydrocarbons such as tricrene, chloroform, and chlorobenzene, and hydrocarbons such as cyclohexane and cyclohexene. The modified 4-methyl-1-pentene polymer of the present invention can also be made into a film by extrusion molding, injection molding, blow molding, vacuum forming, etc. in the same way as a normal 4-methyl-1-pentene polymer or copolymer. sheet,
It can be used by forming into hollow bottles, tubes, and various molded products. In these various applications, stabilizers, antioxidants, ultraviolet absorbers, pigments, dyes,
Various fillers and the like can be appropriately blended. The modified 4-methyl-1-pentene polymer of the present invention can also be used as a modifier for other resins and rubbers by being blended with many resins and rubbers. For example, it can be used in a blend with polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, or the like. It is also possible to improve the solvent paintability, adhesion, printability, etc. of various molded products such as films, sheets, tubes, pipes, and hollow bottles obtained from these compositions by conventional molding methods. Generally, similar effects are observed when amorphous copolymer rubbers are blended, but in this case, there are drawbacks such as a decrease in mechanical strength and curing of the composition after blending, but the copolymer of the present invention A blended composition does not have this drawback because it still has crystallinity. Next, the method of the present invention will be specifically explained using examples. Example 1 4-methyl-1-pentene homopolymer (intrinsic viscosity [η] 3.5 dl/g, w/n 7.3, melting point 240°C,
crystallinity 43%) in toluene solvent at 145°C.
The grafting reaction of maleic anhydride was carried out using a dicumyl peroxide catalyst. By adding a large excess of acetone to the obtained reaction product, the polymer was precipitated and collected, and the precipitate was repeatedly washed with acetone to obtain maleic anhydride graft modification 4.
-Methyl-1-pentene polymer was obtained. The grafting ratio of maleic anhydride in this modified 4-methyl-1-pentene polymer is 3.5g/100g-4
-Methyl-1-pentene polymer, [η]
0.99dl/g, melting point 211℃, crystallinity 19%, w/
The Mn was 2.8. Examples 2 to 8 and Comparative Examples 1 to 3 Using the 4-methyl-1-pentene polymers shown in Table 1, the reaction temperature, the type and amount of unsaturated carboxylic acid or its acid anhydride, and the amount of peroxide Various modified 4-methyl-1-pentene polymers were prepared by carrying out the reaction in the same manner as in Example 1 except for changing the type and amount. The results are shown in Table-1. Example 9 0.2 parts by weight of maleic anhydride and 2,5-dimethyl-2,5-di-tert-butylperoxy-hexyne-3 were added to 100 parts by weight of the 4-methyl-1-pentene homopolymer used in Example 1. After adding 0.16 parts by weight and mixing well, the mixture was supplied to a 20 mmφ extruder (L/D28) set at 260° C. under a nitrogen atmosphere. The obtained polymer was once dissolved in p-xylene at 125° C. under a nitrogen atmosphere, and after cooling to room temperature, the polymer was precipitated by mixing with a large amount of acetone. By collecting the precipitate and repeatedly drying it with acetone, the maleic anhydride graft modified 4-
A methyl-1-pentene polymer was obtained. Table 1 shows the results.
It was shown to. [Printability evaluation method] 4-Methyl-1-pentene polymer [4-methyl-1-pentene content: 97% by weight, 1-decene content: 3
A water-based ink was applied to an injection molded plate made from a composition in which 5% by weight of the graft copolymerized modified 4-methyl-1-pentene polymer prepared by the above method was blended with [η] 2.2 dl/g]. toyo ink manufacturing
Aqua King, manufactured by KK] was applied with a doctor blade (1 mil). The affinity of the ink on the molded plate when the water-based ink was applied (whether or not the ink repellent phenomenon occurs) and the adhesion of the coating film after drying were examined by a checkerboard test. Table 1 shows the results.
It was shown to. In addition, when the modified 4-methyl-1-pentene polymer was not added, the repelling phenomenon was significant and printing was impossible. [Method for evaluating Lamicote properties] 4-Methyl-1-pentene polymer [4-methyl-1-pentene content: 97% by weight, 1-decene content: 3
A 10% by weight composition of graft copolymerized modified 4-methyl-1-pentene polymer prepared by the above method was melted to [η] 3.42 dl/g] and coated on an Al plate with a bar coater to form a film thickness. It was applied to 100μ and adhesion was measured using a grid test. Furthermore, the coating properties and blocking properties during coating were also investigated. In addition,
When the modified 4-methyl-1-pentene polymer was not blended, the adhesion was 5/100.

【table】

【table】

【table】

Claims (1)

[Claims] 1 4-methyl-1-pentene component unit (a) 55~
100% by weight, and 0 to 45% by weight of α-olefin component units (b) having 2 to 20 carbon atoms other than 4-methyl-1-pentene [herein, (a) and ( b)
The sum of
(c) at a reaction temperature of 100°C to 250°C, (c)
The graft copolymerization is carried out in a range of 0.01 to 20 parts by weight based on 100 parts by weight of the 4-methyl-1-pentene polymer, and the intrinsic viscosity [η] measured at 135°C in a decalin solvent is 0.05 to 10 dl/g, molecular weight distribution expressed as weight average molecular weight/number average molecular weight (w/n) of 1 to 6, melting point measured by differential scanning calorimeter of 150 to 245.
A method for producing a substantially linear modified 4-methyl-1-pentene polymer having a crystallinity of 1 to 45% as measured by differential scanning calorimetry.