WO2017148302A1 - Rigidity-enhancing nucleating agent composition containing hydrotalcite - Google Patents

Abstract

The present invention relates to a rigidity-enhancing nucleating agent composition containing hydrotalcite, also relates to thermoplastics containing the nucleating agent composition, and in particular, to nylon containing the nucleating agent composition. The nucleating agent composition contains bis[4-tert-butylbenozic acid]hydroxyl aluminum and hydrotalcite with a weight ratio of 5:1-1:5. The nucleating agent composition has a better nucleating effect, and the resulting nylon products have high tensile strength and bending strength, low impact strength loss, and good thermal resistance. The nucleating agent of the present invention improves the demolding properties during nylon processing and shortens the injection molding cycle, thereby improving the production efficiency. In addition, the nucleating agent not only improves the dimensional stability of products and reduces their shrinkage, but also improves their mechanical properties, transparency, and thermal resistance.

Description

Additive nucleating agent composition containing hydrotalcite Technical field

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the field of nucleating agents, and more particularly to a rigid nucleating agent composition containing hydrotalcite, and to a thermoplastic containing the nucleating agent composition, and more particularly to a nylon containing the nucleating agent composition.

technical background

Thermoplastic refers to plastics with heat softening to flow and cooling hardening properties, which can be processed into various injection molded products by injection, extrusion and blow molding, such as daily life products, medical appliances, electrical appliances, automobiles and pipe pipes. Wait. Thermoplastic polymers to which the present invention relates include, but are not limited to, polyolefins (e.g., polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (e.g., nylon), polyurethanes, polyesters (e.g., poly-pairs). Ethylene phthalate) and its analogs.

Polyamide is commonly known as nylon. Nylon is one of the five most important general engineering plastics and is in great demand. The main varieties of nylon are nylon 6 (PA6) and nylon 66 (PA66). They have a wide variety of nylon products, such as reinforced nylon, high impact (toughened) nylon, conductive nylon, and flame retardant. Nylon, nylon and other polymer blends and alloys, and the like. These nylon injection molded parts have high mechanical strength, heat resistance, low friction coefficient, self-lubricating, oil resistance and many other characteristics, and are widely used in automotive, electronic and electrical, consumer goods, household appliances and other fields. In the production process of many nylon injection molded parts, problems such as slow crystallization rate, difficulty in demolding, and poor dimensional stability are common. For this reason, nylon is modified by adding a nucleating agent to increase the crystallization rate of nylon, and nylon products. The molding cycle, the demolding performance, dimensional stability and mechanical properties have been effectively improved. Nucleating Agents Modified nylons are used in a wide range of applications, such as automotive intake manifolds, engine covers, gears, cable ties, electrical connectors, and electronic connectors. However, there are few types of commercially available nylon nucleating agents, and fewer nucleating agents have excellent application effects.

At present, nylon nucleating agents with good performance in industrial production include the nucleating agent P22 introduced by Bruggolen of Germany, and the nucleating agent CAV102 by Clariant of Germany. At present, the performance of nucleating agents added to thermoplastics, especially nylon, is mainly related to the following aspects: 1. Fast polymer crystallization rate and/or high crystallization temperature, polymer melt cooling and solidification crystallization, macromolecules Long chain from disorder to ordered knot The crystal state requires a long relaxation time, a low crystallization rate and a crystallization temperature, and a large spherulie is formed. There is a distinct interface between the spherulites to cause different internal stresses, and cracks are easily generated when impacted by an external force. And rupture, and after adding a nucleating agent in the cooling process of the polymer melt formulation, the nucleating agent compound is used to provide a nucleation point for crystal growth, so that the crystallization rate is accelerated, thereby allowing crystallization at a higher temperature. High polymer peak crystallization temperature indicates high nucleation efficiency; its ultimate manifestation in manufacturing parts, high nucleation efficiency usually means fast processing cycle and more desirable physical properties such as hardness, modulus of elasticity, pull Stretching strength, impact balance, etc. Generally speaking, the rigidity of thermoplastics is characterized by flexural modulus, and the toughness is characterized by impact strength. 2. High transparency: thermoplastic articles themselves are required to have good transparency and uniformity in plastics. The dispersed nucleating agent becomes smaller, the crystal becomes fine, and the refined crystal reduces the scattering at the interface between the crystalline portion and the amorphous portion. When the body size is less than 1 μm, the transparency sharply increases.

In addition, in the processing of thermoplastics, especially nylon, there are often the following problems: 1. Demolding performance: Most of the nylon on the market is not easy to demould in the injection molding process, and the fluidity is not strong, bringing manufacturing Trouble, so most of the current processing uses the addition of mold release agent, but the release agent contains polycyclic aryl cyanide, which is a strictly restricted component of environmental protection requirements, in order to ensure safety and meet environmental protection requirements, the most direct way is The raw material itself is easily released from the mold and does not require a release agent.

In the prior art, thermoplastic nucleating agents are classified into organic and inorganic. Organic nucleating agents mainly include metal phosphates, metal carboxylates and sorbitol derivatives and polymer types. Organic nucleating agents usually have polymerizations. The good compatibility of the resin can significantly improve the transparency and gloss of the article. The aromatic carboxylic acid metal salt can significantly improve the toughness of the polymer resin by utilizing the crystallization mechanism of the β crystal nucleating agent, but has poor compatibility with it. Inorganic nucleating agents mainly include talc, titanium dioxide, nano-silica, etc. These nucleating agents are rich in source and cheap, but have certain influence on the transparency and surface gloss of the products, and the application effect is poor. Limitations. Hydrotalcite is widely used as an auxiliary agent in the field of high molecular polymers, especially as a synergist for acid acceptors and nucleating agents. For its combined use with other nucleating agents, CN102558683A discloses a polypropylene β. The crystal nucleating agent composition is a mixture of a carboxylic acid metal salt of a β crystal nucleating agent tetrahydrophthalic anhydride and an auxiliary agent calcium carbonate, hydrotalcite or talc, and other than that, it is not Related reports on the use of nuclear agents.

At present, research on the configuration of two or more nucleating agents into composite nucleating agents has become a hot topic. The use of multiple nucleating agents is used in areas that are very difficult to predict in the chemical field, and unless a large amount of work is tried, tested, and done, it is often impossible to know which substance is effective.

There is a need to provide a nucleating agent for thermoplastics, especially nylon, which combines fast polymers. At the same time as crystallization speed and/or high crystallization temperature and high transparency, there are also improvements in release properties and thermal stability properties. The applicant of the present invention has developed a nucleating agent composition which has been greatly improved in the above properties as compared with its individual components after a long period of investigation.

Summary of the invention

One of the objects of the present invention is to provide a rigid nucleating agent composition containing hydrotalcite which simultaneously produces high nucleation efficiency in a target thermoplastic article while also improving the release properties of the article. And thermal stability; the high nucleation efficiency is manifested by a fast polymer crystallization rate and/or a high crystallization temperature, which ultimately results in a significant increase in the impact strength, flexural modulus, and heat distortion temperature of the product.

Another object of the present invention is to provide the use of the above nucleating agent composition in a thermoplastic.

A third object of the present invention is to provide the use of the above nucleating agent composition in nylon.

In order to achieve the above object, the present invention provides a fused nucleating agent composition containing hydrotalcite, the nucleating agent composition comprising bis-[4-tert-butylbenzoic acid] hydroxyaluminum and hydrotalcite, both The weight ratio is 5:1 to 1:5.

Preferably, the weight ratio of bis-[4-tert-butylbenzoic acid]hydroxyaluminum to hydrotalcite is from 3:1 to 1:3; most preferably, the weight ratio of the two is 1:1.

Preferably, the hydrotalcite is a magnesium aluminum hydrotalcite having a general composition of Mg _1-X Al _X (OH) ₂ (A ^n- ) _{x / n} · mH ₂ O, wherein x = 0.2 to 0.33, A N ^- selected from CO ₃ ^2- , NO ₃ ^- or Cl ^- , n is 1 or 2, m = 1 to 10; more preferably, the hydrotalcite is a magnesium aluminum hydrotalcite having an anion of CO ₃ ^2- The average particle diameter is from 0.1 to 2.0 μm; more preferably from 0.1 to 0.4 μm.

The invention further provides for the use of the above nucleating agent composition in a thermoplastic.

The invention further provides for the use of the above nucleating agent composition in nylon.

The present invention provides the above nucleating agent composition for simultaneously improving the impact strength, flexural modulus, mold release property, and thermal stability of a nylon article.

The present invention also provides a nylon material comprising the above nucleating agent composition and nylon, wherein the weight of the nucleating agent composition is from 0.01 to 2.00% by weight of the nylon; preferably from 0.05 to 1.00%; further preferably 0.05-0.50%; particularly preferably 0.05-0.15%.

The term "thermoplastic" as used in the present invention refers to a polymeric material that will melt upon exposure to sufficient heat, but will remain solid when sufficiently cooled, but will not retain its original shape without the use of molds or the like. In particular, the term may also include only polymers defined in the broad range below: after the melt is formed, it may also be cooled by cooling. A polymer exhibiting a crystalline or semi-crystalline form. Thermoplastic polymers to which the present invention relates include, but are not limited to, polyolefins (e.g., polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (e.g., nylon), polyurethanes, polyesters (e.g., poly-pairs). Ethylene phthalate) and its analogs.

"Nylon" as used in the present invention includes nylon 6 (PA6) and nylon 66 (PA66).

Unless otherwise stated, "%" in the present application refers to a percentage by weight.

When the above nucleating agent composition of the present invention is mixed with nylon, other materials may be added to enhance other properties of the nylon article.

The nucleating agent composition provided by the invention makes up for the single nucleating agent to fully exert various kinds in the nucleating agent composition in the case of improving the rigidity, toughness, mold release property and thermal stability of the thermoplastic plastic product. The functional advantages of the nucleating agent allow the final product to combine all of the above properties.

The nucleating agent composition of the present invention can significantly improve the processing thermal stability of the article. Due to the decomposition or release of the auxiliaries used in the plastic processing or the acidic substances of the plastic itself, it is easy to cause disintegration of the plastic and affect the thermal stability of the processing. The nucleating agent composition of the present invention has a suction due to the added hydrotalcite. Acidity guarantees the thermal stability of the process.

The nucleating agent of the present invention has a better nucleating effect than the nylon nucleating agents P22 and CAV102 which are representative in the art, and the obtained nylon has high tensile and bending strength. , low impact strength loss, good heat resistance, etc. The nucleating agent of the invention improves the mold release performance of the nylon processing process, shortens the injection molding cycle, thereby improving the production efficiency, and on the other hand, improves the dimensional stability of the product, reduces the shrinkage rate, and also improves the product. Mechanical properties improve product transparency and heat resistance.

detailed description

The invention is further clarified by the following examples, but the preferred embodiments of the invention are provided herein, and the scope of the invention is not limited thereto.

First, the preparation example:

Source of raw materials: bis-[4-tert-butylbenzoic acid] hydroxyaluminum and hydrotalcite are commercially available products.

Nylon is PA6 (product model: M2800).

1. Preparation of the nucleating agent composition of the present invention

Example 1:

Accurately weigh 8.3g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 1.7g of hydrotalcite, respectively, and then in the blender The mixture was uniformly mixed to obtain the nucleating agent 1 of the present invention.

Example 2:

1.7 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 8.3 g of hydrotalcite were accurately weighed separately, and then uniformly mixed in a stirrer to obtain a nucleating agent 2 of the present invention.

Example 3:

7.5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 2.5 g of hydrotalcite were accurately weighed separately, and then uniformly mixed in a stirrer to obtain a nucleating agent 3 of the present invention.

Example 4:

2.5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 7.5 g of hydrotalcite were accurately weighed separately, and then uniformly mixed in a stirrer to obtain a nucleating agent 4 of the present invention.

Example 5:

5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 5 g of hydrotalcite were accurately weighed separately, and then uniformly mixed in a stirrer to obtain a nucleating agent 5 of the present invention.

2. Application examples

Application of nucleating agent of the invention in PA6

The nucleating agent 1 prepared in Example 1 was extruded and granulated in a twin-screw extruder according to a 0.15% addition amount of PA6 mass, and dried at a processing temperature of 250 ° C to obtain nylon particles 1.

Based on the same method, the nucleating agents 2-5 prepared in the above Examples 2-5 were respectively obtained into nylon particles 2-5.

The nucleating agents 1-5 prepared in the above Examples 1-5 were respectively obtained into nylon particles 6-10, except that the nucleating agent was added in an amount of 0.05%, based on the same method.

Similarly, blank nylon particle control samples were prepared without adding a nucleating agent under the conditions of nylon particle 1 preparation.

Similarly, nylon nucleating agents P22 and CAV102 which are currently used in the market were respectively added in an amount of 0.15% in accordance with the conditions for the preparation of the nylon particles 1, and nylon particles P22 and nylon particles CAV102 were obtained.

Second, performance test examples

1. Test crystallization temperature and release effect

The crystallization temperature of the nylon (PA6) to which the nucleating agent composition of the present invention is added is tested by DSC, as follows: under nitrogen conditions, the temperature is raised to 260 ° C at a temperature increase rate of 10 ° C / min, the temperature is 3 min, and then 10 ° C / min. The temperature was lowered to 25 ° C, and then the temperature was raised to 260 ° C at 10 ° C / min, and the cooling curve and the second heating curve were recorded.

The demolding performance is divided into the following four levels according to the time required for complete demolding:

(1) poor - sticking mold;

(2) Medium - manual assisted demoulding;

(3) Good - basically capable of automatic demoulding, occasionally manual assist;

(4) Excellent - completely automatic demoulding.

Table 1 below shows the compositions of the present invention applied to nylon in their respective crystallization temperatures and release effects in varying amounts and ratios.

Table 1 Release effect of bis-[4-tert-butylbenzoic acid] hydroxyaluminum and hydrotalcite composition on PA6 crystallization temperature and product

It can be seen from Table 1 that when bis-[4-tert-butylbenzoic acid] hydroxyaluminum and hydrotalcite are used in combination, the crystallization temperature of PA6 is significantly higher than that of the components added separately, and the two are heterogeneous in PA6. In the nuclear process, the synergistic effect was achieved, and the demolding performance was also improved. Further, the results showed that when the ratio of the two was 1:1, the effect was the best.

2. Perform haze test, flexural modulus test, impact strength test, heat distortion temperature test

The nylon particles 1 - 10 prepared in the above application examples, the nylon particle control sample, and the nylon nucleating agents P22 and CAV 102 currently on the market were respectively injection molded into standard splines at an injection temperature of 270 ° C. The haze, flexural modulus, impact strength, and heat distortion temperature were tested as follows.

Haze: tested according to the method in ASTM D1003-07 test standard;

The nucleating agent modified nylon is tested according to GB 2918-1998 (standard environment for plastic sample state adjustment and testing), at (23 ± 2) ° C, relative humidity (RH) is (50 ± 5)% The sample state adjustment time was 48 h. Physical performance tests were carried out according to national standards: cantilever beam notched impact strength standard GB/T 1843-1996, flexural modulus implementation standard GB/T9341-2000, heat distortion temperature implementation standard GB/T 1634-2004. The test results are listed in Table 2 below:

Table 2 Various properties of the nucleating agent modified PA6 (M2800) of the present invention

As can be seen from Table 2, the nylon particles 1-10 prepared by using the nucleating agent 1-10 of the present invention are in terms of haze, flexural modulus and heat distortion temperature as compared with the blank control and the conventional P22 and CAV102 on the market. The obvious effect is better, and the loss of impact strength is slightly better; the improvement of the flexural modulus greatly improves the rigidity of the product. In the case of the nylon particles 1-10 itself, the properties of the nylon particles 5 and the nylon particles 10 in which the ratio of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and hydrotalcite in the nucleating agent is 1:1 are expressed. Optimal.

The hydrotalcite-containing reinforced nucleating agent composition of the present invention has been described by a specific example, and those skilled in the art can refer to the content of the present invention and appropriately change the raw materials, process conditions and the like to achieve the corresponding other purposes. All such changes and modifications are obvious to those skilled in the art and are considered to be included within the scope of the present invention.

Claims (10)

A nucleating agent composition containing hydrotalcite, characterized in that the nucleating agent composition contains bis-[4-tert-butylbenzoic acid] hydroxyaluminum and hydrotalcite, and the weight ratio of the two is 5 :1~1:5. The addition nucleating agent composition according to claim 1, wherein the weight ratio of bis-[4-tert-butylbenzoic acid] hydroxyaluminum to hydrotalcite is from 3:1 to 1:3. The reinforced nucleating agent composition according to claim 1, wherein the weight ratio of bis-[4-tert-butylbenzoic acid] hydroxyaluminum to hydrotalcite is 1:1. The addition nucleating agent composition according to any one of claims 1 to 3, wherein the hydrotalcite is a magnesium aluminum hydrotalcite having an anion of CO ₃ ^2- and an average particle diameter of 0.1 to 2.0 μm. The addition nucleating agent composition according to any one of claims 1 to 3, wherein the hydrotalcite is a magnesium aluminum hydrotalcite having an anion of CO ₃ ^2- and an average particle diameter of 0.1 to 0.4 μm. Use of a reinforced nucleating agent composition according to any one of claims 1 to 3 in a thermoplastic. Use of the reinforced nucleating agent composition according to any one of claims 1 to 3 in nylon. The use of the nucleating agent composition for simultaneously improving the impact strength, flexural modulus, mold release property, transparency, and acid absorption of a nylon article according to the application of claim 8. A nylon material, characterized in that the nylon material comprises the nucleating agent composition according to any one of claims 1 to 3 and nylon, wherein the weight of the nucleating agent composition is from 0.01 to 2.00% by weight of the nylon. A nylon material characterized in that the weight of the nucleating agent composition is from 0.05 to 0.15% by weight based on the weight of the nylon.