JPH023822B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to plasticizers for synthetic resins. Various kinds of plasticizers have been known to be added to synthetic resins, especially thermoplastic resins, in order to improve their processability, elongation, etc.
In particular, dioctyl adipate (DOA)
Dioctyl phthalate (DOP) has been widely used as an excellent plasticizer. However, it has recently been discovered that the above-mentioned DOA and the like are suspected of being carcinogenic, and there has been a demand for the development of an excellent plasticizer to replace them. On the other hand, attempts have been made to use polybutene as it is as a plasticizer for synthetic resins, but the compatibility between polybutene and synthetic resins is poor, bleeding phenomena occur, and a sufficient plasticizing effect is often not obtained. The object of the present invention is to provide an excellent plasticizer for synthetic resins that eliminates such disadvantages, and its composition is a plasticizer for synthetic resins whose main ingredient is polybutene that has been modified by epoxidation or aromatization. It is a drug. The main component of the plasticizer of the present invention is chemically modified polybutene, and there are various types of polybutene, which may be appropriately selected depending on the purpose of use. Among these, particularly preferable ones are:
Liquid polybutene is a copolymer of i-butene and a small amount of n-butene and has a number average molecular weight of 350 to 2,500. In addition, such polybutene can be produced, for example, by using the residue of butadiene extracted from the _C4 fraction during naphtha cracking as a raw material, using aluminum chloride as a catalyst, at a temperature of 10 to 20°C, and a pressure of 6 to 8 Kg/cm ² G. It can be produced by polymerization. In the present invention, the above-mentioned polybutene modified by epoxidation or aromatization is used as the main ingredient. The above-mentioned epoxidation modification of polybutene is generally carried out using an organic peracid such as performic acid (obtained by the reaction of formic acid and hydrogen peroxide), peracetic acid, perbenzoic acid, etc. to remove the terminal double bonds from polybutene. This is done by epoxidizing. Further, aromatization modification of polybutene is carried out by bonding benzene, toluene, xylene or other polycyclic aromatic compounds to polybutene by Friedel-Crafts reaction or the like to aromatize the polybutene. The plasticizer of the present invention is based on the epoxidized or aromatized polybutene produced as described above, and may be composed only of this chemically modified polybutene, or may be composed of only this chemically modified polybutene. It may also be configured by mixing other plasticizing components or further desired additive components. Synthetic resins whose plasticity can be improved by the plasticizer of the present invention include various thermoplastic resins, which cover an extremely wide range, such as polyvinyl chloride resin (PVC), methyl methacrylate resin (MMA), etc. , acrylonitrile-styrene resin (AS), polystyrene resin (PS), polyethylene resin (PE), polypropylene resin (PP), acrylonitrile-butadiene-styrene resin (ABS), and the like. When applying the plasticizer of the present invention to these synthetic resins, 0.1 to 5 parts by weight of the epoxidized or aromatized polybutene, which is based on the plasticizer of the present invention, is added to 100 parts by weight of the synthetic resin. , preferably in a proportion of 0.5 to 25 parts by weight. As described above, the plasticizer of the present invention imparts superior plasticity to various synthetic resins, equivalent to or superior to DOA and DOP, and has no risk of carcinogenicity or the like, and has no hygienic effects. It is harmless. Furthermore, it exhibits excellent compatibility with synthetic resins, and there is no risk of clouding when blended, and no bleeding phenomenon occurs. Moreover,
Synthetic resins blended with the plasticizer of the present invention have improved low-temperature properties; for example, vinyl chloride film usually tends to crack at around -10°C, but by adding the above-mentioned plasticizer, it has improved flexibility even at low temperatures. and no cracks will occur. Furthermore, the plasticizer of the present invention, particularly the epoxidized modified polybutene, also acts as a mold inhibitor and processing stabilizer for synthetic resins. In other words, to date, Ca, Pb,
Carbonates, sulfates, etc. of Zn, Ba, etc. are used.
Epoxidized soybean oil is used as a stabilizing agent, but this stabilizing agent has the disadvantage of being susceptible to mold growth. Epoxidized bisphenol, which is resistant to mold, has also been used as a stabilizing agent, but this has the disadvantage that the processability of the synthetic resin is significantly reduced when the amount incorporated is increased. On the other hand, when the epoxidized modified polybutene of the present invention is used in place of or together with the above-mentioned stabilizing aids, it improves the stability of synthetic resins, prevents mold growth, and improves processability. It is also possible to suppress a decrease in Therefore, the plasticizer of the present invention can be widely used as an effective plasticizer for various synthetic resins, and
In particular, epoxidized modified polybutene can be effectively used as a fungicide and a processing stabilizer. Next, production examples, examples, and comparative examples of the plasticizer of the present invention will be shown. Production example 1 0.5 mol of polybutene with a number average molecular weight of 350 and formic acid
Dissolve 1.0 mol in 150 ml of benzene and keep at 40℃.
0.6 mol of hydrogen peroxide was added dropwise while stirring.
After dropping, stirring was continued for about 2 hours, and then washed with water, dried, and concentrated to obtain epoxidized modified polybutene with an epoxidation rate of 40%. Production example 2 1000ml of hydrated benzene and 267g of aluminum chloride
was placed in a flask, and 700 g of polybutene having a number average molecular weight of 350 was added dropwise at room temperature with stirring over 1 hour. After the dropwise addition, stirring was continued at 80°C for 2 hours, and then 100 ml of water was added under ice cooling for hydrolysis. The reaction solution is then filtered, washed with water, and dried to remove excess benzene, resulting in a viscous and transparent liquid with a phenylation rate.
815 g of 95% phenylated modified polybutene were obtained. Comparative Examples 1 to 9 and Examples 1 to 9 A predetermined plasticizer was added to 100 parts by weight of a predetermined synthetic resin, and the mixture was mixed at a temperature of 150°C with an internal mixer (manufactured by Inoue Seisakusho Co., Ltd., model R2-2S). After kneading for 10 minutes, a 0.05 mm sheet was produced using two rolls (manufactured by Minamisenju Seisakusho Co., Ltd., model MS-1.7). This sheet has elongation (JIS K6745), tensile strength (JIS K6745) and tear strength (JIS
K6732) was measured. The results are shown in Table 1.

【table】

[Claims]

1 A coupling composition for improving adhesion between an organic elastomer matrix and an inorganic substrate, the coupling composition comprising: (A) a silicon-bonded hydroxy group containing 1 to 4 carbon atoms reactive with the inorganic substrate; It has at least one alkoxy group and at least one silicon-bonded ethylenically unsaturated group that is polymerizable with the organic elastomer matrix, and the remaining silicon valences are all 1 to 6 carbon atoms. (B) 5 to 95% by weight of an ethylenically unsaturated silane bonded to non-ethylenically unsaturated monovalent hydrocarbon groups having not more than about 10 siloxy units per molecule; At least one silicon-bonded hydroxy or alkoxy group containing 1 to 4 carbon atoms per molecule is reactive with the material, and any remaining silicon valences are hydroxy, alkoxy, or