JP2002538255A - Nucleating agents for crystalline thermoplastic polymers - Google Patents

Abstract

  (57) [Summary] Disclosed are nucleating agents for crystalline thermoplastic polymers, particularly compositions comprising a thermostable nucleating agent that includes moieties capable of forming intermolecular hydrogen bonds and uses thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to nucleating agents for crystalline thermoplastic polymers, in particular compositions comprising moieties capable of forming intermolecular hydrogen bonds and comprising a nucleating agent which is thermally stable, and methods of use thereof.

[0002]

[Prior art]

Nucleating and clarifying agents are used to reduce processing cycle times or to provide improved physicochemical properties such as various optical and mechanical properties, as well as to reduce mold shrinkage, And is commonly used in industrial practice. A thorough list of nucleating and clarifying agents can be found, for example, in US Pat. No. 3,367,
No. 926, Plastics Additives Handbook (
4th Ed, Hanser, Munich, 1990, p 863). Representative nucleating agents that are well known in the art are metal salts of aliphatic or aromatic carboxylic acids, aromatic salts, metal salts of aromatic phosphorus compounds, quinacridone,
Pigments, polymers with melting points, highly branched polymers with dendritic branches (dendrimers), and chalk, gypsum, clay, kaolin, mica, talc and silicates and combinations thereof (US Pat. No. 5,278,216) Specification, U.S. Patent No. 5,137,973, U.S. Patent No. 4,749,736
No. 4,694,064, U.S. Pat. No. 4,338,2
No. 28, U.S. Pat. No. 3,852,237; U. Johnsen and K.-H.
Moos, Angew. Makromol. Chem. Vol. 74, p. 1 (1978); A. Wlochowicz and M. Eder, Angew. Makromol. Chem. Vol. 171, p. 79 (1989); HN Beck, J. Appl.
. Polym. Sci., Vol. 11, p. 673 (1967); FLBinsbergen, Polymer, vol. 11, p. 25
3 (1970)). Furthermore, German Offenlegungsschrift 1951 632 discloses the use of solid, crystalline aromatic carboximide-diphthalimides and N-substituted aromatic carboximide-diphthalimides.

[0003] More recently developed nucleating and clarifying agents have been dissolved in polymer melts (R.
Schlotmann and R. Walker, Kunstoffe, vol. 86, p. 1002 (1996)) have been found to be effective in improving the dispersion of these additives. The best known are the compounds based on D-sorbitol, which belong to the family of common compounds of carbohydrates which are defined as polyhydroxyaldehydes, polyhydroxyketones or compounds capable of hydrolyzing them. (RTMor
rion and Robert Neilson Boyd, Organic Chemistry, 2nd Ed., (Allyn and Bac
on, Inc., Boston, 1966, p. 983). 1,3-2,4-di (benzylidene) -D
-Sorbitol (Millad 3905, Milliken Chemical Co.); 1,3-2,4-di (
4-trilidene) -D-sorbitol (Millad 3490, Milliken Chemical Co.);
1,3-2,4-di (4-ethylbenzylidene) -D-sorbitol (N-4, Mits
There are several commercial nucleating agents based on sorbitol, including ui petrochemical industries, Ltd.). U.S. Pat. No. 5,574,174; U.S. Pat.
No. 98,484; and International Publication WO 95/13317 disclose methods of making and using sorbitol derivatives. U.S. Pat. No. 4,294,7
No. 47 discloses polyalcohol acetals of benzaldehyde and its derivatives. U.S. Pat. No. 5,216,051 discloses triacetal polyol compounds. The use of dibenzylidene sorbitol (U.S. Pat. No. 4,016,118) in combination with a phenyl phosphate compound is disclosed in U.S. Pat. No. 4,585,817. Despite widespread commercial application, there are a number of difficulties with carbohydrate-based compounds as nucleating and clarifying agents. First, the production and purification of sorbitol-based nucleating agents is cumbersome. Another well-known difficulty with the use of sorbitol clarifiers, for example, in polyolefin resins is the formation of small bubbles which appear as white spots in products made from these resins (US Pat. No. 5,198,484). book).
Finally, among other disadvantages, unfortunately, this class of materials has an inherently unsatisfactory temperature stability.

[0004] Thus, it is useful to enhance the processability and physicochemical properties of thermoplastic polymers,
There is a continuing need for effective nucleating agents.

[0005] Certain organic compounds containing moieties capable of forming intermolecular hydrogen bonds are effective nucleating agents for crystalline thermoplastic polymers, provided that these compounds are also compatible with thermoplastic polymers. It has now been found that it also contains soluble parts.

[0006]

[Means for Solving the Problems]

Accordingly, the present invention provides a composition comprising (i) one or more nucleating agents comprising moieties capable of forming intermolecular hydrogen bonds, and (ii) one or more crystalline thermoplastic polymers, which are of the conventional type. And additives that can optionally include additives and fillers. In particular, the present invention relates to (i) a crystalline thermoplastic polymer and (ii) one or more,
formula

Embedded image (Where x represents an integer of 2 to 7; y represents an integer of 0 to 4; z represents an integer of 0 to 4; the sum of x + y + z is equal to an integer of 3 to 7 and m is 1 to 3 And A is a center covalently bonded to moieties B, B 'or X', or a combination thereof; said moieties B and B 'may form one or more intermolecular hydrogen bonds Wherein the moieties X and X 'are compatible with the crystalline thermoplastic polymer; X is covalently bonded to B.)

Another embodiment of the present invention relates to a composition comprising a crystalline thermosetting polymer and a nucleating agent including a portion capable of forming an intermolecular hydrogen bond and a portion compatible with the crystalline thermoplastic polymer.

[0008] Another aspect of the present invention is that, upon cooling from the melt, their peak temperature of crystallization is neat, ie, less than the peak temperature of crystallization of the thermoplastic polymer without the nucleating agent. Also comprising a crystalline thermoplastic polymer and a nucleating agent, characterized in that the composition is at least above about 3 ° C.

[0009] Yet another embodiment is that, after cooling from the melt, the spherulites of the crystallized polymer are no more than 50% of the spherulites of the as-crystallized thermoplastic polymer. A composition comprising a crystalline thermoplastic polymer and a nucleating agent.

[0010] Yet another aspect of the present invention is a composition comprising a crystalline thermoplastic polymer and one or more nucleating agents that has reduced haze when compared to an intact crystallized thermoplastic polymer. About.

[0011] Yet another aspect of the present invention relates to a composition comprising a crystalline thermoplastic polymer having enhanced thermal stability and one or more nucleating agents.

Another aspect of the present invention is a novel method for increasing the rate of crystallization of a melt of a crystalline thermoplastic polymer, comprising adding an effective amount of the nucleating agent of the present invention to the melt. And products produced according to the novel process.

Yet another object of the present invention is to provide an article made from a crystalline thermoplastic polymer comprising an effective amount of the nucleating agent of the present invention.

An advantage resulting from the present invention is a reduction in the processing time of the crystalline thermoplastic polymer. Further, the polymers made in accordance with the present invention are characterized by relatively improved thermal, optical and / or mechanical properties. Other objects, advantages and novel features of the invention will be apparent from the description which follows, and in part will become apparent to those skilled in the art upon a consideration of the following, or Can be learned by practice. The objects and advantages of the invention will be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

The present invention will be more fully understood and further advantages will become apparent in the following detailed description of the invention and the accompanying drawings. FIG. 1 is an optical micrograph of an isotactic polypropylene film containing no nucleating agent. The film was compression molded at 210 ° C, then cooled at a rate of 10 ° C / min and crystallized at 104 ° C. Magnification 120 times. FIG. 2 shows tris [3,4-bis (decyloxy) phenylene-carbonylimino-1,4-phenylene] amine (hereinafter also referred to as compound I-1 in Table 1) as a nucleating agent of 0.75% by weight. 1 is an optical micrograph of a film of isotactic polypropylene containing. The film was compression molded at 210 ° C, then cooled at a rate of 10 ° C / min and crystallized at 104 ° C. Magnification 120 times. FIG. 3 shows the enhanced thermostability of the compounds according to the invention, thermogravimetry performed on compounds I-5 (3) and I-7 (2) and Millad 3988 (1) in Table 1 under nitrogen. 5 shows an analysis (TGA) record.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION

 Nucleating agent The nucleating agent for the crystalline thermoplastic polymer according to the present invention has the following general scheme

Embedded image (Where x represents an integer of 2 to 7; y represents an integer of 0 to 4; z represents an integer of 0 to 4; the sum of x + y + z is equal to an integer of 3 to 7 and m is 1 to 3 Represents an integer.).

In formula (I), A is a center covalently bonded to moiety B, B ′ or X ′, or a combination thereof; said moieties B and B ′ may have one or more intermolecular hydrogen bonds. Consists of at least one unit that can be formed; the moieties X and X 'are compatible with said crystalline thermoplastic polymer; X is covalently linked to B. The role of the central part A is to connect the parts B, B 'or X' and combinations thereof, which is a means which is advantageous for the formation of the structure which causes the nucleation of the crystalline thermoplastic polymer. provide.

A nucleating agent for a preferred crystalline thermoplastic polymer according to the present invention is represented by the following formula (1):
x represents an integer of 3 to 6; y represents an integer of 0 to 3; z represents an integer of 0 to 2; the sum of x + y + z is equal to an integer of 3 to 7; m represents an integer of 1 or 2 Things. Among the preferred nucleating agents according to the present invention, more preferably, in the formula (1), x represents an integer of 3 to 4; y represents an integer of 0 to 2; z represents an integer of 0 or 1; The sum of x + y + z is equal to an integer of 3 to 6, and m represents an integer of 1 or 2. The most preferred nucleating agent for the crystalline thermoplastic polymer according to the invention is represented by the scheme (1)
Wherein x represents 3; y represents an integer of 0 to 2; z represents an integer of 0 or 1; and the sum of x + y + z is equal to an integer of 3 to 6 and m represents an integer of 1 or 2 is there.

Illustrative examples of the moiety useful as the center A of the nucleating agent according to the present invention are a carbon atom, a nitrogen atom, a phosphorus atom, a boron atom and a silicon atom, which are linked to one or more aromatic, aliphatic, With or without cyclic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone linkages, and combinations thereof; unsubstituted or substituted, monocyclic and fused, , 5, 6 or 7 membered aromatic and cycloaliphatic carbocycles, which may include one or more of heteroatoms such as nitrogen, sulfur and oxygen and combinations thereof;
And one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone linkages attached thereto and which may have no combination thereof.

Preferred moieties are carbon and nitrogen atoms and one or more aromatic, cycloaliphatic or — (CH ₂ ) _{p -bonds} linked to them, wherein p represents 1 or 2. .
), And with or without combinations thereof; unsubstituted or substituted, monocyclic and fused, 5- or 6-membered aromatic or cycloaliphatic carbocyclic rings, May comprise one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, and one or more aromatic, cycloaliphatic or — (CH ₂ ) _p -bonds linked thereto (Wherein p represents 1 or 2), and a ring with or without a combination thereof.

More preferred of said preferred moieties are carbon and nitrogen atoms having one or more aromatic or cycloaliphatic linkages attached thereto, and combinations thereof; unsubstituted Or substituted, monocyclic and fused 6-membered aromatic or cycloaliphatic carbocycles, wherein the rings may contain one or more nitrogen atoms and one or more aromatic , An alicyclic or-(CH ₂ ) _p -bond (wherein p
Represents 1 or 2. ), As well as rings with or without combinations thereof.

The most preferred of the more preferred moieties useful as center A of the nucleating agent according to the present invention are those having the following structure, which may be substituted or unsubstituted:

Embedded image

The nucleating agent moieties B and B ′ according to the invention are moieties capable of forming one or more intermolecular hydrogen bonds between the nucleating agent molecules of which they are a part. In this specification,
Hydrogen bonds are electrostatic interactions between hydrogen atoms and, to a lesser extent, chlorine and sulfur atoms, which have a strong electronegativity, such as small atomic radii, for example, fluorine, oxygen and nitrogen atoms. (Lehrbuch der Organischen Chemie, H. Beyer; Hirzel, Stuttgart, 1976, p. 105, 106)
. The function of the moieties B and B 'is to cause and promote and stabilize the formation of an advantageous structure for the crystalline thermoplastic polymer nucleating agent.

Examples of moiety B are the same or different in each case, esters, thioesters,
Ethers, thioethers, ketones, secondary and tertiary amines, amides, imides, imines, azo, azoxy, ureas, urethanes, thiourethanes and sulfonamides.

Preferred moieties B, which in each case may be the same or different, consist of one or more units selected from amides, imides, imines, ureas, urethanes, thiourethanes, sulphonamides and the like. . Among the preferred moieties, the more preferred moieties B, which in each case may be the same or different, consist of one or more units selected from amides, imides and sulfonamides. Particularly preferred are those consisting of amide units.

Examples of preferred moieties B ′, which in each case may be the same or different, are moieties consisting of acids such as carboxylic acids, sulfonic acids, alcohols, phenols, thiols, amines, acetamido, cyano groups, hydrazines and the like. is there.

The nucleating agent for the crystalline thermoplastic polymer according to the present invention is such that its function is compatible with the crystalline thermoplastic polymer and helps to disperse the nucleating agent in the crystalline thermoplastic polymer. Includes portions X and X '. Therefore, the choice of particular chemical properties of moieties X and X 'depends on the choice of crystalline thermoplastic polymer. Generally, a nucleating agent comprising the polar characteristic moieties X and X 'is used in combination with a more polar thermoplastic polymer containing polar groups. Nucleating agents containing less polar moieties X and X 'are used in combination with less polar thermoplastic polymers with little or no polar groups. In general, the moieties X and X ′ may be chiral or non-chiral, and in each case the same or different: H, a linear or branched alkyl group each having from 1 to 20 carbon atoms, Alkenyl, alkoxy, alkanoyl, alkylthio, alkylthioalkyl; linear or branched alkylaryl, arylalkyl, alkylsulfinyl, alkyl or alkoxy each having 1 to 20 carbon atoms Alkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxylic acid; 1 to 20 carbon atoms substituted by one or more of sulfonic acid, carboxylic acid, halogen atom, nitro group, cyano group, diazo group, or epoxy moiety An alkyl group having one or more substituted Or unsubstituted monocyclic and fused 3,4,5
, 6- or 7-membered aromatic and cycloaliphatic carbocycles which can contain one or more heteroatoms consisting of nitrogen, sulfur, sulfinyl, sulfonyl or oxygen, such as thiophenyl, pyrrolyl, A ring that can include furanyl, pyridinyl, or a combination thereof; selected from the group consisting of:

In a most preferred embodiment of the present invention, the nucleating agent consists of those selected from the following groups:

[Table 1]

[0029]

[Table 2]

As an illustration of its use, as well as for further guidance, the above structure is also shown schematically (
It is also given by the notation of 1). Preferably, the nucleating agent is used in combination with a weak or non-polar crystalline thermoplastic polymer such as isotactic polypropylene and its copolymers.

The nucleating agents according to the invention have thermal properties, such as melting temperatures, which can vary widely depending on the exact structure of the nucleating agent. For practical use according to the invention, the nucleating agent is preferably solidified at a temperature or temperature range at which the molten or dissolved nucleating agent forms molecular aggregates or solids in the absence of the nucleating agent of the invention. Having a temperature equal to or higher than the temperature at which the crystalline thermoplastic polymer crystallizes.

Particularly excluded from the invention are those based on carbohydrates or structures based on carbohydrate units, such as sorbitol or its derivatives. Such structures are generally well known and have the disadvantage of limited thermal stability, and therefore crystalline heat with a high melting or softening point, which generally requires high processing temperatures. It is of limited use as a nucleating or clarifying agent for plastic polymers. In comparison, compositions according to the invention have a high decomposition temperature, typically above 230 ° C.

Some of the compounds represented by the general structural formula (1) have been disclosed in the prior art. For example, Yasuda et al. Describe the preparation of N, N ', N "-tristearyl trimesamide (Chem. Letters, vol. 7, p. 575 (1996)). ,
4 ', 4 "-tris (stearoylamino) -triphenylamine (Y.Y.
asuda, Y. Takebe, M, Fukumoto, H. Inada and Y, Shirota, Adv. Mat., vol. 8,
p740 (1996)). However, the use of such compounds in combination with crystalline thermoplastic polymers, especially their use as nucleating agents for crystalline thermoplastic polymers, has not been disclosed or proposed.

[0034] The amount of nucleating agent according to the present invention added to the crystalline thermoplastic polymer is an "effective amount". As used herein, an "effective amount" is an amount sufficient to increase the crystallization peak temperature of the polymer by at least 3 ° C. Such an amount will usually correspond to the amount of a conventional nucleating agent. In a preferred embodiment of the invention, the amount of nucleating agent used is from about 0.005% to about 20% by weight, based on the total amount of polymer in the composition, and in a particularly preferred embodiment, based on the aforementioned base. From about 0.005% to about 10% by weight. Most preferred among these particularly preferred embodiments are those in which the amount of nucleating agent used is from about 0.005% to about 5% by weight, based on the total amount of polymer in the composition according to the invention. .

The composition according to the present invention is characterized in that the size of the polymer spherulites of the thermoplastic polymer composition is typically less than the size of the spherulites of the intact crystallized thermoplastic polymer without the nucleating agent of the invention. 50% or less, so that the former is characterized by lower haze compared to the latter.

Crystalline Thermoplastic Polymers The thermoplastic polymers for use in the practice of the present invention are very diverse and are particularly chosen for the end use of the product comprising the composition of the present invention. As such, crystalline thermoplastic polymers useful in the present invention include all thermoplastic polymers and copolymers commonly used in plastic products. Useful crystalline thermoplastic homopolymers or copolymers are polyolefins such as polyethylene, stereoregular polypropylene and ethylene-propylene copolymer, stereoregular polystyrene, polynorbornene, polyisobutylene, poly (1-butene), poly (3-methyl-
1-butene), poly (1-pentene), poly (4-methyl-1-pentene), poly (1-hexene), poly (5-methyl-1-hexene), poly (2-methylstyrene), poly (2-methylstyrene) (4-methoxystyrene) and the like, and their copolymers, aromatic or alicyclic polyoxides such as polyoxymethylene, poly (ethylene oxide), poly (tetra-methylene oxide), poly (propylene oxide),
Polyphenylene oxide, polysulfides, such as poly (propylene sulfide), and their copolymers, aromatic, cycloaliphatic and aromatic-cycloaliphatic polyamides, such as nylon 6, nylon 12, nylon 6.6, nylon 6.10
And aromatic, cycloaliphatic and aromatic-aliphatic polyesters such as poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene naphthalate), polyvinyl (vinyl alcohol) and polycarbonate.

[0037] In addition to the above essential components, the composition according to the invention can optionally comprise one or more other components, which are additives usually used with thermoplastics. Such optional components are fillers, reinforcing components, plasticizers, dispersing aids, impact modifiers, chain extenders, colorants, release agents, metal deactivators, antioxidants, light stabilizers, Contains lubricants, antistatics, flame retardants, optical brighteners, biostabilizers, chemical blowing agents, crosslinkers, and other nucleating agents. These optional ingredients are well known to those skilled in the art and are described in standard textbooks and handbooks such as the Plastic Additives Handbook (4th edition, Hanser, Munich, 1990).

The compositions according to the present invention can be prepared by blending or mixing the essential and other optional ingredients as uniformly as possible using conventional compounding means. Suitable compounding means, such as extrusion, batch blending, etc., are well known in the art and will not be described in detail herein. Also, all or a portion of the various components can be masterbatch or pre-blended in the melt or a suitably selected solvent.

The compositions according to the invention can be used to produce films, fibers, containers, paints, parts with improved clarity and mechanical properties and with reduced cycle times.
), Membranes, rods, tubes, fabrics, foams and the like. Accordingly, the present invention is further a method for increasing the rate of crystallization of a crystalline thermoplastic polymer, comprising:
Obtaining a shaped article by addition of one or more nucleating agents in an amount of about 0.001% to about 20% by weight.

In a particular embodiment, the composition of the present invention consists of the following combinations: one or more polyolefins, such as polyethylene, stereoregular polypropylene and ethylene-propylene copolymer; and one or more compounds of the formula (1) Wherein the nucleus A is a single atom selected from the group consisting of a nitrogen atom and a phosphorus atom; or A is an unsubstituted or substituted, monocyclic or fused Or a 5- or 6-membered heterocyclic aromatic or non-aromatic ring, wherein the ring comprises a carbon atom and one or more atoms such as a nitrogen, sulfur or oxygen atom, or a combination thereof. And ii) a moiety B, which in each case is the same and consists of an amide or urea; A moiety B consisting of at least one moiety selected from the group consisting of urea and urea; or a moiety consisting of at least two ureas which are not the same in each case and at least two ureas, and esters and amides B, iii) x represents 3; y represents an integer 0 or 1; z represents an integer 0 or 1; m represents an integer 1 or 2.

[0041]

【Example】

The compound represented by the formula (1) can be obtained by a known method under known reaction conditions (eg, Georg Thieme,
It can be prepared by methods known per se, such as those described in Stuttgart's Houben-Weyl, standard work such as Methoden der Organischen Chemie. In carrying out these reactions, it is also possible to employ the advantages of variants which are well-known per se and which are not specifically mentioned here. The starting materials can also be formed in situ, if desired, without isolating them from the reaction mixture, but immediately allowing them to further react to the compound of formula (1).

The compounds according to the present invention are illustrated by the following examples. m. p. = Indicates the melting points of various compounds. In the foregoing and following descriptions, percentages are by weight and all temperatures are given in degrees Celsius, ° C. "Conventional workup" means adding water, filtering the precipitate, extracting with an organic solvent, and / or purifying the product by crystallization and / or chromatography.

Example A 4.05 g (10.2 mmol) of 3,4-bis (octyloxy) benzoic acid chloride and 0.5 g of dry LiCl are placed under an inert atmosphere in 50 ml of dry NM.
Added to P and 5 ml of dry pyridine and cooled to 5 ° C. 0.99 g (3.4 mmol) of tris (4-aminophenylene) amine was added. The reaction mixture was
Heated to 5 ° C. After 2 hours, the reaction mixture was added to 500 ml of distilled water. The precipitate was removed by filtration. Tris [3,4-bis (octyloxy) phenylene-carbonylimino-1,4-phenylene] amine (Table I,
No. I-7) was obtained. m. p. 229 ° C.

The following compounds can be prepared analogously. Tris [3,4-bis (decyloxy) phenylene-carbonylimino-1,4
-Phenylene] amine (compound I-1): m.p. p. 211 ° C. Tris [3,4-bis (nonyloxy) phenylene-carbonylimino-1,4
-Phenylene] amine (compound I-2): m.p. p. 219 ° C. Tris [3,4,5-tris (ethyloxy) phenylene-carbonylimino-
1,4-phenylene] amine (compound I-3): m.p. p. 258 ° C. Tris [cyclopentyl-carbonylimino-1,4-phenylene] amine (Compound I-4): m.p. p. 270 ° C. Tris [cyclohexyl-carbonylimino-1,4-phenylene] amine (Compound I-5): m.p. p. 276 ° C. Tris [3-cyclohexylpropylene-carbonylimino-1,4-phenylene] amine (Compound I-6): m.p. p. 238 ° C. Tris [cyclohexylmethylene-carbonylimino-1,4-phenylene] amine (Compound I-8): m.p. p. 335 ° C. Tris [phenylcarbonylimino-1,4-phenylene] amine (compound I-
9): m. p. 198 ° C.

Example B 1.76 g (12.0 mmol) of cyclohexanecarboxylic acid chloride and 0.5 g of dry LiCl were placed under an inert atmosphere in 50 ml of dry NMP and 5 ml
And cooled to 5 ° C. 0.40 g (3.0 mmol) of 2,
4,6-Triaminotoluene was added. The reaction mixture was heated to 75C. After 2 hours, the reaction mixture was added to 500 ml of distilled water. The precipitate was removed by filtration. Conventional workup gave 2,4,6- (cyclohexanecarbonylimino) toluene (Table I, No. II-7). m. p. 199 ° C.

Example C 1.75 g (10.0 mmol) of 4-cyclohexylphenylamine and 0.5 g of dry LiCl were placed under an inert atmosphere in 50 ml of dry NMP and 5 ml
And cooled to 5 ° C. 0.80 g (3.0 mmol) of 1,
3,5-benzenetricarboxylic acid chloride was added. The reaction mixture was heated to 75C. After 2 hours, the reaction mixture was added to 500 ml of distilled water. The precipitate was removed by filtration. 1,3,5- (cyclohexyl-1,4-
(Phenyleneiminocarbonyl) benzene (Table I, No. III-2) was obtained. m
. p. 317 ° C.

The following compounds were prepared similarly. 1,3,5- (4-t-butylphenyleneiminocarbonyl) benzene (compound III-1), m.p. p. 358 [deg.] C; 1,3,5- (4-hexyloxyphenyleneiminocarbonyl) benzene (Compound III-3), m.p. p. 80 ° C; 1,3,5- (n-butyliminocarbonyl) benzene (compound III-4);
m. p. 219 ° C; 1,3,5- (phenyliminocarbonyl) benzene (compound III-5), m
. p. 311 ° C .;

Example D 3.00 g (10.3 mmol) of tris (4-aminophenylene) amine and 0.1 g of dry LiCl were added under an inert atmosphere to 70 ml of dry NMP and 1
Added to 0 ml of dry pyridine and cooled to 5 ° C. 4.30 g (36.2 mmol) of phenyl isocyanate were added. The reaction mixture was heated to 75C. After 2 hours, the reaction mixture was added to 400 ml of cold distilled water. The precipitate was removed by filtration. Tris [phenyliminocarbonylimino-1,4-phenylene] amine (Table I, No. IV-1) was obtained by conventional workup. m. p. : 278 ° C. The following compounds were similarly prepared. Tris [cyclohexyliminocarbonylimino-1,4-phenylene] amine (Compound IV-2). m. p. : 230 ° C.

Example E 1.89 g (15.0 mmol) of 2,4,6-triamino-1,3,5-triazine and 35 ml of triethylamine were added to 130 ml of dry 1,4-dioxane under an inert atmosphere. And cooled to 5 ° C. 9.28 g (60.0 mmol) of 3-methylbenzoic acid chloride were added. The reaction mixture was heated under reflux for 3 hours. The reaction mixture was cooled to room temperature and added to 600 ml of cold distilled water. The precipitate was removed by filtration and dried. Tris [3-methylphenylenecarbonylimino] -1,3,5-triazine (Table I, No. V-1) by conventional finishing
I got m. p. : 227 ° C. The following compounds were similarly prepared. Tris [phenylcarbonylimino] -1,3,5-triazine (compound V-2
). m. p. : 277 ° C.

Example F 1.89 g (15.0 mmol) of 2,4-diamino-6-hydroxypyrimidine and 0.1 g of dry LiCl are placed under an inert atmosphere in 130 ml of dry NMP
And 25 ml of dry pyridine and cooled to 5 ° C. 8.06 g (55.0 g)
(Mmol) of cyclohexanecarboxylic acid chloride. 75 reaction mixture
Heated to ° C. After 2 hours, the reaction mixture was added to 400 ml of cold distilled water. The precipitate was removed by filtration. 2,4-Bis [cyclohexylcarbonylimino] -6- [cyclohexylcarbonyloxy] pyrimidine (Table I)
, No. VI) was obtained. m. p. : 225 ° C.

Example G 1.40 g (5.8 mmol) of 3,5-diaminobenzoic acid-4-methylphenyl ester were added to 30 ml of dry NMP and 1.3 ml of dry pyridine under an inert atmosphere. Cooled to ° C. 2.16 g (14.0 mmol) of phenylacetyl chloride were added. The reaction mixture was heated to 90C. After 2 hours, the reaction mixture was added to 400 ml of cold distilled water. The precipitate was removed by filtration. Conventional work-up provided 3,5-bis [benzylcarbonylimino] benzoic acid-4-methylphenyl ester (Table I, No. VII). m. p. : 212 ° C.

Example H 1.5 g (9.8 mmol) of 3,5-diaminobenzoic acid-3,5-dimethyl-phenylamide was added to 30 ml of dry NMP under an inert atmosphere and cooled to 5 ° C. . 2.70 g (21.6 mmol) of cyclohexyl isocyanate were added. The reaction mixture was heated to 75C. After 4.5 hours, the reaction mixture was added to 300 ml of cold distilled water. The precipitate was removed by filtration. 3,5 with conventional finish
-Bis [cyclohexyliminocarbonylimino] benzoic acid-3,5-dimethylphenylamide (Table I, No. VIII) was obtained. m. p. : 295 ° C.

I. General Method A. Mixing Method A About 20 mg (1% by weight) of powdered additive was added to about 2 g of powdered isotactic polypropylene and 100 ml of p-xylene (Aldrich Chemical
o.) and refluxed at 120 ° C. for about 1 hour. The flask was then cooled to room temperature. The mixture was further cooled with liquid nitrogen and lyophilized at room temperature under reduced pressure to give a powdered polypropylene-additive mixture. The neat polypropylene was similarly treated to obtain a reference control sample.

B. Mixing Method B-1 About 50 mg (1% by weight) of the powdered additive was added to about 4.95 g of powdered isotactic polypropylene (Aldrich Chemical Co.), and tumbled.
Crushed in a mortar. Unless otherwise indicated, a portion of this mixture was heated to 220 ° C. for about 5-10 minutes and then cooled to room temperature. Polypropylene alone is similarly treated to produce a blank control sample. 1% by weight of additives unless otherwise stated
It is.

B. Mixing Method B-2 About 59.91 g of powdered isotactic polypropylene (Aldrich Chemical
Co.) or a copolymer of isotactic polypropylene containing a small amount of ethylene comonomer (ELF-Atochem), 90 mg (0.15% by weight) of the powdered additive was added and tumbled for 24 hours in a glass container. A portion of this mixture was compounded at 230 ° C. in a small laboratory twin screw, recirculating extruder for about 10 minutes and then collected at room temperature. A blank control sample was prepared by similarly treating only polypropylene.

C. Differential Scanning Calorimetry (DSC) Perkin-Elmer DSC device operating in dry nitrogen atmosphere (
Model DSC 7) was used for analysis of the crystallization behavior of various mixtures and control samples according to standard methods. Approximately 5 to 10 mg of the sample is sealed in an aluminum cup and heated at 130 ° C. to 230 ° C. at a rate of 10 ° C./min.
Minutes and then at a rate of 10 ° C / min to 50 ° C. The data shown as the crystallization peak temperature (Tc) is the peak temperature of the exotherm in the thermogram recorded during cooling.

D. Thermogravimetric analysis (TGA) Automated Netzsch TGA instrument operating under nitrogen (STA 409)
Was used for thermal stability analysis of selected samples. About 10 mg of sample was placed in an aluminum oxide crucible and heated from 50 ° C to 640 ° C at a rate of 10 ° C / min.

E. Optical microscopy Selected samples are prepared by compression molding at 210 ° C and then cooling at a rate of 10 ° C / min to form a film from the melt. These samples were taken in transmitted light, under crossed Nicols, under a polarizing optical microscope (Leitz La Ball Looks).
borlux) 12-Pol).

II. Description of the Examples Example 1 Tris [3,4-bis (decyloxy) phenylene-carbonylimino-1,
4-phenylene] amine (compound I-1 in Table 1) (1% by weight)
And mixed with polypropylene. Both the raw polypropylene reference sample and the above mixture are analyzed by differential scanning calorimetry. The crystallization peak temperature of the mixture is 12.4 ° C. higher than the crystallization peak temperature of the neat control sample.

In the following, this difference between the crystallization temperatures of the mixture according to the invention and of the control sample is indicated by ΔT, which in this example is equal to 12.4 ° C.

Example 2 Compound I-6 in Table 1 (1% by weight) was mixed with polypropylene using Mixing Method B. Both the neat polypropylene reference sample and the mixture were analyzed by differential scanning calorimetry. ΔT = 13.0 ° C.

Example 3 For various compounds mixed with polypropylene, mixing method A (compound I-1)
And I-2) or mixed method B (B1: compounds I-3, I-6, I-8, I-9, II-1, III-
1, III-2, III-3, III-4 and III-5; B2: Compound I-
4, I-5, I-7, IV-1, IV-2, V-1, V-2, VI, VII, V
III) Examples 1 and 2 are repeated using Table 1 below summarizes the results measured using DSC.

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

Example 4 Raw nucleating agent-free polypropylene and 1% by weight of tris [3,4-bis (decyloxy) phenylene-carbonylimino-1,4-phenylene] amine (compound I-1 of Table 1) ) Were compression molded at 210 ° C, then cooled at a rate of 10 ° C / min and crystallized at 104 ° C. FIG. 1 is an optical micrograph of polypropylene containing no nucleating agent. FIG. 2 is a photomicrograph of isotactic polypropylene containing 1% by weight of compound I-1. A comparison between two optical micrographs taken at the same magnification shows that the spherulite size for the polypropylene film containing the additive is about 50% or less than that for the neat reference polypropylene, which It indicates the nucleating ability of the additive and is the cause of the decrease in haze of the former.

Example 5 Thermogravimetric analysis (TGA) was performed on compounds I-5 (curve 3) and I-7 (curve 2) in Table 1.
) And Millad 3988 (curve 1). FIG.
1 represents their respective TGA curves showing the enhanced thermal stability of the compounds according to the invention.

[Brief description of the drawings]

FIG. 1 is an optical micrograph of an isotactic polypropylene film containing no nucleating agent.

FIG. 2 shows the nucleating agent tris [3,4-bis (decyloxy) 0.75% by weight.
1 is an optical micrograph of a film of isotactic polypropylene containing [phenylene-carbonylimino-1,4-phenylene] amine.

FIG. 3 shows the enhanced thermal stability of the compounds according to the invention, carried out on compounds I-5 (3) and I-7 (2) and Millad 3988 (1) in the table under nitrogen. 4 is a graph of a thermogravimetric analysis (TGA) recording.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, B, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG , MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW F-term (reference) 4F071 AA14 AA14X AA15 AA15X AA20 AA20X AA21 AA21X AA22 AA22X AA29 AA29X AA40 AA40X AA43 AA43X AA44 AA44X AA45 AA45X AA46 AA46X AA50 AA50X AA51 AA51X AA54 AA54X AA56 AA56X AA63 AA63X AA69 AA69X AC01 AC02 AC12 AC13 AC15 AC19 AE22 AF14 AF30 AF45 AH04 AH05 AH06 AH12 BA01 BB05 BB06 BC01 BC05 BC06 4J002 BB001 BB021 BB111 BB151 BB171 BB181 BE021 CB001 CF031 CF041 CF051 CF061 CF071 CF081 CG011 CH021 EU071 016 CB001 CE 021 DD001 DE001 DF001 DH001 DK001 JB07 JB13 JB24 JB33 JB36 KA00 NA01 NA11

Claims (12)

[Claims] 1. The method of claim 1, wherein (i) the crystalline thermoplastic polymer and (ii) one or more compounds of the formula (Where x represents an integer of 2 to 7; y represents an integer of 0 to 4; z represents an integer of 0 to 4; the sum of x + y + z is equal to an integer of 3 to 7 and m is 1 to 3 And A is a center covalently bonded to moieties B, B 'or X', or a combination thereof; said moieties B and B 'may form one or more intermolecular hydrogen bonds Wherein the moieties X and X 'are compatible with the crystalline thermoplastic polymer; X is covalently bonded to B.) 2. The center A is a carbon atom, a nitrogen atom, a phosphorus atom, a boron atom and a silicon atom, and is linked to one or more aromatic, cycloaliphatic or aliphatic alkene, alkyne. , Diene, ether, thioether or ketone linkages and combinations thereof; unsubstituted or substituted, monocyclic and fused, 4, 5, 6 or 7 membered aromatic or cycloaliphatic Carbocycles, which may include one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, and may include one or more aromatic, cycloaliphatic,
2. The composition of claim 1, wherein the composition is selected from the group consisting of aliphatic, alkenes, alkynes, dienes, ethers, thioethers or ketone linkages and those that can be replaced by combinations thereof. 3. The said moiety B is the same or different in each case and is selected from esters, thioesters, ethers, thioethers, ketones, secondary and tertiary amines, amides, imides, imines, azo, azoxy, ureas, urethanes, 3. The composition according to claim 1, comprising one or more units selected from the group consisting of thiourethane and sulfonamide. 4. Said moiety B 'is the same or different in each case and is selected from the group consisting of one or more carboxylic and sulfonic acids, alcohols, phenols, thiols, amines, acetamido, cyano and hydrazine groups. The composition according to any one of claims 1 to 3, wherein the composition is prepared. 5. Said moieties X and X 'may or may not be chiral, in each case the same or different: H, linear or branched, each having 1 to 20 carbon atoms. Alkyl or alkenyl group, alkoxy group, alkanoyl group, alkylthio group, alkylthioalkyl group; linear or branched alkylaryl group, arylalkyl group, alkyl group wherein alkyl or alkoxy each has 1 to 20 carbon atoms Sulfinyl group, alkoxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxylic acid; 1 to 20 substituted by one or more sulfonic acid, carboxylic acid, halogen atom, nitro group, cyano group, diazo group, or epoxy moiety Alkyl groups having two carbon atoms; one or more 3 engaged monocyclic and contraction of the substituted or unsubstituted
, 4, 5, 6, or 7-membered aromatic and cycloaliphatic carbocycles containing one or more heteroatoms consisting of nitrogen, sulfur, sulfinyl, sulfonyl or oxygen, or a combination thereof The composition according to any one of claims 1 to 4, wherein the composition is selected from the group consisting of: 6. The composition according to claim 1, wherein a peak temperature of crystallization of the composition is at least 3 ° C. higher than a peak temperature of crystallization of the crystalline thermoplastic polymer. Composition. 7. The composition, wherein the size of the spherulite of the polymer of the composition is not more than 50% of the size of the spherulite of the crystallized thermoplastic polymer without containing the nucleating agent. The composition according to any one of claims 1 to 6, wherein 8. A crystalline thermoplastic polymer comprising the addition of a fixed amount of about 0.001% to about 20% by weight of one or more nucleating agents as defined in any one of claims 1 to 6. To increase the crystallization rate of 9. The method according to claim 1, which is selected from the group consisting of films, fibers, containers, paints, molded parts, membranes, bars, tubes, fabrics, and foams. A shaped article comprising the composition of 10. A compound of the general formula Wherein A, B, B ′, X, X ′, m, x, y and z have the meanings as defined in claim 1 and A represents substituted or unsubstituted triphenylamine;
B consists of amide units, y and z are equal to 0. ) Except that compound 4,4 ′, 4 ″ -tris (stearoylamino) triphenylamine is excluded. 11. The use of a compound of the formula (1) as defined in claim 1 as a nucleating agent for a crystalline thermoplastic polymer. 12. A) one or more polyolefins selected from the group consisting of polyethylene, stereoregular polypropylene and ethylene-propylene copolymers; and b) one or more nucleating agents according to formula (1), Wherein i) the center A is a single atom selected from the group consisting of a nitrogen atom and a phosphorus atom; or A is an unsubstituted or substituted, monocyclic or fused 5 or 6 membered heteroaromatic Or a non-aromatic ring, wherein said ring comprises a carbon atom and one or more of such atoms as a nitrogen, sulfur or oxygen atom or a combination thereof; and ii) in each case the same A moiety B consisting of amide, amide or urea; or at least two amides which are not the same in each case and at least two selected from the group consisting of esters and urea A moiety B consisting of at least one moiety; or a moiety B which is not the same in each case and comprises at least two moieties selected from the group consisting of urea and esters and amides; iii) x represents 3 Y represents an integer 0 or 1; z represents an integer 0 or 1; m represents an integer 1 or 2, a thermoplastic polymer composition comprising a nucleating agent.