JP2008527071A - Modified chlorinated polypropylene, process for producing the same, and polyolefin mixture - Google Patents

Abstract

The present invention relates to polyolefin blends containing modified chlorinated polypropylene. The present invention relates to a polyolefin containing a new amine-modified chlorinated polypropylene which can increase the adhesion of the ink and improve the printability when the ink is printed or coated on various plastic moldings including films or sheets. Provide a mixture. The present invention provides a modified chlorinated polypropylene obtained by substituting 1-99.9 mol% of chlorine element of chlorinated polypropylene having a number average molecular weight of 100-400,000 and a chlorine content of 1-75 wt% with ammonia or an amine compound. The present invention relates to a new polyolefin mixture having improved dyeability and adhesion. The present invention also provides the modified chlorinated polypropylene and a method for producing the same.

Description

  The present invention relates to a modified chlorinated polypropylene, a method for producing the same, and a polyolefin, particularly a polypropylene mixture using the same, and increases ink adhesion during ink printing and coating with various plastic moldings, films or sheets. To provide a new mixture capable of improving printability.

  A plastic film as a packaging material often requires good printability. Printability is judged as a wetness index. As is known, the wetting index of plastics is low. In particular, the wetting index of polypropylene is very low, and various surface processing such as printing cannot be performed. In order to solve such problems and increase the wetting index, it is common to perform corona discharge treatment. However, the forcibly increased plastic surface wetting index decreases with time.

  Films produced on polypropylene-based resins such as propylene homopolymers or propylene-ethylene or α-olefin copolymers based on propylene that have been used in the past have poor printability and are subjected to corona treatment. Even when the wetting index is increased, if the wetting index is left for a long time at a high temperature, the wetting index is remarkably lowered and cannot be used for printing.

  In the case of a film made of homopolypropylene, the surface tension of the biaxially stretched film and the unstretched film is 33 to 34 dynes / cm, and the surface tension becomes 40 to 45 dynes / cm if corona treatment is performed to improve printability. . However, due to the influence of the external environment such as heat, especially in the summer, the surface tension of the film rapidly decreases with the passage of time, and the workability such as printing and vapor deposition is remarkably reduced.

  In order to solve the above problems, a mixing technique of polypropylene resin and resin having other polar groups has been developed. However, in the case of a mixture, the basic backbone structure is different and there is a problem in affinity. However, there is a problem that mechanical properties are lowered, and a method of incorporating a polar group through graft polymerization has been studied, but it cannot be commonly used due to the complexity of the fundamental polymerization process. In addition, the graft efficiency of the polar monomer is poor and sufficient adhesion and printability cannot be ensured.

  As a result of various studies to solve the above problems, the present inventor has used modified chlorinated polypropylene modified into amine compounds for use in processing various molded products, films, various laminates, etc. The present invention has been completed as a result of finding properties that impart a wide range of properties and improve the printability and adhesiveness of various resins.

  Accordingly, it is an object of the present invention to provide a new modified chlorinated polypropylene that incorporates a polar group that improves the wetting index when mixed with a polyolefin, particularly polypropylene, and is mixed with the polyolefin, particularly polypropylene, to produce dyeability and colorability. And a new mixture with improved adhesion.

  It is yet another object of the present invention to provide a method by which new modified chlorinated polypropylene can be prepared easily and easily with minimal side reactions. Still another object of the present invention is to provide a polyolefin composition having improved printability and dyeability using the new modified chlorinated polypropylene.

  In the modified chlorinated polypropylene of the present invention, a chlorinated polypropylene having a chlorine content of 1 to 75% by weight and a number average molecular weight of 100 to 400,000 is dissolved in a solvent, and then an amine compound is added to the reaction mass. Thus, it is produced by substituting chlorine with an amine compound. The present invention also provides a method for producing a modified chlorinated polypropylene that can be produced without substantial elimination reaction by reacting chlorinated polypropylene with ammonia or amine in the presence of CaO and MgO. To do. The production method according to the present invention includes a step of dissolving chlorinated polypropylene in an organic solvent, a step of adding an amine derivative to the reaction solution and further heating to react the mixture, adding a base, an unreacted amine compound, The present invention provides a modified chlorinated polypropylene comprising a step of removing residual base and salt, and a step of recovering modified chlorinated polypropylene from an organic layer, and a method for producing the same. By adding CaO or MgO, the yield of amination can be increased and side reactions can be eliminated, thereby making the amine modification modification more stable and with high substitution yield without side reactions. The body (amine modified product) is obtained.

  The chlorinated polypropylene used in the present invention has a number average molecular weight of 100 to 400,000 and a chlorine content of 1 to 75% by weight. By reacting chlorinated polypropylene with ammonia or an amine compound having at least one primary or secondary amine group, amine-modified chlorinated polypropylene in which 1 to 99.9 mol% of chlorine is substituted with amine groups is produced. Is done.

  The organic solvent is not limited as long as it can dissolve chlorinated polypropylene. Desirably, an organic solvent such as toluene, xylene, chlorobenzene, tetrahydrofuran, dimethylformamide, morpholine, dioxane, acetonitrile and methylene chloride is used alone or in combination. And use it.

The primary amine or secondary amine compound used as a modifier in the reaction may be either with or without a substituent. The usable primary amine is represented by a compound of the following formula.
A ₁ -NH ₂
(A ₁ is branched (Branched), cyclic (Cyclic) or carbon atoms 1 to 18 hydrocarbon containing an aromatic group, the nitrogen in the main chain (main chain) or side chain (side chain), oxygen And one or more hetero groups selected from the group consisting of sulfur

  Primary amines of the structural formula include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, isooctylamine, aniline, Ethylenediamine, propylenediamine, 1,2-propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, aminobutanol, benzidine, 4,4'-diaminobenzanilide, aminobenzenesulfonic acid, diaminobenzene, phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl oxide, 4,4'-diamino Cyclohexyl ether, 4,4'-diaminodiphenyl-3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, and the like dimethylaminopropylamine.

In the secondary amine of the present invention, a compound having the following structural formula is used.
A ₂ -NH-A ₃
(A ₂ and A ₃ are branched hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic groups, and one selected from the group consisting of nitrogen, oxygen and sulfur in the main chain or side chain. (Having the above hetero-functional groups)

  Representative examples of the compound include dimethyldiamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctyl. Amine (dioxtylamine), diisooxtylamine, diphenylamine, methylaniline, ethylaniline, propylaniline, butylaniline, hydroxyethylaniline, hydroxypropylaniline, methylethanolamine, ethylethanolamine, diethanolamine, dipropanolamine, Morpholine can be raised.

It is also possible to use the following amine compounds as the secondary amine of the present invention.
A ₄ -HN- (A ₅ -NH-A ₆ -NH) n-A ₇
(A ₄ to A ₇ are branched hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic groups, and one selected from the group consisting of nitrogen, oxygen and sulfur in the main chain or side chain. (It has one or more hetero-functional groups. N is a positive integer between 1 and 10.)

  Examples of secondary amines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, dicyandiamide, and aminoethylethanolamine.

  The denaturation reaction temperature can be changed according to the solvent and reactivity. Usually, the reaction is carried out in the range of 30 to 150 ° C., but is not limited thereto. The reaction time can be changed depending on the amine compound to be substituted, but it is usually carried out in the range of 8 to 120 hours. The modification was achieved by first dissolving chlorinated polypropylene (CPP) in a solvent, then heating the reaction mass, adding an amine-based reactant, and replacing the chlorine with an amine compound.

  According to the modified polymer of the present invention, an ultraviolet blocking agent (such as t-butylamine is used to generate an amine structure in a form shielded by a main chain of CPP by a modification reaction according to the structure of the amine compound to be substituted. Etc.), antioxidants (2-hydroxyaniline, etc.), antistatic agents (ethyl alcohol amine, etc.), flame retardants (diethylenetriamine, etc.), and the usual structure used for sequestering agents, the above functions are adopted. It can be used as a modifier.

  In addition, the present invention surprisingly adds substantially one component selected from CaO and MgO to the reaction mixture at the time of producing the modified body, so that the elimination reaction during the reforming is not substantial. A method that can be manufactured can be provided. Even if the reaction time is longer, it is possible to obtain a modified product in a high yield without causing a substantial side reaction, preventing discoloration of the reaction solution due to the side reaction, and an amine with respect to chlorine. Can be increased by 30 mol% or more without any other side reaction.

  The modification produced according to the present invention can be processed into a film, a sheet and a molded body, and can be imparted to the entire resin composition with the properties of the modified CPP by mixing with other resins. The resin used at this time is preferably a resin such as polypropylene, polyethylene, polypropylene copolymer, and polyethylene copolymer having excellent compatibility with CPP.

  Usually, it is difficult to produce a modified product having a chlorine substitution rate of 30 mol% or more. However, in the present invention, a modified product having a substitution rate of 40 mol% or more can be produced. Therefore, if this is mixed with other resins, excellent dyeability, mechanical strength and other properties are easily improved with the addition of small amounts. When 0.5-30% by weight modified chlorinated polypropylene and 99.9-70% by weight polyolefin are mixed, the resulting product has excellent dyeability, mechanical strength and other properties. Yes.

  In particular, in the case of polypropylene, affinity is a problem when mixed with other resins in order to impart dyeability and adhesiveness to the resin, but when using chlorinated polypropylene modified with ammonia or amine of the present invention, Affinity is very good. In addition, since the polymer backbone has the same structure, it can be substantially completely interchanged and a mixture exhibiting excellent physical properties can be provided.

  Additives such as viscosity improvers, processing oils, antioxidants, pigments, dyes, antistatic agents, flame retardants and the like may be added to the mixture of the present invention as long as necessary. Hereinafter, the present invention will be described in more detail through examples of CPP modification according to the present invention.

[Example 1]
After dissolving 5.6 g of CPP (Toyo Kasei 13-LP, elemental analysis results: C; 61.3%, H; 9.6%, Cl; 26%, N; 0%) in 100 g of toluene After adding 20 g of DETA (Diethylenetriamine), the reaction was carried out by stirring from 50 ° C. for 6 hours while stirring. After 1 hour of stirring, it was well dissolved in a very clear solution. After 6 hours of reaction, an additional 100 g of 10% sodium hydroxide solution was added and stirred vigorously. Remove all toluene and some water with a rotary evaporator to produce a soft yellow elastic solid.

  The step of adding 200 g of water to the elastic solid and washing it was carried out 5 times in succession to remove unreacted amine compound, residual alkali and salt. The remaining solvent was removed through a rotary evaporator and then vacuum-dried to produce a solid CPP. It was found that the amine compound was introduced as elemental analysis results C; 64.5%, H; 11.0%, N; 6.0%.

  10 parts by weight of the CPP-modified resin produced above and 90 parts by weight of polypropylene resin (Hyundai Petrochemical 720) were extruded from a biaxial compressor to produce pellets, and the pellets were press-molded at 185 ° C. to obtain sheets. Lumacron Yellow E3G 200% dye 0.013 parts by weight (0.013% owf) Paianil Red FD-BDY 200% dye 0.3 parts by weight (0.3% owf), Dianthus Blue FBLE 100% After adding 1.7 parts by weight (1.7% owf) of the dye and adjusting the pH to 4 to 4.5 with glacial acetic acid, 0.3 part (0.3% owf) of a dispersant (Sunsol RM-340) is added. The sheet produced in this example was added to the 3000 parts dye bath produced from the Mathis dyeing group at 60 ° C. for 30 minutes and at 130 ° C. for 2 minutes. After staining minutes, washed dyeings with distilled water at 80 ° C..

The dyed product was subjected to reduction treatment at 80 ° C. for 20 minutes in a bath added with 1 g / l of caustic soda and 2 g / l of NaHSO ₃ (sodium hydrosulfide), washed with water and dried to obtain a dyed sheet.

  As a result, the sheet of the resin composition according to the present embodiment includes a sheet manufactured from a CPP mixed with a proportion and content equal to the above-described CPP-modified resin and a polypropylene resin composition, and a sheet manufactured from a single polypropylene resin. Compared to the expected density of hue, the dyeability is very excellent, so the modified chlorinated polypropylene resin according to the present invention provides an excellent affinity effect while improving the dyeability of polyolefin resin. I understood that.

[Example 2]
The same experiment as in Example 1 was conducted except that ethyl alcohol amine was used instead of DETA, and acetonitrile was used in a solvent of 20% relative to toluene. It was found that the amine compound was introduced as elemental analysis results C; 62.7%, H; 10.3%, N; 2.2%. As a result of application to CPP modified equally, unmodified CPP and polypropylene sheets as in Example 1, it was found that the modified CPP had very good dyeability.

[Example 3]
The experiment was performed under the same conditions as in Example 1 except that morpholine was used instead of DETA. It was found that the amine compound was introduced as elemental analysis results C of the product: C; 64.5%, H; 10.2%, N; 2.6%. As a result of application to a CPP modified equally, unmodified CPP and polypropylene sheets as in Example 1, it was found that the modified CPP had very good dyeability.

[Example 4]
The experiment was performed under the same conditions as in Example 1 except that 1- (2-aminoethyl) piperazine was used instead of DETA. It was found that the amine compound was introduced as elemental analysis results C; 62.5%, H; 11.3%, N; 6.0%. As a result of application to a CPP modified equally, unmodified CPP and polypropylene sheets as in Example 1, it was found that the modified CPP had very good dyeability.

[Example 5]
To a 5 L reactor equipped with a mechanical stirrer was added 4,000 g of morpholine, 500 g of chlorinated polypropylene (Toyo Kasei 13-LP: chlorine content 26%), and 200 g of CaO at 130 ° C. for 3 days. The reaction was carried out sequentially from 5 ° C. for 5 days. The remaining morpholine was removed with a rotary evaporator, and then dissolved in 4,000 g of methyl chloride and filtered using a bag filter (1 μm). The surplus liquid was evaporated, concentrated and vacuum dried to obtain a product. As a result of elemental analysis, a modified product in which morpholine was substituted by 63.9 mol% with respect to chlorine was obtained.

  The temperature of the screw composed of 4 zones of 2 parts by weight of the polymer having the morpholine introduced therein and 98 parts by weight of polypropylene (Hyundai Petrochemical, 7620) (210 ° C, 220 ° C, 220 ° C, 210 ° C) Pellets were produced using a Sewan M-Tech extruder with a single screw adjusted in.

The manufactured pellets are put into a raw material hopper of a melt spinning machine, transferred to the supply part of the extruder by rotation of the screw, and after melting and mixing are achieved, a multifilament made up of 90 yarn streaks is made into 900 denier thick. Now spinning. Spinning was performed while maintaining the temperature of the spinner at 210 to 230 ° C. The spinning pressure was maintained at 210 kg / cm ² , and a gear pump was attached to keep the spinning pressure constant in order to obtain a uniform amount of extrusion during melt spinning. The melt-spun fiber was frozen at room temperature to obtain a fiber.

[Example 6]
To a 5 L reactor equipped with a mechanical stirrer was added 4,000 g of morpholine, 500 g of chlorinated polypropylene (Toyo Kasei 16-LP: chlorine content 32%), and 200 g of MgO at 130 ° C. for 3 days. The reaction was sequentially performed at 5 ° C. for 5 days. The remaining morpholine was removed with a rotary evaporator, and the residue was dissolved with 4,000 g of methyl chloride and filtered using a bag filter (1 μm). The surplus liquid was evaporated, concentrated and vacuum dried to obtain a product. As a result of elemental analysis, it was confirmed that a modified body in which morpholine was substituted by 71.4 mol% was obtained. Using this, a fiber was produced by spinning in the same manner as in Example 5.

[Comparative Example 1]
A fiber was produced in the same manner as in Example 2 except that polypropylene (Hyundai Petrochemical, 7620) itself was spun without a separate pellet production process.

Dyeability evaluation of Example 5, Example 6 and Comparative Example 1 (Dyeability evaluation using disperse dye)
In distilled water, 1.1 parts by weight (1.1% owf) of Lumacron Yellow ERD 100% dye, 3.4 parts by weight of Luamcron Red F3BS dye (3.4% owf), 0.03 part by weight of Dianix Blue ACE 100% dye ( 0.03% owf) and adjusted to pH 4 to 4.5 with glacial acetic acid, and then 0.3 parts by weight of dispersant (Sunsol RM-340) (0.3% owf) and 100 parts of salt The bath was dispensed.

The fibers prepared in Examples 5 and 6 and Comparative Example 1 were washed in the salt bath with distilled water and then heated to 130 ° C. for 36 minutes in a Mathis dyer at 40 ° C. After dyeing for 40 minutes, the dyed product was washed with distilled water at 80 ° C. The dyed product was subjected to reduction treatment at 80 ° C. for 20 minutes in a bath with 1 g / l of caustic soda and 2 g / l of NaHSO ₃ (sodium hydrosulfide), washed with water and dried to obtain a dyed yarn. When the stained fibers were observed visually, it was found that the fibers produced in Examples 5 and 6 were better colored than the fibers produced in Comparative Example 1.

(Evaluation of dyeability using acid dyes)
Nylon Yellow N-3RL dye 0.63 parts by weight (0.63% owf), Nyrosan Red N-2RBL dye 3.3 parts by weight (3.3% owf), Telon Blue AFN dye 0.02 parts by weight in distilled water (0.02% owf) and (NH ₄ ) ₂ SO ₄ (ammonium sulfate) 3 g / l, NEWBON MG (salt salt) 1.00 parts by weight (1.00% owf) 100 parts salt bath was dispensed.

After washing the fiber prepared in Example 2 in the salt bath with distilled water, the temperature was increased to 105 ° C. over 44 minutes using a Mathis dyeing device, and dyed from 105 ° C. for 30 minutes. The dyed product was washed with distilled water at 80 ° C. The dyed product was reduced in a bath to which caustic soda 1 g / l and NaHSO ₃ (sodium hydrosulfide) 2 g / l were added at 80 ° C. for 20 minutes, washed with water and dried to obtain a dyed yarn. When the stained fibers were observed with the eye, it was found that the fibers produced in Examples 5 and 6 were more colored than the fibers produced in Comparative Example 1.

  It has been found that a modified CPP in which chlorine is substituted with an amine compound can be produced easily and effectively by the method for modifying a CPP of the present invention. It has been found that when the modified modification is mixed with polypropylene, the affinity of the mixture is very good and the dyeability and printability are greatly increased. In addition, by designing the structure of the modified amine compound, high molecular ultraviolet rays can be obtained by using amine compounds having various functions such as an ultraviolet ray prevention function, an antistatic function and an antioxidant function according to the function of the amine compound. It has been found that it can be used as an additive for various applications such as an inhibitor, an antioxidant, a flame retardant, an antistatic agent and a sequestering agent.

Claims (10)

  Modified chlorine produced by substituting 1 to 99.9 mol% of elemental chlorine of chlorinated polypropylene having a number average molecular weight of 100 to 400,000 and a chlorine content of 1 to 75% by weight with ammonia or an amine compound A polyolefin composition comprising 0.5 to 30% by weight of polypropylene and 99.9 to 70% by weight of polyolefin.   The polyolefin composition according to claim 1, wherein 30 to 99.9 mol% of elemental chlorine in the modified chlorinated polypropylene is substituted with ammonia or an amine compound.   The polyolefin composition according to claim 1, wherein the amine compound is a primary or secondary amine compound.   The polyolefin composition according to claim 1, wherein the polyolefin includes at least one selected from the group consisting of polypropylene, polyethylene, polypropylene copolymer, and polyethylene copolymer.   The polyolefin composition according to claim 1, wherein the polyolefin is polypropylene.   It was prepared by substituting 1 to 99.9 mol% of elemental chlorine of chlorinated polypropylene having a number average molecular weight of 100 to 400,000 and a chlorine content of 1 to 75% by weight with ammonia or an amine compound. Characterized modified chlorinated polypropylene.   The modified chlorinated polypropylene according to claim 6, wherein 30 to 99.9 mol% of elemental chlorine in the chlorinated polypropylene is substituted with ammonia or an amine compound.   The modified chlorinated polypropylene according to claim 6, wherein the amine compound is a primary or secondary amine compound. Dissolving the chlorinated polypropylene in an organic solvent in a reactor and mixing the reaction mass with at least one selected from the group consisting of a primary amine and a secondary amine;
Heating the reactor to react the chlorinated polypropylene with the amine compound;
A step of adding a base, removing unreacted amine compound, residual base and salt, and recovering the modified chlorinated polypropylene from the organic layer of the organic solvent. A method for producing fluorinated polypropylene.   The method for producing a modified chlorinated polypropylene according to claim 9, wherein MgO and CaO are added in the mixing step.