WO2019041961A1 - Transparent nucleating agent, preparation method therefor and use thereof - Google Patents

Transparent nucleating agent, preparation method therefor and use thereof Download PDF

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WO2019041961A1
WO2019041961A1 PCT/CN2018/090934 CN2018090934W WO2019041961A1 WO 2019041961 A1 WO2019041961 A1 WO 2019041961A1 CN 2018090934 W CN2018090934 W CN 2018090934W WO 2019041961 A1 WO2019041961 A1 WO 2019041961A1
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nucleating agent
hydrogen
transparent nucleating
formula
compound represented
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PCT/CN2018/090934
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French (fr)
Chinese (zh)
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孙志强
田国英
孙钰涵
段军堂
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孙志强
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/05—Mono-, di- or tri-ethylamine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/06—Monoamines containing only n- or iso-propyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to a transparent nucleating agent, a preparation method and use thereof, and more particularly to a transparent nucleating agent comprising a compound represented by formula (1) and a preparation method thereof and use thereof derivative.
  • nucleating agent In the crystallization process of a polymer, a substance which promotes crystallization is usually artificially added, which functions as a nucleus during crystallization, and is therefore called a nucleating agent. Nucleating agents are often encountered in the crystallization of small molecules, but few people have proposed this concept. If impurities are present in the small molecule crystals, the crystallization rate is accelerated, and the crystals become smaller or imperfect crystals appear. The phenomenon of rapid crystallization which sometimes occurs when a certain impurity or a small amount of crystal nuclei (that is, a seed crystal commonly referred to in the art) is added to a supersaturated solution is called a nucleation phenomenon.
  • the role of the polymer nucleating agent and its mechanism is that, in the molten state, the nucleating agent provides the desired crystal nucleus, and the polymer changes from the original homogeneous nucleation to heterogeneous nucleation, thereby accelerating crystallization.
  • the speed makes the grain structure finer and helps to increase the rigidity of the product, shorten the molding cycle, maintain the stability of the final product, and improve the physical and mechanical properties of the polymer.
  • the polymer since the polymer has two phases of a crystal region and an amorphous region, visible light is birefringent between the two-phase interfaces and cannot directly transmit light, so generally the crystalline polymer is opaque.
  • a nucleating agent when added, since the crystal size becomes smaller, the possibility of light transmission increases, and the surface of the ray is improved, and when the crystal size is smaller than the wavelength of visible light, the polymer becomes transparent, and the nucleation at this time becomes nucleation.
  • the agent is referred to as a "transparent nucleating agent” or may also be referred to simply as a "clear agent.”
  • transparent nucleating agents are, for example, millad 3988, NX8000 in the United States, NA-11 and NA-21 in Japan, and the like.
  • a transparent nucleating agent can make the crystal form of the polyolefin become smaller during the crystallization process, and the number of small crystals increases remarkably.
  • the crystal is smaller than the wavelength of visible light, light can pass, thereby reducing the turbidity and fog of the polyolefin. Degree to improve the transparency of polyolefins.
  • the present invention provides a transparent nucleating agent comprising a compound represented by the formula (1) and a derivative thereof,
  • R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
  • R1 and R2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide. At least one; R3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl; and R4, R5, R6 and R7 are each independently selected from hydrogen, methyl At least one of ethyl, t-butyl, hydroxy, amino and halogen.
  • R3 is a tert-butyl group
  • R4, R5, R6 and R7 are all hydrogen.
  • the present invention provides a method of preparing a transparent nucleating agent, comprising: contacting a compound represented by the formula (3) with a compound represented by the formula (4) in a solvent, and concentrating the crystal,
  • R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
  • R1 and R2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide. At least one; R3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl; and R4, R5, R6 and R7 are each independently selected from hydrogen, methyl At least one of ethyl, t-butyl, hydroxy, amino and halogen.
  • R3 is a tert-butyl group
  • R4, R5, R6 and R7 are all hydrogen.
  • the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1:0.5-2.
  • the conditions of the contacting include a pH of 7.5-8, a temperature of 40-65 ° C, and a time of 1-3 h.
  • the solvent is at least one of water, methanol, ethanol, formic acid, benzene, toluene, cyclohexane, and dimethylacetamide.
  • the invention also provides the use of the transparent nucleating agent in a thermoplastic.
  • a transparent nucleating agent By the method of the invention, a transparent nucleating agent can be obtained, and the transparent nucleating agent prepared by the method of the invention or the transparent nucleating agent prepared by the method of the invention can effectively increase the crystallization rate of the polyolefin, change the crystal size of the polyolefin and The crystallization temperature, as well as the aesthetics and good visual appeal of the polymer article.
  • the transparent nucleating agents of the present invention have irreplaceable advantages.
  • the present invention provides a transparent nucleating agent comprising a compound represented by formula (1) and a derivative thereof,
  • R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
  • the compound represented by the formula (1) can be understood as a compound of a benzoic acid having an R3-R7 substituent and an amine compound having an R1-R2 substituent.
  • the term “derivative” refers to a compound in which a hydrogen atom or a group of atoms in a compound is substituted by another atom or group of atoms. Further, “derivative” may also refer to a compound which is derived after a compound undergoes a self-condensation reaction.
  • the derivative of the compound represented by the formula (1) of the present invention may be a compound represented by the formula (2).
  • R1 to R7 may be the same as those described in the formula (1), and a detailed description thereof will be omitted herein in order to avoid redundancy.
  • R1 to R7 are not particularly limited as long as they do not affect the main chemical properties of the compound represented by the formula (1).
  • R1 and R2 are each independently selected from at least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide;
  • R3 Is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl;
  • R4, R5, R6 and R7 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and awaketiary At least one of a butyl group, a hydroxyl group, an amino group, and a halogen.
  • R3 is a tert-butyl group
  • R4, R5, R6 and R7 are all hydrogen.
  • the compound when both R1 and R2 are hydrogen, the compound may also exist in the form of an inorganic ammonium salt, for example Can also The form exists.
  • the present invention provides a method of preparing a transparent nucleating agent, comprising: contacting a compound represented by the formula (3) with a compound represented by the formula (4) in a solvent, and concentrating the crystal,
  • R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
  • the compound represented by the formula (3) is a benzoic acid having a substituent of the R3-R7
  • the compound represented by the formula (4) is an amine-based compound having a substituent of R1 to R2.
  • the compound represented by the formula (3) and the compound represented by the formula (4) can be combined to form a compound represented by the formula (1).
  • the above compound can be concentrated and crystallized to obtain a compound represented by the formula (1), wherein the method of concentrating crystallization can be carried out by a step of concentrating crystallization which is common in the art, and for example, can include concentration under reduced pressure (for example, at -0.09 MPa to - under pressure of -0.07Mpa) and cooling crystallization (for example, at a temperature of 40 ° C to 70 ° C) and the like.
  • the process of the present invention may also include various common refining processes, for example, optionally including reflux water, vacuum concentration, temperature reduction crystallization, centrifugal filtration, refining purification, wet pulverization, and vacuum drying. The various processes of drying, pulverizing the drying material, mixing, dispensing, and warehousing, etc., thereby forming the transparent nucleating agent of the present invention into a product.
  • R1 to R7 are not particularly limited as long as they do not affect the main chemical properties of the compound represented by the formula (3) and the compound represented by the formula (4), and R1 and R2 are each independently selected from the group consisting of At least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide; R3 is hydrogen, methyl, ethyl, propyl At least one of a tert-butyl group, an alkoxy group, and an aryl group; and R4, R5, R6, and R7 are each independently selected from at least hydrogen, methyl, ethyl, t-butyl, hydroxy, amino, and halogen.
  • R1 and R2 are each independently selected from the group consisting of At least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobuty
  • R3 is a tert-butyl group
  • R4, R5, R6 and R7 are all hydrogen.
  • the amount of the compound represented by the formula (3) and the compound represented by the formula (4) is not particularly limited, and in view of maximizing the utilization of the compound represented by the formula (3) and the compound represented by the formula (4),
  • the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1:0.5-2; more preferably, the compound represented by the formula (3) and the formula ( 4)
  • the molar ratio of the compound represented is 1:0.8-1.2.
  • the conditions for contacting the compound represented by the formula (3) and the compound represented by the formula (4) are not particularly limited as long as the compound represented by the formula (3) and the compound represented by the formula (4) can be stably combined.
  • the conditions of the contacting include: a pH of 7.5-8, a temperature of 40-65 ° C, and a time of 1-3 h.
  • agitation e.g., reflux agitation
  • the kind of the solvent is not particularly limited as long as the compound represented by the formula (3) and the compound represented by the formula (4) can be easily dissolved, and for example, water or an organic solvent commonly used in the art can be used.
  • the solvent is at least one of water, methanol, ethanol, formic acid, benzene, toluene, cyclohexane, and dimethylacetamide (DMAC).
  • the solvent may be included in an amount of from 5% by weight to 95% by weight based on the total weight of the solution.
  • the invention also provides the use of the transparent nucleating agent in a thermoplastic.
  • the most common material in the thermoplastic is, for example, a polyolefin.
  • the transparent nucleating agent of the present invention can effectively increase the crystallization rate of the polyolefin, change the crystal size and crystallization temperature of the polyolefin, and improve the aesthetics and goodness of the polymer product. Visual sense.
  • the transparent nucleating agent of the present invention has an irreplaceable superiority.
  • the transparent nucleating agent of the present invention may be used singly or in combination with other additives during actual use.
  • Other additives may include antioxidants, acid scavengers, slip agents, light stabilizers, photoreceptors, and the like.
  • R4, R5, R6 and R7 are all hydrogen, and the conditions for concentrated crystallization include: controlling the pressure at -0.08 MPa ⁇ 0.002 MPa and controlling the temperature at 60 ° C ⁇ 2 ° C.
  • Test Example 1 Comparison of effects between the transparent nucleating agents of the present invention
  • the products obtained in Examples 1-13 were separately added as a clearing agent to 1000 g of a polypropylene random copolymer (K4912) in an amount of 2100 ppm (i.e., mg/kg), and 500 ppm of an oxidizing agent Ky-405 was further added to each group.
  • Example 1 Transparent nucleating agent Haze (%) Example 1 13.1 Example 2 12.8 Example 3 12.1 Example 4 11.0 Example 5 8.5 Example 6 10.1 Example 7 9.4 Example 8 12.8 Example 9 13.1 Example 10 13.1 Example 11 13.5 Example 12 11.8 Example 13 13.6
  • the transparent nucleating agent of the present invention can make the haze of the high-permeability polypropylene material reach the index requirement of 15% or less, and therefore the haze of the transparent nucleating agent of the present invention in the polymer.
  • the aspects have very good technical effects.
  • the transparent nucleating agent i.e., 4-tert-butyl-N,N-diisopropyl-benzoic acid amine salt, hereinafter referred to as JH9100
  • Example 5 exhibited the most The good result is that the haze of the high permeability polypropylene material is only 8.5%. Therefore, other tests will continue for the JH9100.
  • Test Example 2 Study on the amount of the transparent nucleating agent of the present invention
  • a high-permeability polypropylene material was synthesized according to the method of Test Example 1, except that JH9100 was added to 1000 g of a polypropylene random copolymer (K4912) in an amount of 2000 ppm, 2100 ppm, 2150 ppm, 2200 ppm, and 2300 ppm, respectively, and the haze thereof.
  • K4912 a polypropylene random copolymer
  • the JH9100 of the present invention can be used in the above-mentioned amounts to achieve the index of the haze of the high-permeability polypropylene material of 15% or less, or even 10.4% or less.
  • the amount of JH9100 is 2100 ppm
  • the haze is the lowest, 8.5%, that is, the JH9100 of the present invention can exhibit the best technical effect when used in this amount, thereby minimizing the haze of the highly permeable polypropylene material.
  • Test Example 3 Comparison of JH9100 with some transparent nucleating agents commonly found in the prior art
  • the high-permeability polypropylene material was synthesized according to the method of Test Example 1, except that the JH9100, the millad 3988, the NX8000, the NA-11, and the NA-21 of the present invention were separately added as a clearing agent to the 1000 g polypropylene randomly in an amount of 2100 ppm.
  • the results of the haze in the copolymer (K4912) are shown in Table 3.
  • the JH9100 of the present invention and other transparent nucleating agents in the prior art can make the haze of the high-permeability polypropylene material reach 15% or less. Claim. However, when using the JH9100 of the present invention, the haze is only 8.5%, which is much lower than the other 12%, 14.6%, 15% and 13.5%, that is, the JH9100 of the present invention exhibits a more transparent nucleating agent than other existing ones. More excellent results. Therefore, the transparent nucleating agent of the present invention has an irreplaceable superiority in the production of polypropylene products and the like.

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Abstract

Provided are a transparent nucleating agent, a preparation method therefor and the use thereof, wherein the transparent nucleating agent comprises a compound represented by formula (1) and a derivative thereof; the method comprises: bringing a compound represented by formula (3) into contact with a compound represented by formula (4) in a solvent, and concentrating and crystallizing same; and there is provided the use of the transparent nucleating agent in a thermoplastic plastic. By means of the method of the present invention, a transparent nucleating agent can be obtained, and the use of the transparent nucleating agent of the present invention or the transparent nucleating agent prepared by means of the method of the present invention can effectively improve the rate of the crystallization of a polyolefin, change the crystal size and the crystallization temperature of the polyolefin, improve the aesthetic quality of a polymer article and give a good visual quality. Especially in the case of polyolefins such as polypropylene and polyethylene, the transparent nucleating agent of the present invention has irreplaceable superiority.

Description

一种透明成核剂及其制备方法和用途Transparent nucleating agent, preparation method and use thereof 技术领域Technical field
本发明涉及一种透明成核剂及其制备方法和用途，更具体地，涉及一种透明成核剂及其制备方法和用途，所述透明成核剂包含式(1)表示的化合物及其衍生物。The present invention relates to a transparent nucleating agent, a preparation method and use thereof, and more particularly to a transparent nucleating agent comprising a compound represented by formula (1) and a preparation method thereof and use thereof derivative.
背景技术Background technique
在高聚物的结晶过程中，通常人为加入一些促进结晶的物质，其在结晶过程中起到晶核的作用，因此被称作成核剂。成核剂在小分子结晶过程中经常遇到，只是很少有人提出这个概念而已。小分子结晶中如果有杂质存在，就会加快结晶速度，使结晶变小或出现不完善结晶。有时在过饱和溶液中加入某种杂质或者少量晶核(即本领域中常说的晶种)而发生的快结晶现象称为成核现象。In the crystallization process of a polymer, a substance which promotes crystallization is usually artificially added, which functions as a nucleus during crystallization, and is therefore called a nucleating agent. Nucleating agents are often encountered in the crystallization of small molecules, but few people have proposed this concept. If impurities are present in the small molecule crystals, the crystallization rate is accelerated, and the crystals become smaller or imperfect crystals appear. The phenomenon of rapid crystallization which sometimes occurs when a certain impurity or a small amount of crystal nuclei (that is, a seed crystal commonly referred to in the art) is added to a supersaturated solution is called a nucleation phenomenon.
高分子成核剂的作用及其机理在于，高聚物在熔融状态下，由于成核剂提供所需的晶核，聚合物由原来的均相成核变成异相成核，从而加速结晶速度，使晶粒结构细化，并有利于提高产品的刚性，缩短成型周期，保持最终产品的稳定性，改善聚合物的物理机械性能等。The role of the polymer nucleating agent and its mechanism is that, in the molten state, the nucleating agent provides the desired crystal nucleus, and the polymer changes from the original homogeneous nucleation to heterogeneous nucleation, thereby accelerating crystallization. The speed makes the grain structure finer and helps to increase the rigidity of the product, shorten the molding cycle, maintain the stability of the final product, and improve the physical and mechanical properties of the polymer.
另一方面由于聚合物都存在晶区和非晶区两相，可见光在两相界面之间发生双折射，不能直接透光，因此一般结晶聚合物都是不透明的。而加入成核剂后，由于结晶尺寸变小，光透过可能性增加，表观光泽也会得到改善，而当结晶尺寸小于可见光波长时，聚合物就会变得透明，此时该成核剂称为“透明成核剂”或也可简称为“透明剂”。目前常见的一些透明成核剂有例如美国的millad3988、NX8000、日本的NA-11和NA-21等。On the other hand, since the polymer has two phases of a crystal region and an amorphous region, visible light is birefringent between the two-phase interfaces and cannot directly transmit light, so generally the crystalline polymer is opaque. When a nucleating agent is added, since the crystal size becomes smaller, the possibility of light transmission increases, and the surface of the ray is improved, and when the crystal size is smaller than the wavelength of visible light, the polymer becomes transparent, and the nucleation at this time becomes nucleation. The agent is referred to as a "transparent nucleating agent" or may also be referred to simply as a "clear agent." Some of the transparent nucleating agents currently in common are, for example, millad 3988, NX8000 in the United States, NA-11 and NA-21 in Japan, and the like.
发明内容Summary of the invention
本发明的目的是提供一种透明成核剂，其能够提高聚烯烃结晶速度，改变聚烯烃结晶体大小及结晶温度，可以提高聚合物制品的美感和良好的视觉感。这类透明成核剂的加入可以使聚烯烃在结晶过程中的晶型变小，小晶体数目明显增多，当晶体小于可见光的波长时，光可以通过，从而可以降低聚烯烃的浊度和雾度，改善聚烯烃的透明度。SUMMARY OF THE INVENTION It is an object of the present invention to provide a transparent nucleating agent which can increase the crystallization rate of a polyolefin, change the crystal size and crystallization temperature of the polyolefin, and can improve the aesthetics and good visual sensation of the polymer article. The addition of such a transparent nucleating agent can make the crystal form of the polyolefin become smaller during the crystallization process, and the number of small crystals increases remarkably. When the crystal is smaller than the wavelength of visible light, light can pass, thereby reducing the turbidity and fog of the polyolefin. Degree to improve the transparency of polyolefins.
为了实现上述目的，在一方面，本发明提供了一种透明成核剂，包含式(1)表示的化合物及其衍生物，In order to achieve the above object, in one aspect, the present invention provides a transparent nucleating agent comprising a compound represented by the formula (1) and a derivative thereof,
Figure PCTCN2018090934-appb-000001
Figure PCTCN2018090934-appb-000001
其中，R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R3、R4、R5、R6和R7各自独立地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。Wherein R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
在一个优选的实施方式中，R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。In a preferred embodiment, R1 and R2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide. At least one; R3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl; and R4, R5, R6 and R7 are each independently selected from hydrogen, methyl At least one of ethyl, t-butyl, hydroxy, amino and halogen.
在一个优选的实施方式中，R3为叔丁基，以及R4、R5、R6和R7均为氢。In a preferred embodiment, R3 is a tert-butyl group, and R4, R5, R6 and R7 are all hydrogen.
在另一方面，本发明还提供了一种制备透明成核剂的方法，包括：在溶剂中，使式(3)表示的化合物和式(4)表示的化合物接触，并浓缩结晶，In another aspect, the present invention provides a method of preparing a transparent nucleating agent, comprising: contacting a compound represented by the formula (3) with a compound represented by the formula (4) in a solvent, and concentrating the crystal,
Figure PCTCN2018090934-appb-000002
Figure PCTCN2018090934-appb-000002
其中，R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R3、R4、R5、R6和R7各自独立地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。Wherein R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
在一个优选的实施方式中，R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。In a preferred embodiment, R1 and R2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide. At least one; R3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl; and R4, R5, R6 and R7 are each independently selected from hydrogen, methyl At least one of ethyl, t-butyl, hydroxy, amino and halogen.
在一个优选的实施方式中，R3为叔丁基，以及R4、R5、R6和R7均为氢。In a preferred embodiment, R3 is a tert-butyl group, and R4, R5, R6 and R7 are all hydrogen.
在一个优选的实施方式中，所述式(3)表示的化合物和所述式(4)表示的化合物的摩尔比为1：0.5-2。In a preferred embodiment, the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1:0.5-2.
在一个优选的实施方式中，所述接触的条件包括：pH为7.5-8，温度为40-65℃，时间为1-3h。In a preferred embodiment, the conditions of the contacting include a pH of 7.5-8, a temperature of 40-65 ° C, and a time of 1-3 h.
在一个优选的实施方式中，所述溶剂为水、甲醇、乙醇、甲酸、苯、甲苯、环己烷和二甲基乙酰胺中的至少一种。In a preferred embodiment, the solvent is at least one of water, methanol, ethanol, formic acid, benzene, toluene, cyclohexane, and dimethylacetamide.
在另一方面，本发明还提供了所述透明成核剂在热塑性塑料中的应用。In another aspect, the invention also provides the use of the transparent nucleating agent in a thermoplastic.
通过本发明的方法，可以获得透明成核剂，并且使用本发明的透明成核剂或者通过本发明的方法制得的透明成核剂可以有效地提高聚烯烃结晶速度，改变聚烯烃结晶体大小及结晶温度，以及提高聚合物制品的美感和良好的视觉感。特别是针对聚烯烃(例如聚丙烯、聚乙烯等)时，本发明的透明成核剂有着不可替代的优越性。By the method of the invention, a transparent nucleating agent can be obtained, and the transparent nucleating agent prepared by the method of the invention or the transparent nucleating agent prepared by the method of the invention can effectively increase the crystallization rate of the polyolefin, change the crystal size of the polyolefin and The crystallization temperature, as well as the aesthetics and good visual appeal of the polymer article. Particularly in the case of polyolefins (e.g., polypropylene, polyethylene, etc.), the transparent nucleating agents of the present invention have irreplaceable advantages.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.
在一方面，本发明提供了一种透明成核剂，包含式(1)表示的化合物及其衍生物，In one aspect, the present invention provides a transparent nucleating agent comprising a compound represented by formula (1) and a derivative thereof,
Figure PCTCN2018090934-appb-000003
Figure PCTCN2018090934-appb-000003
其中，R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R3、R4、R5、R6和R7各自独立 地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。Wherein R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
根据本发明，式(1)表示的化合物可以理解为具有R3-R7取代基的苯甲酸与具有R1-R2取代基的胺基化合物的化合物。术语“衍生物”指的是一种化合物中的氢原子或原子团被其它原子或原子团取代而衍生的化合物。此外，“衍生物”也可以指一种化合物发生自身缩合反应后而衍生的化合物。例如，本发明的式(1)表示的化合物的衍生物可以是式(2)表示的化合物，According to the present invention, the compound represented by the formula (1) can be understood as a compound of a benzoic acid having an R3-R7 substituent and an amine compound having an R1-R2 substituent. The term "derivative" refers to a compound in which a hydrogen atom or a group of atoms in a compound is substituted by another atom or group of atoms. Further, "derivative" may also refer to a compound which is derived after a compound undergoes a self-condensation reaction. For example, the derivative of the compound represented by the formula (1) of the present invention may be a compound represented by the formula (2).
Figure PCTCN2018090934-appb-000004
Figure PCTCN2018090934-appb-000004
其中，R1-R7可以与式(1)中的描述相同，为了避免赘述，在此省略对其的详细描述。Wherein, R1 to R7 may be the same as those described in the formula (1), and a detailed description thereof will be omitted herein in order to avoid redundancy.
根据本发明，对R1-R7没有更多特别的限制，只要其不影响式(1)表示的化合物的主要化学性质即可。优选地，R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。According to the present invention, R1 to R7 are not particularly limited as long as they do not affect the main chemical properties of the compound represented by the formula (1). Preferably, R1 and R2 are each independently selected from at least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide; R3 Is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl; and R4, R5, R6 and R7 are each independently selected from the group consisting of hydrogen, methyl, ethyl, and untertiary At least one of a butyl group, a hydroxyl group, an amino group, and a halogen.
更优选地，R3为叔丁基，以及R4、R5、R6和R7均为氢。More preferably, R3 is a tert-butyl group, and R4, R5, R6 and R7 are all hydrogen.
特别地，当R1和R2均为氢时，该化合物也可以以无机铵盐的形式存在， 例如
Figure PCTCN2018090934-appb-000005
也可以以
Figure PCTCN2018090934-appb-000006
的形式存在。 In particular, when both R1 and R2 are hydrogen, the compound may also exist in the form of an inorganic ammonium salt, for example
Figure PCTCN2018090934-appb-000005
Can also
Figure PCTCN2018090934-appb-000006
The form exists.
在另一方面，本发明还提供了一种制备透明成核剂的方法，包括：在溶剂中，使式(3)表示的化合物和式(4)表示的化合物接触，并浓缩结晶，In another aspect, the present invention provides a method of preparing a transparent nucleating agent, comprising: contacting a compound represented by the formula (3) with a compound represented by the formula (4) in a solvent, and concentrating the crystal,
Figure PCTCN2018090934-appb-000007
Figure PCTCN2018090934-appb-000007
其中，R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R3、R4、R5、R6和R7各自独立地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。Wherein R1 and R2 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 hydroxyalkyl, C4-C6 cycloalkyl, aryl and amide, and R3, R4, R5, R6 And R7 are each independently selected from at least one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 hydroxyalkyl, amino, alkylamino, halogen, and aryl.
根据本发明，式(3)表示的化合物即为具有R3-R7取代基的苯甲酸，式(4)表示的化合物即为具有R1-R2取代基的胺基化合物。在溶剂中，式(3)表示的化合物和式(4)表示的化合物可以进行化合以形成式(1)表示的化合物。对上述的化合物进行浓缩结晶即可得到式(1)表示的化合物，其中，浓缩结晶的方法可以通过本领域中常见的浓缩结晶的步骤进行，例如可以包括减压浓缩(例如在-0.09Mpa至-0.07Mpa的压力下)和降温结晶(例如在40℃至70℃的温度下) 等。除了浓缩结晶之外，本发明的方法还可以包括各种常见的精制工艺，例如可以可选地包括回流带水、减压浓缩、降温结晶、离心过滤、精制提纯、湿料粉碎、减压烘干、粉碎烘干料、混料、分装和入库等的各种工艺，从而将本发明的透明成核剂制成产品。According to the invention, the compound represented by the formula (3) is a benzoic acid having a substituent of the R3-R7, and the compound represented by the formula (4) is an amine-based compound having a substituent of R1 to R2. In the solvent, the compound represented by the formula (3) and the compound represented by the formula (4) can be combined to form a compound represented by the formula (1). The above compound can be concentrated and crystallized to obtain a compound represented by the formula (1), wherein the method of concentrating crystallization can be carried out by a step of concentrating crystallization which is common in the art, and for example, can include concentration under reduced pressure (for example, at -0.09 MPa to - under pressure of -0.07Mpa) and cooling crystallization (for example, at a temperature of 40 ° C to 70 ° C) and the like. In addition to concentrated crystallization, the process of the present invention may also include various common refining processes, for example, optionally including reflux water, vacuum concentration, temperature reduction crystallization, centrifugal filtration, refining purification, wet pulverization, and vacuum drying. The various processes of drying, pulverizing the drying material, mixing, dispensing, and warehousing, etc., thereby forming the transparent nucleating agent of the present invention into a product.
如前所述，对R1-R7没有更多特别的限制，只要其不影响式(3)表示的化合物和式(4)表示的化合物的主要化学性质即可，R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。As described above, R1 to R7 are not particularly limited as long as they do not affect the main chemical properties of the compound represented by the formula (3) and the compound represented by the formula (4), and R1 and R2 are each independently selected from the group consisting of At least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide; R3 is hydrogen, methyl, ethyl, propyl At least one of a tert-butyl group, an alkoxy group, and an aryl group; and R4, R5, R6, and R7 are each independently selected from at least hydrogen, methyl, ethyl, t-butyl, hydroxy, amino, and halogen. One.
更优选地，R3为叔丁基，以及R4、R5、R6和R7均为氢。More preferably, R3 is a tert-butyl group, and R4, R5, R6 and R7 are all hydrogen.
根据本发明，对式(3)表示的化合物和式(4)表示的化合物用量没有特别的限制，考虑到使式(3)表示的化合物和式(4)表示的化合物的利用率最大化，优选地，所述式(3)表示的化合物和所述式(4)表示的化合物的摩尔比为1:0.5-2；更优选地，所述式(3)表示的化合物和所述式(4)表示的化合物的摩尔比为1:0.8-1.2。According to the present invention, the amount of the compound represented by the formula (3) and the compound represented by the formula (4) is not particularly limited, and in view of maximizing the utilization of the compound represented by the formula (3) and the compound represented by the formula (4), Preferably, the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1:0.5-2; more preferably, the compound represented by the formula (3) and the formula ( 4) The molar ratio of the compound represented is 1:0.8-1.2.
根据本发明，对式(3)表示的化合物和式(4)表示的化合物接触的条件没有特别限制，只要式(3)表示的化合物和式(4)表示的化合物能够稳定化合即可。优选地，所述接触的条件包括：pH为7.5-8，温度为40-65℃，时间为1-3h。此外，接触的过程中可以同时进行搅拌(例如回流搅拌)，使得接触更加均匀。According to the present invention, the conditions for contacting the compound represented by the formula (3) and the compound represented by the formula (4) are not particularly limited as long as the compound represented by the formula (3) and the compound represented by the formula (4) can be stably combined. Preferably, the conditions of the contacting include: a pH of 7.5-8, a temperature of 40-65 ° C, and a time of 1-3 h. In addition, agitation (e.g., reflux agitation) can be performed simultaneously during the contacting to make the contact more uniform.
根据本发明，对溶剂的种类没有特别的限制，只要能够易于溶解式(3)表示的化合物和式(4)表示的化合物即可，例如可以为水或本领域常用的有机溶剂。优选地，所述溶剂为水、甲醇、乙醇、甲酸、苯、甲苯、环己烷和二甲基乙酰胺(DMAC)中的至少一种。此外，以溶液总重量计，所述溶剂的含量可以为5重量％-95重量％。According to the present invention, the kind of the solvent is not particularly limited as long as the compound represented by the formula (3) and the compound represented by the formula (4) can be easily dissolved, and for example, water or an organic solvent commonly used in the art can be used. Preferably, the solvent is at least one of water, methanol, ethanol, formic acid, benzene, toluene, cyclohexane, and dimethylacetamide (DMAC). Further, the solvent may be included in an amount of from 5% by weight to 95% by weight based on the total weight of the solution.
在另一方面，本发明还提供了所述透明成核剂在热塑性塑料中的应用。In another aspect, the invention also provides the use of the transparent nucleating agent in a thermoplastic.
其中，热塑性塑料中最常见的材料为例如聚烯烃，使用本发明的透明成核剂可以有效地提高聚烯烃结晶速度，改变聚烯烃结晶体大小及结晶温度，以及提高聚合物制品的美感和良好的视觉感。特别地，当热塑性塑料的材料为聚乙烯或聚丙烯时，本发明的透明成核剂有着不可替代的优越性。Among them, the most common material in the thermoplastic is, for example, a polyolefin. The transparent nucleating agent of the present invention can effectively increase the crystallization rate of the polyolefin, change the crystal size and crystallization temperature of the polyolefin, and improve the aesthetics and goodness of the polymer product. Visual sense. In particular, when the material of the thermoplastic is polyethylene or polypropylene, the transparent nucleating agent of the present invention has an irreplaceable superiority.
在实际使用过程中，本发明的透明成核剂可以单独使用，也可以和其它添加剂组合使用。其它添加剂可以包括抗氧化剂、除酸剂、增滑剂、光稳定剂和光收剂等。The transparent nucleating agent of the present invention may be used singly or in combination with other additives during actual use. Other additives may include antioxidants, acid scavengers, slip agents, light stabilizers, photoreceptors, and the like.
以下将通过实施例对本发明进行详细描述。The invention will be described in detail below by way of examples.
以下实施例中，R4、R5、R6和R7均为氢，浓缩结晶的条件包括：将压力控制在-0.08MPa±0.002Mpa，温度控制在60℃±2℃。In the following examples, R4, R5, R6 and R7 are all hydrogen, and the conditions for concentrated crystallization include: controlling the pressure at -0.08 MPa ± 0.002 MPa and controlling the temperature at 60 ° C ± 2 ° C.
实施例1：4-叔丁基苯甲酸尿酰胺盐的制备Example 1: Preparation of 4-tert-butylbenzoic acid uramide salt
Figure PCTCN2018090934-appb-000008
Figure PCTCN2018090934-appb-000008
在一个四口瓶中，加入250mL甲酸、17.82g(0.1mol)4-叔丁基苯甲酸和6g碳酰二胺，在pH为7.5和温度为50℃的条件下加热3小时，同时进行回流搅拌，然后浓缩结晶，以得到20g白色固体，收率为83.4％。In a four-necked flask, 250 mL of formic acid, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid and 6 g of carbonyldiamine were added, and the mixture was heated at pH 7.5 and a temperature of 50 ° C for 3 hours while refluxing. After stirring, the crystals were concentrated to give 20 g of a white solid (yield: 83.4%).
实施例2：4-叔丁基苯甲酸胺盐的制备Example 2: Preparation of 4-tert-butylbenzoic acid amine salt
Figure PCTCN2018090934-appb-000009
Figure PCTCN2018090934-appb-000009
在一个四口瓶中，加入400mL水、17.82g(0.1mol)4-叔丁基苯甲酸和7mL 25％的氨水，在pH为8和温度为55℃的条件下加热1.5小时，同时进行回流搅拌，然后浓缩结晶，以得到16g白色固体，收率为83.4％。In a four-necked flask, 400 mL of water, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 7 mL of 25% aqueous ammonia were added, and heated at pH 8 and a temperature of 55 ° C for 1.5 hours while refluxing. After stirring, the crystals were concentrated to give 16 g of a white solid.
实施例3：4-叔丁基-N,N-二甲基-苯甲酸胺盐的制备Example 3: Preparation of 4-tert-butyl-N,N-dimethyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000010
Figure PCTCN2018090934-appb-000010
在一个四口瓶中，加入400mL甲醇、200mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和11.25mL 40％的二甲胺水溶液，在pH为7.5和温度为60℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到17g白色固体，收率为76％。In a four-necked flask, 400 mL of methanol, 200 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 11.25 mL of a 40% aqueous solution of dimethylamine were added at a pH of 7.5 and a temperature of 60 ° C. After heating for 2 hours while stirring under reflux, the crystals were concentrated to give 17 g of a white solid.
实施例4：4-叔丁基-N,N-二乙基-苯甲酸胺盐的制备Example 4: Preparation of 4-tert-butyl-N,N-diethyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000011
Figure PCTCN2018090934-appb-000011
在一个四口瓶中，加入150mL甲醇、50mL乙醇、10mL水、17.82g(0.1mol)4-叔丁基苯甲酸和7.3g(0.1mL)二乙基胺，在pH为7.5和温度为40℃的条件下加热3小时，同时进行回流搅拌，然后浓缩结晶，以得到23g白色固体，收率为91％。In a four-necked flask, 150 mL of methanol, 50 mL of ethanol, 10 mL of water, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 7.3 g (0.1 mL) of diethylamine were added at pH 7.5 and temperature 40. The mixture was heated at ° C for 3 hours while stirring under reflux, and then concentrated and crystallized to give 23 g of white solid.
实施例5：4-叔丁基-N,N-二异丙基-苯甲酸胺盐的制备Example 5: Preparation of 4-tert-butyl-N,N-diisopropyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000012
Figure PCTCN2018090934-appb-000012
在一个四口瓶中，加入150mL DMAC、50mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和10.1g(0.1mol)二异丙基胺，在pH为8和温度为60℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到25g白色固体，收率为89％。In a four-necked flask, 150 mL of DMAC, 50 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 10.1 g (0.1 mol) of diisopropylamine were added at a pH of 8 and a temperature of 60 ° C. The mixture was heated under the conditions of 2 hours while stirring under reflux, and then concentrated and crystallized to give 25 g of a white solid.
实施例6：4-叔丁基-N,N-二正丙基-苯甲酸胺盐的制备Example 6: Preparation of 4-tert-butyl-N,N-di-n-propyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000013
Figure PCTCN2018090934-appb-000013
在一个四口瓶中，加入150mL DMAC、50mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和10.1g(0.1mol)二正丙基胺，在pH为8和温度为65℃的条件下加热1小时，同时进行回流搅拌，然后浓缩结晶，以得到25g白色固体，收率为89％。In a four-necked flask, 150 mL of DMAC, 50 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 10.1 g (0.1 mol) of di-n-propylamine were added at a pH of 8 and a temperature of 65 ° C. The mixture was heated for 1 hour while stirring under reflux, and then concentrated and crystallized to give 25 g of a white solid.
实施例7：4-叔丁基-N,N-二正丁基-苯甲酸胺盐的制备Example 7: Preparation of 4-tert-butyl-N,N-di-n-butyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000014
Figure PCTCN2018090934-appb-000014
在一个四口瓶中，加入150mL甲醇、50mL甲苯、17.82g(0.1mol)4-叔丁基苯甲酸和12.9g(0.1mol)二正丁基胺，在pH为8和温度为60℃的条件下加热3小时，同时进行回流搅拌，然后浓缩结晶，以得到26g白色固体，收率为84％。In a four-necked flask, 150 mL of methanol, 50 mL of toluene, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 12.9 g (0.1 mol) of di-n-butylamine were added at a pH of 8 and a temperature of 60 ° C. The mixture was heated under the conditions of 3 hours while stirring under reflux, and then concentrated to give 26 g of a white solid.
实施例8：4-叔丁基-N,N-二异丁基-苯甲酸胺盐的制备Example 8: Preparation of 4-tert-butyl-N,N-diisobutyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000015
Figure PCTCN2018090934-appb-000015
在一个四口瓶中，加入150mL甲醇、50mL甲苯、17.82g(0.1mol)4-叔丁基苯甲酸和12.9g(0.1mol)二异丁基胺，在pH为7.5和温度为60℃的条件下加热3小时，同时进行回流搅拌，然后浓缩结晶，以得到26g白色固体，收率为84％。In a four-necked flask, 150 mL of methanol, 50 mL of toluene, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 12.9 g (0.1 mol) of diisobutylamine were added at a pH of 7.5 and a temperature of 60 ° C. The mixture was heated under the conditions of 3 hours while stirring under reflux, and then concentrated to give 26 g of a white solid.
实施例9：4-叔丁基-N-乙基醇-苯甲酸胺盐的制备Example 9: Preparation of 4-tert-butyl-N-ethyl alcohol-benzoic acid amine salt
Figure PCTCN2018090934-appb-000016
Figure PCTCN2018090934-appb-000016
在一个四口瓶中，加入280mL甲醇、50mL甲苯、17.82g(0.1mol)4-叔丁基苯甲酸和6.1g(0.1mol)N-乙基醇胺，在pH为7.5和温度为45℃的条件下加热3小时，同时进行回流搅拌，然后浓缩结晶，以得到21.5g白色固体，收率为90％。In a four-necked flask, 280 mL of methanol, 50 mL of toluene, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 6.1 g (0.1 mol) of N-ethylolamine were added at a pH of 7.5 and a temperature of 45 ° C. The mixture was heated under the conditions of 3 hours while stirring under reflux, and then concentrated and crystallized to obtain 21.5 g of a white solid in a yield of 90%.
实施例10：4-叔丁基-N,N-二乙基醇-苯甲酸胺盐的制备Example 10: Preparation of 4-tert-butyl-N,N-diethyl alcohol-benzoic acid amine salt
Figure PCTCN2018090934-appb-000017
Figure PCTCN2018090934-appb-000017
在一个四口瓶中，加入150mL甲苯、17.82g(0.1mol)4-叔丁基苯甲酸和10.5g(0.1mol)二乙醇胺，在pH为8和温度为60℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到24.6g白色固体，收率为87％。In a four-necked flask, 150 mL of toluene, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 10.5 g (0.1 mol) of diethanolamine were added, and the mixture was heated at pH 8 and a temperature of 60 ° C for 2 hours. At the same time, reflux stirring was carried out, followed by concentration and crystallization to obtain 24.6 g of a white solid, yield 87%.
实施例11：4-叔丁基-N,N-二苯基-苯甲酸胺盐的制备Example 11: Preparation of 4-tert-butyl-N,N-diphenyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000018
Figure PCTCN2018090934-appb-000018
在一个四口瓶中，加入120mL甲苯、20mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和16.9g(0.1mol)二苯基胺，在pH为7.5和温度为50℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到27.8g白色固体，收率为80％。In a four-necked flask, 120 mL of toluene, 20 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 16.9 g (0.1 mol) of diphenylamine were added at a pH of 7.5 and a temperature of 50 °C. The mixture was heated under reflux for 2 hours while stirring under reflux, followed by concentration and crystallization to obtain 27.8 g of a white solid in a yield of 80%.
实施例12：4-叔丁基-N,N-二苄基-苯甲酸胺盐的制备Example 12: Preparation of 4-tert-butyl-N,N-dibenzyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000019
Figure PCTCN2018090934-appb-000019
在一个四口瓶中，加入125mL环己烷、25mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和19.7g(0.1mol)二苄基胺，在pH为7.5和温度为50℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到32.8g白色固体，收率为87.5％。In a four-necked flask, add 125 mL of cyclohexane, 25 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 19.7 g (0.1 mol) of dibenzylamine at a pH of 7.5 and a temperature of 50 ° C. The mixture was heated for 2 hours while stirring under reflux, and then concentrated and crystallized to give 32.8 g of a white solid.
实施例13：4-叔丁基-N-苯基-苯甲酸胺盐的制备Example 13: Preparation of 4-tert-butyl-N-phenyl-benzoic acid amine salt
Figure PCTCN2018090934-appb-000020
Figure PCTCN2018090934-appb-000020
在一个四口瓶中，加入120mL甲苯、20mL乙醇、17.82g(0.1mol)4-叔丁基苯甲酸和9.3g(0.1mol)苯胺，在pH为7.5和温度为50℃的条件下加热2小时，同时进行回流搅拌，然后浓缩结晶，以得到21.7g白色固体，收率为80％。In a four-necked flask, 120 mL of toluene, 20 mL of ethanol, 17.82 g (0.1 mol) of 4-tert-butylbenzoic acid, and 9.3 g (0.1 mol) of aniline were added, and the mixture was heated at a pH of 7.5 and a temperature of 50 ° C. The mixture was refluxed while refluxing, and then concentrated to give 21.7 g of a white solid.
试验例1：本发明的透明成核剂之间的效果比较Test Example 1: Comparison of effects between the transparent nucleating agents of the present invention
将实施例1-13所得的产物作为透明剂以2100ppm(即mg/kg)的添加量分别加入到1000g聚丙烯无规共聚物(K4912)中，此外各组中还加入500ppm氧化剂Ky-405作为主抗氧化剂、500ppm氧化剂168作为辅抗氧化剂和400ppm硬脂酸钙作为除酸剂，并进行混炼造粒的成型工艺，以得到厚度为1mm的聚合物 制品，其雾度的结果示于表1中，其中，雾度的测量方法可以参照GB/T2410-2008的方法进行。The products obtained in Examples 1-13 were separately added as a clearing agent to 1000 g of a polypropylene random copolymer (K4912) in an amount of 2100 ppm (i.e., mg/kg), and 500 ppm of an oxidizing agent Ky-405 was further added to each group. The main antioxidant, 500 ppm oxidant 168 as a secondary antioxidant and 400 ppm calcium stearate as an acid scavenger, and a mixing process of mixing and granulating to obtain a polymer product having a thickness of 1 mm, the haze results are shown in the table In 1, wherein the measurement method of haze can be carried out by referring to the method of GB/T2410-2008.
[表1][Table 1]
透明成核剂Transparent nucleating agent 雾度(％)Haze (%)
实施例1Example 1 13.113.1
实施例2Example 2 12.812.8
实施例3Example 3 12.112.1
实施例4Example 4 11.011.0
实施例5Example 5 8.58.5
实施例6Example 6 10.110.1
实施例7Example 7 9.49.4
实施例8Example 8 12.812.8
实施例9Example 9 13.113.1
实施例10Example 10 13.113.1
实施例11Example 11 13.513.5
实施例12Example 12 11.811.8
实施例13Example 13 13.613.6
从表1的结果中可以看出，本发明的透明成核剂都可以使高透聚丙烯料的雾度达到15％以下的指标要求，因此本发明的透明成核剂在聚合物的雾度方面都有非常优异的技术效果。特别地，在各个实施例中，实施例5中制得的透明成核剂(即4-叔丁基-N,N-二异丙基-苯甲酸胺盐，以下称为JH9100)表现了最佳的效果，使高透聚丙烯料的雾度仅为8.5％。因此，接下来将针对JH9100继续进行其它试验。It can be seen from the results in Table 1 that the transparent nucleating agent of the present invention can make the haze of the high-permeability polypropylene material reach the index requirement of 15% or less, and therefore the haze of the transparent nucleating agent of the present invention in the polymer. The aspects have very good technical effects. In particular, in various embodiments, the transparent nucleating agent (i.e., 4-tert-butyl-N,N-diisopropyl-benzoic acid amine salt, hereinafter referred to as JH9100) prepared in Example 5 exhibited the most The good result is that the haze of the high permeability polypropylene material is only 8.5%. Therefore, other tests will continue for the JH9100.
试验例2：本发明的透明成核剂的用量的研究Test Example 2: Study on the amount of the transparent nucleating agent of the present invention
按照试验例1的方法合成高透聚丙烯料，不同的是，将JH9100分别以2000ppm、2100ppm、2150ppm、2200ppm、2300ppm的添加量加入到1000g聚 丙烯无规共聚物(K4912)中，其雾度的结果示于下表2中。A high-permeability polypropylene material was synthesized according to the method of Test Example 1, except that JH9100 was added to 1000 g of a polypropylene random copolymer (K4912) in an amount of 2000 ppm, 2100 ppm, 2150 ppm, 2200 ppm, and 2300 ppm, respectively, and the haze thereof. The results are shown in Table 2 below.
[表2][Table 2]
透明成核剂Transparent nucleating agent 用量(ppm)Dosage (ppm) 雾度(％)Haze (%)
JH9100JH9100 20002000 10.410.4
JH9100JH9100 21002100 8.58.5
JH9100JH9100 21502150 8.88.8
JH9100JH9100 22002200 9.89.8
JH9100JH9100 23002300 9.99.9
从表2的结果中可以看出，本发明的JH9100以上述用量使用时均可以使高透聚丙烯料的雾度达到15％以下的指标要求，甚至达到10.4％以下。特别地，当JH9100的用量为2100ppm时，雾度最低，为8.5％，即本发明的JH9100以该用量使用时可以表现出最佳的技术效果，使高透聚丙烯料的雾度的最小化。As can be seen from the results of Table 2, the JH9100 of the present invention can be used in the above-mentioned amounts to achieve the index of the haze of the high-permeability polypropylene material of 15% or less, or even 10.4% or less. In particular, when the amount of JH9100 is 2100 ppm, the haze is the lowest, 8.5%, that is, the JH9100 of the present invention can exhibit the best technical effect when used in this amount, thereby minimizing the haze of the highly permeable polypropylene material. .
试验例3：JH9100与现有技术中常见的一些透明成核剂的比较Test Example 3: Comparison of JH9100 with some transparent nucleating agents commonly found in the prior art
按照试验例1的方法合成高透聚丙烯料，不同的是，将本发明的JH9100、millad3988、NX8000、NA-11和NA-21作为透明剂以2100ppm的添加量分别加入到1000g聚丙烯无规共聚物(K4912)中，其雾度的结果示于表3中，The high-permeability polypropylene material was synthesized according to the method of Test Example 1, except that the JH9100, the millad 3988, the NX8000, the NA-11, and the NA-21 of the present invention were separately added as a clearing agent to the 1000 g polypropylene randomly in an amount of 2100 ppm. The results of the haze in the copolymer (K4912) are shown in Table 3.
[表3][table 3]
透明成核剂Transparent nucleating agent 用量(ppm)Dosage (ppm) 雾度(％)Haze (%)
39883988 21002100 1212
NX8000NX8000 21002100 14.614.6
JH9100JH9100 21002100 8.58.5
NA-11NA-11 21002100 1515
NA-21NA-21 21002100 13.513.5
从表3的结果中可以看出，在制备透明聚合物制品时，本发明的JH9100和现有技术中的其它透明成核剂都能使高透聚丙烯料的雾度达到15％以下的指标要求。但是，使用本发明的JH9100时，雾度仅为8.5％，远低于其它的12％、 14.6％、15％和13.5％，即本发明的JH9100展现出了比其它现有的透明成核剂更优异的效果。因此，本发明的透明成核剂在生产聚丙烯产品及其类似产品有着不可替代的优越性。As can be seen from the results in Table 3, in the preparation of the transparent polymer article, the JH9100 of the present invention and other transparent nucleating agents in the prior art can make the haze of the high-permeability polypropylene material reach 15% or less. Claim. However, when using the JH9100 of the present invention, the haze is only 8.5%, which is much lower than the other 12%, 14.6%, 15% and 13.5%, that is, the JH9100 of the present invention exhibits a more transparent nucleating agent than other existing ones. More excellent results. Therefore, the transparent nucleating agent of the present invention has an irreplaceable superiority in the production of polypropylene products and the like.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (10)

  1. 一种透明成核剂，包含式(1)表示的化合物及其衍生物，A transparent nucleating agent comprising a compound represented by formula (1) and a derivative thereof,
    Figure PCTCN2018090934-appb-100001
    Figure PCTCN2018090934-appb-100001
    其中，among them,
    R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R1 and R2 are each independently selected from at least one of hydrogen, a C1-C12 alkyl group, a C1-C12 hydroxyalkyl group, a C4-C6 cycloalkyl group, an aryl group, and an amide group, and
    R3、R4、R5、R6和R7各自独立地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from at least one of hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 hydroxyalkyl, amino, alkylamino, halogen and aryl. Kind.
  2. 根据权利要求1所述的透明成核剂，其中，The transparent nucleating agent according to claim 1, wherein
    R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R1 and R2 are each independently selected from at least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide groups;
    R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R 3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl;
    R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。R4, R5, R6 and R7 are each independently selected from at least one of hydrogen, methyl, ethyl, t-butyl, hydroxy, amino and halogen.
  3. 根据权利要求1或2所述的透明成核剂，其中，The transparent nucleating agent according to claim 1 or 2, wherein
    R3为叔丁基，以及R3 is a tert-butyl group, and
    R4、R5、R6和R7均为氢。R4, R5, R6 and R7 are all hydrogen.
  4. 一种制备透明成核剂的方法，包括：在溶剂中，使式(3)表示的化合物和式(4)表示的化合物接触，并浓缩结晶，A method for preparing a transparent nucleating agent, comprising: contacting a compound represented by the formula (3) with a compound represented by the formula (4) in a solvent, and concentrating the crystal,
    Figure PCTCN2018090934-appb-100002
    Figure PCTCN2018090934-appb-100002
    其中，among them,
    R1和R2各自独立地选自氢、C1-C12烷基、C1-C12羟烷基、C4-C6环烃基、芳香基和酰胺基中的至少一种，以及R1 and R2 are each independently selected from at least one of hydrogen, a C1-C12 alkyl group, a C1-C12 hydroxyalkyl group, a C4-C6 cycloalkyl group, an aryl group, and an amide group, and
    R3、R4、R5、R6和R7各自独立地选自氢、C1-C12烷基、C1-C12烷氧基、C1-C12羟烷基、氨基、烷基氨基、卤素和芳香基中的至少一种。R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from at least one of hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 hydroxyalkyl, amino, alkylamino, halogen and aryl. Kind.
  5. 根据权利要求4所述的方法，其中，The method of claim 4, wherein
    R1和R2各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、苄基、苯基和酰胺基中的至少一种；R1 and R2 are each independently selected from at least one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, benzyl, phenyl and amide groups;
    R3为氢、甲基、乙基、丙基、叔丁基、烷氧基和芳香基中的至少一种；以及R 3 is at least one of hydrogen, methyl, ethyl, propyl, t-butyl, alkoxy and aryl;
    R4、R5、R6和R7各自独立地选自氢、甲基、乙基、叔丁基、羟基、氨基和卤素中的至少一种。R4, R5, R6 and R7 are each independently selected from at least one of hydrogen, methyl, ethyl, t-butyl, hydroxy, amino and halogen.
  6. 根据权利要求4或5所述的方法，其中，The method according to claim 4 or 5, wherein
    R3为叔丁基，以及R3 is a tert-butyl group, and
    R4、R5、R6和R7均为氢。R4, R5, R6 and R7 are all hydrogen.
  7. 根据权利要求4所述的方法，其中，所述式(3)表示的化合物和所述式(4)表示的化合物的摩尔比为1：0.5-2。The method according to claim 4, wherein the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is 1:0.5-2.
  8. 根据权利要求4所述的方法，其中，所述接触的条件包括：pH为7.5-8， 温度为40-65℃，时间为1-3h。The method according to claim 4, wherein the conditions of the contacting include a pH of 7.5-8, a temperature of 40-65 ° C, and a time of 1-3 h.
  9. 根据权利要求4所述的方法，所述溶剂为水、甲醇、乙醇、甲酸、苯、甲苯、环己烷和二甲基乙酰胺中的至少一种。The method according to claim 4, wherein the solvent is at least one of water, methanol, ethanol, formic acid, benzene, toluene, cyclohexane, and dimethylacetamide.
  10. 根据权利要求1-4中任一项所述的透明成核剂在热塑性塑料中的应用。Use of a transparent nucleating agent according to any one of claims 1 to 4 in a thermoplastic.
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