TWI307340B - - Google Patents

Description

1307340 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a novel polyolefin plastic additive, and more particularly to a bis(substituted thiophenemethyl) alditol diacetal compound and a plastic composition thereof. It can be applied to plastic containers and packaging materials as nucleating agents and transparent agents. [Prior Art] Additives added to plastics such as polyolefins for crystallization are generally referred to as nucleating agents for the purpose of reducing the molding time of the product during the melting process and improving its physical properties. When a nucleating agent is used to promote the visual effect of a semi-CryStamne product (e.g., to increase its transparency), the crystallization agent may also be referred to as a clearing agent. Dibenzyiidene sorbit〇l (DBS) has been used as an additive to improve the transparency of articles (see Japanese Patent Application No. 94424/1974). It has been disclosed in U.S. Patent No. 4, No. 16,118 (1977) that the polyolefin plastic composition comprises from about 1% to about 7% of the additive DBS, which can be used to improve the transparency and reduce the shrinkage when molding. Since then, many of the succinyl sorbitol defoliation derivatives have been published, mainly by designing various functional groups on the benzene ring. Several kinds of materials have been known to be commercially produced and commercially available, and can be applied to polyolefin plastics as a nucieator, and also as a clarifier, such as 1,3:2,4-two. (Benzene subunit)_D-sorbitol diacetal (ECM, Gel)

All D' Irgaclear D, Millad 3905, NC-5); l, 3:2,4-bis(4-indolylbenzylene)-D-sorbitol diacetal (Gei A11 MD, It_gaeleai> DM, 1307340

Millad 3940, NC-6); bis(3,4-xylylene subunit) D sorbitol diacetal (Millad 3988); 1,3:2,4 bis(4-ethylphenylmethylidene)_D _ Sorbitol diacetal (NC-4). However, the aforementioned 1,3:2,4-bis(phenylideneylene)_D_sorbitol diacetal has poor compatibility with polyolefin, and mold scale is easily generated during processing, toluene subunit)-D- The process of processing sorbitol diacetal and polyolefin often produces a defect such as a bad odor (such as tolualdehyde), and the benzene ring structure of the similar compound has different functional groups, and the ability to improve the physical properties of the plastic is also different. The development of a novel, heterocyclic aryl-based subunit _D_sorbitol diacetal has become a new subject in the field. A olefin plastic compound is disclosed in Japanese Patent Application No. 02233737/1990. It is a diacetal (di(substituted coffee bit. 丨; DFS) containing di(substituted furanylbenzylidene)_〇-sorbitol, which has the following structural formula:

Wherein 'R is selected from the group consisting of Η, (^ mentioned in the experimental example, thickness lmm, fog shoulder piece '茗,... ' 3 Γ田 hl'CVC3 yard base. lmm 'haze value is 83% Polypropylene plastic test

Weighing 1,3_two (replaces the stupiditol diacetal, which has the lower 5 1307340

Among the ethnic groups formed by F. In a specific example 1 of the present case, D-sorbitol is first reacted with 2-thiophene-carboxaldehyde to form 2,4-(2-warm phenylmethyl)-D sorbitol monoacetal intermediate. And adding p-toluene with O-tolualdehyde), the reaction yields (4) a 3:1 dikemed mixture containing 1,3-(4-purinylbenzylidene)_2, heart (2_ 瞎 甲 亚 亚)_d _ sorbitan bis-acid compound (1,3_(4_t〇lylidene)_2,4_(2_thenylidene) D_ sorbitol) and 1,3:2,4_bis(4-tolylmethyl)_D_sorbitol The acetal compound (m^diy-tolylidenehD-sorbitol); 0_25% of the mixture is used for polypropylene plastic test pieces with a thickness of 40 mils, and the haze value is 12 · 5 %. The smell of tolualdehyde. In view of the above, the present invention develops a novel plastic additive "symmetric type 1307340 bis(substituted thiophenemethyl)) acid alcohol diacetal "which can improve the nucleation temperature of polyolefin plastics and shorten the processing time' compatibility, and Effectively reducing the plastic haze value makes the transparency higher and industrially usable. SUMMARY OF THE INVENTION The present invention relates to a novel plastic additive, which belongs to a transparent agent for polyolefin plastics, especially a di(substituted thiophene fluorenyl)_D_sorbose diacetal and a plastic composition thereof. It can be used in polyolefin plastics to increase its nucleation temperature, shorten processing time, and effectively reduce its haze value to increase transparency. The present invention relates to a compound having the general formula (I),

Wherein 'heart, R2 and I are respectively selected from the group consisting of ruthenium, CVC8 alkyl, phenyl, N〇2, Cl and Br, and ^ or i. Preferred is the compound of the formula (I) which is 13:2,4-:(%methyl_2_warmoleyl)-D-sorbitol diacetal. The invention further relates to a nucleating agent for plastic polymerization comprising a compound of the formula (1). Preferred are the aforementioned nucleating agents which include 13:2,4-bis(5-fluorenyl-2-thiophenemethyl)-D-sorbitol diacetal. The invention further relates to a polyolefin composition characterized in that at least one of the aforementioned nucleating agents having a compound of the formula (1) is utilized in the manufacture of 1307340. Preferably, the 'polyolefin composition' is characterized in that it is used in the manufacture of I, 3:2,4·di(5.methylmethylphenanthylene)-D-sorbitol-. Acid nucleating agent. Preferably, the polyolefin composition is characterized in that the nucleating agent is I,3:2,4-di(5-methyl_2-thienylmethylidene)-D-sorbitol condensate during manufacture. The present invention is further related to a transparent polyolefin plastic comprising the aforementioned polyalkylene composition having the compound of the formula (I). Preferably, the transparent polyanthracene plastic comprises at least one 1,3:2,4·di(5-methyl-2-toxin sorbitan diacetal) used in the manufacture. More preferably, the transparent polyolefin plastic is a nucleating agent at the time of manufacture, which is 1,3:2,4-di(5-methyl-2-? Polyolefin composition of sorbitan diacetal. Tailu B-day S;!: Day about a box of private. · 4+ β + formula (Π),

Wherein Ri, R.2 and R3 are each selected from the group consisting of ruthenium, CrC8 alkyl, phenyl, N〇2, C1 and Br, and η is 0 or 1. Preferably, the compound is 1,3:2,4_bis(3--phenethyl)-t>- 10 1307340 sorbitol diacetal. The invention further relates to a nucleating agent for plastics polymerization comprising a compound of formula (II). Preferably, the aforementioned nucleating agent comprises 1,3:2,4-di(3-thienyl' subunit)-D-sorbitol diacetal. The invention further relates to a polythene hydrocarbon composition characterized in that at least one of the aforementioned nucleating agents having a compound of the formula (II) is utilized in the manufacture. Preferably, the poly thin composition is characterized in that at least one of 1, 3:2, 4-(3-indolyl)-D-sorbitol is used in the manufacture. Nucleating agent. Preferably, the polyolefin composition is characterized in that the nucleating agent is 1,3:2,4-bis(3--phenethyl)-D-sorbitol dicondensate. Further, the present invention relates to a transparent polyolefin plastic comprising the above-described polyene smoke composition having the compound of the formula (II). Preferably, the transparent polyolefin plastic comprises the above-mentioned at least one hydrazine, 3:] fluorene-bis(3·thiophenemethylidene)_D_sorbitol di vine as a nucleating agent. A polythene composition. More preferably, the transparent polyolefin plastic is a polyolefin composition in which the nucleating agent is 1,3.2,4-mono(3-thiophenemethylidene)_d_sorbitol diacetate.实施 , [Embodiment] The present invention relates to a novel and practical plastic additive which can simultaneously improve the efficiency of nucleation and reduce the haze value of polyolefin plastics, thereby making polyolefin plastics have good properties. Transparency, therefore, 1307340 can be used as a transparent agent and prevent mechanical or chemical deterioration of the final product. The following terms are fully understood by those of ordinary skill in the art to which the invention pertains; the following definitions are Any meaning in the specific embodiments or patent claims of the present invention is not explicitly explained. The term "polyolefin plastic" as used in the present invention means (I) isotactic or syndiotactic polymerization. Propylene and mixtures thereof; (π) crystalline and semi-crystalline random copolymers and terpolymers comprising a plurality of polyacryls and at least one selected from the group consisting of ethylene and C4-C8 alpha monoolefins and a comonomer (C〇m〇nomer) in a group consisting of a mixture of binary copolymers. Other common polyolefins contain linear low density Polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), polydecylpentene, and mixtures of any of the foregoing. In the present invention, polyolefin is preferred. The resin is a propylene unit polymer, a propylene/ethylene copolymer, a linear low density polyethylene, and a low density polyethylene. Particularly preferred is a polypropylene which has significant uniformity. 1 Name (5) used in the present invention "Crystallinity" means a degree of crystallization in which the X-ray winding test is at least about 5% to 1% by crystallization. The term "symmetrical" as used in the present invention means the phase gas in the alcohol disk. Dicarboxylic acid, here derived from the same substituted porphin A. The invention is made by providing a special additive to make a polyolefin plasticized compound which has a good alignment and can increase its transparency. 'The present invention can be 1,3:2,4-di(substituted thiophene ia 12 1307340 yl)-D- by adding at least one symmetrical di(substituted pheno-indolyl) alcohol glycoconstriction. Sorbitol II wake up (IJJ^-dKsubstituted theny Lidene)-D-sorbitol diacetals; referred to as DTS), and 1,3:2,4-di(substituted porphinyl subunit)-D-xylitol dicarboxylic acid (l,3:2,4-di( Substituted thenylidene-D-xylitol diacetals; referred to as DTX), which have the general formula (I) and the general formula (II):

Wherein ' Ri , R 2 and R 3 are each selected from the group consisting of ruthenium, q-C 8 alkyl, phenyl, N 〇 2, Cl and Br, and η is 〇成i. Here, the present inventors have surprisingly found that 1,3:2,4_bis(5-substituted-phenenyl)-D-sorbitol diacetal is an excellent polyolefin plastic. Nucleation and transparency additives. Polyolefin The polyolefin plastic of the present invention may be composed of a crystalline and semi-junction polymer or a polyolefin resin, which mainly utilizes a polymer containing at least one aliphatic monooleic HN, or a type of q to q alpha- Monoolefin copolymers, especially mixtures of propylene polymers or polyolefin copolymers.

13 1307340 The crystalline polypropylene known as polypropylene is generally a solid, mostly semi-crystalline, semi-crystalline, thermoplastic monomeric polymer. Usually, the average molecular weight of the solid polypropylene is 100, _ to 4, deleted, deleted. Its charm is about 159 °C to 169 °c. 1,3:2,4-di(substituted thiophenemethyl) D sorbitol diacetal (DTS) ' and 1,3:2,4-di(substituted thiophenemethyl) in the present invention Xylitol diacetal (DTX) obtained by acetalization of i molar equivalents of D_sorbitol or < xylitol with 2 molar equivalents of substituted thiophene furfural The structures of the following formulae (ΠΙ) and (IV) are obtained by reaction in the presence of an acid catalyst.

Wherein Ri, R2 and Rs are each selected from the group consisting of ruthenium, ruthenium, phenyl, N〇2, Cl and Br. For example, it may be 3__phene formaldehyde, 2-thiophenecarboxaldehyde, 3-methyl-2-thiophenecarboxaldehyde, 5-methyl-3-thiophenecarboxaldehyde, hong methyl _ • 2 thiophenecarboxaldehyde, ethyl _3 _ thiophene formaldehyde, 5-ethyl 2-thiophene phthalate, 5 _ third butyl _3 · warm phenoxy formaldehyde, 5 · tert-butyl 2 thiophene formaldehyde, 5 _ _ _ _ 3 _ _ _ 5·Phenyl 2 _ 瞳 甲 甲 越 , 5 _ _ _ _ _ 瞳 曱 、, 5 _ _ 甲 搭 5, 5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Block 4 formaldehyde, 5 · bromo-2-thiophene furfural or the like. Preferably, the acidic catalyst is selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid, methylation, camphoric acid, p-nonylbenzene acid, naphthalensulf〇nic acid, and the like. The solvent is preferably selected from the group consisting of decyl alcohol, ethanol, dimercaptomethylamine, acetonitrile, and an aromatic solvent containing decyl alcohol or trimethoxymethane. 1307340 The retort reaction can be carried out at different temperatures depending on various conditions, for example, the <3> porphin formaldehyde can be carried out at room temperature. In the present invention, the amount of DTS and DTX added to the polyolefin compound is from about 0. 0.05% to about 2% by weight. The secret is in the white-knife ratio, preferably about The percentage by weight of 0.05% to about 0.5%; particularly preferably from about 〇% to about 100 parts by weight, the calculation of the weight percentage is based on the weight of the polyolefin compound. The additive provided in the invention can be used in combination with other kinds of transparent agents to achieve excellent nucleation and transparency effects, and can also be separately added to the polyolefin composition, and at the same time, the additive provided by the present invention is not Limited to the type of polyalkylene polymer used in the mono-steroid, the polyolefin polymer synthesized by using the additive provided by the present invention may further add dye coloring or other additives to promote the visual effect of the polymer. Or strengthen other physical properties such as hardness. More importantly, the additive provided by the present invention is a stable and safe plastic additive, and can effectively improve the transparency of packaging materials, cosmetic container materials, food containers, and the like. The plastic polymer can be provided with excellent transparency and physical properties by adding the additive provided by the present invention. Other features and advantages of the present invention will be apparent from the following detailed description of the invention. EXAMPLES The following examples are provided to illustrate the invention. The examples are not intended to limit the scope of the invention in any way, but are intended to indicate how to practice the materials and methods of the invention. 15 1307340 A: f Preparation 1,3:2,4-di (3-_ phenothyroid vn_ 丰被^^ D-xylool (10.00 g, 〇〇66 mol), sterol (1〇〇 ML), camphorsulfonic acid (〇·5 g, 2.2 mmol), and % thiophenecarboxaldehyde (14 8 g, 〇132 mol) mixed in a 250 ml four-necked flask, device thermometer, nitrogen vent tube and machinery The mixture was stirred at room temperature for 48 hours and then neutralized with 4% sodium hydroxide solution. The white precipitated solid was collected by filtration and dried to give a fine white powder of 1,3:2,4-di (3) - thiophene subunit)_£>_xylitol diacetal, 15.95 g, yield 71% β, its melting point is 2〇9, it is to 21〇; 1hnmr (500Hz > d6-DMSO) 67.53-7.49 (m, 4H), 7.13-7.08 (m5 2H), 5-73 (s, 1H), 5.66 (s, 1H), 4.87-4.70 (bs, 1H), 4.13-4.07 (dd, H, J 12.6, 8.5 Hz), 4.08 (s, 1H), 4.07~3.94 (m, 1H), 3.88 (d iH, "/ = 1.2 Hz).

Acetal mouth - sorbitol (10) Buick ^ ^ this Lu Moer wide methanol ^ (9) ml), methic acid (1.00 g, 10.4 mmol), and 3__ 曱 曱 acid (25 g, 0.2229 mol ) mixed in! In the four-necked flask, the thermometer, nitrogen gas pipe and mechanical stirrer are installed. The reaction mixture was stirred at room temperature for 48 hours and neutralized with a 4% sodium hydroxide solution. The white precipitated solid was filtered and collected, and the precipitated solid was washed with 4% methanol and dried to give <RTI ID=0.0>>&&&&&&&&&&&&&&&& The output is about 72·0〇/〇. 16 1307340 The melting point is 237.0 °C to 239.8 °C; 丨H NMR (500Hz, d6-DMSO) 67.49~7.48 (m, 4H), 7.13-7.08 (m, 2H), 5.68 (s, 2H), 4.81 ( d, 1H, J=7.0 Hz), 4.38 (m, 1H), 4.13-4.09 (m, 3H), 3.89 (s, 1H), 3.81-3.71 (mj 2H), 3.63-3.57 (m, 1H), 3.48-3.39 (m, 1H). Example Lan" Preparation of l,3:2,4-^£j_曱基·2_η蹇唂甲亚))_〇_山犁糖醢 Diacetal D-sorbitol (20.00 g, 〇.1〇) 98 moles, methanol (2 milliliters), sulfonic acid (1.00 grams, 1 〇 · 4 millimoles), and % methyl 2 - thiophene furfural (25 grams, 0.1982 moles) mixed In the i-liter four-necked flask, a thermometer, a nitrogen vent tube and a mechanical stirrer were installed. The reaction mixture was stirred at room temperature for 48 hours and neutralized with a 4% sodium hydroxide solution. The white precipitated solid was filtered and collected, and the precipitated solid was washed with 4% decyl alcohol and dried to give a fine white powder of 1,3:2,4-di(5-methyl-2-thiopheneinylene)- D-sorbitol diacetal, 27.29 g, yielded about 69.2%. Its melting point is 209.5 ° C to 210.4 ° C; β NMR (500 Hz, d6-DMSO) 56.90-6.87 (m, 4H), 6.68-6.67 (m, 2H), 5.78 (s, 2H), 4.73 (d, 1H , 7=5.8 Hz), 4.35 (t, 1H, /=5.8 Hz), 4.11 (dd, 1H, /=12.6, 1.8 Hz), 4.06-4.02 (s + dd, 2H), 3.87 (d, 1H, • 7=1.3 Hz), 3.77 (dd, 1H, «/=7.3, 1.6Hz), 3.70~3.67 (m,lH), 3.62~3.54(m,lH), 3.40~3.34(m,lH),2.41 (s, 6H). Re-enforcement Example 4: Transparent-grade polyenes such as the liquid raft and the technology of adding a transparent agent to the polyolefin composition have been made.

1307340 is well known, and therefore, in the examples of the present invention, only n, the novel compound first synthesized by the present invention, the test conditions for the polyolefin composition τ as a transparent agent, and the effect thereof are achieved. Preparation of 2-color propylene polypropylene (Feta polyolefin ST868) Primary antioxidant (Irganoxl010) grade antioxidant (Irganoxl68) ------- Calcium stearate Compound of the invention [take from Examples 2 and 31 This basic The constituent resin and all additives are weighed and weighed. Then, the temperature is set to about 180 to 22 (rc) and processed through three heating zones. The dissolution temperature at the exit of the extruder is about 215 < t. ~ "The aspect ratio of the evaluation is 24. The propylene composition is sent to the injection mold after being injected. The mold temperature is set to 19 〇t to 26 (TC, preferably 2 〇 (rc to 24 〇 ° C °, the size of the injection test piece is 142*108*2) 54 cubic millimeters. The mold cooling air is controlled at approximately 23. (: Standard Test Method for Haze and Luminous Transmittance 〇f Transparent Plastics) 'measured with BYK Gardner XL-211 Haze Meter Haze value. Nucleation capability is measured by differential scanning calorimetry (DSC) melting of the standard plastic recrystallization temperature and cooled at a rate of about 1 (rc/min, recording crystallization temperature (Tc). Control group The plastic composition did not add the acetal of this case. 1307340 Test No. Addition Compound Concentration Haze Value Tc(DSC) Thickness (mil) Ma (In this case) (%) (°C) 1 None - 78.7 101.8 100 2 Example 2 0.20 61.4 113.2 100 3 Real Example 3 0.20 31.3 119.4 1004 26.9 119.7 Example 3 0.25 100

The various modifications and variations of the present invention may be made without departing from the scope and spirit of the invention. Although this month has described the specifics of the characteristics of the amnesty, it must be understood that the invention should not be unduly limited to such specific specific facts. In fact, it is obvious to those skilled in the art that the above-mentioned modes are implemented. Different amendments are also covered by the following patent applications. [Simple description of the diagram] None [Main component symbol description]

Claims (1)

Announcement, "Monthly", "Revision and Replacement Page" -----J 1307340 Wide Ten, the scope of application for patents: a compound having the general formula (I), In the group of constituents, η is 〇 or 1. -c8 alkyl base. The compound of claim 1 is l53:2,4 (methyl 2 - fluorene methyl subunit) _d_ sorbitol dicarboxylic acid _. Three nucleating agents for plastic polymerization, including the compound of claim 1 of the scope of the patent application. 4. A nucleating agent according to claim 3, which comprises bis(5-methyl-2-thienylmethylidene)_D_sorbitol diacetal. A polyolefin composition characterized in that at least one nucleating agent as claimed in claim 3 is used in the production. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; 7. The polyolefin composition of claim 6, wherein the nucleating agent is i,3:2,4_bis(5-methyl_2-thiophene sorbitol II). Acetal. 8. A kind of transparent polyolefin plastic, which is included in the patent application scope 20 1307340 • The polyolefin composition of item 5. -1. 9 - A transparent polyolefin plastic according to claim 8 of the patent application, which comprises a polyolefin composition as in claim 6 of the patent application. 〜10. The transparent polyolefin plastic as claimed in claim 9 which comprises the olefinic composition of claim 7 of the scope of the patent application. a compound having the formula (π), Wherein 'R!, and r3 are each selected from the group consisting of hydrazine and CrC8 alkyl, and n is hydrazine or 1. 1 2 . The compound of claim 11 of the patent, which is 1,3:2,4-mono(3-indolylmethylidene)_d-sorbitol diminishing. 13. A nucleating agent for plastic polymerization&apos; which comprises a compound as claimed in claim 11. 1 4 · A nucleating agent according to claim 13 of the patent scope, which comprises 1,3:2,4-di(3-expressive subunit)_D_sorbitol dicondensation. A polyolefin composition characterized by the use of at least one nucleating agent as in claim 1 of the patent application. • A polyolefin composition according to claim 15 of the patent application, characterized in that at least one nucleating agent as claimed in claim 14 is used in the manufacture. 21 1307340 1 7. A polyolefin composition according to claim 16 of the patent application, characterized in that the nucleating agent is 1,3:2,4-di(3-thienylmethylidene)-D-sorbose at the time of manufacture. Alcohol diacetal. A transparent polyolefin plastic comprising the polyolefin composition of item 15 of the patent application. A transparent polyolefin plastic as claimed in claim 18, which comprises the polyolefin composition of claim 16 of the patent application. A transparent polyolefin plastic according to claim 9 of the patent application, which comprises the polyolefin composition of claim 17 of the patent application. Η一,图: None twenty two