CN103627087A

CN103627087A - Method for nucleating and modifying polypropylene through rare earth complex

Info

Publication number: CN103627087A
Application number: CN201310604550.XA
Authority: CN
Inventors: 肖荔人; 左冬强; 陈庆华; 黄宝铨; 陈荣国; 钱庆荣; 刘欣萍; 许兢
Original assignee: Fujian Normal University
Current assignee: Fujian Normal University
Priority date: 2013-11-25
Filing date: 2013-11-25
Publication date: 2014-03-12

Abstract

The invention discloses a method for nucleating and modifying polypropylene through a rare earth complex. The method is characterized by comprising the steps of firstly uniformly mixing 100% of polypropylene and 0.2-4.0% of maleic acid lanthanum (MALa) by weight, then fusing and internally mixing uniformly, cooling and curing so as to obtain the modified polypropylene. The invention also discloses a direct sedimentation method for preparing lanthanum maleate. The method is characterized by comprising the steps of mixing a hydrogen maleate salt solution with an inorganic lanthanum salt solution according to certain proportion, regulating pH to be 4.0-7.0 with aqueous alkali at 30-80 DEG C, reacting completely so as to generate precipitate, and filtering, purifying and drying the precipitate so as to obtain the maleic acid lanthanum. According to the method, MALa is added for modifying PP (polypropylene), so that the nonisothermal crystallization peak temperatures respectively rise toward high temperature, and the peak width at half height of the crystallization peak is narrowed. A DSC (differential scanning calorimetry) test result shows that the MALa is an effective nucleating and modifying agent for the PP and can improve the crystallization property of the PP.

Description

A kind of method of rare earth compounding nucleation modified polypropene

Technical field

The invention belongs to chemosynthesis and Application Areas, be specifically related to a kind of preparation of rare earth compounding and the application of nucleation modified polypropene thereof.

Background technology

Title complex is a subclass larger in compound, is widely used in daily life, industrial production and life science, and development is in the last few years especially rapid.The method of preparing title complex mainly contains direct method, solid-phase synthesis and component exchange synthesis method etc.Direct method is directly to carry out the synthetic method of coordination by central ion and part, for central ion easily with part generation coordination and resultant easily the reaction separated with substrate be applicable to using this method.Solid state reaction rule is the heterogeneous reaction between metal ion and part, and in this method, the fusing point of part is generally lower, and during reaction, part is molten state.Component exchange synthesis method, is mainly the difference of utilizing complexes stability, metal ion or part in a kind of title complex is replaced, thereby generate new title complex.Direct synthesis step is simple, and separating-purifying is convenient, is easy to realize scale operation.

Polypropylene (PP) is one of five large general-purpose plastics, and it has abundant raw material, cost is low, mechanical property is excellent and the advantage such as easy-formation processing, in productive life field, is widely applied.But PP has the shortcomings such as low temperature brittleness is large, heat-drawn wire is low, easy contraction, so its application at extreme environment is very limited.To the modification key of PP, be the regulation and control to its molecular chain regularity, spherulite size, nucleater modified is method relatively simple in polypropylene modification.Conventional polypropylene nucleater be generally fusing point higher than the fines of PP Tc, comprising: (1) inorganics nucleator, as calcium carbonate, calcium oxide, kaolin, talcum powder, mica, carbon black, mineral dye etc.; (2) organism nucleator, replaces the mixture class nucleator of phosphoric acid salt, phosphate metal salt, carboxylic acid metal's salt, rosin based and the second main group metal salt and dicarboxylic acid as aromatic ring structure divides subclass, glucitols, aryl.Organism nucleator is the developing direction of high-performance PP nucleator from now on.

Summary of the invention

The object of this invention is to provide a kind of method of rare earth compounding nucleation modified polypropene, and by this title complex as the novel nucleator of PP, for research and development high-performance, PP becomes nuclear technique to offer reference.

For achieving the above object, the technical solution used in the present invention is:

The method of a kind of rare earth compounding nucleation MODIFIED PP of the present invention, is characterized in that: (1) usings rare earth compounding as the nucleator of PP, and described rare earth compounding is maleic acid lanthanum (MALa); (2) rare earth compounding accounts for the 0.2-4.0% of PP gross weight; (3) concrete steps of rare earth compounding nucleation MODIFIED PP are, first dried PP, MALa are mixed in high-speed kneading machine, and then, after melting banburying evenly, cooling curing is sealed up for safekeeping.Described melting banburying is preferable at 170-200 ℃ of temperature to be carried out.

Described rare earth compounding maleic acid lanthanum (MALa) can adopt prior art preparation maybe can prepare by following the inventive method: maleic acid hydrogen salt solution and inorganic lanthanum salts solution are mixed by a certain percentage, in temperature, be at 30-80 ℃, with alkaline solution, regulate pH=4.0-7.0, fully reaction generates precipitation, precipitation after filtration, purifying and dry can obtaining.

The preparation method of rare earth compounding of the present invention, is characterized in that the concentration of maleic acid hydrogen salt solution is preferably 0.1-0.6mol/L, and the concentration of inorganic lanthanum salts solution is preferably 0.05-0.5mol/L.

The preparation method of rare earth compounding of the present invention, is characterized in that the mol ratio of inorganic lanthanum salt and maleic acid hydrogen salt is preferably 1:1.5-4.

The preparation method of rare earth compounding of the present invention, is characterized in that described maleic acid hydrogen salt is preferably ammonium salt, sodium salt or the sylvite of maleic acid hydrogen root.

The preparation method of rare earth compounding of the present invention, is characterized in that described inorganic lanthanum salt is preferably Lanthanum trichloride or lanthanum nitrate.

The preparation method of rare earth compounding of the present invention, is characterized in that described alkaline solution regulates pH=4.0-7.0 preferably by ammoniacal liquor, sodium hydroxide or potassium hydroxide solution, to regulate.

Advantage of the present invention is: 1) utilize direct precipitation method, one step is implemented to synthesize rare earth compounding PP to nucleogenesis, this building-up process mild condition, required solvent is distilled water, low in the pollution of the environment, and preparation technology is simple, be easy to scale operation, may for realizing that the widespread use of rare earth compounding class nucleator in polypropylene product provide.2), for pure PP, the present invention adds MALa MODIFIED PP moves respectively its nonisothermal crystallization peak temperature to high temperature direction, and the peak width at half height of peak crystallization all narrows down.DSC test result shows that MALa is the effective nucleation properties-correcting agent of PP, can improve the crystal property of PP.

Accompanying drawing explanation

Fig. 1 is nonisothermal crystallization graphic representation, and wherein A is the nonisothermal crystallization curve of comparative example 1 pure PP, and B, C, D curve are respectively the nonisothermal crystallization curve of embodiment 5, embodiment 6, embodiment 7 gained samples.

Embodiment

By specific embodiment, the present invention is done to statement more in detail below, rather than limit the invention.

One, MALa's is synthetic

Embodiment 1

To adding mol ratio in container, be maleic acid hydrogen ammonium solution (0.1mol/L) and the lanthanum chloride solution (0.05mol/L) of 4:1, in temperature, be under the condition of 30 ℃, with ammoniacal liquor, regulate pH=4.0, stirring reaction generates precipitation, precipitation is with after the abundant washing and filtering of distilled water, at 90 ℃, vacuum-drying 18h, obtains MALa, productive rate 11%.

Embodiment 2

To adding mol ratio in container, be maleic acid hydrogen sodium solution (0.3mol/L) and the lanthanum nitrate hexahydrate (0.1mol/L) of 3:1, in temperature, be under the condition of 50 ℃, with sodium hydroxide solution, regulate pH=5.5, stirring reaction generates precipitation, precipitation is with after the abundant washing and filtering of distilled water, at 90 ℃, vacuum-drying 18h, obtains MALa, productive rate 42%.

Embodiment 3

To adding mol ratio in container, be maleic acid hydrogen potassium solution (0.5mol/L) and the lanthanum chloride solution (0.3mol/L) of 1.8:1, in temperature, be under the condition of 60 ℃, with potassium hydroxide solution, regulate pH=6.0, stirring reaction generates precipitation, precipitation is with after the abundant washing and filtering of distilled water, at 90 ℃, vacuum-drying 18h, obtains MALa, productive rate 63%.

Embodiment 4

To adding mol ratio in container, be maleic acid hydrogen ammonium solution (0.6mol/L) and the lanthanum nitrate hexahydrate (0.5mol/L) of 1.5:1, in temperature, be under the condition of 80 ℃, with ammoniacal liquor, regulate pH=7.0, stirring reaction generates precipitation, precipitation is with after the abundant washing and filtering of distilled water, at 90 ℃, vacuum-drying 18h, obtains MALa, productive rate 46%.

Embodiment 1-4 gained MALa all has following character: be white powder, be insoluble in the nonpolar or weak polar solvents such as dimethylbenzene, ether, hexanaphthene, ethanol, acetone, be slightly soluble in DMF and methyl-sulphoxide isopolarity solvent, can be dissolved in the carboxylic acids such as pyruvic acid, acetic acid.

Two, MALa nucleation modified polypropene

Embodiment 5

PP dry 10h in the loft drier of 80 ℃ is standby, get 5 kilograms of PP and 0.01 kilogram of MALa, and their high-speed kneadings mixed, then in 185 ℃ of melting banburyings, to system mixing evenly after, cooling curing obtains rare earth compounding nucleation modified polypropene sample.

Embodiment 6

PP dry 10h in the loft drier of 80 ℃ is standby, get 5 kilograms of PP and 0.1 kilogram of MALa, and their high-speed kneadings mixed, then in 170 ℃ of melting banburyings, to system mixing evenly after, cooling curing obtains rare earth compounding nucleation modified polypropene sample.

Embodiment 7

PP dry 10h in the loft drier of 80 ℃ is standby, get 5 kilograms of PP and 0.2 kilogram of MALa, and their high-speed kneadings mixed, then in 200 ℃ of melting banburyings, to system mixing evenly after, cooling curing obtains rare earth compounding nucleation modified polypropene sample.

Comparative example 1

PP dry 10h in the loft drier of 80 ℃ is standby, gets 5 kilograms of PP and by its high-speed kneading, then in 185 ℃ of melting banburyings, to system evenly after, cooling curing obtains virgin pp control sample.

Get respectively embodiment 5-7 and comparative example 1 gained sample 5mg, make DSC differential scanning, carry out nonisothermal crystallization tracing analysis, concrete steps are: by taken dry sample, put into aluminium matter crucible, first the speed with 10 ℃/min is warming up to 190 ℃, balance 3 min; Then the speed with 10 ℃/min is cooled to 30 ℃, balance 3 min; Finally the speed with 10 ℃/min is warming up to 190 ℃, and as shown in Figure 1, wherein A is the nonisothermal crystallization curve of the pure PP sample of comparative example 1 to result, and B, C, D curve are respectively the nonisothermal crystallization curve of embodiment 5, embodiment 6, embodiment 7 gained samples.As shown in Figure 1, for pure PP, its nonisothermal crystallization peak temperature of MODIFIED PP that adds 0.2,2.0,4.0% MALa moves 2.1,4.2 to high temperature direction respectively, and 2.8 ℃, and the peak width at half height of peak crystallization all narrows down.DSC test result shows that MALa is the effective nucleation properties-correcting agent of PP, can improve the crystal property of PP.

Claims

1. a method for rare earth compounding nucleation modified polypropene, is characterized in that:

(1) by weight percentage, rare earth compounding accounts for the 0.2-4.0% of polypropylene (PP), and described rare earth compounding is maleic acid lanthanum (MALa);

(2) first polypropylene (PP), rare earth compounding are mixed, then after melting banburying evenly cooling curing.

2. a kind of method of rare earth compounding nucleation modified polypropene according to claim 1, is characterized in that described melting banburying refers to the melting banburying of carrying out at 170-200 ℃ of temperature.

3. the method for a kind of rare earth compounding nucleation modified polypropene according to claim 1, is characterized in that described maleic acid lanthanum is made by direct precipitation method.

4. the method for a kind of rare earth compounding nucleation modified polypropene according to claim 3, it is characterized in that: maleic acid hydrogen salt solution and inorganic lanthanum salts solution are mixed by a certain percentage, in temperature, be at 30-80 ℃, with alkaline solution, regulate pH=4.0-7.0, fully reaction generates precipitation, precipitation after filtration, purifying and dryly can obtain maleic acid lanthanum (MALa).

5. the method for a kind of rare earth compounding nucleation modified polypropene according to claim 4, is characterized in that the concentration of described maleic acid hydrogen salt solution is 0.1-0.6mol/L, and the concentration of inorganic lanthanum salts solution is 0.05-0.5mol/L.

6. the method for a kind of rare earth compounding nucleation modified polypropene according to claim 4, is characterized in that the described mol ratio that refers to by a certain percentage inorganic lanthanum salt and maleic acid hydrogen salt is 1:1.5-4.

7. the method for a kind of rare earth compounding nucleation modified polypropene according to claim 4, is characterized in that, described alkaline solution adopts ammoniacal liquor, sodium hydroxide or potassium hydroxide solution.

8. according to the method for the arbitrary described a kind of rare earth compounding nucleation modified polypropene of claim 3-7, it is characterized in that described maleic acid hydrogen salt is ammonium salt, sodium salt or the sylvite of maleic acid hydrogen root.

9. according to the method for the arbitrary described a kind of rare earth compounding nucleation modified polypropene of claim 3-7, it is characterized in that described inorganic lanthanum salt is Lanthanum trichloride or lanthanum nitrate.