A high rigidity, low warpage, flame retardant reinforced PPA / PPO material

Abstract

The present invention relates to a high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material, belonging to the technical field of polyamide alloy material preparation. The material includes the following raw materials by weight: 60-80 parts of PPA, 20-40 parts of PPO, 15-30 parts of impact-resistant additives, 6-14 parts of fillers, 1-3 parts of compatibilizers, 1-3 parts of antioxidants, and 1-3 parts of lubricants; the impact-resistant additive is a hyperbranched polyurethane prepared by hyperbranched polyester, diisocyanate and chain extender under the catalytic action of an organic tin catalyst; wherein the hyperbranched polyester is prepared by esterification of glycerol and silicon skeleton dibasic acid. The present invention improves the miscibility of PPA and PPO by introducing a homemade impact-resistant additive, and improves the overall mechanical properties, rigidity and impact resistance of the resulting alloy material.

Description

Technical Field

[0001] The invention belongs to the technical field of polyamide alloy material preparation, and specifically relates to a high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material. Background Art

[0002] Polyphthalamide (PPA) resin is a semi-aromatic polyamide made of terephthalic acid or phthalic acid. It has excellent thermal oxidation stability, resistance to chemical organic reagents, resistance to extremely strong acids and strong oxidants, etc. However, it is easy to absorb moisture and has poor impact resistance. Polyphenylene ether (PPO) has good electrical insulation, water resistance, rigidity and flame retardancy, but it also has the following disadvantages: poor resistance to inorganic acids, alkalis, aromatic hydrocarbons, halogenated hydrocarbons, oils, etc., easy swelling and stress cracking, poor meltability, and difficult processing. PPO and PPA are used as base materials to make a blended alloy. The two can complement each other in some properties, such as reducing the hygroscopicity of the alloy material, improving the solvent resistance of the alloy material, improving the problem of PPO processing difficulties through PPA and processing aids, and forming a blended alloy with high rigidity, good flame retardancy and good dielectric properties through blending. This will greatly broaden the application scenarios of PPA and PPO.

[0003] However, both PPA and PPO are rigid polymer materials. Although the two can be blended and processed by adding existing compatibilizers, the resulting alloy material is prone to warping and has poor impact resistance. Summary of the invention

[0004] In view of the problems in the background technology, the object of the present invention is to provide a high-rigidity, low-warping, flame-retardant, reinforced PPA / PPO material.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material, comprising the following raw materials in parts by weight: 60-80 parts of PPA, 20-40 parts of PPO, 15-30 parts of impact-resistant additives, 6-14 parts of fillers, 1-3 parts of compatibilizers, 1-3 parts of antioxidants, and 1-3 parts of lubricants;

[0007] The impact-resistant additive is a hyperbranched polyurethane prepared from hyperbranched polyester, diisocyanate and chain extender under the catalytic action of an organic tin catalyst; wherein the hyperbranched polyester is prepared from glycerol and silicon skeleton dibasic acid through an esterification reaction.

[0008] Furthermore, the mass ratio of the hyperbranched polyester, diisocyanate and chain extender is 40-60:40-55:4-8.

[0009] Further, the chain extender is one of 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol; preferably, the chain extender is 1,4-butanediol.

[0010] Furthermore, the reaction of the hyperbranched polyester, diisocyanate and chain extender comprises:

[0011] After the hyperbranched polyester, diisocyanate, organotin catalyst and the first organic solvent are uniformly mixed, the mixture is heated to a first reaction temperature and stirred for a first predetermined time. The mixture is then heated to a second reaction temperature, a chain extender is added, and stirring is continued for a second predetermined time. After post-treatment, a hyperbranched polyurethane is obtained.

[0012] Furthermore, the first organic solvent is one of N,N-dimethylacetamide, toluene and benzene. Preferably, the first organic solvent is N,N-dimethylacetamide.

[0013] Furthermore, the first reaction temperature is 50-80° C., and the first predetermined time is 2-4 hours.

[0014] Furthermore, the second reaction temperature is 70-100° C., and the second predetermined time is 2-4 hours.

[0015] Furthermore, the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

[0016] Furthermore, the esterification reaction of glycerol and silicon skeleton dibasic acid comprises:

[0017] The glycerol, silicon skeleton dibasic acid, esterification reaction catalyst and the second organic solvent are mixed, heated to the esterification reaction temperature, and stirred and heated to react until the reaction is completed. After post-treatment, a hyperbranched polyester is obtained.

[0018] Furthermore, the second organic solvent is one of ethanol, acetic acid, tetrahydrofuran, toluene and benzene. Preferably, the second organic solvent is tetrahydrofuran.

[0019] Furthermore, the esterification reaction temperature is 60-90° C., and the heating reaction time is 4-8 hours.

[0020] Preferably, the molar ratio of glycerol to silicon skeleton dibasic acid is 2:3.1-3.5.

[0021] Furthermore, the silicon skeleton dibasic acid is prepared by a hydrosilylation reaction of acrylic acid and 1,1,3,3-tetramethyldisiloxane at a molar ratio of 2.1-2.2:1.

[0022] Furthermore, the silicon skeleton dibasic acid is prepared by reacting acrylic acid and 1,1,3,3-tetramethyldisiloxane, comprising:

[0023] Acrylic acid, 1,1,3,3-tetramethyldisiloxane, a hydrosilylation catalyst and a third organic solvent are mixed, heated to a hydrosilylation reaction temperature, and stirred to react until the reaction is completed. After post-treatment, a silicon skeleton dibasic acid is obtained.

[0024] Furthermore, the third organic solvent is one of toluene and benzene.

[0025] Furthermore, the hydrosilylation reaction temperature is 85-95° C., and the hydrosilylation reaction time is 5-8 h.

[0026] Furthermore, the filler is an inorganic nanofiller, and the inorganic nanofiller is one of nano-silicon dioxide and calcium carbonate whiskers. Preferably, the filler is silica modified by a silane coupling agent. The preparation of silica modified by a silane coupling agent adopts a thermal coupling method well known in the technical field, and the present invention does not make any specific limitation here.

[0027] Furthermore, the compatibilizer is maleic anhydride grafted polyphenylene ether (PPO-G-MAH).

[0028] Beneficial effects of the present invention:

[0029] In order to solve the problem in the background technology, the present invention introduces a self-made impact-resistant additive into the system during the blending process of PPA and PPO as a promoter for improving the rigidity and impact resistance of PPA / PPO, wherein the self-made impact-resistant additive is a hyperbranched polyurethane, which is not only an excellent elastomer, but also a hyperbranched polymer with numerous branches, and the soft chains in the branches are silicon skeleton alkyl chains. Compared with the alkyl chains in ordinary polyurethanes, the flexibility and toughness of the silicon skeleton alkyl chains are greater. The hyperbranched polyurethane with the silicon skeleton alkyl chains as units can be respectively combined with PPA and PPO in the PPA / PPO blending system. , PPO produce intermolecular physical and chemical forces, among which, the intermolecular physical force, under the dual support of the hyperbranched structure and the silicon skeleton alkyl chain, makes the impact-resistant additive easy to entangle with the main chain of the PPA / PPO molecule, and the chemical force is the hydrogen bond formed by the silicon oxygen in the silicon skeleton alkyl chain. The above two effects make the impact-resistant additive further enhance the miscibility of PPA and PPO. On the one hand, it coordinates with the compatibilizer to promote the blending processing of PPA and PPO. On the other hand, after the blending of PPA and PPO, the overall mechanical properties, rigidity and impact resistance of the obtained alloy material are improved. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] Preparation of impact-resistant additives:

[0033] (1) 0.22 mol of acrylic acid, 0.1 mol of 1,1,3,3-tetramethyldisiloxane, 1.3 g of carbon-supported platinum catalyst (Pt / C) and 100 mL of toluene were mixed, heated to 95° C., stirred and reacted for 5 h, rotary evaporated, cooled, washed with water, and dried to obtain a silicon skeleton dibasic acid;

[0034] (2) 0.2 mol of propylene glycol, 0.35 mol of silicon skeleton dibasic acid and 100 mL of tetrahydrofuran were mixed, and 2 g of concentrated sulfuric acid was added dropwise under stirring. After the addition was complete, the mixture was heated to 90° C. and continued to stir and heat for 4 h. The mixture was rotary evaporated, washed with water and dried to obtain a hyperbranched polyester.

[0035] (3) After 60 g of hyperbranched polyester, 55 g of diphenylmethane diisocyanate, 2.8 g of dibutyltin dilaurate and 120 mL of N,N-dimethylacetamide are mixed uniformly, heated to 80° C., stirred for 2 h, then heated to 100° C., 6 g of 1,4-butanediol is added, and stirring is continued for 2 h. The mixture is rotary evaporated, washed with water, and dried to obtain a hyperbranched polyurethane (i.e., an impact-resistant additive).

[0036] Example 2

[0037] Preparation of impact-resistant additives:

[0038] (1) 0.21 mol of acrylic acid, 0.1 mol of 1,1,3,3-tetramethyldisiloxane, a carbon-supported platinum catalyst and 100 mL of toluene were mixed, heated to 85° C., stirred and reacted for 8 h, rotary evaporated, cooled, washed with water and dried to obtain a silicon skeleton dibasic acid;

[0039] (2) 0.2 mol of propylene glycol, 0.31 mol of silicon skeleton dibasic acid and 100 mL of tetrahydrofuran were mixed, and 2 g of concentrated sulfuric acid was added dropwise under stirring. After the addition was complete, the mixture was heated to 60° C. and continued to stir and heat for 8 h. The mixture was rotary evaporated, washed with water and dried to obtain a hyperbranched polyester.

[0040] (3) After 40 g of hyperbranched polyester, 40 g of diphenylmethane diisocyanate, 2.1 g of dibutyltin dilaurate and 120 mL of N,N-dimethylacetamide were mixed uniformly, heated to 70 ° C, stirred for 2 h, then heated to 85 ° C, 4 g of 1,4-butanediol was added, and stirring was continued for 4 h. The mixture was rotary evaporated, washed with water, and dried to obtain a hyperbranched polyurethane (i.e., an impact-resistant additive).

[0041] Example 3

[0042] Preparation of PPA / PPO materials:

[0043] 1. Prepare the following raw materials in parts by weight: 60 parts of PPA, 40 parts of PPO, 15 parts of the impact-resistant additive prepared in Example 1, 10 parts of silica modified by a silane coupling agent, 1 part of PPO-G-MAH, 1 part of an antioxidant, and 1 part of a lubricant, wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 2:1, and the lubricant is zinc stearate;

[0044] 2. Mix the above-mentioned parts by weight of PPA, PPO, PPO-G-MAH, impact additive, silane coupling agent-modified silica, antioxidant and lubricant in a mixer at 140-190° C., transfer to a twin-screw extruder, melt-blend and extrude at 250-300° C., and shape to obtain a PPA / PPO material.

[0045] Example 4

[0046] Preparation of PPA / PPO materials:

[0047] 1. Prepare the following raw materials in parts by weight: 70 parts of PPA, 30 parts of PPO, 20 parts of the impact-resistant additive prepared in Example 2, 6 parts of silica modified by a silane coupling agent, 2 parts of PPO-G-MAH, 2 parts of an antioxidant, and 2 parts of a lubricant, wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 2:1, and the lubricant is zinc stearate;

[0048] 2. Mix the above-mentioned parts by weight of PPA, PPO, PPO-G-MAH, impact additive, silane coupling agent-modified silica, antioxidant and lubricant in a mixer at 140-190° C., transfer to a twin-screw extruder, melt-blend and extrude at 250-300° C., and shape to obtain a PPA / PPO material.

[0049] Example 5

[0050] Preparation of PPA / PPO materials:

[0051] 1. Prepare the following raw materials in parts by weight: 80 parts of PPA, 20 parts of PPO, 30 parts of the impact-resistant additive prepared in Example 1, 14 parts of silica modified by a silane coupling agent, 3 parts of PPO-G-MAH, 3 parts of an antioxidant, and 3 parts of a lubricant, wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1010 in a mass ratio of 2:1, and the lubricant is zinc stearate;

[0052] 2. Mix the above-mentioned parts by weight of PPA, PPO, PPO-G-MAH, impact additive, silane coupling agent-modified silica, antioxidant and lubricant in a mixer at 140-190° C., transfer to a twin-screw extruder, melt-blend and extrude at 250-300° C., and shape to obtain a PPA / PPO material.

[0053] Comparative Example 1

[0054] Preparation of PPA / PPO materials: Compared with Example 3, the impact-resistant additive was replaced by an equal amount of the hyperbranched polyester prepared in step (2) of Example 1, and the rest was the same.

[0055] Comparative Example 2

[0056] Preparation of PPA / PPO materials: Compared with Example 3, the impact-resistant additive was replaced with WHT-1185EC polyurethane pellets in equal parts, and the rest was the same.

[0057] Comparative Example 3

[0058] Preparation of PPA / PPO material: Compared with Example 3, an equal amount of the impact-resistant additive was deleted, and the rest was the same.

[0059] The following physical property tests were performed on the PPA / PPO materials obtained in Examples 3-5 and Comparative Examples 1-3, and the test results are shown in Table 1. The warpage test is performed by injection molding a disc-shaped sample during molding, the disc-shaped sample has a diameter of d=100 mm, a thickness of 2.0=mm, and after being placed for 48 hours, the maximum height h of the disc after warping is measured, and the warpage a=(h / d)×100%.

[0060] Table 1

[0061] Tensile Strength Bending Strength Notched impact strength Warpage GB / T 1040.2 GB / T 9341 GB / T 1043.1 / unit Mpa Mpa <![CDATA[KJ / m 2 ]]> ％ Example 3 168 222 20 1.7 Example 4 175 236 23 1.4 Example 5 188 247 25 1.2 Comparative Example 1 112 175 11 4.5 Comparative Example 2 141 203 15 3.3 Comparative Example 3 135 194 9 5.9

[0062] It can be seen from the data in Table 1 that Examples 3-5 have excellent impact resistance and low warpage performance.

[0063] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0064] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A high rigidity, low warpage, flame retardant, reinforced PPA / PPO material, characterized in that: The invention comprises the following raw materials in parts by weight: 60-80 parts of PPA, 20-40 parts of PPO, 15-30 parts of impact-resistant additive, 6-14 parts of filler, 1-3 parts of compatibilizer, 1-3 parts of antioxidant, and 1-3 parts of lubricant; The impact-resistant additive is a hyperbranched polyurethane prepared from hyperbranched polyester, diisocyanate and chain extender under the catalytic action of an organic tin catalyst; wherein the hyperbranched polyester is prepared from glycerol and silicon skeleton dibasic acid through an esterification reaction; The esterification reaction of glycerol and silicon skeleton dibasic acid comprises: mixing glycerol, silicon skeleton dibasic acid, esterification reaction catalyst and second organic solvent, heating to esterification reaction temperature, continuing stirring and heating reaction until the reaction is completed, and post-processing to obtain hyperbranched polyester; The silicon skeleton dibasic acid is prepared by a hydrosilylation reaction of acrylic acid and 1,1,3,3-tetramethyldisiloxane at a molar ratio of 2.1-2.2:1; The molar ratio of the glycerol to the silicon skeleton dibasic acid is 2:3.1-3.

5.

2. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 1, characterized in that: The mass ratio of the hyperbranched polyester, diisocyanate and chain extender is 40-60:40-55:4-8.

3. The high rigidity, low warpage, flame retardant, reinforced PPA / PPO material according to claim 1, characterized in that: The chain extender is one of 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol.

4. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 1, characterized in that: The reaction of the hyperbranched polyester, diisocyanate and chain extender comprises: uniformly mixing the hyperbranched polyester, diisocyanate, an organic tin catalyst and a first organic solvent, heating to a first reaction temperature, stirring for a first predetermined time, then heating to a second reaction temperature, adding a chain extender, continuing stirring for a second predetermined time, and obtaining a hyperbranched polyurethane through post-treatment.

5. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 4, characterized in that: The first organic solvent is one of N,N-dimethylacetamide, toluene and benzene, the first reaction temperature is 50-80°C, the first predetermined time is 2-4h, the second reaction temperature is 70-100°C, and the second predetermined time is 2-4h.

6. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 1, characterized in that: The second organic solvent is one of ethanol, acetic acid, tetrahydrofuran, toluene and benzene, the esterification reaction temperature is 60-90° C., and the reaction time of the heating reaction is 4-8 hours.

7. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 1, characterized in that: The silicon skeleton dibasic acid is prepared by the reaction of acrylic acid and 1,1,3,3-tetramethyldisiloxane, comprising: mixing acrylic acid, 1,1,3,3-tetramethyldisiloxane, a hydrosilylation catalyst and a third organic solvent, heating to a hydrosilylation reaction temperature, continuing to stir the reaction until the reaction is completed, and performing post-treatment to obtain the silicon skeleton dibasic acid.

8. The high-rigidity, low-warpage, flame-retardant, reinforced PPA / PPO material according to claim 7, characterized in that: The third organic solvent is one of toluene and benzene, the hydrosilylation reaction temperature is 85-95° C., and the hydrosilylation reaction time is 5-8 hours.