Flexible PPS film and preparation method thereof

Abstract

The invention relates to a flexible PPS film and a preparation method thereof, and belongs to the technical field of film preparation. The film is prepared from the following raw materials in parts by weight: 60 to 80 parts of polyphenylene sulfide, 25 to 40 parts of castor oil-based toughening agent and 5 to 12 parts of organic modified glass fiber. The castor oil-based toughening agent is prepared from a derivative of castor oil and a double-bond end-capping substance; the castor oil derivative is generated by carrying out esterification reaction on castor oil and an isomannitol derivative; the isomannitol derivative is generated by mixing isomannitol and 1, 6-adipic acid according to a molar ratio of 1: (2-3) and carrying out esterification reaction. The castor oil-based toughening agent and the organic modified glass fiber are introduced into the polyphenylene sulfide base material, toughness enhancement of a flexible chain segment of the castor oil and rigidity enhancement of the glass fiber are utilized, and the castor oil-based toughening agent and the glass fiber synergistically enhance and modify the toughness of the polyphenylene sulfide, so that a film formed by stretching is uniform in thickness and good in molding.

Description

Technical Field

[0001] The present invention belongs to the technical field of film preparation, and in particular relates to a flexible PPS film and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a high-performance thermoplastic resin, a polymer formed by a para-substituted pattern of sulfur atoms and phenylene rings. Its molecular structure contains highly stable chemical bonds, which give it excellent heat resistance, thermal stability, corrosion resistance, and chemical resistance. It also has a very low dielectric constant and excellent insulation properties in high-temperature and high-humidity environments, showing great potential for use in protective films for flexible circuit boards. However, PPS contains a relatively high content of oligomers and a relatively low content of ultra-high molecular weight polymers, resulting in high brittleness, low toughness, and poor impact resistance. Furthermore, films made from it have uneven thickness and are prone to localized rupture, which in turn limits its application in the film field. Summary of the Invention

[0003] The object of the present invention is to provide a flexible PPS film and a preparation method thereof, so as to solve the problem that the film is prone to unevenness and local rupture during the existing PPS film formation.

[0004] The first object of the present invention is to provide a flexible PPS film, which comprises the following raw materials in parts by weight: 60-80 parts of polyphenylene sulfide, 25-40 parts of castor oil-based toughening agent, and 5-12 parts of organic modified glass fiber.

[0005] Furthermore, the castor oil-based toughening agent is made of a castor oil derivative and a double bond-terminated product;

[0006] The castor oil derivative is produced by esterification reaction of castor oil and an isomannide derivative;

[0007] The isomannide derivative is prepared by mixing isomannide and 1,6-adipic acid in a molar ratio of 1:2-3 and subjecting the mixture to an esterification reaction.

[0008] Furthermore, the reaction of the castor oil derivative and the double-bond end-capped product occurs in the presence of a first esterification catalyst, at a reaction temperature of 130-155° C., and for a reaction time of 2-6 hours.

[0009] Furthermore, the first esterification reaction catalyst is one of concentrated sulfuric acid (mass fraction 98%) and p-toluenesulfonic acid.

[0010] Furthermore, the double bond end-capping substance is propylene alcohol.

[0011] Furthermore, the molar ratio of the double bond capping product to isomannide is 1-3:1.

[0012] Furthermore, the esterification reaction of the castor oil and the derivative of isomannide occurs in the presence of a second esterification catalyst, and the reaction temperature is 130-155° C., and the reaction time is 12-24 hours.

[0013] Furthermore, the second esterification reaction catalyst is one of concentrated sulfuric acid (mass fraction 98%) and p-toluenesulfonic acid.

[0014] Furthermore, the molar ratio of castor oil to isomannide is 1:3-4.

[0015] Furthermore, the esterification reaction of isomannide and 1,6-adipic acid occurs in the presence of a first organic solvent and a third esterification catalyst, with a reaction temperature of 80-100° C. and a reaction time of 4-12 hours.

[0016] Furthermore, the first organic solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide.

[0017] Furthermore, the third esterification reaction catalyst is one of concentrated sulfuric acid (mass fraction 98%) and p-toluenesulfonic acid.

[0018] Furthermore, the organically modified glass fiber is a glass fiber modified with a silane coupling agent.

[0019] Preferably, the organically modified glass fiber is a glass fiber modified with a double bond type silane coupling agent.

[0020] A second object of the present invention is to provide a method for preparing a flexible PPS film, the method comprising:

[0021] Mixing polyphenylene sulfide and a castor oil-based toughening agent to obtain a first mixture;

[0022] The first mixture and the organic modified glass fiber are blended, extruded, stretched and shaped to obtain a flexible PPS film.

[0023] Furthermore, the temperature of the blending extrusion is 270-320°C.

[0024] Furthermore, the stretching temperature is 90-125°C.

[0025] Beneficial effects of the present invention:

[0026] The present invention introduces a castor oil-based toughening agent and an organically modified glass fiber into a polyphenylene sulfide base material, utilizing the toughness enhancement of the castor oil flexible chain segment and the rigidity enhancement of the glass fiber. The two synergistically enhance the toughness of the polyphenylene sulfide, so that the film formed by stretching has a uniform thickness and good molding.

[0027] Notably, the castor oil-based toughening agent of the present invention contains a condensed ring rigid structure of isomannide, which not only avoids the reduction in the heat resistance of polyphenylene sulfide caused by the introduction of the castor oil-based toughening agent generated from castor oil and alkyl chain carboxylic acid, but also the condensed ring rigid structure hinders the regular arrangement of polyphenylene sulfide molecular chains during the stretching film forming process, reduces the crystallinity of the polyphenylene sulfide sheet during the stretching process, is beneficial to stretching film forming, and thus improves the stretching yield of the final PPS film and the uniformity of the film. DETAILED DESCRIPTION

[0028] 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 embodiments described 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0029] Example 1

[0030] Preparation of castor oil-based toughening agent:

[0031] 1. Place 0.31 mol of isomannide and 0.62 mol of 1,6-hexanedioic acid in 150 mL of N,N-dimethylformamide, and add P-TSA (p-toluenesulfonic acid) (the amount of which is 2% of the total mass of the isomannide and 1,6-hexanedioic acid raw materials). Under nitrogen, mix thoroughly and heat to 90° C., stir and react for 4 hours. Stop the reaction, rotary evaporate, wash, and dry to obtain an isomannide derivative (hereinafter referred to as derivative A).

[0032] 2. Mix 0.1 mol CO (castor oil), the derivative A obtained in step 1, and P-TSA (3% of the total mass of CO and derivative A) and heat to 135° C. under nitrogen, and stir and react for 24 hours. Add P-TSA (the mass of the supplement is 1% of the mass of allyl alcohol) and add 0.35 mol of allyl alcohol. Stir and react for 2 hours. Stop the reaction, wash, and dry to obtain a castor oil-based toughening agent.

[0033] Example 2

[0034] Preparation of castor oil-based toughening agent:

[0035] 1. Place 0.31 mol of isomannide and 0.93 mol of 1,6-hexanedioic acid in 150 mL of N,N-dimethylformamide, and add P-TSA (p-toluenesulfonic acid) (the added mass is 2% of the total mass of the isomannide and 1,6-hexanedioic acid raw materials). Under nitrogen, mix well and heat to 100° C., stir and react for 4 hours. Stop the reaction, rotary evaporate, wash, and dry to obtain an isomannide derivative (hereinafter referred to as derivative A).

[0036] 2. Mix 0.1 mol CO (castor oil), the derivative A obtained in step 1, and P-TSA (3% of the total mass of CO and derivative A) and heat to 155° C. under nitrogen, and stir and react for 12 h. Add P-TSA (1% of the mass of allyl alcohol) and add 0.4 mol allyl alcohol. Stir and react for 6 h. Stop the reaction, wash, and dry to obtain a castor oil-based toughening agent.

[0037] Comparative Example 1

[0038] Preparation of castor oil-based toughening agent:

[0039] 0.1 mol CO (castor oil), 0.31 mol 1,6-adipic acid and P-TSA (the added mass is 3% of the total mass of CO and 1,6-adipic acid) are mixed evenly, heated to 130°C under nitrogen, and stirred for reaction for 24 hours. P-TSA is added (the added mass is 1% of the mass of allyl alcohol) while keeping warm, 0.35 mol allyl alcohol is added, stirred for reaction for 2 hours, the reaction is stopped, washed, and dried to obtain a castor oil-based toughening agent.

[0040] Example 3

[0041] Preparation of PPS film:

[0042] The first step is to prepare the materials: including the following raw materials in parts by weight: 80 parts of polyphenylene sulfide, 25 parts of the castor oil-based toughening agent prepared in Example 1, and 5 parts of organic modified glass fiber (KH-560 modified glass fiber);

[0043] In the second step, after drying the raw materials, polyphenylene sulfide and a castor oil-based toughening agent are mixed to obtain a first mixture. The first mixture is then blended with organically modified glass fiber and extruded into a 0.1-0.2 mm film. The film is then stretched and shaped (heat treated) to obtain a flexible PPS film. The blending and extrusion temperature is 270-320°C, and the stretching temperature is 95°C.

[0044] Example 4

[0045] Preparation of PPS film:

[0046] The first step is to prepare the materials: including the following raw materials in parts by weight: 70 parts of polyphenylene sulfide, 30 parts of the castor oil-based toughening agent prepared in Example 2, and 9 parts of organic modified glass fiber (KH-560 modified glass fiber);

[0047] In the second step, after drying the raw materials, polyphenylene sulfide and a castor oil-based toughening agent are mixed to obtain a first mixture. The first mixture is then blended with organically modified glass fiber and extruded into a 0.1-0.2 mm film. The film is then stretched and shaped (heat treated) to obtain a flexible PPS film. The blending and extrusion temperature is 270-320°C, and the stretching temperature is 95°C.

[0048] Example 5

[0049] Preparation of PPS film:

[0050] The first step is to prepare the materials: including the following raw materials in parts by weight: 60 parts of polyphenylene sulfide, 40 parts of the castor oil-based toughening agent prepared in Example 1, and 12 parts of organic modified glass fiber (KH-560 modified glass fiber);

[0051] In the second step, after drying the raw materials, polyphenylene sulfide and a castor oil-based toughening agent are mixed to obtain a first mixture. The first mixture is then blended with organically modified glass fiber and extruded into a 0.1-0.2 mm film. The film is then stretched and shaped (heat treated) to obtain a flexible PPS film. The blending and extrusion temperature is 270-320°C, and the stretching temperature is 95°C.

[0052] Comparative Example 2

[0053] Preparation of PPS film: Compared with Example 1, the castor oil-based toughening agent was replaced by the castor oil-based toughening agent prepared in the comparative example in equal parts, and the rest were the same.

[0054] Comparative Example 3

[0055] Preparation of PPS film: Compared with Example 1, the castor oil-based toughening agent and the like were deleted, and the rest were the same.

[0056] The films obtained in Examples 3-5 and Comparative Examples 2-3 were subjected to physical property tests, and the test results are shown in Table 1.

[0057] Table 1

[0058] Serial number tensile strength Elongation at break Heat resistance Film appearance Test standards GB / T 1040 GB / T 1040 ISO 75 / unit MPa ％ ℃ / Example 3 106.5 105.2 167.4 Uniform thickness Example 4 114.2 110.8 173.7 Uniform thickness Example 5 118.7 113.3 180.5 Uniform thickness Comparative Example 2 96.3 98.1 126.3 Uniform thickness Comparative Example 3 88.6 21.3 140.6 Wrinkles

[0059] From the data in Table 1, it can be seen that the films obtained in Examples 3-5 of the present invention have good toughness and heat resistance.

[0060] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0061] 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 described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A flexible PPS film, characterized in that , including the following raw materials in parts by weight: 60-80 parts of polyphenylene sulfide, 25-40 parts of castor oil-based toughening agent, and 5-12 parts of organic modified glass fiber.

2. A flexible PPS film according to claim 1, characterized in that , the castor oil-based toughening agent is made of a castor oil derivative and a double bond end-capping product; The castor oil derivative is produced by esterification reaction of castor oil and an isomannide derivative; The isomannide derivative is prepared by mixing isomannide and 1,6-adipic acid in a molar ratio of 1:2-3 and subjecting the mixture to an esterification reaction.

3. A flexible PPS film according to claim 2, characterized in that The reaction of the castor oil derivative and the double bond-capped product occurs in the presence of a first esterification catalyst, at a reaction temperature of 130-155° C., and for a reaction time of 2-6 hours.

4. A flexible PPS film according to claim 2, characterized in that , the double bond end-capping substance is propylene alcohol.

5. A flexible PPS film according to claim 2, characterized in that The esterification reaction of the castor oil and the derivative of isomannide occurs in the presence of a second esterification catalyst, and the reaction temperature is 130-155° C. and the reaction time is 12-24 hours.

6. A flexible PPS film according to claim 2, characterized in that , the molar ratio of castor oil and isomannide is 1:3-4.

7. A flexible PPS film according to claim 2, characterized in that The esterification reaction of isomannide and 1,6-adipic acid occurs in the presence of a first organic solvent and a third esterification catalyst, and the reaction temperature is 80-100° C. and the reaction time is 4-12 hours.

8. The flexible PPS film according to claim 1, characterized in that: The organic modified glass fiber is a glass fiber modified by a silane coupling agent.

9. The method for preparing a flexible PPS film according to any one of claims 1 to 8, characterized in that: include: Mixing polyphenylene sulfide and a castor oil-based toughening agent to obtain a first mixture; The first mixture and the organic modified glass fiber are blended, extruded, stretched and shaped to obtain a flexible PPS film.

10. The method for preparing a flexible PPS film according to claim 9, characterized in that: The temperature of the blending extrusion is 270-320°C, and the temperature of the stretching is 90-125°C.