阅读说明：本技术 一种聚合物复合成核剂及聚合物组合物 (Polymer composite nucleating agent and polymer composition ) 是由 张文龙 王艳丽 董小攀 于 2021-04-27 设计创作，主要内容包括：本发明提供了一种聚合物复合成核剂,其中含有至少一种取代芳基磷酸盐、至少一种铁氧化物和至少一种脂肪酸盐。本发明还公开了包含有效量的该聚合物复合成核剂的聚合物组合物,以及该聚合物组合物的制备方法,包括将聚合物和该聚合物复合成核剂同时加入高速混合机内混合,通过双螺杆挤出机挤出造粒,将所得的共混物粒料干燥后得到该聚合物组合物。本发明含有取代芳基磷酸盐、铁氧化物和脂肪酸盐的聚合物复合成核剂能有效提高聚合物的结晶度、成型速度以及刚性、韧性等力学性能,减小聚合物制品的翘曲变形,拓宽了聚丙烯材料的应用领域。(The invention provides a polymer composite nucleating agent which contains at least one substituted aryl phosphate, at least one iron oxide and at least one fatty acid salt. The invention also discloses a polymer composition containing an effective amount of the polymer composite nucleating agent and a preparation method of the polymer composition. The polymer composite nucleating agent containing the substituted aryl phosphate, the iron oxide and the fatty acid salt can effectively improve the crystallinity, the forming speed, the rigidity, the toughness and other mechanical properties of the polymer, reduce the buckling deformation of polymer products and widen the application field of polypropylene materials.)

1. A polymeric composite nucleating agent comprising at least one substituted aryl phosphate, at least one iron oxide, and at least one fatty acid salt.

2. The polymer composite nucleating agent of claim 1, wherein the substituted aryl phosphate is selected from the group consisting of sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, bis [4- (1, 1-dimethylethyl) benzoyl-oxy ] aluminum hydroxide, lithium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, and bis [2, 2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxy salt.

3. The polymer composite nucleating agent of claim 2, wherein the substituted aryl phosphate is bis [2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphate ] hydroxy aluminum salt.

4. The polymer composite nucleating agent of claim 1, wherein the iron oxide is selected from the group consisting of FeO and Fe₂O₃、Fe₃O₄、Fe₂O₃·H₂O。

5. The polymer composite nucleating agent of claim 4, wherein the iron oxide is Fe₂O₃。

6. The polymer composite nucleating agent of claim 4, wherein the iron oxide has a particle size in the range of 30 to 500 nanometers.

7. The polymer composite nucleating agent of claim 1, wherein the fatty acid salt is selected from the group consisting of alkali metal stearates and alkaline earth metal stearates.

8. The polymer composite nucleating agent of claim 7, wherein the fatty acid salt is sodium stearate.

9. The polymer composite nucleating agent according to any one of claims 1 to 8, which comprises the following components in parts by weight: 12-48 parts of substituted aryl phosphate, 20-80 parts of iron oxide and 8-32 parts of fatty acid salt.

10. The polymer composite nucleating agent is characterized by comprising the following components in parts by weight: bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate]34-38 parts of hydroxyl aluminum salt and Fe₂O₃38-42 parts of sodium stearate and 22-26 parts of sodium stearate.

11. A polymer composition comprising an effective amount of the polymer composite nucleating agent according to any one of claims 1 to 10 in a polymer.

12. The polymer composition of claim 11, wherein the polymer is a natural or synthetic polymer selected from the group consisting of polyethylene, high density high molecular weight polyethylene, high density ultra high molecular weight polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, polyisobutylene, polypropylene homopolymer, or polypropylene random, alternating, segmented, or block copolymer containing one or more comonomers selected from the group consisting of: ethylene, C₄-C₂₀Alpha-olefins, vinylcyclohexane, vinylcyclohexene, C₄-C₂₀Alkadiene, C₅-C₁₂Cyclic dienes and norbornene derivatives; wherein the total amount of propylene and comonomer is 100% for a polypropylene random copolymer, alternating copolymer, segmented copolymer or block copolymer.

13. The polymer composition of claim 12, wherein the polymer is a polypropylene homopolymer or a polypropylene random, alternating, segmented, or block copolymer containing one or more comonomers.

14. The polymer composition of claim 12, wherein the polymer is a polypropylene homopolymer.

15. The polymer composition according to any one of claims 11 to 14, wherein the polymer composite nucleating agent is used in an amount of 0.02 to 0.5 parts by weight based on 100 parts by weight of the polymer.

16. A process for preparing a polymer composition according to any one of claims 11 to 15, comprising the steps of: simultaneously adding a polymer and the polymer composite nucleating agent into a high-speed mixer for mixing, extruding and granulating through a double-screw extruder to obtain a blend granule, and drying the blend granule to obtain the polymer composition.

17. The method as claimed in claim 16, wherein the rotation speed of the high-speed mixer is 700-1000rpm, and the extrusion temperature of the twin-screw extruder is 190-210 ℃.

Technical Field

The invention relates to the technical field of polymer preparation, in particular to a polymer composite nucleating agent and a polymer composition prepared by adopting the polymer composite nucleating agent.

Background

With the development of times and the progress of technology, polymers have been widely applied in various fields such as automobiles, building materials, packaging and the like due to unique material properties. The polypropylene is one of the most widely used polymers at present, is thermoplastic plastic polymerized by propylene monomers, has the advantages of sufficient source, low price, low density, good corrosion resistance and the like, and is widely applied to the fields of household appliances, automobiles, textile fibers, building engineering, biological medical treatment and sewage treatment. However, polypropylene has limited versatility due to its disadvantages such as poor impact properties, low heat distortion temperature, poor dimensional stability, etc. Various studies have been made to widen the application range of the polymer. Among them, adding nucleating agent is one of the most effective and convenient polymer modification methods at present.

At present, most of polymer nucleating agents in the market are organic nucleating agents, and compared with inorganic nucleating agents, the organic nucleating agents have the advantages of small addition amount and obvious nucleating effect. Among them, substituted aryl phosphates are the most widely used organic nucleating agents. The nucleating agent containing the substituted aryl phosphate can obviously improve the mechanical property of polypropylene products, but the plastic products containing the nucleating agent containing the substituted aryl phosphate generally have higher shrinkage rate, which often causes the warping and denaturation of the products, thereby influencing the use and safety of the products. For example, as described in patent CN101400729B, "plastic articles using nucleating agents generally have higher shrinkage than articles not using nucleating agents.

The expansion of polymer product applications requires an increase in the overall properties, and thus the market continues to have a strong need for additive products that can improve the overall properties of polymer products (e.g., modulus, impact strength, and shrinkage) in a comprehensive manner.

Disclosure of Invention

The invention aims to provide a polymer composite nucleating agent and a polymer composition prepared by adopting the polymer composite nucleating agent, so as to solve the defects in the background technology.

In a first aspect of the invention, a polymeric composite nucleating agent is provided which comprises at least one substituted aryl phosphate, at least one iron oxide, and at least one fatty acid salt.

The substituted aryl phosphate is selected from sodium bis (4-tert-butylphenyl) phosphate (CAS #: 10491-31-3), sodium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate (CAS #: 85209-91-2), bis [4- (1, 1-dimethylethyl) benzoyl-oxy ] aluminum hydroxide (CAS #: 13170-05-3), lithium 2,2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate (CAS #: 85209-93-4), bis [2, 2 ' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxy salt (CAS #: 151841-65-5).

Preferably, the substituted aryl phosphate is bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxy salt, which has the structural formula (I):

the iron oxide is selected from FeO and Fe₂O₃、Fe₃O₄、Fe₂O₃·H₂O, preferably Fe₂O₃。

The particle size of the iron oxide is in the range of 30-500 nm, preferably 50-200 nm, more preferably 100-150 nm.

The fatty acid salt is selected from alkali metal stearate or alkaline earth metal stearate, preferably magnesium stearate, zinc stearate, calcium stearate, lithium stearate, sodium stearate, more preferably sodium stearate.

As a preferred technical scheme, the polymer composite nucleating agent comprises the following components in parts by weight: 12-48 parts of substituted aryl phosphate, 20-80 parts of iron oxide and 8-32 parts of fatty acid salt.

As a preferred embodiment, the polymer composite nucleating agent comprises the following components in parts by weight: bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate]34-38 parts of hydroxyl aluminum salt and Fe₂O₃38-42 parts of sodium stearate and 22-26 parts of sodium stearate.

The polymer composite nucleating agent can be prepared by adopting a conventional method in the field, for example, the following preparation method is adopted: weighing the components according to the proportion, crushing according to a conventional method, and uniformly mixing to obtain the composition.

Other materials may also optionally be added to the compositions of the present invention in concentration ranges that do not adversely affect the advantageous effects of the present invention. These materials may include lubricants, stabilizers, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, neutralizers, acid scavengers, antistatic agents, antiblocking agents, heavy metal deactivators, flame retardants, nucleating agents, clarifying agents, foaming agents, processing aids, peroxides, silane compounds, fluorine compounds, hydrotalcites, elastomers, pigments, fillers, reinforcing materials, and other mixtures.

In a second aspect of the invention, there is provided a polymer composition comprising an effective amount of said polymer complexed nucleating agent in a polymer.

The polymer may be a natural or synthetic polymer, preferably a synthetic polymer. Examples of synthetic polymers include, but are not limited to: polyethylene, high density high molecular weight polyethylene, high density ultra high molecular weight polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, polyisobutylene, polypropylene homopolymer or polypropylene random, alternating, segmented or block copolymer containing one or more comonomers selected from the group consisting of: ethylene, C₄-C₂₀Alpha-olefins, vinylcyclohexane, vinylcyclohexene, C₄-C₂₀Alkadiene, C₅-C₁₂Cyclic dienes and norbornene derivatives; wherein the total amount of propylene and comonomer is 100% for a polypropylene random copolymer, alternating copolymer, segmented copolymer or block copolymer.

More preferably, the polymer is a polypropylene homopolymer or a polypropylene random, alternating, segmented or block copolymer containing one or more comonomers.

More preferably, the polymer is a polypropylene homopolymer.

The effective amount of the polymeric compounding additive to be added to the polymeric composition can be determined by one of ordinary skill in the art through routine experimental testing. Preferably, the polymer composite additive is used in an amount of 0.02 to 0.5 parts by weight, based on 100 parts by weight of the polymer.

A third aspect of the present invention provides a method for preparing the polymer composition, comprising the steps of: simultaneously adding a polymer and the polymer composite nucleating agent into a high-speed mixer for mixing, extruding and granulating through a double-screw extruder to obtain a blend granule, and drying the blend granule to obtain the polymer composition.

Preferably, the rotating speed of the high-speed mixer is 700-1000rpm, and the extrusion temperature of the double-screw extruder is 190-210 ℃.

Aiming at the problems of low crystallinity, poor dimensional stability and defective mechanical property of common polymers, the polymer composite nucleating agent containing substituted aryl phosphate, iron oxide and fatty acid salt has unexpected synergistic effect, can effectively improve the crystallinity, the forming speed, the rigidity, the toughness and other mechanical properties of the polymers, and reduces the buckling deformation of polymer products. The composite nucleating agent improves the performance of the polymer and widens the application field of the polymer.

The invention is further described with reference to the following figures and examples.

Drawings

FIG. 1 is a plot comparing flexural modulus for a portion of the polymer composition examples and comparative examples;

FIG. 2 is a graph comparing Izod impact strength of a portion of the examples of polymer compositions and a comparative example;

FIG. 3 is a graph comparing warpage rates of portions of polymer composition examples and comparative examples.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are intended to be illustrative only and are not intended to be limiting as other obvious modifications may occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.

The instruments or reagents used in the examples of the present invention are not specified by the manufacturer, and are all conventional commercial instruments or reagents. Wherein the iron oxide adopts Bayferrox series products of Bayer Leco, and the average particle size is 100 nanometers.

Examples E1 to E4

According to the compounds and the mixture ratio listed in the table 1, the components are mixed to prepare the polymer composite nucleating agent E1-E4.

TABLE 1 composition and compounding ratio of Polymer composite nucleating agent in each example

Comparative examples C1-C3

Nucleating agent comparative examples C1-C3 were prepared by mixing the ingredients in the proportions and compounds listed in Table 2.

TABLE 2 composition and compounding ratio of nucleating agent comparative examples

Application examples

Preparation of the Polymer composition: 100 parts by weight of homo-polypropylene (Dajin chemical) were mixed with 0.2 part by weight of polymer to form nucleating agent E1-E4 and nucleating agent comparative example C1-C3, respectively, and the mixture was extruded and pelletized in a twin-screw extruder at a melt extrusion temperature of 190 ℃ and 210 ℃ for 10 minutes in a high-speed mixer at a speed of 800r/min, and the pellets were dried and molded into test specimens on an injection molding machine to obtain the polymer compositions of examples 1-4 and comparative examples 1-3, respectively. The sample numbers are consistent with the nucleating agent used, for example, the sample number using nucleating agent comparative example C1 is comparative example 1, the sample number using polymer composite nucleating agent E3 is example 3, and so on. The homopolypropylene without the additive was treated in the same manner as a blank sample.

The prepared samples were tested for mechanical properties and dimensional stability, and the test results are shown in table 3. The higher the flexural modulus and tensile strength, the better the rigidity of the polymer; the higher the cantilever beam impact strength is, the better the toughness of the polymer is; the lower the warpage, the better the dimensional stability of the polymer.

Wherein, the cantilever beam impact strength is tested according to GB/T1843-2008, the tensile strength is tested according to GB/T1040.2-2006, the flexural modulus is tested according to GB/T9341-2008, and the shrinkage rate is tested according to GB/T15585-1995. The warping rate calculation formula is as follows:

warpage rate ═ transverse shrinkage rate-longitudinal shrinkage rate)/(transverse shrinkage rate + longitudinal shrinkage rate) ] × 100%.

TABLE 3 Polymer composition Property testing

As shown in Table 3 for comparative example 1 of Polymer composition, bis [2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphate was added alone]When aluminum hydroxide is used, the rigidity and toughness of the polypropylene are improved, but the shrinkage rate and warpage of the polypropylene are increased simultaneously, which often causes severe warpage denaturation of the product, thereby affecting the use and safety of the product. As shown in comparative example 2, Fe alone was added₂O₃Meanwhile, the dimensional stability of polypropylene is improved, but the impact resistance is reduced, which limits the application fields of products. As shown in comparative example 3, the performance of polypropylene was almost not improved by adding sodium stearate alone, similar to the blank.

Polymer composition examples 1-4 of Table 3 show bis [2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphate]Hydroxy aluminium salt, Fe₂O₃And sodium stearate, each property tested (flexural modulus, tensile)Tensile strength, longitudinal shrinkage, transverse shrinkage and warping rate) are improved relative to a blank sample, so that the application field of polypropylene can be greatly expanded. Examples 3 and 4 in particular show that, despite the bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate in examples 3 and 4]The effective amount of the aluminum hydroxy salt added was less than half of that in comparative example 1, while Fe₂O₃Or sodium stearate has no obvious effect on the flexural modulus and the impact strength of the polypropylene composite material when used independently, but the flexural modulus and the cantilever beam impact strength of the examples 3 and 4 are greatly superior to those of the comparative example 1 and are far higher than those of the comparative examples 2 and 3; and meanwhile, the shrinkage rate and the warpage rate of the samples 3 and 4 are smaller than those of the blank samples, so that the mechanical property is improved and the side effect on the dimensional stability is not brought as in the comparative example 1.

The best solution is selected from the embodiment 3 by combining various factors. As shown in fig. 1, 2 and 3, example 3 has a flexural modulus 9% higher than that of comparative example 1 and an impact strength 36% higher than that of the blank sample; example 3 had an impact strength 48% higher than that of comparative example 1 and 119% higher than that of the blank; meanwhile, in example 3, the warpage rate was 43% lower than that of comparative example 1 and 29% lower than that of the blank sample.

Table 3 shows the results of the tests that bis [2, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate]Hydroxy aluminium salt, Fe₂O₃And the sodium stearate have strong unexpected synergistic effect, the polymer property can be comprehensively improved in all directions, the rigidity and the toughness of the polymer are greatly improved, the shrinkage rate is reduced, the warpage rate is reduced, and the dimensional stability of a product is improved. The polymer composite nucleating agent is an extremely effective polymer rigidity-enhancing toughening anti-warping additive, can greatly expand the application field of polymers, and meets the market demand.

It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are given by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.